JP2011225783A - Tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tire having excellent abrasion resistance while configured by using a rubber composition having excellent workability.SOLUTION: The tire comprises: an organic silicon compound (A) having one or more silicon-oxygen bonds and one or more sulfur atoms in one molecule and further having one or more nitrogen atoms at a position three to eight carbons away from the silicon atom; a partial ester (B) of a maleic anhydride and a polyoxypropylene derivative; and a silica (C).

Description

  The present invention relates to a tire using a rubber composition having good workability in which a specific organosilicon compound and a partial ester of maleic anhydride and a (poly) oxypropylene derivative are blended, and particularly excellent in wear resistance. It relates to tires.

  Conventionally, it is known that a technique using silica as a filler of a rubber composition used for a tire tread is effective as a technique for achieving both improvement in performance on a wet road surface of a tire and reduction in rolling resistance. However, since a rubber composition containing silica has a high viscosity in an unvulcanized state (unvulcanized viscosity) and has a difficulty in workability, a dispersion improver is used. However, when a dispersion improver is used, hysteresis loss and wear resistance are not sufficient. For this reason, when a silica is mix | blended with a rubber composition, it is also essential to add a silane coupling agent.

US Pat. No. 3,842,111 US Pat. No. 3,873,489

  However, as a result of studies by the present inventors, the conventional silane coupling agent has an unnecessarily high reactivity with the rubber component, and therefore the unvulcanized viscosity of the rubber composition is extremely high, and the workability of the rubber composition is high. However, it was not enough, and there was still room for improvement.

  Then, an object of this invention is to provide the tire excellent in abrasion resistance, using the rubber composition with favorable workability | operativity.

  In order to solve the above problems, the present inventors have developed a silica-containing rubber composition in which a specific organosilicon compound having a high reaction rate with silica is blended together with a partial ester of maleic anhydride and a (poly) oxypropylene derivative. It has been found that by using it in a tire, the unvulcanized viscosity of the rubber composition can be reduced while maintaining the efficiency of the coupling reaction, and the wear resistance of the tire can be improved, and the present invention has been completed.

That is, the tire of the present invention has one or more silicon-oxygen bonds and one or more sulfur atoms in the molecule, and has nitrogen atoms at positions 3 to 8 away from the silicon atoms. A rubber composition containing at least one organosilicon compound (A), a partial ester (B) of maleic anhydride and a (poly) oxypropylene derivative, and silica (C) is used.
The organosilicon compound (A) preferably has 1 to 6 silicon-oxygen bonds and 1 to 10 sulfur atoms in the molecule.

［式中、Ａ¹は、下記一般式(II)又は式(III)：

で表わされ、
式(I)及び式(II)中のＲ¹、Ｒ²及びＲ³は、少なくとも一つが下記一般式(IV)又は式(V)：

（式中、Ｍは−Ｏ−又は−ＣＨ₂−で、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸で、但し、Ｒ⁸は−Ｃ_nＨ_2n+1であり、Ｒ⁹は−Ｃ_qＨ_2q+1であり、ｌ、ｍ、ｎ及びｑはそれぞれ独立して０〜１０である）で表わされ、その他が−Ｍ−Ｃ_lＨ_2l+1（ここで、Ｍ及びｌは上記と同義である）で表わされ、但し、Ｒ¹、Ｒ²及びＲ³の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式(VI)又は式(VII)：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、ｌ及びｍは上記と同義であり、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−で、但し、Ｒ⁸は上記と同義である）或いは−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍ及びｌは上記と同義である）で表され、
式(III)中のＲ⁵は上記一般式(IV)又は式(V)或いは−Ｃ_lＨ_2l−Ｒ¹¹（ここで、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｍ、ｌ及びｍは上記と同義である）で表わされ、
ｘは１〜１０である］で表わされるものであってもよい。 The organosilicon compound (A) is represented by the following general formula (I):

[Wherein A ¹ represents the following general formula (II) or formula (III):

Represented by
At least one of R ¹ , R ² and R ³ in formula (I) and formula (II) is the following general formula (IV) or formula (V):

(In the formula, M is —O— or —CH ₂ —, X and Y are independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R. ⁹ or -R ⁸ , R ⁷ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ or -N = NR ⁸ , provided that R ⁸ is -C _n H _{2n + 1} , R ⁹ is a _{-C q H 2q + 1, l} , m, n and q are represented by each independently a 0-10), others _{-M-C l H 2l + 1} ( wherein, M and l is as defined above, provided that at ^{least one} of R ¹ , R ² and R ³ is M is —O—;
R ⁴ represents the following general formula (VI) or formula (VII):

(In the formula, M, X, Y, R ⁶ , l and m are as defined above, and R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ Is as defined above) or -M-C ₁ H _2l- (wherein M and l are as defined above),
R ⁵ in formula (III) is the above general formula (IV), formula (V), or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9). -N = NR ⁸ or -M-C _m H _{2m + 1} , wherein R ⁸ , R ⁹ , M, l and m are as defined above.
x is 1 to 10].

