JP2006131683A - Rubber composition and pneumatic tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition having a lower unvulcanized viscosity than those of conventional ones and a high dispersibility of silica, showing a high abrasion resistance and low rolling resistance in using as a tread member of a tire, and also capable of aiming at the improvement of braking property and steering stability on a wet road surface, and a tire by using the same. <P>SOLUTION: This rubber composition contains based on 100 pts.mass polymer, 10-200 pts.mass silica, 1-30 pts.mass 1 kind or ≥2 kinds of sulfur-containing silane compounds expressed by general formula (I): (R<SP>1</SP>O)<SB>3-p</SB>(R<SP>2</SP>)<SB>p</SB>SiR<SP>3</SP>SR<SP>4</SP>SR<SP>3</SP>Si(R<SP>2</SP>)<SB>p</SB>(OR<SP>1</SP>)<SB>3-p</SB>[wherein, R<SP>4</SP>is a divalent functional group expressed by general formula (II): SR<SP>5</SP>S or (III): R<SP>6</SP>S<SB>x</SB>R<SP>7</SP>] and 0.1-20 pts.mass amine salt compound expressed by general formula (IV). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a rubber composition and a pneumatic tire, and in particular, the processability is good because the viscosity of unvulcanized rubber is low, and particularly when used in a tire tread, the wear resistance is high and the rolling resistance is high. The present invention relates to a rubber composition that is low and excellent in braking performance and handling stability on wet road surfaces, and a tire using the rubber composition.

  Of the many fillers used in rubber compositions, silica has lower rolling resistance and higher braking and handling stability on wet road surfaces than carbon black, but in an unvulcanized state. Due to its high viscosity, workability such as multi-stage kneading is necessary. In addition, the dispersibility of the filler is low, vulcanization is delayed, and further, the breaking strength and wear resistance are greatly reduced.

  Therefore, usually, when silica is blended with rubber, a coupling agent is added to lower the unvulcanized viscosity and improve the modulus and wear resistance. However, since these coupling agents are expensive, there is a problem in that the production cost is increased by blending. Further, a dispersion improving additive is used to improve workability by improving the dispersibility of silica and lowering the unvulcanized viscosity, but there is a problem that the wear resistance is lowered. Furthermore, when a strong ionic compound is used as the dispersant, there are cases where deterioration of workability such as roll adhesion is observed.

In order to solve these problems, Patent Document 1 proposes a rubber composition containing a sulfur-containing silane compound having a specific structure, and Patent Document 2 contains an amine addition salt having a specific structure. Proposed rubber compositions have been proposed.
International Publication No. 2004/000930 Pamphlet JP 2001-139727 A

  According to Patent Documents 1 and 2, the viscosity of unvulcanized rubber is lower than before, the workability is good, and when used in a tire tread, the wear resistance is high, the rolling resistance is low, Although it has become possible to realize a rubber composition that can improve braking performance and handling stability on a wet road surface, with the advancement of today's technology, further improvements in these performances are desired.

  Accordingly, an object of the present invention is to provide a rubber composition having a low unvulcanized viscosity and a high dispersibility of silica that is higher in wear resistance and rolling resistance when used as a tread member of a tire. It is an object of the present invention to provide a rubber composition that can reduce the braking performance and handling stability of a wet road surface, and a tire using the rubber composition.

  As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by blending a rubber composition with a sulfur-containing silane compound having a specific structure and an amine salt compound, The present invention has been completed.

