JP5524652B2 - Rubber composition for tire and pneumatic tire - Google Patents

Description

The present invention relates to a rubber composition for a tire and a pneumatic tire using the same.

Conventionally, vehicle fuel efficiency has been reduced by reducing tire rolling resistance and suppressing heat generation. In recent years, there has been a strong demand for low fuel consumption of tires, and among the tire members, excellent low heat generation (low fuel consumption) is required particularly for treads with a high occupation ratio in tires. .

In order to satisfy the above requirements, in recent years, silica is blended in a rubber composition (tread rubber composition) used for a tire tread. However, compared with carbon black, silica has a low affinity for rubber and its reinforcing effect is small. Therefore, by adding silica, there is a problem in that wear resistance and grip performance are greatly reduced, and fuel economy, wear resistance, and grip performance cannot be improved in a well-balanced manner.

Therefore, it is known that a silane coupling agent having an alkoxysilyl group is blended with silica for the purpose of chemically bonding rubber and silica and increasing the reinforcing effect (for example, Patent Documents 1 and 2). ). However, there is room for improvement in improving fuel efficiency and wear resistance (in particular, improving fuel efficiency).

JP 2001-240700 A JP-A-2005-41960

The present invention solves the above-mentioned problems, and has excellent low heat build-up (low fuel consumption) and wear resistance, and a rubber composition for tires, and each tire component (particularly, tread, side) An object of the present invention is to provide a pneumatic tire used for a wall.

（式（Ｉ）中、ｎは、同一又は異なって、１〜１０の整数である。ｍは２〜６の整数である。ｐは１〜３の整数である。Ｒ^１は、同一若しくは異なって、−Ｒ^３−（ＯＲ^４）_ｑ−ＯＲ^５で表されるポリエーテル基又は下記一般式（ＩＩ）で表されるアミノ基を示す。Ｒ^２は、同一若しくは異なって、炭素数１〜１０のアルキル基を示す。Ｒ^３及びＲ^４は、同一若しくは異なって、炭素数２〜６のアルキレン基を示し、Ｒ^５は、同一若しくは異なって、水素原子又は炭素数１〜８のアルキル基を示す。ｑは２〜６の整数である。）

（式（ＩＩ）中、Ｒ^６及びＲ^７は、同一若しくは異なって、水素原子、炭素数１〜８のアルキル基又はアリール基を示す。ｒは２〜６の整数である。） The present invention relates to a rubber composition for tires containing silica and a sulfur-containing silane compound represented by the following general formula (I).

(In formula (I), n is the same or different and is an integer of 1 to 10. m is an integer of 2 to 6. p is an integer of 1 to 3. R ¹ is the same or different. A polyether group represented by -R ^3- (OR ⁴ ) _q -OR ⁵ or an amino group represented by the following general formula (II), wherein R ² is the same or different and has 1 to R ³ and R ⁴ are the same or different and each represents an alkylene group having 2 to 6 carbon atoms, and R ⁵ is the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Q is an integer of 2 to 6.)

(In formula (II), R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. R is an integer of 2 to 6)

The rubber composition for a tire includes 2-150 parts by mass of the silica with respect to 100 parts by mass of the rubber component, and includes 0.1-45 parts by mass of the sulfur-containing silane compound with respect to 100 parts by mass of the silica. Is preferred.

The tire rubber composition is preferably used as a tread rubber composition or a sidewall rubber composition.

The present invention also relates to a pneumatic tire produced using the rubber composition.

According to the present invention, since the rubber composition for a tire includes silica and the sulfur-containing silane compound represented by the above general formula (I), the rubber composition is used for each member of the tire (particularly, tread, sidewall). ) Can be used to provide a pneumatic tire having excellent low heat build-up (low fuel consumption) and wear resistance.

The rubber composition for tires of this invention contains a silica and the sulfur containing silane compound represented by the said general formula (I).

The rubber components that can be used in the present invention include natural rubber (NR), epoxidized natural rubber (ENR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and styrene isoprene butadiene rubber (SIBR). And diene rubbers such as chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR) and butyl rubber (IIR). Diene rubbers may be used alone or in combination of two or more. Among these, SBR, NR, and BR are preferable because grip performance and wear resistance can be obtained in a well-balanced manner.

