JP2011140567A - Rubber composition and method of manufacturing the same, and tire obtained using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition that enhances braking properties on a wet road surface without detriment to rolling resistance, processability and other performances, a method of manufacturing the same, and a tire using the same. <P>SOLUTION: The rubber composition comprises (A) a rubber component comprising at least one from among a natural rubber and synthetic diene rubbers, (B) silica and (C) at least 1 pt.mass and at most 30 pts.mass, based on 100 pts.mass of the rubber component, of a metallic soap, and contains (D) a silane coupling agent represented by general formula (I) and the like. In the formula, each symbol has a specific definition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a rubber composition, a method for producing the same, and a tire using the rubber composition, and in particular, can improve braking performance on a wet road surface without impairing the steering stability of the tire, and can greatly reduce rolling resistance. The present invention relates to a rubber composition for a tread of a tire that is possible and has good processability.

  In recent years, in connection with the movement of global carbon dioxide emission regulations due to the growing concern about environmental problems, in addition to the increasing demand for lower fuel consumption of automobiles, the safety during driving of automobiles has further increased. In order to improve it, a technique for greatly improving braking performance while greatly reducing the rolling resistance of the tire is required. On the other hand, among many fillers used in rubber compositions, it is known that silica can lower the rolling resistance of the tire and improve the braking performance on the wet road surface of the tire.

  In the rubber composition containing the silica, increasing the silica filling amount further improves the braking performance on the wet road surface, but there is a problem that the workability is lowered and the rolling resistance is also deteriorated. In this case, as a method of reducing the rolling resistance of the tire, a method of reducing the blending amount of the filler is known, but when the blending amount of the filler is decreased, the elastic modulus of the rubber composition is decreased. When such a rubber composition is used for a tread of a tire, there is a problem that the steering stability of the tire is deteriorated.

  In addition, it is known that the rolling resistance of the tire can be reduced by lowering the glass transition temperature of the rubber component of the rubber composition used for the tread. In this case, however, the braking performance on the wet road surface of the tire is deteriorated at the same time. There is a problem. Conversely, increasing the glass transition temperature of the rubber component improves braking performance on wet road surfaces, but reduces other performance such as rolling resistance.

On the other hand, a rubber composition in which a metal soap having a specific structure is mixed with a diene rubber has been disclosed as one capable of improving tire traction and durability and maintaining the same rolling resistance (see, for example, Patent Document 1). ).
In recent years, modified polymers have been developed in which the polymer ends are easily reacted with a silane coupling agent. However, when the modified polymer is used as a rubber component of a rubber composition, the elastic modulus of the rubber composition decreases. There is a problem that the steering stability of the tire deteriorates.

  Furthermore, by blending a silane coupling agent having a specific structure with silica, gelation of the rubber component and the silane coupling agent is suppressed, and the processability of the rubber composition is improved and the silica rubber component is improved. Although it is known that the dispersibility of the rubber composition is improved and the hysteresis loss of the rubber composition is reduced (see, for example, Patent Document 2), in this case, the elastic modulus of the rubber composition decreases at the same time. There is a problem that steering stability deteriorates.

JP 2009-185281 A Special table 2001-505225 gazette

  The present invention has been made in view of such circumstances, and a rubber composition capable of improving braking performance on a wet road surface without impairing performance such as rolling resistance and workability, a method for producing the same, and a method for using the same. The object is to provide a tire.

The above problems are solved by the present invention described below.
That is, the present invention
[1] (A) A rubber component comprising at least one of natural rubber and synthetic diene rubber, (B) silica, and 100 parts by mass of the rubber component (C) 1 part by mass or more and 30 parts by mass of metal soap And (D) a rubber composition comprising at least one selected from silane coupling agents represented by the following general formula (I) and general formula (II).

In the above formula, R ¹ represents or linear C1-20, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is Any group selected from [—O—] _0.5 , [—O—G—] _0.5, and [—O—G—O—] _0.5, each independently capable of bonding to two silicon atoms; Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and Z ^C is independently Functionalities represented by Cl, —Br, —OR ² , R ² C (═O) O—, R ² R ³ C═NO—, R ² R ³ N—, R ² —, and HO—G—O— is any one selected from the group, G is consistent with the notation, the straight R ² and R ³ having 1 to 20 carbon atoms each independently or branched, cyclic Al A Le group. M, n, u, v, and w are each independently a real number of 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, And (u / 2) + v + 2w = 2 or 3.
In addition, when there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, in a plurality of B parts Z ^a _u , Z ^b _v and Z ^c _w may be the same or different.

In the above formula, R ⁴ is ^{-Cl, -Br, R 9 O-,} R 9 C (= O) O-, R 9 R 10 C = NO-, R 9 R 10 CNO-, R 9 R 10 N- And-(OSiR ⁹ R ¹⁰ ) _h (OSiR ⁹ R ¹⁰ R ¹¹ ), the monovalent groups (R ⁹ , R ¹⁰ and R ¹¹⁾ may be the same or different and each has a hydrogen atom or a carbon number of 1 a to 18 monovalent hydrocarbon group, h is 1 to 4 as an average value.), R ⁵ is selected from a hydrocarbon group R ^4, a hydrogen atom and monovalent C1-18 R ⁶ is R ⁴ , R ⁵ , a hydrogen atom, and — [O (R ¹² O) _j ] _0.5 — group (R ¹² is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4). R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y, and z are , X + y + 2z Is an integer satisfying 3,0 ≦ x ≦ 3,0 ≦ y ≦ 2,0 ≦ z ≦ 1 relationship.