［式中、Ａ²は、下記一般式(IX)又は式(III)：

で表わされ、
式(VIII)及び式(IX)中のＷは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍ、ｎ及びｑはそれぞれ独立して０〜１０である）で表わされ、
Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜１０である）で表わされ、
Ｒ¹⁴は−Ｍ−Ｃ_lＨ_2l+1又は−Ｍ−Ｃ_lＨ_2l−Ｒ⁷（ここで、Ｍ、Ｒ⁷及びｌは上記と同義である）で表わされ、但し、Ｒ¹²、Ｒ¹³及びＲ¹⁴の一つ以上はＭが−Ｏ−であり、
Ｒ⁴は下記一般式(VI)又は式(VII)：

（式中、Ｍ、ｌ及びｍは上記と同義であり、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−であり、但し、Ｒ⁸及びＲ⁹は上記と同義である）或いは−ＭＣ_lＨ_2l−（ここで、Ｍ及びｌは上記と同義である）で表され、
式(III)中のＲ⁵は下記一般式(IV)又は式(V)：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、Ｒ⁷、ｌ及びｍは上記と同義である）或いは−Ｃ_lＨ_2l−Ｒ¹¹（ここで、Ｒ¹¹は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1であり、但し、Ｒ⁸、Ｒ⁹、Ｍ、ｌ及びｍは上記と同義である）で表わされ、
ｘは１〜１０である］で表わされるものであってもよい。 The organosilicon compound (A) is represented by the following general formula (VIII):

[In the formula, A ² represents the following general formula (IX) or formula (III):

Represented by
W in formula (VIII) and formula (IX) is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ ; However, R ⁷ is -NR ⁸ R ^9, a -NR ⁸ -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1} M, n and q are each independently 0 to 10),
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 10),
R ¹⁴ is -M-C _l H _{2l + 1} or ^{_{-M-C l H 2l -R 7}} ( wherein, M, R ⁷ and l has the same meaning as mentioned above) is represented by, where, R ^12, One or more of R ¹³ and R ¹⁴ is M is —O—;
R ⁴ represents the following general formula (VI) or formula (VII):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are as defined above), or -MC _l H _2l- (wherein M and l are as defined above),
R ⁵ in the formula (III) is the following general formula (IV) or formula (V):

(Wherein, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above) or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ -NR ⁸ R ⁹ , -N = NR ⁸ or -M-C _m H _{2m + 1} , wherein R ⁸ , R ⁹ , M, l and m are as defined above.
x is 1 to 10].

  Furthermore, the organosilicon compound (A) has a cyclic structure containing a nitrogen atom and a silicon atom in the molecule, and a site where one or more groups having small steric hindrance are bonded to the silicon atom. The group having a small steric hindrance may be at least one selected from the group consisting of a hydrogen atom, a methyl group and a hydroxyl group.

［式中、Ａ³は硫黄原子を含み且つゴム成分と反応する基であり、
Ｗは−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁸Ｒ¹⁵−（ここで、Ｒ¹⁵は−Ｒ⁹又は−Ｃ_mＨ_2m−Ｒ⁷であり、但し、Ｒ⁷は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹又は−Ｎ＝ＮＲ⁸であり、Ｒ⁸は−Ｃ_nＨ_2n+1で、Ｒ⁹は−Ｃ_qＨ_2q+1で、ｍ、ｎ及びｑはそれぞれ独立して０〜１０である）で表わされ、
Ｒ¹²及びＲ¹³はそれぞれ独立して−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−で、ｌは０〜１０である）で表わされ、但し、Ｒ¹²及びＲ¹³の一つ以上は、Ｍが−Ｏ−であり、
Ｒ¹⁶は水素原子、メチル基又はヒドロキシル基である］で表わされるものであってもよい。 The organosilicon compound (A) is represented by the following general formula (X):

[Wherein A ³ is a group containing a sulfur atom and reacting with a rubber component,
W is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ is —NR ⁸ R ⁹ , -NR ⁸ is -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is _{-C q H 2q + 1, m} , n and q are each independently 0 to 10)
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 10), provided that R ^At least one of ¹² and R ¹³ is M is —O—;
R ¹⁶ may be a hydrogen atom, a methyl group or a hydroxyl group].