（式（ＩＶ）中、Ｒ⁸は炭素数８〜２４の直鎖状または分枝を有するアルキル基、アルケニル基またはアルキニル基、炭素数６〜２４のアリール基、または炭素数７〜２４のアラルキル基、Ｒ⁹およびＲ¹⁰はそれぞれ水素原子、炭素数１〜１２の直鎖状または分枝を有するアルキル基、アルケニル基またはアルキニル基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、または
−（ＣＨ₂Ｏ）_nＨ、−（ＣＨ₂ＣＨ₂Ｏ）_nＨ、−（ＣＨ（ＣＨ₃）ＣＨ₂Ｏ）_nＨまたは−（ＣＨ₂ＣＨ₂ＣＨ₂Ｏ）_nＨであって、式中、ｎの合計は１〜４、Ｒ¹¹は炭素数６〜２４の直鎖状または分枝を有するアルキル基、アルケニル基またはアルキニル基、炭素数６〜２４のアリール基、または炭素数７〜２４のアラルキル基である。）で表されるアミン塩化合物０．１〜２０質量部とを含有することを特徴とするものである。 That is, the rubber composition of the present invention comprises 10 to 200 parts by mass of silica, 100 parts by mass of the polymer, the following general formula (I),
_{^{(R 1 O) 3-p}} (R 2) p Si-R 3 -S k -R 4 -S m -R 3 -Si (R 2) p (OR 1) 3-p ··· (I),
(In the formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, k and m is an average value of 1 or more and less than 4, R ⁴ is the following general formula (II) or (III),
—S—R ⁵ —S— (II)
—R ⁶ —S _x —R ⁷ — (III)
In which R ⁵ , R ^6, and R ⁷ may be the same or different, and are linear or branched divalent having 1 to 20 carbon atoms A divalent organic group containing a hetero atom other than a sulfur atom and an oxygen atom, and x is an average value of 1 or more and less than 4. 1 to 2 parts by mass of one or more sulfur-containing silane compounds represented by the following general formula (IV),

(In formula (IV), R ⁸ is a linear or branched alkyl group, alkenyl group or alkynyl group having 8 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, or aralkyl having 7 to 24 carbon atoms. Groups R ⁹ and R ¹⁰ are each a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkenyl group or an alkynyl group, an aryl group having 6 to 12 carbon atoms, or a 7 to 12 carbon atom. Aralkyl group, or — (CH ₂ O) _n H, — (CH ₂ CH ₂ O) _n H, — (CH (CH ₃ ) CH ₂ O) _n H or — (CH ₂ CH ₂ CH ₂ O) _n H Wherein n is 1 to 4 in total, R ¹¹ is a linear or branched alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, Or an aralkyl group having 7 to 24 carbon atoms. It contains 0.1 to 20 parts by mass of the amine salt compound.

  The tire of the present invention is characterized by using a member containing the rubber composition.

  As a result of the combined use of a sulfur-containing silane compound having a specific structure and an amine salt compound, the rubber composition of the present invention has low unvulcanized viscosity, high dispersibility of silica, and excellent workability. The productivity can be greatly improved. Therefore, particularly when this rubber composition is used as a tire tread member, a tire having high wear resistance, low rolling resistance, and excellent wet road surface braking performance and steering stability can be obtained.

Hereinafter, preferred embodiments of the present invention will be described in detail.
The rubber composition of the present invention is 10 to 200 parts by mass of silica and 1 to 30 parts by mass of one or more sulfur-containing silane compounds represented by the above general formula (I) with respect to 100 parts by mass of the polymer. And 0.1 to 20 parts by mass of an amine salt compound represented by the above general formula (IV). By using such a sulfur-containing silane compound and an amine salt compound in combination, the reaction between the alkoxy group in the silane compound and the silanol group on silica is promoted, and the combined effect expected from the effect when each is used alone It was found that a far superior performance was obtained.

The sulfur-containing silane compound used in the present invention is a compound represented by the above general formula (I) having an organooxysilyl group at both ends of the molecule and a sulfide or polysulfide at the center of the molecule. In formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- Examples thereof include a butyl group, a t-butyl group, a vinyl group, an allyl group, and an isopropenyl group. R ¹ and R ² may be the same or different. R ³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, and includes, for example, a methylene group, an ethylene group, a propylene group, an n-butylene group, an i-butylene group, a hexylene group, a decylene group, and a phenylene group. And methylphenylethylene group. In addition, p is an integer of 0-2.