[2] The rubber according to [1], wherein the content of the silane coupling agent as the component (D) is 5% by mass or more and 15% by mass or less with respect to the content of the silica as the component (B). It is a composition.
[3] The content of silica as the component (B) is 20 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the rubber component as the component (A). The rubber composition.
[4] The component (D) represented by the general formula (I) is at least selected from silane coupling agents represented by the structural formula (III), the structural formula (IV), and the structural formula (V). The rubber composition according to any one of [1] to [3], which is a kind.

In said formula, L is respectively independently a C1-C9 alkanediyl group or alkenediyl group, and is x = m and y = n. )
[5] A tire using the rubber composition according to any one of [1] to [4].

[6] (A) For rubber components comprising at least one of natural rubber and synthetic rubber, (B) silica, (C) metal soap, and (D) in the following general formulas (I) and (II) A step of adding and kneading the silane coupling agent represented,
It is a method for producing a rubber composition in which the kneading steps of at least the metal soap as the component (C) and the silane coupling agent as the component (D) are different.

In the above formula, R ¹ represents or linear C1-20, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is Any group selected from [—O—] _0.5 , [—O—G—] _0.5, and [—O—G—O—] _0.5, each independently capable of bonding to two silicon atoms; Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and Z ^C is independently Functionalities represented by Cl, —Br, —OR ² , R ² C (═O) O—, R ² R ³ C═NO—, R ² R ³ N—, R ² —, and HO—G—O— is any one selected from the group, G is consistent with the notation, the straight R ² and R ³ having 1 to 20 carbon atoms each independently or branched, cyclic Al A Le group. M, n, u, v, and w are each independently a real number of 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, And (u / 2) + v + 2w = 2 or 3.
In addition, when there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, in a plurality of B parts Z ^a _u , Z ^b _v and Z ^c _w may be the same or different.

In the above formula, R ⁴ is ^{-Cl, -Br, R 9 O-,} R 9 C (= O) O-, R 9 R 10 C = NO-, R 9 R 10 CNO-, R 9 R 10 N- And-(OSiR ⁹ R ¹⁰ ) _h (OSiR ⁹ R ¹⁰ R ¹¹ ), the monovalent groups (R ⁹ , R ¹⁰ and R ¹¹⁾ may be the same or different and each has a hydrogen atom or a carbon number of 1 a to 18 monovalent hydrocarbon group, h is 1 to 4 as an average value.), R ⁵ is selected from a hydrocarbon group R ^4, a hydrogen atom and monovalent C1-18 R ⁶ is R ⁴ , R ⁵ , a hydrogen atom, and — [O (R ¹² O) _j ] _0.5 — group (R ¹² is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4). R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y, and z are , X + y + 2z Is an integer satisfying 3,0 ≦ x ≦ 3,0 ≦ y ≦ 2,0 ≦ z ≦ 1 relationship.
[7] The method for producing a rubber composition according to [6], wherein the kneading step of the metal soap as the component (C) is after the kneading step of the silane coupling agent as the component (D). is there.

  According to the present invention, it is possible to provide a rubber composition capable of improving braking performance on a wet road surface without impairing performance such as rolling resistance and workability, a manufacturing method thereof, and a tire using the rubber composition. it can.

Hereinafter, the present invention will be described with reference to embodiments.
<Rubber composition>
The rubber composition of this embodiment comprises (A) a rubber component composed of at least one of natural rubber and synthetic diene rubber, (B) silica, and (C) metal soap with respect to 100 parts by mass of the rubber component. 1 part by mass or more and 30 parts by mass or less, and (D) containing at least one selected from silane coupling agents represented by the following general formula (I) and general formula (II) And

In the above formula, R ¹ represents or linear C1-20, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is Any group selected from [—O—] _0.5 , [—O—G—] _0.5, and [—O—G—O—] _0.5, each independently capable of bonding to two silicon atoms; Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and Z ^C is independently Functionalities represented by Cl, —Br, —OR ² , R ² C (═O) O—, R ² R ³ C═NO—, R ² R ³ N—, R ² —, and HO—G—O— is any one selected from the group, G is consistent with the notation, the straight R ² and R ³ having 1 to 20 carbon atoms each independently or branched, cyclic Al A Le group. M, n, u, v, and w are each independently a real number of 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, And (u / 2) + v + 2w = 2 or 3.
In addition, when there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, in a plurality of B parts Z ^a _u , Z ^b _v and Z ^c _w may be the same or different.

In the above formula, R ⁴ is ^{-Cl, -Br, R 9 O-,} R 9 C (= O) O-, R 9 R 10 C = NO-, R 9 R 10 CNO-, R 9 R 10 N- And-(OSiR ⁹ R ¹⁰ ) _h (OSiR ⁹ R ¹⁰ R ¹¹ ), the monovalent groups (R ⁹ , R ¹⁰ and R ¹¹⁾ may be the same or different and each has a hydrogen atom or a carbon number of 1 a to 18 monovalent hydrocarbon group, h is 1 to 4 as an average value.), R ⁵ is selected from a hydrocarbon group R ^4, a hydrogen atom and monovalent C1-18 R ⁶ is R ⁴ , R ⁵ , a hydrogen atom, and — [O (R ¹² O) _j ] _0.5 — group (R ¹² is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4). R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y, and z are , X + y + 2z Is an integer satisfying 3,0 ≦ x ≦ 3,0 ≦ y ≦ 2,0 ≦ z ≦ 1 relationship.