In the rubber composition of the present invention, usable SBR is not particularly limited, and emulsion polymerization SBR (E-SBR), solution polymerization SBR (S-SBR) and the like can be used.

In the present invention, silica is used. By blending silica together with the sulfur-containing silane compound represented by the general formula (I), good low heat generation (low fuel consumption) and wear resistance can be obtained. The silica is not particularly limited, and examples thereof include dry process silica (anhydrous silicic acid), wet process silica (hydrous silicic acid), and the like, but wet process silica is preferable because of its large number of silanol groups.

The nitrogen adsorption specific surface area _(N 2 SA) of silica is preferably not less than ^{30 m} 2 / g, more preferably at least ^{50m 2 / g, 100m 2 /} g or more, and particularly preferably equal to or greater than 150m ² / g. If it is less than 30 m ² / g, the fracture strength after vulcanization tends to decrease. The _N 2 SA of the silica is preferably 500 meters ² / g or less, more preferably ^{300m 2 / g, 200m 2 /} g or less is more preferable. When it exceeds 500 m < ² > / g, there exists a tendency for the workability of rubber to fall.
The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

The content of silica is preferably 2 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 25 parts by mass or more, and most preferably 30 parts, relative to 100 parts by mass of the rubber component. More than part by mass. When the amount is less than 2 parts by mass, there is a tendency that a sufficient effect due to silica blending cannot be obtained. The content of the silica is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and still more preferably 70 parts by mass or less. When the amount exceeds 150 parts by mass, it is difficult to disperse silica in rubber, and the processability of rubber tends to deteriorate.

In the present invention, the sulfur-containing silane compound represented by the general formula (I) is used as a silane coupling agent. Thereby, favorable low heat build-up (low fuel consumption) and abrasion resistance are obtained. This is because the bond formation between the sulfur-containing silane compound and silica occurs more efficiently than the conventional silane coupling agent in which three alkoxy groups are bonded to the silicon atom (for example, Si266 manufactured by Degussa). It is guessed.

In formula (I), n is the same or different and is an integer of 1-10. In addition, (CH ₂ ) _n means an alkylene group and is preferably linear, but may be branched. n is preferably 1 to 5 and more preferably 3 because good low heat build-up (low fuel consumption) and wear resistance can be obtained.

In formula (I), m is an integer of 2-6. m is preferably 2 to 4 and more preferably 2 because of the stability of the bonding state with the polymer. When m is 1, the flexibility of the crosslinking site is lost, and when m is 7 or more, the heat resistance is lowered and the physical properties may deteriorate over time.

In the formula (I), p is an integer of 1 to 3. As p, 3 is preferable because good low heat build-up (low fuel consumption) and wear resistance can be obtained.

In the formula (I), R ^{1 s} are the same or different and represent a polyether group represented by —R ³ — (OR ⁴ ) _q —OR ⁵ or the above general formula (II) [— (CH ₂ ) _r —N An amino group represented by (R ⁶ ) (R ⁷ )] is shown.

R ³ and R ⁴ are the same or different and represent a branched or unbranched alkylene group having 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms, more preferably 2 carbon atoms).

Examples of the branched or unbranched alkylene group having 2 to 6 carbon atoms of R ³ and R ⁴ include an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

R ⁵ is the same or different and represents a hydrogen atom or a branched or unbranched alkyl group having 1 to 8 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms).

Examples of the branched or unbranched alkyl group having 1 to 8 carbon atoms of R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, and an octyl group.

q is an integer of 2-6. q is preferably 2 to 3 and more preferably 2 because the cost is relatively low. When q is 1, it is not much different from the conventional product, and when q is 7 or more, the cost tends to be high.

In the formula (II), R ⁶ and R ⁷ are the same or different and are each a hydrogen atom, branched or unbranched C 1-8 (preferably C 1-4, more preferably C 1-2). An alkyl group or an aryl group having 6 to 30 carbon atoms (preferably 6 to 12 carbon atoms) is shown.

Examples of the branched or unbranched alkyl group having 1 to 8 carbon atoms of R ⁶ and R ⁷ include the same groups as those described above for R ⁵ .

Examples of the aryl group having 6 to 30 carbon atoms of R ⁶ and R ⁷ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.