R ^{4 in the} general formula (I) is a divalent functional group represented by the general formula (II) or (III). In the formula (II) or (III), R ⁵ , R ⁶ and R ⁷ Is a linear or branched divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent aromatic group, or a divalent organic group containing a hetero atom other than a sulfur atom and an oxygen atom. , Methylene group, ethylene group, propylene group, n-butylene group, i-butylene group, hexylene group, decylene group, phenylene group, methylphenylethylene group, etc., and nitrogen which is a hetero atom other than sulfur atom and oxygen atom Examples thereof include a group having an atom, a phosphorus atom or the like introduced therein. From the viewpoint of the intended effect and production cost of the present invention, R ⁵ in the formula (II) or R ⁶ and R ⁷ in the formula (III) is preferably a hexylene group. Moreover, x is 1 or more and less than 4 as an average value, and in order to obtain the desired effect of the present invention, x is preferably 2 or more and less than 4 as an average value, and more preferably 2 or more and 3 or less. Is most preferred.

  The method for synthesizing the compound represented by the general formula (I) is not particularly limited, and can be synthesized by combining known reactions. The method described in International Publication No. 2004/000930 pamphlet can be used. It can be used suitably.

  Further, the sulfur-containing silane compound according to the present invention may produce a multimer such as a dimer or a trimer of the general formula (I) at the time of production, and 3 or more silicon atoms in one molecule. The sulfur-containing silane compound containing an atom may adversely affect the effect of the present invention. Therefore, in the present invention, when the sulfur-containing silane compound according to the present invention is blended, the content of the sulfur-containing silane compound having 3 or more silicon atoms per molecule is 30% by mass or less based on the rubber composition. It is preferable that the amount is 10% by mass or less, and most preferably not substantially contained.

  In the present invention, in order to obtain the desired effect of the present invention, 1 to 30 parts by mass of the sulfur-containing silane compound is blended with respect to 100 parts by mass of the polymer. It is preferable to be within the range of parts by mass.

Next, the amines of the amine salt compound represented by the formula (IV) used in the present invention are as follows: R ⁸ is a linear or branched alkyl group having 8 to 24 carbon atoms in the formula (IV). , An alkenyl group or an alkynyl group, an aryl group having 6 to 24 carbon atoms, or an aralkyl group having 7 to 24 carbon atoms, R ⁹ and R ¹⁰ each have a hydrogen atom, a linear or branched chain having 1 to 12 carbon atoms An alkyl group, an alkenyl group or an alkynyl group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or — (CH ₂ O) _n H, — (CH ₂ CH ₂ O) _n H, — ( CH (CH ₃ ) CH ₂ O) _n H or — (CH ₂ CH ₂ CH ₂ O) _n H, where n is 1 to 4 in total.

  Preferred examples include decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, behenylamine, oleylamine, monomethyldecylamine, monomethyllaurylamine, monomethylmyristylamine, monomethylpalmitylamine, monomethylstearylamine, monomethyloleylamine, mono Ethyldecylamine, monoethyllaurylamine, monoethylmyristylamine, monoethylpalmitylamine, monoethylstearylamine, monoethyloleylamine, monopropyldecylamine, monopropyllaurylamine, monopropylmyristylamine, monopropylpalmitylamine, Monopropylstearylamine, monopropyloleylamine, dimethyldecylamine, dimethyllaurylamine , Dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethyloleylamine, diethyldecylamine, diethyllaurylamine, diethylmyristylamine, diethylpalmitylamine, diethylstearylamine, diethyloleylamine, methylethyldecylamine, methyletherlaurylamine , Methylethyl myristylamine, methylethyl palmitylamine, methylethyl stearylamine, methylethyl oleylamine, di (hydroxyethyl) decylamine, di (hydroxyethyl) laurylamine, di (hydroxyethyl) myristylamine, di (hydroxyethyl) pal Methyl amine, di (hydroxyethyl) stearylamine, di (hydroxyethyl) oleylamine, etc. It is.