<(A) Rubber component>
Examples of the rubber component that can be used in the rubber composition of the present embodiment include at least one selected from natural rubber (NR) and various synthetic diene rubbers. Specific examples of the synthetic diene rubber include polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR). ), Ethylene-propylene-diene rubber (EPDM), crosslinked polyethylene rubber, chloroprene rubber and nitrile rubber. These rubber components may be used alone or in a combination of two or more.
Of the above, the use of diene rubbers such as natural rubber (NR), styrene / butadiene copolymer rubber (SBR), and polybutadiene rubber (BR) provides lower heat buildup and wear resistance. This is preferable.

<(B) Silica>
Examples of the silica that is the component (B) in this embodiment include wet silica (hydrous silicic acid) and dry silica (anhydrous silicic acid). Among them, the effect of improving fracture characteristics, wet grip properties, and low rolling resistance are mentioned. The wet silica is most preferable because the compatibility effect is the most remarkable.
The silica in the present embodiment does not indicate only silicon dioxide in a narrow sense, but means a silicic acid-based filler. Specifically, in addition to anhydrous silicic acid, hydrous silicic acid, calcium silicate, silica Contains silicates such as aluminum acid.

The wet silica has a nitrogen adsorption specific surface area (N ₂ SA) according to the BET method in the range of 140 to 280 m ² / g in terms of balance between reinforcement, workability, wet grip properties, and wear resistance. Preferably, it is in the range of 170 to 250 m ² / g. Suitable wet silica includes, for example, AQ, VN3, LP, NA, etc. manufactured by Tosoh Silica Co., Ltd. and Ultrazil VN3 (N ₂ SA: 210 m ² / g) manufactured by Degussa.
The silica which is this (B) component is 20 mass parts or more and 120 mass parts or less with respect to 100 mass parts of rubber components which are (A) components, More preferably, they are 20 mass parts or more and 100 mass parts or less, More preferably, 40 masses. More than 90 parts by weight. If the blending amount of the silica is 20 parts by mass or more and 120 parts by mass or less, the braking performance on a wet road surface can be improved without causing deterioration of workability and deterioration of rolling resistance.

In the rubber composition in the present embodiment, an inorganic filler other than silica as the component (B) can be appropriately blended as necessary. Examples of the inorganic filler other than the silica include at least one selected from compounds represented by the following general formula (IX).
nM · xSiO _y · zH ₂ O (IX)
(In the formula, M is selected from metals selected from aluminum, magnesium, titanium, calcium and zirconium, and oxides or hydroxides of these metals, hydrates thereof, and carbonates of the metals. And at least one type, n, x, y and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10.
By using the compound represented by the above general formula (IX) or silica, the reinforcing effect can be enhanced efficiently, and both the wear resistance and the low heat generation property (low fuel consumption) when used as a tire are achieved. be able to.

Specific examples of the compound represented by the general formula (IX) include alumina (Al ₂ O ₃ ) such as γ-alumina and α-alumina, and alumina monohydrate (Al ₂ O such as boehmite and diaspore). ₃ · H ₂ O), Gibbsite, Bayerite, etc. Aluminum hydroxide [Al (OH) ₃ ], Aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], 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], magnesium aluminum oxide _{(MgO · Al 2 O 3)} , clay _{(Al 2 O 3 · 2SiO 2} ), mosquitoes Phosphorus _{(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], carbonic acid zirconium _{[Zr (CO 3) 2]} , crystalline aluminosilicate containing hydrogen to correct, an alkali metal or alkaline earth metal charge as various zeolites Etc. can be used. The compound represented by the general formula (IX) is preferably at least one selected from M selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate.
These compounds represented by the general formula (IX) may be used alone or in combination of two or more.

<(C) Metal soap>
The metal soap which is the component (C) in this embodiment is an organic acid metal salt composed of a divalent or higher valent metal ion and an organic acid. Specific examples of the metal soap include, for example, calcium soap, magnesium soap, aluminum soap, zinc soap and the like as the single metal soap. Magnesium soap, aluminum soap and zinc soap are preferable, and aluminum soap is particularly preferable. . Examples of the complex metal soap include calcium complex soap, barium complex soap, and aluminum complex soap. Among these metal soaps, a single metal soap that can be added by a pre-soap mixing method without using a saponification reaction is preferable.

The organic acid portion of the metal soap is preferably a straight chain or a fatty acid having a hydroxy group, and more preferably a straight chain saturated fatty acid. In this case, when the organic acid is a carboxylic acid, the structure is represented by M (O ₂ CR) _n (M is a metal element), and R may be, for example, a C2 to C5 acid or a C6 to C22 fatty acid. Alternatively, higher fatty acids such as C23 to C50 may be used. N is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, depending on the metal used.

Such fatty acid metal soaps include calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, strontium stearate, barium stearate, zinc laurate, calcium laurate, barium laurate, calcium montanate, zinc montanate , Magnesium montanate, zinc behenate, magnesium behenate, barium ricinoleate, zinc myristate, zinc palmitate, barium 2-ethylhexoate, barium ricinoleate, aluminum dilaurate, aluminum diethylhexanoate, and stearic acid Aluminum, aluminum dilaurate and aluminum diethylhexanoate are particularly preferred.
These may use 1 type and may use 2 or more types together.

