JP2019001873A - Rubber composition and tire prepared therewith - Google Patents

Abstract

To provide a tire rubber composition excellent in low heat build-up properties and wear resistance.SOLUTION: The present invention provides a wet master batch rubber composition, wherein, a dispersant (E) is blended with a wet master batch (D) in which a rubber liquid containing a rubber component (A) composed of natural rubber is blended with carbon black (B) and inorganic filler (C).SELECTED DRAWING: None

Description

  The present invention relates to a rubber composition and a tire using the same, which have improved low heat buildup and wear resistance.

  In order to meet social demands for resource and energy savings in recent years, development of rubber compositions with low heat generation and wear resistance has been actively conducted in the rubber industry. The tire, which is the product, contributes to energy saving because it has low heat loss and low energy loss. On the other hand, it contributes to resource saving from the point of long life due to wear resistance.

As one of the low exothermic rubber compositions, Patent Document 1 discloses that carbon black and a specific hydrazide compound are added to an elastomer containing natural rubber for the purpose of improving the chemical interaction between the rubber component and carbon black. Is disclosed. Specifically, the interaction of these compounding components aims at uniform dispersion of carbon black.
In addition, as another means for realizing low heat generation, a method of blending silica is also known.

  However, in the method of Patent Document 1, low exothermic property is not sufficient, and further improvement is necessary. Furthermore, in addition to low heat build-up, further improvement in wear resistance is also demanded. In general, it is not easy to improve both low heat generation and wear resistance. In addition, consideration is required for workability.

  In any case, in order to further improve the above characteristics, it is necessary to uniformly disperse an inorganic filler such as carbon black or silica, particularly when used in combination.

Special table 2014-501827 gazette

  A rubber composition excellent in low heat buildup and wear resistance and a tire using the rubber composition are desired.

  It is characterized by being highly dispersed by blending a rubber liquid composed of a rubber component including natural rubber and carbon black and / or an inorganic filler selected from a specific range in a liquid phase, and further blending a specific dispersant. Thus, the dispersion effect is enhanced, so that a tire using a rubber composition having both low heat buildup and wear resistance and excellent workability is provided.

式中、Ａは、アリール基であり、少なくとも１つの極性基を有し、２つ以上の場合、該極性基は同じであっても、異なっていてもよい。Ｒ^１１及びＲ^１２は、それぞれ独立して、水素原子、アシル基、アミド基、アルキル基、シクロアルキル基及びアリール基からなる群から選択される少なくとも一種の置換基であり、さらに、該置換基は、酸素、硫黄及び窒素原子のうちの一種以上を含んでいてもよい。

式中、Ａは、アリール基であり、少なくとも１つの極性基を有し、２つ以上の場合、該極性基は同じであっても、異なっていてもよい。Ｒ^１３は、アルカンジイル基、シクロアルカンジイル基、アレーンジイル基からなる置換基であり、炭化水素の同一又は異なる炭素上から２つの水素を除いてなる２価の炭化水素基であり、さらに、該置換基は、酸素、硫黄及び窒素原子のうちの一種以上を含んでいてもよい。

式中、Ｒは炭素数１〜６の直鎖状又は分岐状のアルカンジイル基を表す。

式中、Ｍ^ｎ＋は、Ｈ^＋又はｎ価の金属イオンを表す。ｎは、１又は２の整数を表す。Ｒ^３１及びＲ^３２は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表すか、あるいは、Ｒ^３１とＲ^３２とが互いに結合して、それらが結合している窒素原子とともに環を形成する。ｍは、２〜９の整数を表す。

式中、Ｒ^１は置換基を有していてもよい炭素数２〜１２のアルカンジイル基、置換基を有していてもよい炭素数３〜１２のシクロアルカンジイル基、又は＊−Ｂ^１−Ａｒ−Ｂ^２−＊基を表し、＊は結合手を表す。Ｂ^１及びＢ^２は、単結合又は炭素数１〜１２のアルカンジイル基を表す。Ａｒは、置換基を有していてもよい炭素数６〜１２のアレーンジイル基を表す。Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ヒドロキシ基又は炭素数１〜６のアルコキシ基を表すか、或いは、互いに結合して炭素数２〜１２のアルカンジイル基を形成する。Ｒ^４は、ヒドロキシ基、炭素数１〜６のアルコキシ基、炭素数６〜１２のアリールオキシ基、炭素数７〜１５のアリールアルコキシ基、−ＮＲ^５Ｒ^６又は−Ｏ−（Ｙ^ｎ＋）_１／ｎを表し、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。Ｘは、−ＮＨ−又は−Ｏ−を表す。
及び、式（ＶＩ）で表される化合物の塩、溶媒和物、及び塩の溶媒和物。
（２） 前記（Ｅ）成分の配合量は、ウェットマスターバッチの（Ａ）ゴム成分１００質量部に対して、０．０５〜３０質量部含まれることを特徴とする、（１）に記載のタイヤ用ゴム組成物。
（３） ゴム成分１００質量部に対して、カーボンブラックを１０〜１６０質量部含むことを特徴とする、（１）又は（２）に記載のタイヤ用ゴム組成物。
（４） 前記一般式（Ｉ）で表わされる無機充填材が、シリカ：ＳｉＯ_２、アルミナ：Ａｌ_２Ｏ_３、アルミナ−水和物：Ａｌ_２Ｏ_３・Ｈ_２Ｏ、水酸化アルミニウム：Ａｌ（ＯＨ）_３、炭酸アルミニウム：Ａｌ_２（ＣＯ_３）_３、水酸化マグネシウム：Ｍｇ（ＯＨ）_２、酸化マグネシウム：ＭｇＯ、炭酸マグネシウム：ＭｇＣＯ_３、タルク：３ＭｇＯ・４ＳｉＯ_２・Ｈ_２Ｏ、アタパルジャイト：５ＭｇＯ・８ＳｉＯ_２・９Ｈ_２Ｏ、チタン白：ＴｉＯ_２、チタン黒：ＴｉＯ_２ｎ−１、酸化カルシウム：ＣａＯ、水酸化カルシウム：Ｃａ（ＯＨ）_２、酸化アルミニウムマグネシウム：ＭｇＯ・Ａｌ_２Ｏ_３）、クレー：Ａｌ_２Ｏ_３・２ＳｉＯ_２、カオリン：Ａｌ_２Ｏ_３・２ＳｉＯ_２・２Ｈ_２Ｏ、パイロフィライト：Ａｌ_２Ｏ_３・４ＳｉＯ_２・Ｈ_２Ｏ、ベントナイト：Ａｌ_２Ｏ_３・４ＳｉＯ_２・２Ｈ_２Ｏ、ケイ酸アルミニウム：Ａｌ_２ＳｉＯ_５、Ａｌ_４・３ＳｉＯ_４・５Ｈ_２Ｏ等、ケイ酸マグネシウム：Ｍｇ_２ＳｉＯ_４、ＭｇＳｉＯ_３等、ケイ酸カルシウム：Ｃａ_２・ＳｉＯ_４等、ケイ酸アルミニウムカルシウム：Ａｌ_２Ｏ_３・ＣａＯ・２ＳｉＯ_２等、ケイ酸マグネシウムカルシウム：ＣａＭｇＳｉＯ_４、炭酸カルシウム：ＣａＣＯ_３、酸化ジルコニウム：ＺｒＯ_２、水酸化ジルコニウム：ＺｒＯ（ＯＨ）_２・ｎＨ_２Ｏ、炭酸ジルコニウム：Ｚｒ（ＣＯ_３）_２、結晶性アルミノケイ酸塩からなる群から選ばれる少なくとも一種である（１）〜（３）のいずれか１つに記載のタイヤ用ゴム組成物。
（５） （１）〜（４）のいずれか１つに記載のタイヤ用ゴム組成物を用いてなることを特徴とするタイヤ。 That is, the present invention resides in the following (1) to (5).
(1) In a rubber liquid containing a rubber component (A) containing natural rubber,
Carbon black (B) and
At least one inorganic filler (C) selected from the following group (i):
For the wet masterbatch (D) obtained by mixing the slurry liquid previously dispersed in water, coagulating, dehydrating and drying,
The rubber composition for tires containing the dispersing agent (E) which is at least 1 sort (s) selected from the following (ii) group.
(I): the compound represented by formula _{(I) nM1 · xSiO y ·} zH 2 O ··· (I)
In the formula, M1 is selected from the group consisting of metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of these metals. It is at least 1 type, and n, x, y, and z are an integer of 0-5, an integer of 0-10, an integer of 2-5, and an integer of 0-10, respectively. However, the case where n = 0 and x = 0 are satisfied at the same time is excluded.
(Ii): Compounds represented by the following general formulas (II) to (VI)

In the formula, A is an aryl group having at least one polar group, and in the case of two or more, the polar groups may be the same or different. R ¹¹ and R ¹² are each independently at least one substituent selected from the group consisting of a hydrogen atom, an acyl group, an amide group, an alkyl group, a cycloalkyl group, and an aryl group. May contain one or more of oxygen, sulfur and nitrogen atoms.