In the organosilicon compound (A), the group containing the sulfur atom and reacting with the rubber component is a polysulfide group, a thioester group, a thiol group, a dithiocarbonate group, a dithioacetal group, a hemithioacetal group, a vinylthio group, α- It is desirable to include at least one selected from the group consisting of a thiocarbonyl group, a β-thiocarbonyl group, an S—CO—CH ₂ —O moiety, an S—CO—CO moiety, and an S—CH ₂ —Si moiety, It is more desirable to include at least one of a polysulfide group and a thioester group.

［式(XI)中のＷ、Ｒ¹²、Ｒ¹³及びＲ¹⁶は上記と同義であり、
式(XI)及び式(XII)中のＲ⁴は、下記一般式(VI)又は式(VII)：

（式中、Ｍ、ｌ及びｍは上記と同義であり、Ｘ及びＹはそれぞれ独立して−Ｏ−、−ＮＲ⁸−又は−ＣＨ₂−で、Ｒ⁶は−ＯＲ⁸、−ＮＲ⁸Ｒ⁹又は−Ｒ⁸で、Ｒ¹⁰は−ＮＲ⁸−、−ＮＲ⁸−ＮＲ⁸−又は−Ｎ＝Ｎ−であり、但し、Ｒ⁸及びＲ⁹は上記と同義である）或いは−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍ及びｌは上記と同義である）で表わされ、
式(XII)中のＲ¹⁷は下記一般式(IV)又は式(Ｖ)：

（式中、Ｍ、Ｘ、Ｙ、Ｒ⁶、Ｒ⁷、ｌ及びｍは上記と同義である）或いは−Ｃ_lＨ_2l−Ｒ¹⁸（ここで、Ｒ¹⁸は−ＮＲ⁸Ｒ⁹、−ＮＲ⁸−ＮＲ⁸Ｒ⁹、−Ｎ＝ＮＲ⁸又は−Ｍ−Ｃ_mＨ_2m+1或いは炭素数６〜２０の芳香族炭化水素基であり、但し、Ｒ⁸、Ｒ⁹、Ｍ、ｌ及びｍは上記と同義である）で表わされ、
式(XI)及び式(XII)中のｘは１〜１０である］で表わされるものであってもよい。 In the organosilicon compound (A), A ³ is represented by the following general formula (XI) or formula (XII):

[W, R ¹² , R ¹³ and R ¹⁶ in the formula (XI) are as defined above,
R ^{4 in} formula (XI) and formula (XII) is the following general formula (VI) or formula (VII):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are as defined above) or -M-C _l H _2l- (wherein M and l are as defined above),
R ¹⁷ in formula (XII) is the following general formula (IV) or formula (V):

Wherein M, X, Y, R ⁶ , R ⁷ , l and m are as defined above, or —C ₁ H _2l —R ¹⁸ (where R ¹⁸ is —NR ⁸ R ⁹ , —NR ⁸ -NR ⁸ R ⁹ , -N = NR ⁸ or -M-C _m H _{2m + 1} or an aromatic hydrocarbon group having 6 to 20 carbon atoms, provided that R ⁸ , R ⁹ , M, l and m Is synonymous with the above),
X in Formula (XI) and Formula (XII) may be 1-10.

The rubber composition comprises 1 to 30 parts by mass of a partial ester (B) of the maleic anhydride and a (poly) oxypropylene derivative, and 10 to 200 parts by mass of the silica (C) with respect to 100 parts by mass of the rubber component. It is desirable that the organosilicon compound (A) is further contained in an amount of 1 to 20% by mass based on the amount of the silica (C).
The silica (C) preferably has a BET surface area of 40 to 350 m ² / g, and the rubber component is preferably a diene rubber.
The average degree of polymerization of the oxypropylene moiety of the (poly) oxypropylene derivative may be 3 to 7, and the (poly) oxypropylene derivative is preferably polyoxypropylene lauryl ether.

  According to the tire of the present invention, a silica having a specific molecular structure, employing an organosilicon compound that can greatly reduce the hysteresis loss of the rubber composition and can greatly improve the wear resistance. Thus, it is possible to provide a tire that exhibits excellent wear resistance while maintaining a high reaction rate and good workability.