  The metal soap that is the component (C) is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the rubber component that is the component (A). When the blending amount of the metal soap is less than 1 mass, the effect of improving the braking performance on a wet road surface cannot be obtained sufficiently. When it exceeds 30 mass parts, workability | operativity will deteriorate. The blending amount of the metal soap is preferably 2 parts by mass or more and 25 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less.

<(D) Silane coupling agent>
As the component (D) in this embodiment, a silane coupling agent containing at least an element or a functional group capable of binding to silica and a protected mercapto group is used. By having a protected mercapto group, it is possible to prevent the occurrence of initial vulcanization (scorch) during processing prior to the vulcanization process, so that processability is improved and combined with silica and inorganic fillers. Since they have possible elements or functional groups, their dispersibility in the rubber component is good. Among these, as a functional group which can be combined with silica, an alkoxysilane group is preferable because the above effect is excellent.

  As described above, by applying the metal soap which is the component (C) to the rubber component, the braking performance on the wet road surface can be improved. However, in this case, at the same time, the viscosity of the rubber composition is increased and the hysteresis loss is also increased, so that the rolling resistance of the tire is deteriorated. In the present embodiment, the silica and metal soap are combined with the sulfur-containing silane coupling agent having the above specific structure to improve the dispersibility of silica in the rubber component and the reactivity of silica and polymer. It has been found that hysteresis loss can be reduced without lowering the elastic modulus. As a result, compared to the case where the dispersibility of silica is simply improved with a normal silane coupling agent, in addition to maintaining the workability, both rolling resistance and wet road surface braking are improved, and the dry road surface is improved. The handling stability can be improved.

  Specifically, a silane coupling agent composed of a protected mercaptosilane represented by the general formula (I) is used first.

In the general formula (I), R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, and G is independently an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms. Z ^a is ^a group capable of independently bonding to two silicon atoms, and is selected from [—O—] _0.5 , [—O—G—] _0.5 and [—O—G—O—] _0.5. Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and Z ^c is independently ^{-Cl, -Br, -OR 7, R} 7 C (= O) O-, R 2 R 3 C = NO-, R 2 R 3 N-, R 2 - and HO-G-O- in is any one selected from the functional groups represented, G coincides with the notation, the straight R ² and R ³ having 1 to 20 carbon atoms each independently or Toki, a cyclic alkyl group. M, n, u, v, and w are each independently a real number of 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, And (u / 2) + v + 2w = 2 or 3.
In addition, when there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, in a plurality of B parts Z ^a _u , Z ^b _v and Z ^c _w may be the same or different.

  The silane coupling agent obtained by the general formula (I) is at least one selected from silane coupling agents represented by the following structural formula (III), structural formula (IV) and structural formula (V). Is preferred.

  In said formula, L is respectively independently a C1-C9 alkanediyl group or alkenediyl group, and is x = m and y = n.

As the silane coupling agent represented by the structural formula (III), a product name “NXT Low-V Silane (registered trademark)” manufactured by Momentive Performance Materials is commercially available.
Further, as the silane coupling agent represented by the structural formula (IV), a product name “NXT Ultra Low-V Silane (registered trademark)” manufactured by Momentive Performance Materials is also available as a commercial product.
Furthermore, examples of the silane coupling agent represented by the structural formula (V) include a product name “NXT Z (registered trademark)” manufactured by Momentive Performance Materials.

  The rubber composition in the present embodiment is at least selected from silane coupling agents represented by the above structural formulas (III), (IV) and (V) (hereinafter sometimes referred to as “NXT silane”). By using one type, it is possible to increase workability during rubber processing due to a decrease in the viscosity of the unvulcanized rubber, and it is possible to increase the amount of metal soap, resulting in rolling resistance and braking of wet road surfaces. In addition, the tire can be improved, and in addition, the driving stability of the dry road surface can be improved.

In addition, since the silane coupling agent represented by the structural formula (V) (particularly the trade name “NXT Z (registered trademark)”) has a large number of alkoxysilane carbon atoms, that is, a small number of ethoxy groups, it is a volatile compound. This is preferable because VOC (particularly alcohol) is not generated and the environmental load is small. The silane coupling agent represented by the structural formula (V) (especially the trade name “NXT Z (registered trademark)”) is excellent in tire performance with low heat build-up, greatly improving rolling resistance and wet road braking performance. It is more preferable because a rubber composition that improves and also has improved wear resistance can be obtained.
In the present embodiment, a silane coupling agent represented by the general formula (II) can also be used as the component (D).

Wherein, R ⁴ is ^{-Cl, -Br, R 9 O-,} R 9 C (= O) O-, R 9 R 10 C = NO-, R 9 R 10 CNO-, R 9 R 10 N- and -(OSiR ⁹ R ¹⁰ ) _h (OSiR ⁹ R ¹⁰ R ¹¹ ) monovalent groups selected from (R ⁹ , R ¹⁰ and R ¹¹⁾ may be the same or different, each having a hydrogen atom or a carbon number of 1 to 18 is a monovalent hydrocarbon group having an average value of 1 to 4, and R ⁵ is R ⁴ , a hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ⁶ Is R ⁴ , R ⁵ , a hydrogen atom or a — [O (R ¹² O) _j ] _0.5 — group (R ¹² is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4), R ⁷ Represents a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁸ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y and z are x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, 0 ≦ z ≦ 1 Plus an integer.