In the formula, A is an aryl group having at least one polar group, and in the case of two or more, the polar groups may be the same or different. R ¹³ is a substituent composed of an alkanediyl group, a cycloalkanediyl group, and an arenediyl group, and is a divalent hydrocarbon group formed by removing two hydrogens from the same or different carbon of the hydrocarbon, The substituent may contain one or more of oxygen, sulfur and nitrogen atoms.

In the formula, R represents a linear or branched alkanediyl group having 1 to 6 carbon atoms.

In the formula, M ^{n +} represents H ⁺ or an n-valent metal ion. n represents an integer of 1 or 2. R ³¹ and R ³² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ³¹ and R ³² are bonded to each other, and together with the nitrogen atom to which they are bonded, a ring Form. m represents an integer of 2 to 9.

In the formula, R ¹ is an optionally substituted alkanediyl group having 2 to 12 carbon atoms, an optionally substituted cycloalkanediyl group having 3 to 12 carbon atoms, or * -B ^1. —Ar—B ² — * represents a group, and * represents a bond. B ¹ and B ² represent a single bond or an alkanediyl group having 1 to 12 carbon atoms. Ar represents an arenediyl group having 6 to 12 carbon atoms which may have a substituent. R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Or it couple | bonds together and forms a C2-C12 alkanediyl group. R ⁴ is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylalkoxy group having 7 to 15 carbon atoms, —NR ⁵ R ⁶ or —O— (Y ^{n +} ) _{1. / N} , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents -NH- or -O-.
And salts, solvates and solvates of the compounds represented by formula (VI).
(2) The compounding amount of the component (E) is 0.05 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A) of the wet masterbatch. Rubber composition for tires.
(3) The rubber composition for tire according to (1) or (2), comprising 10 to 160 parts by mass of carbon black with respect to 100 parts by mass of the rubber component.
(4) The inorganic filler represented by the general formula (I) is silica: SiO ₂ , alumina: Al ₂ O ₃ , alumina-hydrate: Al ₂ O ₃ .H ₂ O, aluminum hydroxide: Al ( OH) ₃ , aluminum carbonate: Al ₂ (CO ₃ ) ₃ , magnesium hydroxide: Mg (OH) ₂ , magnesium oxide: MgO, magnesium carbonate: MgCO ₃ , talc: 3MgO · 4SiO ₂ · H ₂ O, attapulgite: 5MgO 8SiO ₂ · 9H ₂ O, titanium white: TiO ₂ , titanium black: TiO _2n-1 , calcium oxide: CaO, calcium hydroxide: Ca (OH) ₂ , aluminum oxide magnesium: MgO · Al ₂ O ₃ ), clay _{: Al 2 O 3 · 2SiO 2} , _{kaolin: Al 2 O 3 · 2SiO 2} · 2H 2 O, pyrophyllite: A _{2 O 3 · 4SiO 2 · H} 2 O, _{bentonite: Al 2 O 3 · 4SiO 2} · 2H 2 O, aluminum _{silicate: Al 2 SiO 5, Al 4} · 3SiO 4 · 5H 2 O and the like, magnesium: Mg ₂ SiO ₄ , MgSiO ₃ etc., calcium silicate: Ca ₂ · SiO ₄ etc., aluminum calcium silicate: Al ₂ O ₃ · CaO · 2SiO ₂ etc., magnesium calcium silicate: CaMgSiO ₄ , calcium carbonate: CaCO ₃ , oxidation (1) to (3) which are at least one selected from the group consisting of zirconium: ZrO ₂ , zirconium hydroxide: ZrO (OH) ₂ .nH ₂ O, zirconium carbonate: Zr (CO ₃ ) ₂ and crystalline aluminosilicate. The rubber composition for tires as described in any one of 1).
(5) A tire comprising the tire rubber composition according to any one of (1) to (4).

According to (1), the rubber composition for tires in which the filler is highly dispersed by combining the wet masterbatch and the dispersant and has both low heat buildup and wear resistance can be obtained.
(2) to (4) specifically show the composition for realizing low heat build-up and improved wear resistance.
By (5), a tire having both low heat build-up and wear resistance can be obtained.

  The rubber composition for tires of the present invention comprises a slurry containing at least one filler selected from carbon black (B and inorganic filler (C) in a rubber liquid comprising a rubber component (A) containing natural rubber. The master batch (D) prepared by mixing is characterized by containing a dispersant (E).

<< Rubber component (A) >>
The rubber component (A) used in the rubber composition of the present invention contains natural rubber: NR of 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more. By setting the NR content in the rubber component (A) to 50% by mass or more, excellent low heat buildup and wear resistance can be obtained. As the natural rubber, a modified natural rubber obtained by introducing a polar functional group into the terminal or main chain may be used.

  The natural rubber which may be modified is particularly preferably used as natural rubber latex. Moreover, when performing a modification reaction, what carried out the modification reaction with respect to natural rubber latex, or after performing the modification reaction from natural rubber and re-emulsifying may be used.

  Further, the rubber component (A) includes other rubber materials such as polyisoprene rubber: IR, butadiene rubber: BR, styrene-butadiene copolymer rubber: SBR, acrylonitrile-butadiene copolymer rubber: NBR, chloroprene rubber: CR, butyl rubber: IIR, ethylene-propylene-diene copolymer rubber: rubber such as EPDM, and polar functional groups are introduced into the ends and main chains of these rubber components to appropriately contain modified rubber. May be.

  The rubber that may be used in addition to the natural rubber is a solid rubber produced by solution polymerization in the case of the rubber component latex obtained by emulsion polymerization or a rubber component polymer not suitable for emulsion polymerization. It may be a rubber component latex obtained by dispersing and emulsifying in an aqueous medium with rosin acid soap, tall oil soap, fatty acid soap or the like. The same applies to the modified rubber obtained by the modification reaction.

<< carbon black (B) >>
The present invention preferably contains carbon black (B) in addition to the rubber component (A). As the carbon black used, those usually used in the rubber industry can be used. For example, various grades of carbon black such as SAF, HAF, ISAF, FEF, and GPF can be used alone or in combination.

  The carbon black (B) is preferably contained in an amount of 10 to 160 parts by mass with respect to 100 parts by mass of the rubber component (A). When the amount is 10 parts by mass or more, a necessary reinforcing effect is obtained, and when the amount is 160 parts by mass or less, the exothermic property is suppressed to an appropriate range, and a balanced performance can be obtained. It is more preferable to contain 20-140 mass parts, and 30-100 mass parts is still more preferable.

<< Inorganic filler (C) >>
The rubber composition of the present invention has the following general formula as an inorganic filler selected from the group (i):
nM1 · xSiO _y · zH ₂ O (I)
[Wherein, M1 is selected from the group consisting of metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of these metals. N, x, y and z are each an integer of 0 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. However, the case where n = 0 and x = 0 are satisfied at the same time is excluded. ]
It is characterized by including the inorganic filler (C) represented by these. In the above general formula (I), when n = 0, x = 1, y = 2, this particularly represents silica. When silica is used, it is not particularly limited, but wet silica, dry silica, and colloidal silica are preferable. BET specific surface area is preferably 50 to 300 m ² / g, CTAB specific surface area; cetyltrimethylammonium bromide adsorption specific surface area is preferably 50 to 300 m ² / g. Silica having a BET specific surface area and a CTAB specific surface area in this range has an advantage that both rubber reinforcement and dispersibility in a rubber component can be achieved. Examples of such silica include Tosoh Silica Co., Ltd., trade names “Nipsil AQ”, “Nipsil KQ”, Evonik, trade name “Ultra Gil VN3”, Solvay, trade name “Zeosil Premium 200MP”. A commercially available product such as can be used.

On the other hand, as the inorganic filler (C), a compound other than silica in the case of n = 0, x = 1, and y = 2 can also be selected. More specifically, alumina: Al ₂ O ₃ , alumina-hydrate: Al ₂ O ₃ .H ₂ O, aluminum hydroxide: Al (OH) ₃ , aluminum carbonate: Al ₂ (CO ₃ ) ₃ , water magnesium oxide: Mg _{(OH) 2,} magnesium oxide: MgO, magnesium carbonate: MgCO _{3, talc: 3MgO · 4SiO 2 · H 2} O, _{attapulgite: 5MgO · 8SiO 2 · 9H 2} O, titanium white: TiO _2, titanium black : TiO _2n-1 , calcium oxide: CaO, calcium hydroxide: Ca (OH) ₂ , aluminum magnesium oxide: MgO · Al ₂ O ₃ ), clay: Al ₂ O ₃ · 2SiO ₂ , kaolin: Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O, pyrophyllite: Al ₂ O ₃ · 4SiO ₂ · H ₂ O, bentonite: Al ₂ O ₃ · 4SiO ₂ · 2H ₂ O, aluminum silicate: Al ₂ SiO ₅ , Al ₄ · 3SiO ₄ · 5H ₂ O, etc., magnesium silicate: Mg ₂ SiO ₄ , MgSiO ₃ etc., calcium silicate: Ca ₂ SiO ₄ etc., aluminum calcium silicate: Al ₂ O ₃ .CaO.2SiO ₂ etc., magnesium calcium silicate: CaMgSiO ₄ , calcium carbonate: CaCO ₃ , zirconium oxide: ZrO ₂ , zirconium hydroxide: ZrO (OH) ₂ · _nH 2 O, zirconium carbonate: Zr _{(CO 3) 2,} such as crystalline aluminosilicate, compounds and minerals can be mentioned. One or more compounds represented by the general formula (I) described above may be selected and used.