In the formula (II), r is an integer of 2-6. r is preferably 2 to 3 and more preferably 2 because the cost is relatively low. When r is 1, volatile nitrosamine may be generated in the system, and when r is 7 or more, the cost tends to increase.

Specific examples of the polyether group represented by —R ³ — (OR ⁴ ) _q —OR ⁵ of R ¹ include, for example, —C ₂ H ₄ — (OC ₂ H ₄ ) ₂ —OCH ₃ , —C _{2. H 4 - (OC 2 H 4} ) 2 -OC 2 H 5, -C 2 H 4 - (OC 2 H 4) 2 -OC 3 H 7, -C 2 H 4 - (OC 2 H 4) 2 -OC _{4 H 9, -C 2 H 4} - (OC 2 H 4) 2 -OC 5 H 11, -C 3 H 6 - (OC 2 H 4) 2 -OCH 3, -C 3 H 6 - (OC 2 H _{4) 2 -OC 2 H 5,} -C 3 H 6 - (OC 2 H 4) 2 -OC 3 H 7, -C 3 H 6 - (OC 2 H 4) 2 -OC 4 H 9, -C 3 _{H 6 - (OC 2 H 4} ) 2 -OC 5 H 11, -C 2 H 4 - (OC 2 H 4) 3 -OCH 3, -C 2 H 4 - (O _{C 2 H 4) 3 -OC 2} H 5, -C 2 H 4 - (OC 2 H 4) 3 -OC 3 H 7, -C 2 H 4 - (OC 2 H 4) 3 -OC 4 H 9, _{-C 2 H 4 - (OC 2} H 4) 3 -OC 5 H 11 and the like. Of _{these, -C 2 H 4 - (OC} 2 H 4) 2 -OC 4 H 9 is preferred.

Specific examples of the amino group represented by the general formula (II) of R ¹ include, for example, —C ₂ H ₄ —NH ₂ , —C ₂ H ₄ —N (CH ₃ ) ₂ , —C ₂ H _{4. -N (C 2 H 5) 2} , -C 2 H 4 -N (C 3 H 7) 2, -C 2 H 4 -N (C 4 H 9) 2, -C 2 H 4 -N (C 5 _{H 11) 2, -C 2 H} 4 -N (C 6 H 13) 2, -C 3 H 6 -NH 2, -C 3 H 6 -N (CH 3) 2, -C 3 H 6 -N ( _{C 2 H 5) 2, -C} 3 H 6 -N (C 3 H 7) 2, -C 3 H 6 -N (C 4 H 9) 2, -C 3 H 6 -N (C 5 H 11) _{2, -C 3 H 6 -N (} C 6 H 13) 2, -C 4 H 8 -NH 2, -C 4 H 8 -N (CH 3) 2, -C 4 H 8 -N (C 2 H _{5) 2, -C 4 H 8} - _{N (C 3 H 7) 2} , -C 4 H 8 -N (C 4 H 9) 2, -C 4 H 8 -N (C 5 H 11) 2, -C 4 H 8 -N (C 6 H _{13) 2, -C 4 H 8} -N (C 6 H 13) (C 5 H 11), - C 2 H 4 -N (C 6 H 5) (CH 3), - C 2 H 4 -N ( C ₆ H ₅ ) (C ₂ H ₅ ) and the like. Of _{these, -C 2 H 4 -NH 2,} -C 2 H 4 -N (CH 3) 2, -C 2 H 4 -N (C 6 H 5) (C 2 H 5) are preferred.

Examples of the alkyl group having 1 to 10 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, Examples include pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group and the like.