In the above general formula (II), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different, preferably each a straight-chain, 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 aralkyl group. When R ⁵ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, it is a group selected from the group consisting of a linear, cyclic or branched alkyl group, alkenyl group, aryl group and aralkyl group. Preferably there is. R ¹² is preferably a linear, cyclic or branched alkylene group, particularly preferably a linear one. R ⁷ is, for example, an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, a cycloalkylalkylene group having 6 to 18 carbon atoms, or an arylene having 6 to 18 carbon atoms. And aralkylene groups having 7 to 18 carbon atoms. The alkylene group and alkenylene group may be linear or branched, and the cycloalkylene group, cycloalkylalkylene group, arylene group, and aralkylene group may have a substituent such as a lower alkyl group on the ring. You may have. R ⁷ is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group. it can.

Specific examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms of R ⁵ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 in} the general formula (II) include a methyl group, an ethyl group, and an n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group , Allyl group, hexenyl group, octenyl group, cyclopentenyl group, cyclohexenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenethyl group, naphthylmethyl group and the like.
Examples of R ¹² in the general formula (II) include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group and the like.

Specific examples of the silane coupling agent (D) represented by the general formula (II) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltri Ethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane Down, 2-octanoylthiopropyl ethyltrimethoxysilane, 2- deca Neu thio ethyltrimethoxysilane, and 2-lauroyl thio ethyl trimethoxysilane. Of these, 3-octanoylthiopropyltriethoxysilane (manufactured by General Electric Silicones, registered trademark: NXT silane) is particularly preferable.
In the rubber composition of the present embodiment, by using such a silane coupling agent as the component (D), the tire has excellent workability during rubber processing and good braking performance and rolling resistance on a wet road surface. Can be given.

In the present embodiment, the blending amount of the silane coupling agent as the component (D) is preferably selected from 5% by mass to 15% by mass with respect to the silica as the component (B). . When the amount of the silane coupling agent is within the above range, the viscosity of the unvulcanized rubber is sufficiently lowered, so that desirable workability can be obtained, and rolling resistance and wet road surface braking performance can be improved.
A preferable compounding amount is 5% by mass or more and 12% by mass or less, and a more preferable compounding amount is 6% by mass or more and 10% by mass or less.

  In the present embodiment, in addition to the silane coupling agent represented by the general formula (I) as the component (D), other silane coupling agents (hereinafter sometimes referred to as “other silane coupling agents”). Can be used. Moreover, it is preferable to make the compounding quantity into 1 mass% or more and 20 mass% or less with respect to the silica which is (B) component. The other silane coupling agent is preferable because it can further improve the reinforcing property and dispersibility of the silica (B).

  The other silane coupling agent used in the present embodiment is preferably at least one selected from the group consisting of compounds represented by the following general formulas (VI) to (VIII). This is because a bond bridge between silica or the like and rubber acts more suitably, and a more suitable reinforcing phase is formed.

A _a B _3-a Si—X—S _b —X—SiA _a B _3-a (VI)
_Wherein A is C _c H _{2c + 1} O (c is an integer of 1 to 3) or a chlorine atom, B is an alkyl group having 1 to 3 carbon atoms, and X is a saturated or unsaturated alkylene having 1 to 9 carbon atoms. Or an arylene group having 7 to 15 carbon atoms, a being an integer of 1 to 3, and b being an integer of 1 or more, provided that when a is 1, two Bs are the same. And when a is 2 or 3, two or three A's may be the same or different.)
A _a B _3-a Si-XY (VII)
(In the formula, A, B, X, and a are the same as described above, and Y is any of a mercapto group, a vinyl group, an amino group, a glycidoxy group, and an epoxy group.)
A _a B _3-a Si-X-S _b -Z (VIII)
(In the formula, A, B, X, a, and b are the same as described above, and Z is a benzothiazolyl group, N, N-dimethylthiocarbamoyl group, methacryloyl group, and a saturated or unsaturated hydrocarbon having 1 to 15 carbon atoms. Any of the groups.)

  Specifically, examples of the silane coupling agent represented by the general formula (VI) include bis- (3-triethoxysilylpropyl) tetrasulfide, bis- (3-trimethoxynylpropyl) tetrasulfide, and bis- (3 -Methyldimethoxysilylpropyl) tetrasulfide, bis- (3-triethoxysilylethyl) tetrasulfide, bis- (3-triethoxysilylpropyl) disulfide, bis- (3-trimethoxysilylpropyl) disulfide, bis- (3-tri And ethoxysilylpropyl) trisulfide.

  Examples of the silane coupling agent represented by the general formula (VII) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-glycindkinpropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.

  Examples of the silane coupling agent represented by the general formula (VIII) include 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3 -Trimethoxysilylpropyl methacryloyl monosulfide, 3-triethoxysilylpropyl n-octyl disulfide, etc. are mentioned.

It is preferable that the usage-amount of said other silane coupling agent is 1 mass% or more and 20 mass% or less with respect to the quantity of the silica which is (B) component. When the amount used is in the above range, a sufficient coupling effect can be obtained without causing gelation of the polymer. Considering the blending effect and economy, the more preferable amount of use is 3% by mass or more and 15% by mass or less.
In the present embodiment, the other silane coupling agents may be used alone or in combination of two or more.

  Further, in the rubber composition according to the present embodiment, the viscosity of unvulcanized rubber is reduced by using such other silane coupling agent, so that it takes a long time until the scorch occurs. Therefore, kneading can be performed for a long time, and workability during kneading of the rubber composition can be improved. Further, the hysteresis loss can be reduced by improving the dispersion of the rubber component such as silica and the reactivity between the silica and the polymer. This improvement can be utilized to increase the blending amount of the reinforcing filler, and as a result, a tire with good wear resistance can be obtained.