  The inorganic filler (C) is blended in an amount of 10 to 90 parts by mass, preferably 15 to 70 parts by mass with respect to 100 parts by mass of the rubber component (A). If it is the above range, a reinforcement effect and workability can be ensured. The inorganic filler (C) preferably contains 10 to 90% by mass of silica, and more preferably 10 to 70% by mass.

  In the present invention, at least one filler selected from carbon black (B) and inorganic filler (C) is dispersed in water in advance in a rubber liquid containing the rubber component (A) made of the natural rubber. The water-dispersed slurry is mixed, coagulated, dehydrated and dried to obtain a wet masterbatch (D).

Further, in the water-dispersed slurry, the particle size distribution of the filler in the solution has a volume average particle size: mv of 25 μm or less, preferably 20 μm or less, and 90% by volume particle size: D90 of 30 μm or less, preferably 25 μm or less. It is. When the particle size is less than this size, the filler dispersion in the rubber is good, and sufficient reinforcement and wear resistance can be secured.
On the other hand, if an excessive shearing force is applied to the slurry to reduce the particle size, the structure of the filler is destroyed and the reinforcing property is lowered. Therefore, the 24M4DBP oil absorption amount of the filler recovered by drying from the aqueous dispersion slurry is It is preferably 93% or more, preferably 96% or more of the 24M4DBP oil absorption amount of the filler before being put into the slurry.

  The slurry concentration of at least one filler selected from the carbon black (B) and the inorganic filler (C) is preferably 0.5 to 60% by weight with respect to the slurry, and a particularly preferable range is 1. ~ 30% by weight.

  Next, as a mixing method of the slurry liquid and the rubber liquid, for example, the slurry liquid is put in a homomixer and the latex is dropped while stirring, or conversely, the latex is stirred while stirring. There is a method of dropping the slurry liquid. Also, a method of mixing a slurry flow having a constant flow rate and a latex flow under conditions of vigorous hydraulic stirring can be used.

  The wet masterbatch (D) is solidified using an acid such as formic acid or sulfuric acid or a salt coagulant such as sodium chloride as usual. In addition to the carbon black (B) and the inorganic filler (C), the wet masterbatch (D) includes a surfactant, a vulcanizing agent, an anti-aging agent, a colorant, a dispersing agent and the like as desired. Various additives such as chemicals can be added.

  As a drying method of the wet masterbatch (D), a normal dryer such as a vacuum dryer, an air dryer, a drum dryer, a band dryer or the like can be used. In order to further improve the dispersibility of the filler, It is preferable to perform drying while applying a mechanical shearing force. Thereby, rubber excellent in processability, reinforcement, and low fuel consumption can be obtained. Although this drying can be performed using a general kneader, it is preferable to use a continuous kneader from the viewpoint of industrial productivity. Furthermore, it is more preferable to use a twin-screw kneading extruder that rotates in the same direction or in different directions.

  In the step of drying while applying the shearing force, the moisture in the wet masterbatch (D) before the drying step is preferably 10% or more. When the water content is 10% or more, a sufficiently large improvement width of the filler dispersion in the drying process can be secured.

  The wet masterbatch rubber composition of the present invention is blended with the dispersant (E) which is at least one selected from the compounds represented by the general formulas (II) to (VI) in the filler-containing wet masterbatch. Can be obtained.

式中、Ａは、アリール基であり、少なくとも１つの極性基を有し、２つ以上の場合、該極性基は同じであっても、異なっていてもよい。Ｒ^１１及びＲ^１２は、それぞれ独立して、水素原子、アシル基、アミド基、アルキル基、シクロアルキル基及びアリール基からなる群から選択される少なくとも一種の置換基であり、さらに、該置換基は、酸素、硫黄及び窒素原子のうちの一種以上を含んでいてもよい。

In the formula, A is an aryl group having at least one polar group, and in the case of two or more, the polar groups may be the same or different. R ¹¹ and R ¹² are each independently at least one substituent selected from the group consisting of a hydrogen atom, an acyl group, an amide group, an alkyl group, a cycloalkyl group, and an aryl group. May contain one or more of oxygen, sulfur and nitrogen atoms.

For the compound represented by the formula (II), the aryl group represented by A has a high affinity with a filler such as carbon black, and the portion having a hydrazide skeleton has a high affinity with the rubber component. Therefore, the chemical interaction between the rubber component and the filler such as carbon black can be greatly improved by being blended in the rubber composition. As a result, the hysteresis due to the friction between the fillers can be reduced, and as a result, extremely low exothermicity can be obtained as compared with the prior art. In addition, by improving the dispersibility of the filler, it is possible to achieve better reinforcement.
In addition, the chemical interaction between the rubber component and the filler is greatly improved. As a result, the scorch resistance is increased while maintaining the low exothermic property of the rubber composition, that is, the scorch time is increased, so that the processability is also improved. Is possible.

Moreover, it is preferable that the number of polar groups which the aryl group shown by A in the compound represented by the said formula (II) has is two or more. This is because by having two or more polar groups in the aromatic ring of the aryl group, high affinity with a filler such as carbon black can be obtained.
The type of the polar group is not particularly limited, and examples thereof include an amino group, an imino group, a nitrile group, an ammonium group, an imide group, an amide group, a hydrazo group, an azo group, a diazo group, a hydroxyl group, and a carboxy group. Carbonyl group, epoxy group, oxycarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group, tin-containing group, alkoxysilyl group, alkylamino group, nitro group and the like. Among them, at least one of the polar groups is preferably a hydroxyl group, an amino group or a nitro group, more preferably a hydroxyl group, and particularly preferably at least two are hydroxyl groups. This is because the rubber composition exhibits excellent affinity with the filler and can further improve the low heat buildup of the rubber composition.

In the hydrazide group connected to A in the compound represented by the formula (II), R ¹¹ and R ¹² are each independently a hydrogen atom, an acyl group, an amide group, an alkyl group, a cycloalkyl group, and an aryl group. It is at least one substituent selected from the group consisting of groups. In addition, these substituents may contain 1 or more types of oxygen, sulfur, and a nitrogen atom.
Furthermore, R ¹¹ and R ¹² are preferably a hydrogen atom or an alkyl group among the substituents described above, and more preferably R ¹¹ and R ¹² are both hydrogen atoms. This is because it has a high affinity with the rubber component, and more excellent low heat build-up and processability can be obtained.

  Here, examples of the compound represented by the formula (II) described above include 3-hydroxy-2-naphthoic acid hydrazide, 2,3-dihydroxybenzohydrazide, 2,4-dihydroxybenzohydrazide, and 2,5-dihydroxy. Examples thereof include benzohydrazide and 2,6-dihydroxybenzohydrazide.

In addition, the molecular weight of the compound represented by the formula (II) is preferably 200 or less, and more preferably 180 or less. This is because the affinity with each molecule of the diene rubber is increased, a more excellent low heat generation property can be obtained, and the wear resistance can be improved.

  Moreover, about melting | fusing point of the compound represented by the said formula (II), it is preferable that it is 80 degreeC or more and less than 250 degreeC, and it is more preferable that it is 80-200 degreeC. This is because, by lowering the melting point of the hydrazide compound, the affinity with the diene-based molecules is increased, a more excellent low heat generation property can be obtained, and the wear resistance can be increased.

式中、Ａは、アリール基であり、少なくとも１つの極性基を有し、２つ以上の場合、該極性基は同じであっても、異なっていてもよい。Ｒ^１３は、アルカンジイル基、シクロアルカンジイル基又はアレーンジイル基からなる置換基であり、炭化水素の同一又は異なる炭素上から２つの水素を除いてなる２価の炭化水素基であり、さらに、該置換基は、酸素、硫黄及び窒素原子のうちの一種以上を含んでいてもよい。

In the formula, A is an aryl group having at least one polar group, and in the case of two or more, the polar groups may be the same or different. R ¹³ is a substituent composed of an alkanediyl group, a cycloalkanediyl group or an arenediyl group, a divalent hydrocarbon group formed by removing two hydrogens from the same or different carbons of the hydrocarbon, and The substituent may contain one or more of oxygen, sulfur and nitrogen atoms.

For the compound represented by the above formula (III), the aromatic ring having the polar group represented by A has a high affinity with a filler such as carbon black, and the portion having a hydrazone skeleton is a rubber component. Since it has high affinity, the chemical interaction between the rubber component and the filler can be greatly improved by being blended in the rubber composition. As a result, the hysteresis due to the friction between the fillers can be reduced, and as a result, extremely low exothermicity can be obtained as compared with the prior art. In addition, by improving the dispersibility of the filler, it is possible to achieve better reinforcement.
In addition, the chemical interaction between the rubber component and the filler is greatly improved. As a result, the scorch resistance is increased while maintaining the low exothermic property of the rubber composition, that is, the scorch time is increased. Improvement is possible.