Specific examples of the sulfur-containing silane compound represented by the general formula (I), for _{example, (BuO (C 2 H 4} O) 3) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 - _{Si - ((OC 2 H 4} ) 3 OBu) 3, (PrO (C 2 H 4 O) 3) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si - ((OC 2 H 4 ) ₃ OBu) ₃ , (PrO (C ₂ H ₄ O) ₃ ) ₃ —Si—C ₃ H ₆ —S ₂ —C ₃ H ₆ —Si — ((OC ₂ H ₄ ) ₃ OPr) ₃ , (BuO _{(C 2 H 4 O) 3} ) 3 -Si-C 2 H 4 -S 2 -C 2 H 4 -Si - ((OC 2 H 4) 3 OBu) 3, (BuO (C 2 H 4 O) 3 ) ₃ -Si-C ₂ H ₄ -S ₂ -C ₃ H ₆ -Si-((OC ₂ H ₄ ) ₃ OBu) ₃ , (BuO (C ₃ H _{6 O) 3) 3 -Si-} C 3 H 6 -S 2 -C 3 H 6 -Si - ((OC 3 H 6) 3 OBu) 3, (Me 2 NC 2 H 4 O) 3 -Si-C _{3 H 6 -S 2 -C 3 H} 6 -Si- (OC 2 H 4 NMe 2) 3, (Et 2 NC 2 H 4 O) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 - _{Si- (OC 2 H 4 NEt 2} ) 3, (Et 2 NC 2 H 4 O) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- (OC 2 H 4 NMe 2) 3, _{(Me 2 NC 3 H 6 O} ) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- (OC 2 H 4 NMe 2) 3, (Me 2 NC 3 H 6 O) 3 -Si _{-C 3 H 6 -S 2 -C 3} H 6 -Si- (OC 3 H 6 NMe 2) 3, (H 2 NC 2 H 4 O) 3 -S _{-C 3 H 6 -S 2 -C 3} H 6 -Si- (OC 2 H 4 NH 2) 3, (H 2 NC 2 H 4 O) 3 -Si-C 2 H 4 -S 2 -C 3 H _{6 -Si- (OC 2 H 4 NH} 2) 3, (H 2 NC 3 H 6 O) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- (OC 3 H 6 NH 2) _{3, (BuO (C 2 H} 4 O) 3) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- (OC 2 H 4 NH 2) 3, (BuO (C 2 H 4 O _{) 3) 3 -Si-C 3} H 6 -S 2 -C 3 H 6 -Si- (OC 2 H 4 NMe 2) 3, ((Et) (C 6 H 5) NC 2 H 4 O) 3 - _{Si-C 3 H 6 -S 2} -C 3 H 6 -Si- (OC 2 H 4 N (Et) (C 6 H 5)) 3 , and the like. These may be used alone or in combination of two or more. Among _{them, (BuO (C 2 H 4} O) 3) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si - ((OC 2 H 4) 3 OBu) 3, (Me 2 NC 2 _{H 4 O) 3 -Si-C} 3 H 6 -S 2 -C 3 H 6 -Si- (OC 2 H 4 NMe 2) 3, (H 2 NC 2 H 4 O) 3 -Si-C 3 H 6 _{-S 2 -C 3 H 6 -Si- (} OC 2 H 4 NH 2) 3, ((Et) (C 6 H 5) NC 2 H 4 O) 3 -Si-C 3 H 6 -S 2 -C _{3 H 6 -Si- (OC 2 H} 4 N (Et) (C 6 H 5)) 3 is preferred. In the present specification, Me, Et, Pr, and Bu represent a methyl group, an ethyl group, a propyl group, and a butyl group, respectively.

The sulfur-containing silane compound can be prepared, for example, as follows. (A) (sulfide), (B) (catalyst), and (C) (monoalcohol having a polyether structure) and / or (D) (monoalcohol having an amino group) are mixed, Stir at ~ 170 ° C for 1-12 hours. And after filtering a reaction mixture, the said sulfur containing silane compound is obtained by concentrating.

Examples of (A) include bis (3-triethoxysilylpropyl disulfide), bis (3-triethoxysilylpropyl trisulfide), bis (3-triethoxysilylethyl disulfide), and bis (3-trimethoxysilylethyl). Disulfide) and the like. Among these, bis (3-triethoxysilylpropyl disulfide) is preferable because of good processability.

Examples of (B) include titanium tetrabutyrate, p-toluenesulfonic acid, sulfuric acid and the like. Of these, titanium tetrabutyrate is preferred because the desired product can be obtained in good yield.

Examples of (C) include triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, pentaethylene glycol monododecyl ether, hexaethylene glycol monomethyl. Examples include ether, hexaethylene glycol monododecyl ether, pentaethylene glycol monomethyl ether, heptaethylene glycol monododecyl ether, and octaethylene glycol monopropyl ether. Of these, triethylene glycol butyl ether is preferred because of its relatively low cost.

Examples of (D) include 2-dimethylaminoethanol, 2-aminoethanol, 2-dibutylaminoethanol, 2-diethylaminoethanol, N, N-ethylphenylaminoethanol, N, N-methylaminoethanol, and the like. .