  Furthermore, in order to couple the silane coupling agent and the polymer, it is preferable that a proton donor represented by DPG (diphenylguanidine) or the like is used as a deprotecting agent in the final kneading step. The amount used is preferably in the range of 0.1 to 5.0 parts by weight, more preferably in the range of 0.2 to 3.0 parts by weight, with respect to 100 parts by weight of the rubber component.

(Other ingredients)
In the rubber composition according to this embodiment, carbon black may be further blended. The blending amount of the carbon black is preferably in the range of 5 to 100 parts by weight, more preferably in the range of 5 to 80 parts by weight, with respect to 100 parts by weight of the rubber component. It is particularly preferable to set the mass range. Further, when the mass ratio to silica (silica: carbon black) is in the range of (10:90) to (95: 5), the fracture characteristics can be ensured and excellent low hysteresis loss can be obtained. In this respect, the mass ratio (30:70) to (95: 5) is more preferable, and the mass ratio (50:50) to (95: 5) is particularly preferable.

  It is preferable to use at least one carbon black selected from HAF grade, N339 grade, IISAF grade, ISAF grade and SAF grade, and in order to ensure reinforcement, the SAF grade and ISAF grade are used. In order to ensure low hysteresis loss, it is preferable to use HAF grade, N339 grade, and IISAF grade.

The rubber composition in the present embodiment includes various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and anti-aging, as long as the purpose of the present embodiment is not impaired. Agents, scorch inhibitors, zinc white, stearic acid, and the like.
Examples of the vulcanizing agent include sulfur, and the amount used thereof is preferably in the range of 0.1 to 10.0 parts by mass, more preferably 1.0 to 100 parts by mass with respect to 100 parts by mass of the rubber component. The range is 5.0 parts by mass. If the amount is less than 0.1 parts by mass, the rupture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, the rubber elasticity is lost.

  The vulcanization accelerator is not particularly limited. For example, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide) ) And other guanidine vulcanization accelerators such as DPG (diphenylguanidine), and the amount used is 0.1-5. The range of 0 mass part is preferable, More preferably, it is the range of 0.2-3.0 mass part.

  Examples of the process oil include paraffinic, naphthenic and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component. When the amount exceeds 100 parts by mass, the tensile strength and low heat build-up of the vulcanized rubber tend to deteriorate.

  Furthermore, examples of the anti-aging agent include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine], Examples thereof include AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), a high-temperature condensate of diphenylamine and acetone, etc. The amount used is based on 100 parts by mass of the rubber component. The range of 0.1-5.0 mass parts is preferable, More preferably, it is the range of 0.3-3.0 mass parts.

<Method for producing rubber composition>
The rubber composition of the present embodiment can be produced by kneading the above components with a kneader such as a roll, a Banbury mixer, a kneader, or an internal mixer. In this case, usually, after kneading the rubber component and the filler in the kneading stage A (also referred to as “non-pro kneading stage”), the rubber composition is cooled to room temperature and allowed to stand for a certain period of time, and then kneading stage B (Also referred to as the “professional stage”).

In the present embodiment, it is preferable to first knead the rubber component, silica, metal soap, and the like in the kneading stage A, and then knead the vulcanizing compound in the kneading stage B. In particular, by kneading a rubber component and a filler such as silica in kneading step A, the filler functions as a reinforced rubber component, which contributes to improved wet performance and can improve fracture resistance. .
Further, a kneading stage C (also referred to as “second non-pro kneading stage”) or a kneading stage D (also referred to as “X-mill”) may be provided between the kneading stage A and the kneading stage B. Good. The kneading step C is mainly performed when the filler is dividedly charged. In the kneading step D, kneading is performed for the purpose of lowering the viscosity of the rubber composition obtained in the kneading step A or the kneading step C and for improving the dispersibility of the filler. Usually, in the kneading stage B, a vulcanizing compound (zinc white, sulfur, vulcanization accelerator) or the like is blended with the rubber composition obtained in the previous kneading, but a foaming agent or the like is blended. In this case, it may be kneaded in a separate kneading step with the vulcanizing compounding agent.

In this embodiment, it is preferable that the kneading steps of at least the metal soap as the component (C) and the silane coupling agent as the component (D) are different. Since the metal soap is acidic, it may interfere with the reaction of the silane coupling agent when it is added to the kneading system at the same time as the silane coupling agent. Because it can be done.
From the above viewpoint, it is preferable that the kneading step of the metal soap as the component (C) is after the kneading step of the silane coupling agent as the component (D). This is because the reaction of the silane coupling agent can be accelerated to some extent by kneading the silane coupling agent before the metal soap is added.

Specifically, in order to change the kneading stage of the metal soap and the silane coupling agent, the charging timing of the metal soap and the silane coupling agent into the kneading system may be changed. More specifically, for example, the kneading stage A and the kneading stage C may be provided as the non-pro kneading stage, and the metal soap and the silane coupling agent may be added and kneaded separately in these two stages.
Moreover, in order to make the kneading step of the metal soap after the kneading step of the silane coupling agent, for example, the silane coupling agent is added and kneaded in the kneading step A, and the kneading step What is necessary is just to put metal soap in C and knead.

  In the rubber composition of the present embodiment configured as described above, silica, metal soap, and a silane coupling agent are contained in at least one rubber component selected from natural rubber and synthetic diene rubber, A rubber composition that is excellent in workability and rolling resistance characteristics, and further excellent in braking performance on a wet road surface as compared with the prior art will be obtained.