Here, the number of polar groups of the aromatic ring represented by A in the compound represented by the formula (III) is 2 or more, and preferably 3 or more. By having two or more polar groups in the aromatic ring, it is possible to obtain a high affinity with a filler such as carbon black. In the case of less than two, the affinity with the filler is sufficient. The low heat build-up of the rubber composition may be reduced.
The type of the polar group is not particularly limited, and examples thereof include an amino group, an imino group, a nitrile group, an ammonium group, an imide group, an amide group, a hydrazo group, an azo group, a diazo group, a hydroxyl group, and a carboxyl group. Carbonyl group, epoxy group, oxycarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group, tin-containing group, alkoxysilyl group, alkylamino group, nitro group and the like. Among these, the polar group preferably includes a hydroxyl group or an amino group, and more preferably includes a hydroxyl group. This is because the rubber composition exhibits excellent affinity with the filler and can further improve the low heat buildup of the rubber composition.

  Moreover, it is preferable that the aromatic ring shown by A in the compound represented by the formula (III) is 2 or more, and more preferably 3 or more. Because of its excellent affinity with fillers, it can realize better low heat generation.

In the hydrazone group connected to A in the compound represented by the formula (III), R ¹³ is a substituent composed of an alkanediyl group, a cycloalkanediyl group, and an arenediyl group, and the same or different carbons of the hydrocarbon It is a divalent hydrocarbon group obtained by removing two hydrogens from above, and these functional groups may contain one or more of oxygen, sulfur and nitrogen atoms.

  Here, examples of the compound represented by the formula (III) described above include 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide, 2,3-dihydroxy-N ′. -(4-Methylpentane-2-ylidene) benzohydrazide, 2,4-dihydroxy-N '-(4-methylpentane-2-ylidene) benzohydrazide, 2,5-dihydroxy-N'-(4-methylpentane 2-ylidene) benzohydrazide, 2,6-dihydroxy-N ′-(4-methylpentane-2-ylidene) benzohydrazide and the like.

式中、Ｒは炭素数１〜６の直鎖状又は分岐状のアルカンジイル基を表す。

In the formula, R represents a linear or branched alkanediyl group having 1 to 6 carbon atoms.

The benzimidazolylalkylthiosulfuric acid represented by the formula (IV) is characterized in that it has a structure in which an alkyl group having a thiosulfuric acid group is substituted at the 2-position of benzimidazole.
Examples of the benzimidazolylalkylthiosulfuric acid include S-((benzimidazolyl-2) methyl) thiosulfuric acid, S- (2- (benzimidazolyl-2) ethyl) thiosulfuric acid, S- (3- (benzimidazolyl-2). ) N-propyl) thiosulfuric acid, S- (2- (benzimidazolyl-2) isopropyl) thiosulfuric acid, S- (4- (benzimidazolyl-2) n-butyl) thiosulfuric acid, S- (5- (benzimidazolyl) -2) n-pentyl) thiosulfuric acid, S- (6- (benzimidazolyl-2) n-hexyl) thiosulfuric acid and the like.
In addition, you may use these benzimidazolyl alkyl thiosulfuric acid as a component of a dispersing agent 1 type, or in combination of 2 or more types.

  The benzimidazolylalkylthiosulfuric acid represented by the formula (IV) can be synthesized by a known method disclosed in JP-A-2006-003236.

式中、Ｍ^ｎ＋は、Ｈ^＋又はｎ価の金属イオンを表す。ｎは、１又は２の整数を表す。Ｒ^３１及びＲ^３２は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表すか、あるいは、Ｒ^３１とＲ^３２とが互いに結合して、それらが結合している窒素原子とともに環を形成する。ｍは、２〜９の整数を表す。

In the formula, M ^{n +} represents H ⁺ or an n-valent metal ion. n represents an integer of 1 or 2. R ³¹ and R ³² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ³¹ and R ³² are bonded to each other, and together with the nitrogen atom to which they are bonded, a ring Form. m represents an integer of 2 to 9.

Examples of the alkyl group having 1 to 6 carbon atoms in R ³¹ and R ³² include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, and 2-methyl-1-propyl. Group, 2-methyl-2-propyl group, pentyl group, hexyl group.
When R ³¹ and R ³² are bonded to each other to form a ring with the nitrogen atom to which they are bonded, examples of the group formed by combining R ³¹ and R ³² with each other include a polymethylene group. Examples of the polymethylene group include an ethylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Each is a linear α, ω-alkanediyl group, but may be any linear, branched or cyclic alkanediyl group or arenediyl group, not limited to bonding at both ends. R ³¹ and R ³² are preferably a hydrogen atom.

As M ^{n +} , H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Cu ⁺ , Cu ²⁺ , Zn ^2+, etc. And preferably H ⁺ or an alkali metal ion, more preferably H ⁺ or Na ⁺ .

  Examples of the compound represented by the formula (V) include S- (aminoalkyl) thiosulfuric acid, S- (aminoalkyl) thiosulfate, S- (N, N-dialkylaminoalkyl) thiosulfuric acid, S- ( N, N-dialkylaminoalkyl) thiosulfate, S- (N-monoalkylaminoalkyl) thiosulfate, S- (N-monoalkylaminoalkyl) thiosulfate and the like, preferably S- (aminoalkyl) ) Thiosulfuric acid or S- (aminoalkyl) thiosulfate.

Here, as S- (aminoalkyl) thiosulfuric acid, S- (aminoethyl) thiosulfuric acid, S- (aminopropyl) thiosulfuric acid, S- (aminobutyl) thiosulfuric acid, S- (aminopentyl) thiosulfuric acid, Examples include S- (aminohexyl) thiosulfuric acid, S- (aminoheptyl) thiosulfuric acid, S- (aminooctyl) thiosulfuric acid, S- (aminononyl) thiosulfuric acid, and the like.
Examples of S- (aminoalkyl) thiosulfate include sodium S- (aminoethyl) thiosulfate, sodium S- (aminopropyl) thiosulfate, sodium S- (aminobutyl) thiosulfate, and S- (aminopentyl) thiosulfate. Examples include sodium, sodium S- (aminohexyl) thiosulfate, sodium S- (aminoheptyl) thiosulfate, sodium S- (aminooctyl) thiosulfate, and sodium S- (aminononyl) thiosulfate.
Examples of S- (N, N-dialkylaminoalkyl) thiosulfuric acid include S- (N, N-dimethylaminoethyl) thiosulfuric acid, S- (N, N-dimethylaminopropyl) thiosulfuric acid, S- (N, N -Dimethylaminobutyl) thiosulfuric acid, S- (N, N-dimethylaminopentyl) thiosulfuric acid, S- (N, N-dimethylaminohexyl) thiosulfuric acid, S- (N, N-dimethylaminoheptyl) thiosulfuric acid, S- (N, N-dimethylaminooctyl) thiosulfuric acid, S- (N, N-dimethylaminononyl) thiosulfuric acid and the like can be mentioned.
Examples of S- (N, N-dialkylaminoalkyl) thiosulfate include sodium S- (N, N-dimethylaminoethyl) thiosulfate, sodium S- (N, N-dimethylaminopropyl) thiosulfate, S- ( N, N-dimethylaminobutyl) sodium thiosulfate, S- (N, N-dimethylaminopentyl) sodium thiosulfate, S- (N, N-dimethylaminohexyl) sodium thiosulfate, S- (N, N-dimethyl) Aminoheptyl) sodium thiosulfate, S- (N, N-dimethylaminooctyl) sodium thiosulfate, sodium S- (N, N-dimethylaminononyl) thiosulfate and the like.
Examples of S- (N-monoalkylaminoalkyl) thiosulfuric acid include S- (N-methylaminoethyl) thiosulfuric acid, S- (N-methylaminopropyl) thiosulfuric acid, S- (N-methylaminobutyl) thiosulfuric acid. S- (N-methylaminopentyl) thiosulfuric acid, S- (N-methylaminohexyl) thiosulfuric acid, S- (N-methylaminoheptyl) thiosulfuric acid, S- (N-methylaminooctyl) thiosulfuric acid, S -(N-methylaminononyl) thiosulfuric acid and the like.
Examples of S- (N-monoalkylaminoalkyl) thiosulfate include sodium S- (N-methylaminoethyl) thiosulfate, sodium S- (N-methylaminopropyl) thiosulfate, and S- (N-methylaminobutyl). ) Sodium thiosulfate, S- (N-methylaminopentyl) sodium thiosulfate, S- (N-methylaminohexyl) sodium thiosulfate, S- (N-methylaminoheptyl) sodium thiosulfate, S- (N-methyl) Aminooctyl) sodium thiosulfate, S- (N-methylaminononyl) sodium thiosulfate and the like.

  The compound represented by the formula (V) can be synthesized and used by a known method disclosed in JP2013-159678A.