In order to obtain a more desirable effect of the present invention, in the formula (IV) of the amine salt compound according to the present invention, in particular, R ⁹ and R ¹⁰ are each a linear or branched alkyl having 1 to 8 carbon atoms. A tertiary amine which is a group, an alkenyl group or an alkynyl group and has a total carbon number of R ⁸ , R ⁹ and R ¹⁰ of ¹⁰ to 24.

In addition, as the carboxylic acid in the above formula (IV), R ¹¹ is a linear or branched alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, or An aralkyl group having 7 to 24 carbon atoms, preferably a saturated or unsaturated linear fatty acid having 10 to 20 carbon atoms. Preferable examples of such carboxylic acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid and the like. The molecular weight of the amine salt compound represented by the general formula (IV) is preferably in the range of 400 to 800 from the viewpoint of the desired effect. In the present invention, one such amine salt compound may be used, or two or more may be used in combination.

  The polymer used in the present invention is not particularly limited as long as it can form a rubber composition, but is preferably a diene rubber. Specifically, natural rubber or various diene synthetic rubbers can be used, and diene synthetic rubber is particularly preferable. Diene synthetic rubbers include polybutadiene (BR), copolymers of butadiene and aromatic vinyl compounds, butadiene polymers such as copolymers of butadiene and other diene monomers, polyisoprene (IR), isoprene. And copolymers of aromatic vinyl compounds, isoprene polymers such as copolymers of isoprene and other diene monomers, butyl rubber (IIR), ethylene-propylene copolymers, and mixtures thereof. Of these, a butadiene polymer and an isoprene polymer are preferable, and a styrene-butadiene copolymer (SBR) is more preferable. The microstructure of SBR is not particularly limited, but among them, the amount of bound styrene is preferably 5% by mass to 60% by mass, and more preferably 15% by mass to 45% by mass. Furthermore, in the present invention, the styrene-butadiene copolymer is preferably contained in an amount of 50% by mass or more in the rubber component, and it is particularly preferable that the entire rubber component is a styrene-butadiene copolymer (SBR) alone. .

  Examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and the like. These may be used individually by 1 type, may mix 2 or more types, and also may be used by copolymerizing with other dienes, such as 1, 3- hexadiene. Of these, 1,3-butadiene is preferred.

The rubber composition of this invention mix | blends 10-200 mass parts of silica with respect to 100 mass parts of polymers. Silica is not particularly limited and includes, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among them, the effect of improving the fracture resistance, wet Wet silica is most preferred because it has the most remarkable effect of achieving both grip properties and low rolling resistance. Moreover, it is preferable that a BET surface area is the range of 40-350 m < ² > / g. When the BET surface area is within this range, there is an advantage that both rubber reinforcement and dispersibility in rubber can be achieved. From this viewpoint, the BET surface area is more preferably in the range of 80 to 300 m ² / g.

  In addition, in the rubber composition of the present invention, additives added to a normal rubber composition can be added to such an extent that the effects of the present invention are not impaired, and carbon black commonly used in the rubber industry, anti-aging Additives such as an agent, zinc oxide, stearic acid, antioxidant, ozone deterioration inhibitor, etc. can be appropriately blended.

  The rubber composition of the present invention is obtained by kneading using a kneader such as an open kneader such as a roll or a closed kneader such as a Banbury mixer, and vulcanized after molding to produce various rubber products. Applicable. For example, it can be used for tire applications such as tire treads, under treads, carcass, sidewalls, bead parts, vibration proof rubber, fenders, belts, hoses, and other industrial products. It is suitably used as a tread rubber.

  Moreover, in the tire of the present invention using the rubber composition, it is possible to obtain high wear resistance, low rolling resistance, and excellent performance in braking performance and steering stability on wet road surfaces. Examples of the gas filled in the tire include air or an inert gas such as nitrogen.

Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. In addition, the physical property of the rubber composition obtained by each Example and the comparative example was measured with the following method.
(1) Mooney viscosity (ML _{1 + 4} )
Based on JIS K6300-1994, the Mooney viscosity (ML _{1 +} 4/130 ° C.) was measured at 130 ° C., and the value of Comparative Example 2 was indexed to 100. The smaller the Mooney viscosity, the higher the workability.
(2) Hardness Measured according to JIS K6253-1997, and the value of Comparative Example 2 was indexed as 100.
(3) Rebound resilience It was measured using a Dunlop trypometer in accordance with JIS K6255-1996. The measured values were indexed with the value of Comparative Example 2 as 100.
(4) Abrasion resistance (rubber composition)
Using a Lambourn type wear tester, the amount of wear at a slip rate of 60% at room temperature was measured. The results were indexed with the reciprocal of the amount of wear in each example as 100, with the value of the reciprocal of the amount of wear obtained in Comparative Example 2 being 100.

Moreover, the physical properties relating to the tire were measured by the following methods.
(5) Rolling resistance test The rolling resistance was rotated at a speed of 80 km / h using a rotating drum having a steel smooth surface with an outer diameter of 1707.6 mm and a width of 350 mm under a load of 4500 N (460 kg). It was measured and evaluated using the lameness method. The measured values were indexed with the value of Comparative Example 2 as 100. The larger this value, the better (smaller) the rolling resistance.
(6) Abrasion resistance (tire)
After traveling 20,000 km on a paved road surface with an actual vehicle, the remaining groove was measured, and the travel distance required for the tread to wear by 1 mm was relatively compared. It shows that abrasion resistance is so favorable that an index | exponent is large.

(Synthesis of sulfur-containing silane compounds)
Synthesis example 1
First, a sulfur-containing silane compound was synthesized. In a 0.5 liter separable flask equipped with a nitrogen gas inlet tube, thermometer, Dimroth condenser and dropping funnel, ethanol 80 g, anhydrous sodium sulfide 10.93 g (0.14 mol), sulfur 6.73 g (0.21 mol) ) And heated to 80 ° C. While this solution was stirred, 33.7 g (0.14 mol) of propyltriethoxysilane chloride ((CH ₃ CH ₂ O) ₃ Si— (CH ₂ ) ₃ —Cl) and 1,6-dichlorohexane (ClCH ₂ — 10.8 g (0.07 mol) of (CH ₂ ) ₄ —CH ₂ Cl) was slowly added dropwise. After completion of dropping, stirring was continued at 80 ° C. for 10 hours. After completion of the stirring, the mixture was cooled and the produced salt was filtered off.

The obtained solution was subjected to infrared absorption spectrum analysis (IR analysis), ¹ H nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis), and supercritical chromatography analysis. As a result, the general formula (CH ₃ CH ₂ O) ₃ Si — (CH ₂ ) ₃ —S _k —S— (CH ₂ ) ₆ —S—S _m — (CH ₂ ) ₃ —Si (OCH ₂ CH ₃ ) ₃ , ie, chemical formula (I) and In (II), it was confirmed that R ¹ was an ethyl group, R ³ was a propylene group, R ⁵ was a hexylene group, and the average value of p = 0, k and m was 1.5. The purity of this product in gel permeation chromatographic analysis (GPC analysis) was 82.5%.

Synthesis example 2
In a 0.5 liter separable flask equipped with a nitrogen gas inlet tube, thermometer, Dimroth condenser and dropping funnel, ethanol 80 g, anhydrous sodium sulfide 16.38 g (0.21 mol), sulfur 10.10 g (0.315 mol) ) And heated to 80 ° C. While the solution was stirred, 33.7 g (0.14 mol) of propyltriethoxysilane chloride ((CH ₃ CH ₂ O) ₃ Si— (CH ₂ ) ₃ —Cl) and 1,6-dichlorohexane (ClCH ₂ — 21.70 g (0.14 mol) of (CH ₂ ) ₄ —CH ₂ Cl) was slowly added dropwise. After completion of dropping, stirring was continued at 80 ° C. for 10 hours. After completion of the stirring, the mixture was cooled and the formed salt was filtered off, and then ethanol as a solvent was distilled under reduced pressure.