The content of the sulfur-containing silane compound is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more with respect to 100 parts by mass of silica. If the amount is less than 1 part by mass, a chemical bond between the rubber and the silica via the sulfur-containing silane compound (silane coupling agent) cannot be sufficiently formed, and the dispersibility of the silica is insufficient. , Wear resistance and grip performance tend to decrease. Moreover, 45 mass parts or less are preferable with respect to 100 mass parts of silica, as for content of the said sulfur containing silane compound, 25 mass parts or less are more preferable, 20 mass parts or less are further more preferable, and 15 mass parts or less are especially preferable. When it exceeds 45 mass parts, there exists a tendency for workability to deteriorate.

In addition to the above components, the rubber composition of the present invention includes compounding agents generally used in the production of rubber compositions, for example, reinforcing fillers such as clay and carbon black, zinc oxide, stearic acid, various anti-aging agents. Agents, softeners such as oil, vulcanizing agents such as wax and sulfur, vulcanization accelerators and the like can be appropriately blended.

The tire rubber composition of the present invention may contain an anti-aging agent. As the anti-aging agent, amine-based, phenol-based, and imidazole-based compounds, carbamic acid metal salts, waxes, and the like can be appropriately selected and used.

The tire rubber composition of the present invention may contain a softening agent. Softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly, and fatty oil-based softeners such as soybean oil, palm oil, castor oil, linseed oil, rapeseed oil, and coconut oil. Agents, waxes such as tall oil, sub, beeswax, carnauba wax and lanolin, and fatty acids such as linoleic acid, palmitic acid, stearic acid and lauric acid.

The tire rubber composition of the present invention may contain a vulcanizing agent. As the vulcanizing agent, an organic peroxide or a sulfur vulcanizing agent can be used. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2, Use 5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 1,3-bis (t-butylperoxypropyl) benzene, etc. Can do. Moreover, as a sulfur type vulcanizing agent, sulfur, morpholine disulfide, etc. can be used, for example. Of these, sulfur is preferred.

The tire rubber composition of the present invention may contain a vulcanization accelerator. Vulcanization accelerators include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine or aldehyde-ammonia, imidazoline, or xanthate vulcanization accelerators. At least one of them can be used.

The tire rubber composition of the present invention may contain a vulcanization aid. As the vulcanization aid, stearic acid, zinc oxide or the like can be used.

As a method for producing the rubber composition of the present invention, a known method can be used. For example, the above components are kneaded using a rubber kneader such as an open roll or a Banbury mixer, and then vulcanized. Can be manufactured.

The rubber composition of the present invention can be suitably used for each member of a tire. Especially, it is preferable to use for a tread or a sidewall from the reason that the contribution rate which contributes to low fuel consumption is large.

The pneumatic tire of the present invention is produced by a usual method using the rubber composition. That is, if necessary, a rubber composition containing various additives is extruded in accordance with the shape of each member (particularly, tread, sidewall) of the tire at an unvulcanized stage, and then on a tire molding machine. After forming by a normal method and bonding together with other tire members to form an unvulcanized tire, the tire can be manufactured by heating and pressing in a vulcanizer.

The tire of the present invention is suitably used as a passenger car tire, bus tire, truck tire, and the like.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

Hereinafter, various chemicals used in the production examples will be described together.
Si266: Sigus coupling agent Si266 (bis (3-triethoxysilylpropyl disulfide)) manufactured by Degussa
Titanium tetrabutyrate: Triethylene glycol butyl ether manufactured by Tokyo Chemical Industry Co., Ltd .: Dimethylaminoethanol manufactured by Tokyo Chemical Industry Co., Ltd .: Aminoethanol manufactured by Wako Pure Chemical Industries, Ltd .: N, N-ethyl manufactured by Wako Pure Chemical Industries, Ltd. Phenylaminoethanol: manufactured by Tokyo Chemical Industry Co., Ltd.