Hereinafter, the present invention will be specifically described.
The tire of the present invention has one or more silicon-oxygen bonds and one or more sulfur atoms in the molecule, and one nitrogen atom at a position 3 to 8 away from the silicon atom. A rubber composition containing the organosilicon compound (A) having the above, a partial ester (B) of maleic anhydride and a (poly) oxypropylene derivative, and silica (C) is used. In the rubber composition used in the present invention, in addition to the partial ester (B) and silica (C) of maleic anhydride and a (poly) oxypropylene derivative, the specific organosilicon compound (A) is blended. Therefore, the unvulcanized viscosity of the rubber composition is low, the workability is excellent, and the wear resistance can be improved.

[Rubber component]
The rubber component of the rubber composition used in the present invention is not particularly limited, but is preferably a diene rubber. Examples of the diene rubber include natural rubber and diene synthetic rubber, but diene synthetic rubber is preferable. Examples of the diene synthetic rubber include polybutadiene rubber (BR), a copolymer of butadiene and an aromatic vinyl compound, a butadiene polymer such as a copolymer of butadiene and another diene monomer, and polyisoprene. Isoprene-based polymers such as rubber (IR), copolymers of isoprene and aromatic vinyl compounds, copolymers of isoprene and other diene monomers; butyl rubber (IIR), ethylene / propylene copolymers, and these A mixture etc. are mentioned, Among these, a butadiene polymer and an isoprene polymer are preferable. Examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, etc. Among these, Most preferred is 3-butadiene. These monomers may be used singly or in combination of two or more, and may further be used by copolymerizing with other dienes such as 1,3-hexadiene. Moreover, styrene etc. are mentioned as said aromatic vinyl compound.

  Among the rubber components, styrene / butadiene copolymer rubber (SBR) is particularly preferable. The microstructure of the styrene / butadiene copolymer rubber is not particularly limited, but the amount of bound styrene is preferably 5 to 60% by mass, more preferably 15 to 45% by mass. In the rubber composition used in the present invention, the content of the styrene / butadiene copolymer rubber in the rubber component is preferably 50% by mass or more, and the rubber component is particularly a styrene / butadiene copolymer rubber alone. preferable.

[Organic silicon compound (A)]
The organosilicon compound (A) used in the present invention has one or more silicon-oxygen bonds (Si-O) and one or more sulfur atoms (S) in the molecule, and is a silicon atom (Si). It has one or more nitrogen atoms (N) at positions 3 to 8 away from the number of atoms. The organosilicon compound (A) is an amino group, imino group, substituted amino group, substituted imino group having a high affinity for the surface of silica at a position 3 to 8 atoms away from the silicon atom (Si) in the molecular structure. Therefore, the unshared electron pair of the nitrogen atom can participate in the reaction between the silane coupling agent and silica, and the coupling reaction speed is high. Therefore, instead of the conventional silane coupling agent, by adding an organosilicon compound (A) represented by the following general formula to the silica-blended rubber composition, the coupling efficiency is improved, and as a result, It is possible to greatly improve the wear resistance while greatly reducing the hysteresis loss of the rubber composition. Moreover, since the said organosilicon compound (A) has high addition efficiency, a high effect is acquired even if it is a small amount, and it contributes also to the reduction of a compounding cost.

  In addition, when the number of atoms between the silicon atom (Si) and the nitrogen atom (N) is less than 3 or more than 8, the coupling efficiency is not sufficiently improved, and the hysteresis loss of the rubber composition is greatly reduced. However, the wear resistance cannot be significantly improved. The organosilicon compound (A) preferably has 1 to 6 silicon-oxygen bonds (Si-O). In this case, the reactivity with silica is high, and the coupling efficiency is further improved. Furthermore, the organosilicon compound (A) preferably has 1 to 10 sulfur atoms.

  More specifically, as the organosilicon compound (A), a compound represented by the above general formula (I) and a compound represented by the above general formula (VIII), or represented by the above general formula (X) The compound is preferably a compound having a cyclic structure containing a nitrogen atom and a silicon atom in the molecule and having one or more groups having small steric hindrance bonded to the silicon atom. These organosilicon compounds (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

<< Organic silicon compound of formula (I) (A) >>
In the general formula (I), A ¹ is represented by the general formula (II) or the formula (III), and x is 1 to 10. Here, x is preferably in the range of 2-4.