式中、Ｒ^１は置換基を有していてもよい炭素数２〜１２のアルカンジイル基、置換基を有していてもよい炭素数３〜１２のシクロアルカンジイル基、又は＊−Ｂ^１−Ａｒ−Ｂ^２−＊基を表し、＊は結合手を表す。Ｂ^１及びＢ^２は、単結合又は炭素数１〜１２のアルカンジイル基を表す。Ａｒは、置換基を有していてもよい炭素数６〜１２のアレーンジイル基を表す。Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ヒドロキシ基又は炭素数１〜６のアルコキシ基を表すか、或いは、互いに結合して炭素数２〜１２のアルカンジイル基を形成する。Ｒ^４は、ヒドロキシ基、炭素数１〜６のアルコキシ基、炭素数６〜１２のアリールオキシ基、炭素数７〜１５のアリールアルコキシ基、−ＮＲ^５Ｒ^６又は−Ｏ−（Ｙ^ｎ＋）_１／ｎを表し、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。Ｘは、−ＮＨ−又は−Ｏ−を表す。

In the formula, R ¹ is an optionally substituted alkanediyl group having 2 to 12 carbon atoms, an optionally substituted cycloalkanediyl group having 3 to 12 carbon atoms, or * -B ^1. —Ar—B ² — * represents a group, and * represents a bond. B ¹ and B ² represent a single bond or an alkanediyl group having 1 to 12 carbon atoms. Ar represents an arenediyl group having 6 to 12 carbon atoms which may have a substituent. R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Or it couple | bonds together and forms a C2-C12 alkanediyl group. R ⁴ is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylalkoxy group having 7 to 15 carbon atoms, —NR ⁵ R ⁶ or —O— (Y ^{n +} ) _{1. / N} , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents -NH- or -O-.

The salt of compound (VI) is a carboxylate salt of compound (VI) wherein R ⁴ is a hydroxy group, and an addition formed with an acid in the amine moiety (—NH ₂ or —NH—) in compound (VI) Contains salt.
Examples of the carboxylate salt of compound (VI) include a salt in which R ⁴ is —O— (Y ^{n +} ) _{1 / n} in the compound or salt represented by formula (VI).
Examples of the acid in the addition salt formed with an acid in the amine moiety in compound (VI) include inorganic acids and organic acids.
Examples of solvates of compound (VI) include methanol solvates and hydrates.
Regarding the bond between the carbon-carbon double bond in compound (VI) and R ³ and CO—R ⁴ , the carbon-carbon double bond has an E-form compound, a Z-form compound, or an E-form compound. Either a compound or a mixture of Z-form compounds may be used. Among them, a compound in which the carbon-carbon double bond steric is a Z-form is preferable.

式（ＶＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＸは、上記と同じ意味を表す。 Moreover, as compound (VI), the compound represented by Formula (VII) is preferable.

In formula (VII), R ¹ , R ² , R ³ , R ⁴ and X represent the same meaning as described above.

Examples of the alkanediyl group having 2 to 12 carbon atoms in R ¹ include a methylene group, an ethylene group (1,2-ethanediyl group), a trimethylene group (1,3-propanediyl group), and a tetramethylene group (1,4 -Butanediyl group), pentamethylene group (1,5-pentanediyl group), straight-chain alkanediyl group such as hexamethylene group (1,6-hexanediyl group); isopropylene group (1,2-propanediyl group) ), Isobutylene group (1,2-butanediyl group, 1,3-butanediyl group, 2-methyl-1,2-propanediyl group), 2-methyltrimethylene group (2-methyl-1,3-propanediyl group) ), Branched alkanediyl groups such as isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, and isodecylene group; It is done. Especially, 3-12 are preferable and, as for carbon number of an alkanediyl group, 3-6 are more preferable. Moreover, a linear alkanediyl group is preferable.

  Examples of the substituent that the alkanediyl group may have include, for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; a halogen atom such as chlorine, bromine, iodine, and fluorine; a phenyl group Aryl groups having 6 to 12 carbon atoms such as naphthyl group and biphenyl group; and hydroxy groups. Examples of the alkanediyl group having a substituent include the following groups. * Represents a bond.

Examples of the cycloalkanediyl group having 3 to 12 carbon atoms in R ¹ include a cyclopropylene group (1,2-cyclopropanediyl group) and a cyclopentylene group (1,2- and 1,3-cyclopentanediyl group). ), Cyclohexylene groups (1,2-, 1,3- and 1,4-cyclohexanediyl groups), cyclododecylene groups (1,2-, 1,3-, 1,4-, 1,5-, 1,6- and 1,7-cyclododecanediyl groups) and the like.
Examples of the substituent that the cycloalkanediyl group having 3 to 12 carbon atoms may have include, for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, C1-C4 alkyl groups such as 2-methyl-1-propyl group and t-butyl group (2-methyl-2-propyl group); Carbon numbers such as phenyl group, 4-methylphenyl group and naphthyl group An aryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group and 1-butoxy group; an acyl group having 1 to 7 carbon atoms such as acetyl group, benzoyl group, formyl group and pivaloyl group; C3-C4 alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; C7-C11 aryloxycarbonyl groups such as phenoxycarbonyl group and naphthyloxycarbonyl group Acetoxy group, an acyloxy group having 2 to 7 carbon atoms such as benzoyloxy group; and the like.
The cycloalkanediyl group having 3 to 12 carbon atoms is preferably a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group or a t-butylcyclohexylene group.

Examples of the alkanediyl group having 1 to 12 carbon atoms in B ¹ and B ² include those mentioned for the alkanediyl group having 3 to 12 carbon atoms and a methylene group.
Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms in Ar include a phenylene group, a naphthylene group, and a biphenylene group.
Examples of the * —B ¹ —Ar—B ² — * group in R ¹ include a phenylene group, a naphthylene group, a biphenylene group, an α, α′-xylylene group, and the like.
The hydrogen atom contained in Ar is one or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a nitro group, a cyano group, a sulfo group, and a halogen atom. It may be substituted with a group.

R ¹ is preferably an alkylene group having 2 to 12 carbon atoms, a phenylene group or a benzal group, and more preferably a phenylene group.

Examples of the halogen atom in R ² and R ³ include fluorine, chlorine, bromine and iodine.
Examples of the alkyl group having 1 to 6 carbon atoms in R ² and R ³ include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, and 2-methyl-1- Examples include propyl group, t-butyl group (2-methyl-2-propyl group), 1-pentyl group, isopentyl group, 1-hexyl group and the like.
The aryl group having 6 to 12 carbon atoms in R ² and R ³ represents a monocyclic or condensed polycyclic aromatic hydrocarbon having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group. It is done.
Examples of the alkoxy group having 1 to 6 carbon atoms in R ² and R ³ include methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, isobutoxy group, 2-butoxy group, tert- Examples include butoxy group, 1-pentoxy group, isopentoxy group, 1-hexyloxy group and the like.
Examples of the alkanediyl group having 2 to 12 carbon atoms in which R ² and R ³ are bonded to each other include the same groups as those described above for the alkanediyl group having 3 to 12 carbon atoms, and the alkanediyl group having 3 or 4 carbon atoms. It is preferable that Examples of the cyclic structure formed by R ² and R ³ together with the carbon atom to which they are bonded include a cyclopentene ring and a cyclohexene ring.
The R ² and ^{R 3, R 2} is a hydrogen atom, it is preferred that ^{R 3} is an alkyl group having 1 to 6 carbon hydrogen or C, and more preferably ^{R 2} and ^{R 3} are hydrogen atoms .

Examples of the alkoxy group having 1 to 6 carbon atoms in R ⁴ include the same groups as the alkyl groups having 1 to 6 carbon atoms in R ² and R ³ described above.
Examples of the aryloxy group having 6 to 12 carbon atoms in R ⁴ include a group in which an oxy group is bonded to the aryl group having 6 to 12 carbon atoms in R ² and R ³ described above, and examples thereof include a phenyloxy group and a naphthyl group. An oxy group, a biphenyloxy group, etc. are mentioned.
Examples of the arylalkoxy group having 7 to 15 carbon atoms in R ⁴ include a phenylethyloxy group, a benzyloxy group, and phenylpropyloxy.
Examples of —NR ⁵ R ⁶ in R ⁴ include a methylamino group, an ethylamino group, a phenylamino group, an ethylmethylamino group, a dimethylamino group, a diethylamino group, a methylphenylamino group, an ethylphenylamino group, and a diphenylamino group. Can be mentioned.

Y ^{n +} in R ⁴ represents an n-valent cation capable of forming a carboxylate salt of the compound represented by the formula (VI).
Y ^{n +} includes a cation of an alkali metal, an alkaline earth metal, a metal selected from the group consisting of transition elements of Groups 11 and 12 of the periodic table, a cation of an organic base capable of forming a salt with a carboxy group such as an amine, and the like. For example, Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Zn ²⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , (NH ₄ ) ⁺ , [NH (C ₂ H ₅ ) ₃ ] _{^{+, [NH (C 2 H}} 5) (i-C 3 H 7) 2] +, + H 3 N- (CH 2) 2 -NH 3 +, + H 3 N- (CH 2) 6 -NH 3 ⁺ Etc. are mentioned.
The R ^4, hydroxy or _{^{-O- (Y n +) 1 /}} n is preferably a hydroxy group or ^{-O- (Y} n ₊₎ A _{1 / n,} Y is more preferably when an alkali metal.