The obtained solution was subjected to infrared absorption spectrum analysis (IR analysis), ¹ H nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis), and supercritical chromatography analysis. As a result, the general formula (CH ₃ CH ₂ O) ₃ Si _{- (CH 2) 3 -S k} - (CH 2) 6 -S x - (CH 2) 6 -S m - (CH 2) 3 -Si (OCH 3 CH 2) 3, i.e., formula (I) and In (III), it was confirmed that R ¹ was an ethyl group, R ³ was a propylene group, R ⁶ and R ⁷ were hexylene groups, and the average value of p = 0, k, m and x was 2.5.

Examples 1-4
110 parts by weight of diene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name “# 1712”) and 20 parts by weight of natural rubber were kneaded with a 1.8 L Banbury mixer at 70 rpm and a starting temperature of 80 ° C. for 30 seconds. To this, 20 parts by mass of ISAF grade carbon black (trade name “SEAST 7HM” manufactured by Tokai Carbon Co., Ltd.), 50 parts by mass of silica (trade name “Nipsil AQ” manufactured by Nippon Silica Industry Co., Ltd.), and stearic acid 1 part by mass, anti-aging agent 6PPD (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine) 1.0 part by mass, and further according to the formulation shown in Table 1 below, The sulfur-containing silane compound synthesized in Synthesis Example 1 (referred to as “Compound A”) or the sulfur-containing silane compound synthesized in Synthesis Example 2 (referred to as “Compound A ′”) and dimethylstearyl alcohol And stearic acid salt (referred to as “amine salt compound B”) or oleate salt of dimethyl stearylamine (referred to as “amine salt compound C”), kneaded to 160 ° C., and then released. It was made into a sheet by a roll. Subsequently, after a remill operation was performed for 1 minute and 30 seconds at 70 rpm and a starting temperature of 80 ° C. with a 1.8 L Banbury mixer, it was discharged and formed into a sheet by a roll. After sufficiently cooling to room temperature, 3 parts by mass of active zinc, 0.5 parts by mass of vulcanization accelerator DM (dibenzothiazyl disulfide), vulcanization accelerator NS (Nt-butyl-2-benzothiazylsulfenamide) ) 1.0 part by mass and 1.5 parts by mass of sulfur were mixed and kneaded for 1 minute at 60 rpm and a starting temperature of 80 ° C. to obtain a rubber composition. The physical properties of the obtained rubber composition were measured. In Table 1, the addition amount is parts by mass with respect to 100 parts by mass of the rubber component.

  In addition, tires were produced by ordinary methods using each rubber composition. The tire size was 205 / 65R15, the rim 15 × 6JJ, and the internal pressure was 220 kPa. Using this tire, a rolling resistance test and an abrasion resistance test (tire) were carried out. The respective evaluation results are shown in Table 1.

Comparative Example 1
In Example 1, instead of the compound synthesized in Synthesis Example 1, a commercially available silane coupling agent (“Si69” manufactured by Degussa) (structure: (CH ₃ CH ₂ O) ₃ —Si— (CH ₂ ) ₃ -S ₄ - to _{(CH 2) 3 -Si (OCH} 2 CH 3) 3) 100 parts by mass of the rubber component, was added 5.5 parts by weight, except that no addition of amine salt compound, as in example 1 A rubber composition was obtained in the same manner. An evaluation result is shown in Table 1 (the test regarding a tire has not been implemented).

Comparative Example 2
In Example 1, in place of the compound synthesized in Synthesis Example 1, a commercially available silane coupling agent (“Si75” manufactured by Degussa) (structure: (CH ₃ CH ₂ O) ₃ —Si— (CH ₂ ) ₃ -S _2- (CH ₂ ) ₃ -Si (OCH ₂ CH ₃ ) ₃ ) is added to 5.0 parts by weight with respect to 100 parts by weight of the rubber component, except that no amine salt compound is added. Similarly, a rubber composition and a tire were obtained. The evaluation results are shown in Table 1.