In the above formulas (I) and (II), at least one of R ¹ , R ² and R ³ is represented by the above general formula (IV) or formula (V), and the others are -M-C _l H _{2l + 1} (wherein M is —O— or —CH ₂ —, and l is 0 to 10). Provided that M is —O— in one or more of R ¹ , R ² and R ³ . Note that -C _l H _{2l + 1} is hydrogen or an alkyl group having 1 to 10 carbon atoms because l is 0 to 10. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched.

In the above formulas (IV) and (V), M is —O— or —CH ₂ —, and 1 is 0 to 10. In the above formula (IV), m is 0-10.

In the above formula (IV), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —. Wherein, R ⁸ is -C _n H _{2n + 1, n} is 0-10. Note that -C _n H _{2n + 1} is hydrogen or an alkyl group having 1 to 10 carbon atoms because n is 0 to 10. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched.

In the above formula (IV), R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Wherein, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1,} n and q are 0 independently. Note that the -C _n H _{2n + 1,} are as described above, -C _q H _{2q + 1,} since q is 0, is hydrogen or an alkyl group having 1 to 10 carbon atoms. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched.

In the above formula (V), R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9, or —N═NR ⁸ . Wherein, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1,} n and q are 0 independently. Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

In the above formulas (I) and (II), R ⁴ is represented by the above general formula (VI) or formula (VII), or —M—C ₁ H _2l —, particularly —C ₁ H _2l. - it is preferably represented by, where, M is -O- or -CH ₂ -, l is 0. In addition, since l is 0 to 10, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched.

In the above formulas (VI) and (VII), M is —O— or —CH ₂ —, and l and m are 0-10. In the above formula (VI), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . is there. R ⁸ and R ⁹ are as described above. Further, in the above formula (VII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, wherein R ⁸ is —C _n H _{2n + 1} , the -C _n H _{2n + 1,} as described above.

R ⁵ in the above formula (III) is represented by the above general formula (IV) or (V), or —C ₁ H _2l —R ¹¹ , particularly represented by —C ₁ H _{2l + 1} . Wherein R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or —M—C _m H _{2m + 1} , provided that R ⁸ , R ⁹ , M, l and m are as defined above. Incidentally, -C _l H _2l - is as described above and -C _l H _{2l + 1.} Further, -C _m H _{2m + 1,} since m is 0-10, is hydrogen or an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group having 1 to 10 carbon atoms, a methyl group, Examples thereof include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. The alkyl group may be linear or branched.

In the compound of the above formula (I), M is preferably —O— (oxygen). In this case, the reactivity with silica is high as compared with the compound in which M is —CH ₂ —.

In the compound of the above formula (I), at least one of R ¹ , R ² and R ³ is represented by —OC ₁ H _2l —R ⁷ , and the other is —O—C ₁ H _{2l + 1} . R ⁴ is preferably represented by —C ₁ H _2l —, and R ⁵ is preferably represented by —C ₁ H _2l —R ¹¹ .

Further, in the compound of the above formula (I), it is more preferable that at least one of R ¹ , R ² and R ³ is represented by —OC ₁ H _2l —NR ⁸ R ⁹ , and R ⁴ represents —C ₁ It is preferably represented by H _2l- , and more preferably, R ⁵ is represented by -C ₁ H _{2l + 1} .

<< Organic silicon compound of formula (VIII) (A) >>
In the general formula (VIII), A ² is represented by the general formula (IX) or the formula (III), and x is 1 to 10. Here, x is preferably in the range of 2-4.

In the above formulas (VIII) and (IX), W is represented by —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ —, wherein R ¹⁵ is —R ⁹ or —C _m H _2m —. R ⁷ wherein R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , and R ⁹ is —C _{In qH2q + 1} , m, n, and q are each independently 0-10. Incidentally, -C _m H _2m -, since m is 0-10, a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched. Moreover, -C _n H _{2n + 1} and -C _q H _{2q + 1,} since n and q are 0, is hydrogen or an alkyl group having 1 to 10 carbon atoms. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched.