Production Example 1 (Synthesis of Silane Coupling Agent 2)
A 200 mL eggplant flask was charged with 8.4 mL of Si266, 62.5 mL of triethylene glycol butyl ether, and 6 μL of titanium tetrabutyrate, and then stirred at 150 ° C. for 4 hours under reduced pressure. The reaction mixture is filtered, concentrated, and silane coupling agent 2 ((BuO (C ₂ H ₄ O) ₃ ) ₃ —Si—C ₃ H ₆ —S ₂ —C ₃ H ₆ —Si — ((OC ₂ H ₄ ) ₃ OBu) ₃ ) was obtained.

Production Example 2 (Synthesis of Silane Coupling Agent 3)
After charging 8.4 mL of Si266, 27.0 mL of dimethylaminoethanol and 6 μL of titanium tetrabutyrate into a 200 mL eggplant flask, the mixture was stirred at 150 ° C. under reduced pressure for 4 hours. The reaction mixture is filtered, concentrated, and silane coupling agent 3 ((Me ₂ NC ₂ H ₄ O) ₃ —Si—C ₃ H ₆ —S ₂ —C ₃ H ₆ —Si— (OC ₂ H ₄ NMe _{2). 3} ) was obtained.

Production Example 3 (Synthesis of Silane Coupling Agent 4)
After charging 8.4 ml of Si266, 18.5 mL of aminoethanol and 6 μL of titanium tetrabutyrate in a 200 mL eggplant flask, the mixture was stirred at 150 ° C. for 4 hours under reduced pressure. The reaction mixture is filtered, concentrated, and silane coupling agent 4 ((H ₂ NC ₂ H ₄ O) ₃ —Si—C ₃ H ₆ —S ₂ —C ₃ H ₆ —Si— (OC ₂ H ₄ NH _{2). 3} ) was obtained.

Production Example 4 (Synthesis of Silane Coupling Agent 5)
A 200 mL eggplant flask was charged with 8.4 mL of Si266, 34.3 mL of N, N-ethylphenylaminoethanol and 6 μL of titanium tetrabutyrate, and then stirred at 150 ° C. for 4 hours under reduced pressure. After filtering the reaction mixture was concentrated, a silane coupling agent _{5 ((Et) (C 6} H 5) NC 2 H 4 O) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- ( _{OC 2 H 4 N (Et)} (C 6 H 5)) 3) was obtained.

Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
S-SBR: NS116 manufactured by Nippon Zeon Co., Ltd. (styrene content: 22% by mass, vinyl bond content: 65% by mass)
Silica: Ultrazil VN3 manufactured by Degussa (N ₂ SA: 175 m ² / g)
Silane coupling agent 1: Si266 (bis (3-triethoxysilylpropyl disulfide)) manufactured by Degussa
Silane coupling agent 2: Preparation Example 1 silane was prepared with a coupling agent _{2 ((BuO (C 2 H} 4 O) 3) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- ( (OC ₂ H ₄ ) ₃ OBu) ₃ )
Silane coupling agent 3: Silane coupling agent 3 ((Me ₂ NC ₂ H ₄ O) ₃ —Si—C ₃ H ₆ —S ₂ —C ₃ H ₆ —Si— (OC ₂ ) prepared in Production Example 2 above H ₄ NMe ₂ ) ₃ )
Silane coupling agent 4: Production Example 3 Silane coupling agent ₄ prepared in _{((H 2 NC 2 H 4} O) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 -Si- (OC 2 H ₄ NH ₂ ) ₃ )
Silane coupling agent 5: Preparation Example 4 Silane coupling agent ₅ prepared in _{((Et) (C 6 H} 5) NC 2 H 4 O) 3 -Si-C 3 H 6 -S 2 -C 3 H 6 _{-Si- (OC 2 H 4 N (} Et) (C 6 H 5)) 3)
Zinc oxide: Zinc Hana No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Stearic acid “Kashiwa” manufactured by NOF Corporation
Anti-aging agent: Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
Sulfur: Sulfur powder vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. 1: Noxeller NS (N-tert-butyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Vulcanization accelerator 2: Noxeller D (N, N'-diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

Examples 1-7 and Comparative Examples 1-2
In accordance with the formulation shown in Table 1, S-SBR, silica, silane coupling agent, zinc oxide and stearic acid were kneaded using a 1.7 L Banbury mixer. The kneaded material was once discharged from the Banbury mixer, and then the anti-aging agent was added to the discharged kneaded material and kneaded again using a 1.7 L Banbury mixer. Next, using an open roll, sulfur and a vulcanization accelerator were added to the obtained kneaded product and kneaded to obtain an unvulcanized rubber composition. Further, the obtained unvulcanized rubber composition was press vulcanized for 15 minutes at 170 ° C. to obtain a vulcanized rubber composition.
Further, the obtained unvulcanized rubber composition was molded into a tread shape, and bonded to other tire members, and vulcanized under conditions of 25 kgf at 150 ° C. for 35 minutes, so that a test tire (tire size: 195 / 65R15).