<Tire>
The tire of this embodiment is manufactured by a normal method using the rubber composition. That is, if necessary, a rubber composition containing various chemicals as described above is processed into a tread rubber at an unvulcanized stage, and is pasted and molded by a normal method on a tire molding machine. Molded. The green tire is heated and pressed in a vulcanizer to obtain a tire.

  As mentioned above, although this invention was demonstrated by embodiment, this invention is not limited to said form, In the range which does not deviate from the objective of the invention, arbitrary change and a change can be performed.

  Hereinafter, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples. In the following, “part” means part by mass and “%” means mass% unless otherwise specified.

<Examples 1-7 and Comparative Examples 1-5>
Each mixture having the formulation shown in Table 1 below was kneaded using a Banbury mixer to obtain an unvulcanized rubber composition. Here, the kneading is divided into two stages of non-pro kneading from SBR to metal soap in Table 1 (referred to as “first non-pro kneading” and “second non-pro kneading”, respectively). The kneading was carried out at any kneading stage (indicated as “first” or “second” in the table). About the obtained rubber composition, workability was evaluated by the method shown below.

  Further, the 12 kinds of rubber compositions thus obtained are respectively arranged on the tread (tread cap portion) of a pneumatic radial tire for a passenger car (tire size 195 / 60R15), and 12 types of pneumatic radial tires for a passenger car are obtained. Manufactured in accordance with a conventional method, and using these 12 types of tires, rolling resistance and wet road surface braking performance were evaluated according to the following methods. The evaluation results are shown in Table 1.

(Processability of rubber composition)
The Mooney viscosity (ML _{1 +} 4/130 ° C.) was measured at 130 ° C. in accordance with JIS K6300, the reciprocal thereof was determined, and the value of Comparative Example 1 was displayed as an index. The larger the index value, the lower the unvulcanized viscosity and the better the workability.

(Rolling resistance)
The rolling resistance when the prototype tire was rotated at a speed of 80 km / h using a rotating drum having a diameter of 1700 mm under the action of a load of 3.92 kN was measured by the coasting method. It was shown as an index. The larger the rolling resistance index, the smaller and better the rolling resistance.

(Brake performance on wet road surface)
Four of the prototype tires were mounted on a 2000 cc passenger car, and the braking distance from an initial speed of 70 km / hr was measured on a wet asphalt road surface of a test course. The measured value of Comparative Example 1 was set to 100, and for the values of other examples, an index was calculated and displayed as an index by the braking distance of Comparative Example 1 / the braking distance of the test tire × 100. Therefore, the larger the numerical value, the better.

(Steering stability on dry road surface)
The prototype tire was mounted on four wheels of a passenger car, and a test driver ran on a test course in this test vehicle. The control tire (Comparative Example 1) was rated as 100 with respect to the feeling of the driving stability and riding comfort on the dry road surface of each tire by the test driver. The higher the score, the better the steering stability.

［注］
１） ＳＢＲ：乳化重合スチレン−ブタジエン共重合体ゴム、ＪＳＲ（株）製、商品名「ＳＢＲ１５００」
２） シリカ：日本シリカ工業（株）製 ニップシールＡＱ（Ｓ_Hg＝１４０ｍ² ／ｇ：ニップシールＶＮ３を顆粒にしたもの）
３） カーボンブラック：デグッサ社製、商品名「Ｎ２３４」
４） デグッサ社製、商品名「Ｓｉ６９」
５） Ｇｅｎｅｒａｌ Ｅｌｅｃｔｒｉｃ社製、商品名「ＮＸＴ ｓｉｌａｎｅ」（３−オクタノイルチオプロピルトリエトキシシラン）
６） 老化防止剤：Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン、大内新興化学（株）製、商品名「ノクラック ６Ｃ」
７） ジラウリル酸アルニニウム石鹸
８） 加硫促進剤ＤＰＧ：ジフェニルグアニジン、大内新興化学工業（株）製、商品名「ノクセラー Ｄ」
９） 加硫促進剤ＣＺ： Ｎ−シクロヘキシル−２−ベンゾジアゾリルスルフェンアミド、大内新興化学工業（株）製、商品名「ノクセラー ＣＺ」
１０） 加硫促進剤ＤＭ：ジ−２−ベンゾチアゾリルジスルフィド、大内新興化学工業（株）製、商品名「ノクセラー ＤＭ」

[note]
1) SBR: Emulsion-polymerized styrene-butadiene copolymer rubber, manufactured by JSR Corporation, trade name “SBR1500”
2) Silica: Nippon Silica Industry Co., Ltd. nip seal AQ (S _Hg = 140 m ² / g: nip seal VN3 granulated)
3) Carbon Black: Product name “N234” manufactured by Degussa
4) Product name “Si69” manufactured by Degussa
5) Product name “NXT silane” (3-octanoylthiopropyltriethoxysilane), manufactured by General Electric
6) Anti-aging agent: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “NOCRACK 6C”
7) Arniumium dilaurate soap 8) Vulcanization accelerator DPG: Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller D”
9) Vulcanization accelerator CZ: N-cyclohexyl-2-benzodiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller CZ”
10) Vulcanization accelerator DM: di-2-benzothiazolyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller DM”

  As is apparent from the results shown in Table 1, in the rubber composition containing a certain amount of metal soap and a silane coupling agent having a specific structure in the examples, Comparative Examples 1 to 1 having the same composition except for not containing these simultaneously. It can be seen that the braking performance of the wet road surface is improved while maintaining the rolling resistance as well as excellent workability as compared with 5.