Specific examples of compound (VI) are shown below.

  The compound represented by the formula (VI) can be synthesized and used by a known method disclosed in JP2013-209605A.

  By including these dispersants of the group (ii), a coupling effect between the rubber component and the filler, particularly carbon black, can be obtained with high efficiency, and the dispersibility of the filler, particularly carbon black, in the rubber composition can be improved. Can be increased. A rubber composition in which the dispersibility of the filler, particularly carbon black, is improved can achieve excellent low heat generation and wear resistance. Since a dispersing agent produces a more effect when it mix | blends carbon black, it is desirable to contain carbon black as a filler component.

  Here, the content of the dispersant is not particularly limited, but 0.05 to 30 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of obtaining more excellent low heat generation and wear resistance. It is preferable that it is 0.05-20 mass parts, It is more preferable that it is 0.05-10 mass parts, It is especially preferable that it is 0.05-5 mass parts. When the content of the dispersant is 0.05 parts by mass or more with respect to 100 parts by mass of the rubber component, a sufficient filler, in particular, carbon black dispersion effect can be obtained. On the other hand, when the content of the dispersant is 30 parts by mass or less with respect to 100 parts by mass of the rubber component, other physical properties such as strength can be kept good.

  As described above, a dispersing agent is used to uniformly disperse the filler, particularly carbon black. However, in order to improve the dispersion of the inorganic filler as well, if necessary, a dispersing agent is used. May be. In particular, when silica is used as the inorganic filler, many various silane coupling agents are conventionally known.

The silane coupling agent used in the present invention is preferably a compound selected from the group consisting of compounds represented by the following general formulas (VIII) to (X).
Hereinafter, the following general formulas (VIII) to (X) will be described in order.

式中、Ｒ^４１は複数ある場合には同一でも異なっていてもよく、各々炭素数１〜８の直鎖、環状又は分枝のアルキル基、炭素数２〜８の直鎖又は分枝のアルコキシアルキル基及びシラノール基から選ばれる置換基であり、Ｒ^４２は複数ある場合には同一でも異なっていてもよく、各々炭素数１〜８の直鎖、環状又は分枝のアルキル基であり、Ｒ^４３は複数ある場合には同一でも異なっていてもよく、各々炭素数１〜８の直鎖又は分枝のアルカンジイル基である。ｐ及びｒは共に３である場合はなく、同一でも異なっていてもよく、各々平均値として０〜３である。スルフィド鎖の硫黄数ａは平均値として２〜６である。

In the formula, when there are a plurality of R ^{41 s} , they may be the same or different, and each of them may be a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 2 to 8 carbon atoms. A substituent selected from an alkyl group and a silanol group, and when there are a plurality of R ^{42 s} , they may be the same or different and each is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms; ⁴³ may be the same or different when there are a plurality, and each is a linear or branched alkanediyl group having 1 to 8 carbon atoms. p and r are not both 3 and may be the same or different, and each is an average value of 0 to 3. The sulfur number a of the sulfide chain is 2 to 6 as an average value.

  Specific examples of the silane coupling agent represented by the general formula (VIII) include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (3-methyldimethoxysilylpropyl). ) Tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-methyldimethoxysilylpropyl) trisulfide Bis (2-triethoxysilylethyl) trisulfide, bis (3-monoethoxydimethylsilylpropyl) tetrasulfide, bis (3-monoethoxydimethylsilylpropyl) trisulfide, bis (3-monoethoxydimethylsilylpropyl) Disulfide, bis (3-monomethoxydimethylsilylpropyl) tetrasulfide, bis (3-monomethoxydimethylsilylpropyl) trisulfide, bis (3-monomethoxydimethylsilylpropyl) disulfide, bis (2-monoethoxydimethylsilylethyl) Examples thereof include tetrasulfide, bis (2-monoethoxydimethylsilylethyl) trisulfide, and bis (2-monoethoxydimethylsilylethyl) disulfide.

式中、Ｒ_４ ^４は−Ｃｌ、−Ｂｒ、各々水素原子又は炭素数１〜１８の一価の炭化水素基で置換されたＲ^９Ｏ−アルコキシ基、Ｒ^４９Ｃ（＝Ｏ）Ｏ−カルボキシル基、Ｒ^４９Ｒ^５０Ｃ＝ＮＯ−オキシマト基、Ｒ^４９Ｒ^５０ＣＮＯ−、ＮＲ^４９Ｒ^５０−アミノ基、及びシロキシ鎖長２〜５のポリシロキシ基−（ＯＳｉＲ^４９Ｒ^５０）_ｈ（ＯＳｉＲ^４９Ｒ^５０Ｒ^５１）から選択される一価の基である。以上において、Ｒ^４９、Ｒ^５０及びＲ^５１は各々水素原子又は炭素数１〜１８の一価の炭化水素基であり、ｈは平均値として１〜４である。Ｒ^４５はＲ^４９、水素原子又は炭素数１〜１８の一価の炭化水素基であり、Ｒ^４６はＲ^４４、Ｒ^４５、水素原子又は−[Ｏ（Ｒ^４２Ｏ）_ｊ]_１／２−基である。なお、Ｒ^４２は炭素数１〜１８のアルカンジイル基、ｊは１〜４の整数である。Ｒ^４７は炭素数１〜１８の二価の炭化水素基であり、Ｒ^４８は炭素数１〜１８の一価の炭化水素基である。ｘ、ｙ及びｚは、ｘ＋ｙ＋２ｚ＝３、０≦ｘ≦３、０≦ｙ≦２、０≦ｚ≦１の関係を満たす数である。

In the formula, R ₄ ⁴ is —Cl, —Br, an R ⁹ O-alkoxy group substituted with a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ⁴⁹ C (═O) O-carboxyl. ^group, R ⁴⁹ R 50 C = NO- oximato ^{group, R 49 R 50 CNO-, NR} 49 R 50 - amino group, and a siloxy chain length 2-5 polysiloxy group _{^{- (OSiR 49 R 50) h}} (OSiR 49 R ⁵⁰ R ⁵¹ ). In the above, R ⁴⁹ , R ⁵⁰ and R ⁵¹ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and h is 1 to 4 as an average value. R ⁴⁵ is R ⁴⁹ , a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ⁴⁶ is R ⁴⁴ , R ⁴⁵ , a hydrogen atom or — [O (R ⁴² O) _j ] _1/2 − It is a group. R ⁴² is an alkanediyl group having 1 to 18 carbon atoms, and j is an integer of 1 to 4. R ⁴⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, and R ⁴⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms. x, y, and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1.

In the above general formula (IX), R ⁴⁸ , R ⁴⁹ , R ⁵⁰ and R ⁵¹ may be the same or different, and each preferably a linear, cyclic or branched alkyl group or alkenyl group having 1 to 18 carbon atoms. And a group selected from the group consisting of an aryl group and an arylalkyl group. In addition, when R ⁴⁵ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, a group selected from the group consisting of a linear, cyclic or branched alkyl group, alkenyl group, aryl group and arylalkyl group It is preferable that R ⁵² is preferably a linear, cyclic or branched alkanediyl group, and particularly preferably a linear one. R ⁴⁷ has, for example, a linear or branched alkanediyl group having 1 to 18 carbon atoms, an alkenediyl group having 2 to 18 carbon atoms, or a substituent such as a lower alkyl group on the ring. C5-C18 cycloalkanediyl group, C6-C18 cycloalkylalkanediyl group, C6-C18 arenediyl group, C7-C18 arylalkanediyl group which may be Can do. As this R ⁴⁷ , an alkanediyl group having 1 to 6 carbon atoms is preferable, and a linear alkanediyl group such as a methanediyl group, an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, or a hexanediyl group is particularly preferable. Can do.

Specific examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms of R ⁵¹ include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, and a 2-methyl-1-propyl group. 2-butyl group, 2-methyl-2-propyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, Examples include octenyl group, cyclopentenyl group, cyclohexenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenethyl group, and naphthylmethyl group.
Examples of R ⁵² in the general formula (IX) include a methanediyl group, an ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, an octanediyl group, a decandiyl group, and a dodecandiyl group.

  Specific examples of the silane coupling agent represented by the general formula (IX) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3- Hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane 2 octanoylthiopropyl ethyltrimethoxysilane, 2- deca Neu thio ethyltrimethoxysilane, and 2-lauroyl thio ethyltrimethoxysilane. Of these, 3-octanoylthiopropyltriethoxysilane (manufactured by Momentive Performance Materials, trademark “NXT silane”) is particularly preferable.