The following evaluation was performed about the obtained vulcanized rubber composition and the tire for a test. The results are shown in Table 1.

(Abrasion resistance)
About the obtained vulcanized rubber composition, the amount of lamborn wear was measured under the conditions of a temperature of 20 ° C., a slip rate of 20% and a test time of 2 minutes using a lamborn wear tester. Further, the volume loss amount was calculated from the measured lamborn wear amount, the lamborn wear index of Comparative Example 1 was set to 100, and the volume loss amount of each formulation was displayed as an index according to the following formula. In addition, it shows that it is excellent in abrasion resistance, so that a Lambourn abrasion index is large.
(Lambourn wear index) = (volume loss amount of Comparative Example 1) ÷ (volume loss amount of each formulation) × 100

(Low fuel consumption (1) (Viscoelasticity test))
A test piece of a predetermined size was cut out from the obtained vulcanized rubber composition, and was used under the conditions of an initial strain of 10%, a dynamic strain of 2%, and a frequency of 10 Hz, using a viscoelastic spectrometer manufactured by Ueshima Seisakusho Co., Ltd. The loss tangent (tan δ) of the vulcanized rubber sheet at 0 ° C. was measured, and the low fuel consumption index of Comparative Example 1 was set to 100, and the tan δ of each blend was indicated by an index using the following formula. In addition, it shows that it is excellent in low fuel consumption, so that a low fuel consumption index is large.
(Low fuel consumption index) = (tan δ of Comparative Example 1) ÷ (tan δ of each formulation) × 100

(Low fuel consumption (2) (tire evaluation))
Using a rolling resistance tester, the rolling resistance when the obtained test tire was run under conditions of rim 15 × 6JJ, tire internal pressure 230 kPa, load 3.43 kN, and speed 80 km / h was measured and compared. The rolling resistance index of Example 1 was set to 100, and the rolling resistance of each formulation was indicated by an index according to the following formula. In addition, it shows that rolling resistance is reduced and a fuel-consumption property is excellent, so that a rolling resistance index | exponent is large.
(Rolling resistance index) = (Rolling resistance of Comparative Example 1) / (Rolling resistance of each formulation) × 100

In Examples including silica and the sulfur-containing silane compound (silane coupling agent 2 to 5) represented by the general formula (I), excellent fuel economy and wear resistance were obtained. In the comparative example which did not mix | blend the sulfur containing silane compound represented by the said general formula (I), all the performances were inferior to the Example.

Claims (6)

Rubber component, silica, a sulfur-containing silane compound represented by the following general formula (I) seen including,
The tire rubber composition, wherein the silica content is 2 to 70 parts by mass with respect to 100 parts by mass of the rubber component .

(In Formula (I), n is the same or different and is an integer of 1 to 10. m is an integer of 2 to 6. p is 3. R ¹ is the same or different and is —R. A polyether group represented by ^3- (OR ⁴ ) _q -OR ⁵ or an amino group represented by the following general formula (II): R ² is the same or different and is an alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ are the same or different and each represents an alkylene group having 2 to 6 carbon atoms, and R ⁵ is the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is an integer from 2 to 6.)

(In formula (II), R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. R is an integer of 2 to 6) Against Shi silica 100 parts by weight, the sulfur-containing silane compound the rubber composition for a tire of claim 1 further comprising 0.1 to 45 parts by weight. The silica has a nitrogen adsorption specific surface area of 100 to 200 m. ² The rubber composition for tires according to claim 1 or 2, which is / g. The rubber composition for tires according to any one of claims 1 to 3 in which said rubber ingredient contains solution polymerization SBR. The tire rubber composition according to any one of claims 1 to 4, which is used as a rubber composition for a tread or a rubber composition for a sidewall. The pneumatic tire produced using the rubber composition in any one of Claims 1-5 .