Claims (7)

(A) A rubber component composed of at least one of natural rubber and synthetic diene rubber, (B) silica, and 100 parts by mass of the rubber component (C) 1 to 30 parts by mass of metal soap (D) A rubber composition comprising at least one selected from silane coupling agents represented by the following general formula (I) and general formula (II).

(In the formula, R ¹ or a straight-chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is Any group selected from [—O—] _0.5 , [—O—G—] _0.5, and [—O—G—O—] _0.5, each independently capable of bonding to two silicon atoms; Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and Z ^C is independently Functionalities represented by Cl, —Br, —OR ² , R ² C (═O) O—, R ² R ³ C═NO—, R ² R ³ N—, R ² —, and HO—G—O— is any one selected from the group, G is consistent with the notation, the straight R ² and R ³ having 1 to 20 carbon atoms each independently or branched, cyclic alkyl M, n, u, v, and w are each independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1. It is a real number and (u / 2) + v + 2w = 2 or 3.
In addition, when there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, in a plurality of B parts Z ^a _u , Z ^b _v and Z ^c _w may be the same or different. )

(Wherein, R ⁴ is ^{-Cl, -Br, R 9 O-,} R 9 C (= O) O-, R 9 R 10 C = NO-, R 9 R 10 CNO-, R 9 R 10 N- And-(OSiR ⁹ R ¹⁰ ) _h (OSiR ⁹ R ¹⁰ R ¹¹ ), the monovalent groups (R ⁹ , R ¹⁰ and R ¹¹⁾ may be the same or different and each has a hydrogen atom or a carbon number of 1 a to 18 monovalent hydrocarbon group, h is 1 to 4 as an average value.), R ⁵ is selected from a hydrocarbon group R ^4, a hydrogen atom and monovalent C1-18 R ⁶ is R ⁴ , R ⁵ , a hydrogen atom, and — [O (R ¹² O) _j ] _0.5 — group (R ¹² is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4). R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y, and z are , X + y + 2z = Is an integer satisfying the relation 0 ≦ x ≦ 3,0 ≦ y ≦ 2,0 ≦ z ≦ 1.)   The rubber composition according to claim 1, wherein the content of the silane coupling agent as the component (D) is 5% by mass or more and 15% by mass or less with respect to the content of the silica as the component (B).   The rubber composition according to claim 1 or 2, wherein the content of silica as the component (B) is 20 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the rubber component as the component (A). The component (D) represented by the general formula (I) is at least one selected from silane coupling agents represented by the structural formula (III), the structural formula (IV), and the structural formula (V). The rubber composition according to any one of claims 1 to 3.

(In the formula, each L is independently an alkanediyl group or alkenediyl group having 1 to 9 carbon atoms, and x = m and y = n.)   A tire using the rubber composition according to claim 1. (A) The rubber component consisting of at least one of natural rubber and synthetic rubber is represented by (B) silica, (C) metal soap, and (D) the following general formula (I) and general formula (II). Having a step of adding and kneading a silane coupling agent;
The manufacturing method of the rubber composition from which the kneading | mixing step of the metal soap which is at least said (C) component, and the silane coupling agent which is (D) component differs.

(In the formula, R ¹ or a straight-chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a is Any group selected from [—O—] _0.5 , [—O—G—] _0.5, and [—O—G—O—] _0.5, each independently capable of bonding to two silicon atoms; Z ^b is a group capable of independently bonding to two silicon atoms, a functional group represented by [—O—G—O—] _0.5 , and Z ^C is independently Functionalities represented by Cl, —Br, —OR ² , R ² C (═O) O—, R ² R ³ C═NO—, R ² R ³ N—, R ² —, and HO—G—O— is any one selected from the group, G is consistent with the notation, the straight R ² and R ³ having 1 to 20 carbon atoms each independently or branched, cyclic alkyl M, n, u, v, and w are each independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1. It is a real number and (u / 2) + v + 2w = 2 or 3.
In addition, when there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, in a plurality of B parts Z ^a _u , Z ^b _v and Z ^c _w may be the same or different. )

(Wherein, R ⁴ is ^{-Cl, -Br, R 9 O-,} R 9 C (= O) O-, R 9 R 10 C = NO-, R 9 R 10 CNO-, R 9 R 10 N- And-(OSiR ⁹ R ¹⁰ ) _h (OSiR ⁹ R ¹⁰ R ¹¹ ), the monovalent groups (R ⁹ , R ¹⁰ and R ¹¹⁾ may be the same or different and each has a hydrogen atom or a carbon number of 1 a to 18 monovalent hydrocarbon group, h is 1 to 4 as an average value.), R ⁵ is selected from a hydrocarbon group R ^4, a hydrogen atom and monovalent C1-18 R ⁶ is R ⁴ , R ⁵ , a hydrogen atom, and — [O (R ¹² O) _j ] _0.5 — group (R ¹² is an alkylene group having 1 to 18 carbon atoms, j is an integer of 1 to 4). R ⁷ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and x, y, and z are , X + y + 2z = Is an integer satisfying the relation 0 ≦ x ≦ 3,0 ≦ y ≦ 2,0 ≦ z ≦ 1.)   The method for producing a rubber composition according to claim 6, wherein the kneading step of the metal soap as the component (C) is after the kneading step of the silane coupling agent as the component (D).