式中、Ｒ^５３は複数ある場合には同一でも異なっていてもよく、各々炭素数１〜８の直鎖、環状又は分枝のアルキル基、炭素数２〜８の直鎖又は分枝のアルコキシアルキル基及びシラノール基から選ばれる置換基であり、Ｒ^５４は複数ある場合には同一でも異なっていてもよく、各々炭素数１〜８の直鎖、環状又は分枝のアルキル基であり、Ｒ^５５は複数ある場合には同一でも異なっていてもよく、各々炭素数１〜８の直鎖又は分枝のアルカンジイル基である。Ｒ^５６は一般式（−Ｓ−Ｒ^５７−Ｓ−）、（−Ｒ^５８−Ｓ_ｍ１−Ｒ^５９−）及び（−Ｒ^６０−Ｓ_ｍ２−Ｒ^６１−Ｓ_ｍ３−Ｒ^６２−）から選ばれる二価の基（Ｒ^５７〜Ｒ^６２は各々炭素数１〜２０の二価の炭化水素基、二価の芳香族基、並びに硫黄及び酸素以外のヘテロ元素を含む二価の有機基から選ばれる二価の置換基であり、ｍ１、ｍ２及びｍ３は各々平均値として１以上４未満である。）であり、複数あるｋは同一でも異なっていてもよく、各々平均値として１〜６であり、ｓ及びｔは各々平均値として０〜３である。但しｓ及びｔの双方が３であることはない。

In the formula, when there are a plurality of R ^{53 s} , they may be the same or different, and each of them may be a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 2 to 8 carbon atoms. A substituent selected from an alkyl group and a silanol group, and when there are a plurality of R ^{54 s} , they may be the same or different and each is a linear, cyclic or branched alkyl group having 1 to 8 carbon atoms; ⁵⁵ may be the same as or different from each other, and each is a straight chain or branched alkanediyl group having 1 to 8 carbon atoms. R ⁵⁶ is selected from general formulas (—S—R ⁵⁷ —S—), (—R ⁵⁸ —S _m1 —R ⁵⁹ —) and (—R ⁶⁰ —S _m2 —R ⁶¹ —S _m3 —R ⁶² —). Divalent groups (R ^{57 to} R ⁶² are each selected from a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, and a divalent organic group containing a hetero element other than sulfur and oxygen. Each of m1, m2 and m3 is an average value of 1 or more and less than 4, and a plurality of k's may be the same or different, and each of the average values is 1 to 6 , S, and t are 0 to 3 as average values. However, both s and t are not 3.

Specific examples of the silane coupling agent represented by the general formula (X) are all represented by an average composition formula,
_{(C 2 H 5 O) 3} SiC 3 H 6 S 2 C 6 H 12 S 2 C 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 S 2 C 10 H 20 S 2 C 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 S 3 C 6 H 12 S 3 C 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 S 4 C 6 H 12 S 4 C 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 SC 6 H 12 S 2 C 6 H 12 SC 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 SC 6 H 12 S 2.5 C 6 H 12 SC 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 SC 6 H 12 S 3 C 6 H 12 SC 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 SC 6 H 12 S 4 C 6 H 12 SC 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 SC 10 H 20 S 2 C 10 H 20 SC 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 S 4 C 2 H 4 S 4 C 6 H 12 S 4 C 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 S 2 C 6 H 12 S 2 C 6 H 12 S 2 C 3 H 6 Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} SiC 3 H 6 SC 6 H 12 S 2 C 6 H 12 S 2 C 6 H 12 SC 3 H 6 Si (OC 2 H 5) compounds represented by ₃ are preferably exemplified . Here, C ₂ H ₄ = (CH ₂ ) ₂ , C ₃ H ₆ = (CH ₂ ) ₃ , C ₆ H ₁₂ = (CH ₂ ) ₆ , C ₁₀ H ₂₀ = (CH ₂ ) ₁₀ , respectively , A straight-chain alkanediyl group obtained by removing one hydrogen from each end of a straight-chain alkane having 2, 3, 6, 10 carbon atoms.
In addition, the silane coupling agent represented by the said general formula (X) can be manufactured by the method described in Unexamined-Japanese-Patent No. 2006-167919, for example. In addition, commercially available products can be widely used.

  About content of the said silane coupling agent, although it changes with kinds etc. of a silane coupling agent, Preferably it is the range of 2-25 mass% with respect to a silica, The range of 2-20 mass% is preferable. It is more preferable that it is 5-18 mass%. If the content is 2% by mass or more, the effect as a coupling agent is sufficiently exhibited, and if it is 25% by mass or less, there is no possibility of causing gelation of the rubber component.

  The rubber composition of this invention can mix | blend a dispersing agent (E) with wet masterbatch (D), and also knead | mix it, and can be used as a wet masterbatch rubber composition. The stage of blending the dispersant (E) is finished as a wet masterbatch (D), particularly from the viewpoint of processability and the balance between the original purpose of filling material, especially carbon black. The blending at the stage of kneading after the stage is preferred.

  Further, when silica is used as the inorganic filler, when a silane coupling agent is blended, the silane coupling agent is preferably blended at the stage of kneading.

The tire of the present invention is produced by an ordinary method using the wet masterbatch rubber composition of the present invention. That is, the rubber composition of the present invention containing various chemicals as described above is processed into each member at an unvulcanized stage, and pasted and molded by a normal method on a tire molding machine to form a raw tire. The The green tire is heated and pressed in a vulcanizer to obtain a tire.
The tire of the present invention thus obtained has good cut resistance and chipping resistance, excellent bead durability, and good processability of the rubber composition. Are better. The wet masterbatch rubber composition of the present invention is not particularly limited in the use part of the tire, and includes tire applications such as tire treads, undertreads, sidewalls, bead fillers, chafers, and bead coating rubbers. Although it can also be used for other industrial products, it is particularly suitably used as a tire tread rubber and bead filler.

  Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited to these.

Preparation of wet masterbatch 10% solid content, 100 parts by mass of solid content in natural rubber latex, using a high shear mixer manufactured by Silverson Co., Ltd., carbon black N234, manufactured by Tokai Carbon Co., Ltd., Seast 7HM 50 parts by mass, inorganic filler: Nipsil KQ was dispersed in 950 parts by mass of water and mixed with the prepared aqueous dispersion slurry.
The volume average particle size: mv of this carbon black / inorganic filler slurry was 7.3 μm, 90% volume% particle size: D90 was 11.5 μm, and the 24M4DBP retention was 98%.
Subsequently, this mixture was adjusted to pH 4-5 with formic acid to form crumbs, washed with water, and then dried with a twin screw extruder to obtain a natural rubber-carbon black-inorganic filler wet masterbatch.

(Compounds a to d)
The chemical formulas for compounds a to d are shown below.
The types of compounds to d, melting ^{point, 1} H-NMR measurement _{(conditions: 300MHz, DMSO-d 6,} δppm) also shown below the results of.

（融点：１９８℃、^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ_６，δｐｐｍ）：６．３（ｄ，２Ｈ），７．１（ｔ，１Ｈ），ＮＨ（３Ｈ）及びＯＨ（２Ｈ）は不検出） Compound a: 2,6-dihydroxybenzohydrazide 5.29 g of methyl 2,6-dihydroxybenzoate and 3.30 g of 100% hydrazine monohydrate were added to 32 mL of 1-butanol, and the mixture was stirred at 117 ° C. for 15 hours. After cooling the reaction solution, the precipitated solid was filtered and washed with isopropyl alcohol. The obtained solid was dried under reduced pressure to obtain 2.85 g (yield 54%) of a pale yellow solid 2,6-dihydroxybenzohydrazide.

(Melting point: 198 ° C., ¹ H-NMR (300 MHz, DMSO-d ₆ , δ ppm): 6.3 (d, 2H), 7.1 (t, 1H), NH (3H) and OH (2H) are not detection)

（融点：２２３℃、^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ_６，δｐｐｍ）：４．７（ｂｒ−ｓ，２Ｈ），６．７（ｍ，１Ｈ），６．９（ｍ，１Ｈ），７．２（ｍ，１Ｈ），１０．１（ｂｒ−ｓ，１Ｈ），ＯＨ（２Ｈ）は不検出） Compound b: 2,3-dihydroxybenzohydrazide 2.75 g of methyl 2,3-dihydroxybenzoate and 7.00 g of 100% hydrazine monohydrate were added to 1.5 mL of water and stirred at 100 ° C. for 3 hours. After the reaction solution was concentrated, isopropyl alcohol was added to the precipitated solid, filtered, and washed with isopropyl alcohol. The obtained solid was dried under reduced pressure to obtain 2.00 g (yield 73%) of a pale yellow solid 2,3-dihydroxybenzohydrazide.

(Melting point: 223 ° C., ¹ H-NMR (300 MHz, DMSO-d ₆ , δ ppm): 4.7 (br-s, 2H), 6.7 (m, 1H), 6.9 (m, 1H), 7.2 (m, 1H), 10.1 (br-s, 1H), OH (2H) not detected)

（融点：２３７℃、^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ_６，δｐｐｍ）：６．２（ｍ，２Ｈ），７．６（ｍ，１Ｈ），ＮＨ（３Ｈ）及びＯＨ（２Ｈ）は不検出） Compound c: 2,4-dihydroxybenzohydrazide 5.50 g of methyl 2,4-dihydroxybenzoate and 13.4 g of 100% hydrazine monohydrate were added to 3 mL of water and stirred at 100 ° C. for 3 hours. After the reaction solution was concentrated, isopropyl alcohol was added to the precipitated solid, filtered, and washed with isopropyl alcohol. The obtained solid was dried under reduced pressure to obtain 4.82 g (88% yield) of a pale yellow solid 2,4-dihydroxybenzohydrazide.