In the above formula (VIII) and (IX), R ¹² and R ¹³ are each independently -M-C _l H _2l - is represented by, R ¹⁴ is -M-C _l H _{2l + 1} or -M- C _l H _2l —R ⁷ , wherein M is —O— or —CH ₂ —, R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR; ⁸ , R ⁸ is —C _n H _{2n + 1} , R ⁹ is —C _q H _{2q + 1} , and l, n, and q are each independently 0-10. However, in one or more of R ¹² , R ¹³ and R ¹⁴ , M is —O—. In addition, since l is 0 to 10, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 10 carbon atoms. Here, the alkylene group having 1 to 10 carbon atoms includes a methylene group, Examples thereof include an ethylene group, a trimethylene group, and a propylene group. The alkylene group may be linear or branched. In addition, since l is 0 to 10, —C ₁ H _{2l + 1} is hydrogen or an alkyl group having 1 to 10 carbon atoms. Here, as the alkyl group having 1 to 10 carbon atoms, a methyl group, Examples thereof include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. The alkyl group may be linear or branched. Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

In the above formulas (VIII) and (IX), R ⁴ is represented by the above general formula (VI) or (VII), or —M—C ₁ H _{2 1} —, particularly —C ₁ H _{2 1} — Wherein M is —O— or —CH ₂ —, and l is 0-10. In addition, -C _l H _2l- is as described above.

In the above formulas (VI) and (VII), M is —O— or —CH ₂ —, and l and m are 0-10. In the above formula (VI), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Yes, where R ⁸ is —C _n H _{2n + 1} and R ⁹ is —C _q H _{2q + 1} . Further, in the above formula (VII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, where R ⁸ is —C _n H _{2n + 1} . Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

R ⁵ in the above formula (III) is represented by the above general formula (IV) or (V), or —C ₁ H _2l —R ¹¹ , particularly represented by —C ₁ H _{2l + 1} . Wherein R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or —M—C _m H _{2m + 1} , provided that R ⁸ , R ⁹ , M, l and m are as defined above. In addition, -C _l H _2l -and -C _l H _{2l + 1} are as described above, and -C _m H _{2m + 1} is hydrogen or carbon number 1 because m is 0-10. Wherein the alkyl group having 1 to 10 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group and the like. And the alkyl group may be linear or branched.

In the compound of the above formula (VIII), M is preferably —O— (oxygen). In this case, the reactivity with silica is high as compared with the compound in which M is —CH ₂ —.

When W is represented by —NR ⁸ —, R ¹² and R ¹³ are preferably each independently represented by —O—C ₁ H _2l —, and R ¹⁴ is represented by —O—C ₁ H. is preferably represented by _2l -R ^7, it said R ⁴ is -C _l H _2l - is preferably represented by the above R ⁵ is preferably represented by -C _l H _{2l + 1.}

On the other hand, when the W is represented by —O— or —CR ⁸ R ⁹ —, the R ¹² and R ¹³ are preferably each independently represented by —O—C ₁ H _2l —, and the R ¹⁴ is It is preferably represented by —O—C ₁ H _2l —NR ⁸ R ⁹ , R ⁴ is preferably represented by —C ₁ H _2l —, and R ⁵ is represented by —C ₁ H _{2l + 1.} It is preferable.

<< Synthesis Method of Organosilicon Compound (A) Represented by Formula (I) and Formula (VIII) >>
The organosilicon compound (A) of the present invention is represented, for example, by the above general formula (I), wherein R ¹ , R ² and R ³ are represented by -M—C ₁ H _{2l + 1} , R ¹ , For compounds in which one or more of M in R ² and R ³ is —O—, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, 2- (dimethylamino) propanol, 2- (diethylamino) An amine compound such as propanol or N-methyldiethanolamine is added, and an acid such as p-toluenesulfonic acid or hydrochloric acid or a titanium alkoxide such as titanium tetra n-butoxide is added as a catalyst, followed by heating, and R ¹ , R ² and One or more of R ³ are substituted with a monovalent nitrogen-containing group represented by formula (IV) or formula (V), or R ¹ and R ² are divalent represented by —R ¹² —W—R ¹³ —. It can be synthesized by substitution with a nitrogen-containing group.