Comparative Example 3
In Example 1, a rubber composition and a tire were obtained in the same manner as in Example 1 except that no amine salt compound was added. The evaluation results are shown in Table 1.

Comparative Example 4
In Example 1, in place of the compound synthesized in Synthesis Example 1, a commercially available silane coupling agent (“Si75” manufactured by Degussa) (structure: (CH ₃ CH ₂ O) ₃ —Si— (CH ₂ ) ₃ -S ₂ - (CH _{2) 3} to _{-Si (OCH 2 CH 3) 3} ) 100 parts by mass of the rubber component, except for the addition of 5.0 parts by mass, the rubber composition in the same manner as in example 1 and I got a tire. The evaluation results are shown in Table 1.

  As is apparent from Table 1, Examples 1 to 4 have excellent properties in terms of Mooney viscosity, hardness and abrasion resistance of the rubber composition as compared with Comparative Examples 1 to 4, and the rubber composition Both the rolling resistance and the wear resistance are good in the tire produced from the above.

Claims (8)

10 to 200 parts by mass of silica with respect to 100 parts by mass of the polymer, the following general formula (I),
_{^{(R 1 O) 3-p}} (R 2) p Si-R 3 -S k -R 4 -S m -R 3 -Si (R 2) p (OR 1) 3-p ··· (I),
(In the formula (I), R ¹ and R ² are each a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 15 carbon atoms, p is an integer of 0 to 2, k and m is an average value of 1 or more and less than 4, R ⁴ is the following general formula (II) or (III),
—S—R ⁵ —S— (II)
—R ⁶ —S _x —R ⁷ — (III)
In which R ⁵ , R ^6, and R ⁷ may be the same or different, and are linear or branched divalent having 1 to 20 carbon atoms A divalent organic group containing a hetero atom other than a sulfur atom and an oxygen atom, and x is an average value of 1 or more and less than 4. 1 to 2 parts by mass of one or more sulfur-containing silane compounds represented by the following general formula (IV),

(In formula (IV), R ⁸ is a linear or branched alkyl group, alkenyl group or alkynyl group having 8 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, or aralkyl having 7 to 24 carbon atoms. Groups R ⁹ and R ¹⁰ are each a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkenyl group or an alkynyl group, an aryl group having 6 to 12 carbon atoms, or a 7 to 12 carbon atom. Aralkyl group, or — (CH ₂ O) _n H, — (CH ₂ CH ₂ O) _n H, — (CH (CH ₃ ) CH ₂ O) _n H or — (CH ₂ CH ₂ CH ₂ O) _n H Wherein n is 1 to 4 in total, R ¹¹ is a linear or branched alkyl group, alkenyl group or alkynyl group having 6 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, Or an aralkyl group having 7 to 24 carbon atoms. A rubber composition comprising 0.1 to 20 parts by mass of an amine salt compound.   The rubber composition according to claim 1, wherein x in the formula (III) is 2 or more and 3 or less as an average value. The rubber composition according to claim 1 or 2, wherein R ⁵ in the formula (II) or R ⁶ and R ⁷ in the formula (III) is a hexylene group. R ⁹ and R ¹⁰ in the formula (IV) are each a linear or branched alkyl group, alkenyl group or alkynyl group having 1 to ⁸ carbon atoms, and the carbon number of R ⁸ , R ⁹ and R ¹⁰ The rubber composition according to any one of claims 1 to 3, wherein the total number of the rubber composition is 10 to 24. The rubber composition according to claim 1, wherein the silica has a BET surface area of 40 to 350 m ² / g.   The rubber composition according to any one of claims 1 to 5, wherein the polymer is a diene rubber.   A tire using a member containing the rubber composition according to claim 1.   The tire according to claim 7, wherein the member is a tire tread.