(Melting point: 237 ° C., ¹ H-NMR (300 MHz, DMSO-d ₆ , δ ppm): 6.2 (m, 2H), 7.6 (m, 1H), NH (3H) and OH (2H) are not detection)

（融点：２１０℃、^１Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ_６，δｐｐｍ）：４．６（ｂｒ−ｓ，２Ｈ），６．７（ｍ，１Ｈ），６．８（ｍ，１Ｈ），７．２（ｍ，１Ｈ），９．０（ｂｒ−ｓ，１Ｈ），９．９（ｂｒ−ｓ，１Ｈ），１１．５（ｂｒ−ｓ，１Ｈ）） Compound d: 2,5-dihydroxybenzohydrazide 5.39 g of methyl 2,5-dihydroxybenzoate and 3.29 g of 100% hydrazine monohydrate were added to 32 mL of 1-butanol, and the mixture was stirred at 117 ° C. for 15 hours. After cooling the reaction solution, the precipitated solid was filtered and washed with isopropyl alcohol. The obtained solid was dried under reduced pressure to obtain 4.26 g (yield 79%) of a pale yellow solid 2,5-dihydroxybenzohydrazide.

(Melting point: 210 ° C., ¹ H-NMR (300 MHz, DMSO-d ₆ , δ ppm): 4.6 (br-s, 2H), 6.7 (m, 1H), 6.8 (m, 1H), 7.2 (m, 1H), 9.0 (br-s, 1H), 9.9 (br-s, 1H), 11.5 (br-s, 1H))

Preparation of rubber composition In accordance with the formulation in Table 1, Comparative Examples 1 and 2 were mixed and mixed with the above-mentioned wet masterbatch by the usual kneading mixing, and further added with an additional component such as a dispersant according to the formulation in Table 1. Comparative Example 3 and Example 1 were prepared, and both were vulcanized at 145 ° C. for 33 minutes to obtain a vulcanized rubber.

(1) tan δ: Evaluation of low heat build-up The vulcanized rubber obtained from the rubber composition of each sample was lost at a temperature of 50 ° C., a strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device manufactured by Rheometrics. Tangent: tan δ was measured. It shows that low exothermic property is so favorable that an index value is small.
(2) Abrasion test: Evaluation of wear resistance DIN according to JIS-K6264-2: 2005, using test pieces cut out from each prepared vulcanized rubber into a disk shape having a diameter of 16.2 mm and a thickness of 6 mm. A wear test was performed, and the volume of wear when the DIN wear test was performed at room temperature was measured in units of mm ³ .
In addition, about the abrasion amount measured in each sample, the reciprocal number of the abrasion amount of each sample when the reciprocal number of the abrasion amount of the comparative example 1 is set to 100 is displayed as an index | exponent. The larger the index value, the smaller the amount of wear and the better the wear resistance.

In Table 1, the numerical values in the compounding content column are numerical values in parts by mass: phr, and the total amount of rubber components is 100 phr. * 1: Natural rubber, RSS # 3
* 2: Manufactured by the above method, carbon black is included * 3: Carbon black: N234, “Seast 7HM” manufactured by Tokai Carbon Co., Ltd.
* 4: Anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 5: Zinc oxide, manufactured by Hakusui Chemical Co., Ltd., “No. 1 Zinc Hana”
* 6: Vulcanization accelerator: 1,3-diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., “Noxeller D”
* 7: Vulcanization accelerator: N-tert-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., “Noxeller NS”
* 8: Sulfur: manufactured by Karuizawa Smelter Co., Ltd. * 9: Silica: manufactured by Tosoh Silica Co., Ltd., “Nipsil KQ”

  Compared to Comparative Examples 1 to 4, Comparative Example 5 can achieve both high heat generation and wear resistance, and Examples 1 to 4 combining natural rubber masterbatch and compounds a to d have particularly good low heat generation and A rubber composition exhibiting wear resistance can be provided. Further, when the same compound is used as the dispersant (E), that is, in the case of Comparative Example 1 and Example 1, the example using the natural rubber masterbatch is superior in exothermic property. Abrasion resistance is achieved.

  By using the present invention, a pneumatic tire having both low heat generation and wear resistance can be obtained.

Claims (5)

In the rubber liquid containing the rubber component (A) containing natural rubber,
Carbon black (B) and
At least one inorganic filler (C) selected from the following group (i):
For the wet masterbatch (D) obtained by mixing the slurry liquid previously dispersed in water, coagulating, dehydrating and drying,
The rubber composition for tires containing the dispersing agent (E) which is at least 1 sort (s) selected from the following (ii) group.
(I): the compound represented by formula _{(I) nM1 · xSiO y ·} zH 2 O ··· (I)
In the formula, M1 is selected from the group consisting of metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of these metals. It is at least 1 type, and n, x, y, and z are an integer of 0-5, an integer of 0-10, an integer of 2-5, and an integer of 0-10, respectively. However, the case where n = 0 and x = 0 are satisfied at the same time is excluded.
(Ii): Compounds represented by the following general formulas (II) to (VI)

In the formula, A is an aryl group having at least one polar group, and in the case of two or more, the polar groups may be the same or different. R ¹¹ and R ¹² are each independently at least one substituent selected from the group consisting of a hydrogen atom, an acyl group, an amide group, an alkyl group, a cycloalkyl group, and an aryl group. May contain one or more of oxygen, sulfur and nitrogen atoms.

In the formula, A is an aryl group having at least one polar group, and in the case of two or more, the polar groups may be the same or different. R ¹³ is a substituent composed of an alkanediyl group, a cycloalkanediyl group, and an arenediyl group, and is a divalent hydrocarbon group formed by removing two hydrogens from the same or different carbon of the hydrocarbon, The substituent may contain one or more of oxygen, sulfur and nitrogen atoms.

In the formula, R represents a linear or branched alkanediyl group having 1 to 6 carbon atoms.

In the formula, M ^{n +} represents H ⁺ or an n-valent metal ion. n represents an integer of 1 or 2. R ³¹ and R ³² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ³¹ and R ³² are bonded to each other, and together with the nitrogen atom to which they are bonded, a ring Form. m represents an integer of 2 to 9.

In the formula, R ¹ is an optionally substituted alkanediyl group having 2 to 12 carbon atoms, an optionally substituted cycloalkanediyl group having 3 to 12 carbon atoms, or * -B ^1. —Ar—B ² — * represents a group, and * represents a bond. B1 and B2 represent a single bond or an alkanediyl group having 1 to 12 carbon atoms. Ar represents an arenediyl group having 6 to 12 carbon atoms which may have a substituent. R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Or it couple | bonds together and forms a C2-C12 alkanediyl group. R ⁴ is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylalkoxy group having 7 to 15 carbon atoms, —NR ⁵ R ⁶ or —O— (Y ^{n +} ) _{1. / N} , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents -NH- or -O-.
And salts, solvates and solvates of the compounds represented by formula (VI).
  The tire rubber according to claim 1, wherein the blending amount of the component (E) is 0.05 to 30 parts by mass with respect to 100 parts by mass of the rubber component (A) of the wet masterbatch. Composition.   The rubber composition for tires according to claim 1 or 2, comprising 10 to 160 parts by mass of carbon black with respect to 100 parts by mass of the rubber component. The inorganic filler represented by the general formula (I) is silica: SiO ₂ , alumina: Al ₂ O ₃ , alumina-hydrate: Al ₂ O ₃ .H ₂ O, aluminum hydroxide: Al (OH) _3. , aluminum _{carbonate: Al 2 (CO 3) 3} , magnesium hydroxide: Mg _{(OH) 2,} magnesium oxide: MgO, magnesium carbonate: MgCO _{3, talc: 3MgO · 4SiO 2 · H 2} O, attapulgite: 5MgO · 8SiO ₂ 9H ₂ O, titanium white: TiO ₂ , titanium black: TiO _2n−1 , calcium oxide: CaO, calcium hydroxide: Ca (OH) ₂ , aluminum magnesium oxide: MgO · Al ₂ O ₃ ), clay: Al ₂ O ₃ · 2SiO ₂ , Kaolin: Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O, Pyrophyllite: Al ₂ O _{3 · 4SiO 2 · H 2 O} , _{bentonite: Al 2 O 3 · 4SiO 2} · 2H 2 O, aluminum _{silicate: Al 2 SiO 5, Al 4} · 3SiO 4 · 5H 2 O and the like, magnesium _silicate: Mg 2 SiO ₄ , MgSiO ₃ etc., calcium silicate: Ca ₂ · SiO ₄ etc., aluminum calcium silicate: Al ₂ O ₃ · CaO · 2SiO ₂ etc., magnesium calcium silicate: CaMgSiO ₄ , calcium carbonate: CaCO ₃ , zirconium oxide: Either of ZrO ₂ , zirconium hydroxide: ZrO (OH) ₂ .nH ₂ O, zirconium carbonate: Zr (CO ₃ ) ₂ , crystalline aluminosilicate, or at least one selected from the group consisting of crystalline aluminosilicates. 2. The rubber composition for tires according to 1.   A tire comprising the rubber composition for a tire according to any one of claims 1 to 4.