<< Specific Examples of Organosilicon Compound (A) Represented by Formula (I) and Formula (VIII) >>
As the organosilicon compound (A) represented by the formula (I) and the formula (VIII), specifically, 3-octanoylthio-propyl (monodimethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (didimethylaminoethoxy) ) Monoethoxysilane, 3-octanoylthio-propyltridimethylaminoethoxysilane, 3-octanoylthio-propyl (monodiethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (monodimethylaminopropyloxy) diethoxysilane, 3-octanoylthio- Propyl (monodiethylaminopropyloxy) diethoxysilane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-5-methylaza-2-silacyclohexane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-5- Ethylaza-2-silacyclohe Sun, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclohexane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclohexane, bis ( 3- (monodimethylaminoethoxy) diethoxysilyl-propyl) disulfide, bis (3- (didimethylaminoethoxy) monoethoxysilyl-propyl) disulfide, bis (3- (tridimethylaminoethoxy) silyl-propyl) disulfide, Bis (3- (monodimethylaminoethoxy) diethoxysilyl-propyl) disulfide, bis (3- (monodiethylaminoethoxy) diethoxysilyl-propyl) disulfide, bis (3- (monodimethylaminopropyloxy) diethoxysilyl- Propyl) disulfide, bis (3- (monodiethylaminopropyloxy) diethyl Silyl-propyl) disulfide, bis (3- (monodimethylaminoethoxy) diethoxysilyl-propyl) tetrasulfide, bis (3- (didimethylaminoethoxy) monoethoxysilyl-propyl) tetrasulfide, bis (3- (tri Dimethylaminoethoxy) silyl-propyl) tetrasulfide, bis (3- (monodimethylaminoethoxy) diethoxysilyl-propyl) tetrasulfide, bis (3- (monodiethylaminoethoxy) diethoxysilyl-propyl) tetrasulfide, bis ( 3- (monodimethylaminopropyloxy) diethoxysilyl-propyl) tetrasulfide, bis (3- (monodiethylaminopropyloxy) diethoxysilyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa- 5-methylaza-2-silacyclohexyl-propyl) disulfide, bis ( 3- (ethoxy) 1,3-dioxa-5-ethylaza-2-silacyclohexyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclohexyl-propyl) disulfide, Bis (3- (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclohexyl-propyl) disulfide, bis (3- (ethoxy) 1,3-dioxa-5-methylaza-2-silacyclohexyl-propyl) Tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-5-ethylaza-2-silacyclohexyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6-methylaza-2-sila (Cyclohexyl-propyl) tetrasulfide, bis (3- (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclohexyl-propyl) tetrasulfide.

<< Organic silicon compound (A) having a cyclic structure containing a nitrogen atom and a silicon atom in the molecule and having one or more groups having small steric hindrance bonded to the silicon atom >>
The organosilicon compound (A) used in the present invention includes one or more silicon-oxygen bonds in the molecule, in addition to the organosilicon compound (A) represented by the above general formula (I) and the above general formula (VIII). A ring containing a nitrogen atom (N) and a silicon atom (Si) while having one or more nitrogen atoms at a position 3 to 8 atoms away from the silicon atom. It may be a compound having a structure and having a site where one or more groups having a small steric hindrance are bonded to one or more silicon atoms (Si). Such an organosilicon compound (A) has a cyclic structure including a nitrogen atom (N) and a silicon atom (Si), and the cyclic structure includes a silicon-oxygen bond (Si-O). , Stable. Therefore, the silicon-oxygen bond (Si—O) is not hydrolyzed to generate an alcohol component, and the volatile organic compound (VOC) gas in use can be reduced.

  Here, when the cyclic structure containing a nitrogen atom (N) and a silicon atom (Si) is a bicyclic structure, since the steric hindrance around the silicon atom (Si) is large, the reactivity with silica is low, and the cup Ring efficiency is greatly reduced. On the other hand, since the organosilicon compound (A) has a site where one or more groups having small steric hindrance are bonded to a silicon atom, the reactivity with silica is high. Therefore, by adding the organosilicon compound (A) to the silica-containing rubber composition instead of the conventional silane coupling agent, the coupling efficiency is improved, and as a result, the hysteresis loss of the rubber composition is greatly increased. Thus, the wear resistance can be greatly improved. Moreover, since the said organosilicon compound (A) has high addition efficiency, a high effect is acquired even if it is a small amount, and it contributes also to the reduction of a compounding cost.

As the group having a small steric hindrance, a hydrogen atom (—H), a methyl group (—CH ₃ ) and a hydroxyl group (—OH) are preferable. When a hydrogen atom, a methyl group or a hydroxyl group is bonded to a silicon atom (Si), the reactivity between the organosilicon compound (A) and silica is particularly high, and the coupling efficiency can be greatly improved.

  In addition, the said organosilicon compound (A) is 1-6 silicon-oxygen bonds (Si-O) similarly to the organosilicon compound (A) represented by the said general formula (I) and the said general formula (VIII). It preferably has 1 to 10 sulfur atoms.

  More specifically, such an organosilicon compound (A) is preferably a compound represented by the above general formula (X). The organosilicon compound (A) may be used alone or in combination of two or more.

<< Organic silicon compound of formula (X) (A) >>
In the general formula (X), A ³ is a group containing a sulfur atom (S) and reacting with the rubber component. In the organosilicon compound (A) represented by the formula (X), since the cyclic structure portion reacts with silica, it has a group capable of reacting with the rubber component in the molecule, thereby providing a coupling ability between the rubber component and silica. Will have. Here, the group containing a sulfur atom (S) and reacting with the rubber component is a polysulfide group, a thioester group, a thiol group, a dithiocarbonate group, a dithioacetal group, a hemithioacetal group, a vinylthio group, an α-thiocarbonyl group, It preferably contains at least one selected from the group consisting of β-thiocarbonyl group, S—CO—CH ₂ —O moiety, S—CO—CO moiety (thiodiketone group), and S—CH ₂ —Si moiety, It is particularly preferable that at least one of a polysulfide group and a thioester group is included.

In the general formula (X), W is represented by —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ —, wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ . Provided that R ⁷ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ or —N═NR ⁸ , R ⁸ is —C _n H _{2n + 1} , and R ⁹ is —C _q H _{2q. +1} , m, n, and q are each independently 0-10. Incidentally, -C _m H _2m -, since m is 0-10, a single bond or an alkylene group having 1 to 10 carbon atoms. Here, examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and the alkylene group may be linear or branched. Moreover, -C _n H _{2n + 1} and -C _q H _{2q + 1,} since n and q are 0, is hydrogen or an alkyl group having 1 to 10 carbon atoms. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched.

In the general formula (X), R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} —, wherein M is —O— or —CH ₂ —, and 1 is 0 -10. However, in one or more of R ¹² and R ¹³ , M is —O—. In addition, since l is 0 to 10, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 10 carbon atoms. Here, the alkylene group having 1 to 10 carbon atoms includes a methylene group, Examples thereof include an ethylene group, a trimethylene group, and a propylene group. The alkylene group may be linear or branched.

In the above general formula (X), R ¹⁶ is a hydrogen atom, a methyl group or a hydroxyl group. Since R ¹⁶ has small steric hindrance, it greatly contributes to the improvement of the coupling reaction between the rubber component and silica.

A ³ in the general formula (X) is preferably represented by the general formula (XI) or the formula (XII). Here, W, R ¹² , R ¹³ and R ¹⁶ in the formula (XI) have the same meanings as above, and R ⁴ in the formula (XI) and the formula (XII) represents the general formula (VI) or the formula ( VII) or -M-C _l H _2l - is represented by, R ¹⁷ in formula (XII), represented by the general formula (IV) or formula (V) or -C _l H _2l -R ¹⁸ In the formulas (XI) and (XII), x is 1 to 10, preferably 2 to 4. Here, M is -O- or -CH ₂ -, l is 0. In addition, -C _l H _2l- is as described above.

In the above formulas (VI) and (VII), M is —O— or —CH ₂ —, and l and m are 0-10. In the above formula (VI), X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or —R ⁸ . Yes, where R ⁸ is —C _n H _{2n + 1} and R ⁹ is —C _q H _{2q + 1} . Further, in the above formula (VII), R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ —, or —N═N—, where R ⁸ is —C _n H _{2n + 1} . Note that the -C _n H _{2n + 1} and -C _q H _{2q + 1,} is as described above.

R ¹⁷ in the above formula (XII) is represented by the above general formula (IV) or (V), or —C ₁ H _2l —R ¹⁸ , particularly represented by —C ₁ H _{2l + 1} . However, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above. Here, R ¹⁸ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ⁹ , —N═NR ⁸ or —M—C _m H _{2m + 1,} or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Provided that R ⁸ , R ⁹ , M, l and m are as defined above. In addition, -C _l H _2l- is as described above, and -C _m H _{2m + 1} is hydrogen or an alkyl group having 1 to 10 carbon atoms because m is 0 to 10. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group. It may be linear or branched. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, cumenyl group, naphthylene group and tolylene group, and aralkyl groups such as benzyl group and phenethyl group. .

In the compound of the above formula (X), M is preferably —O— (oxygen). In this case, the reactivity with silica is high as compared with the compound in which M is —CH ₂ —.

When W is represented by —NR ⁸ —, R ¹² and R ¹³ are preferably independently represented by —O—C ₁ H _2l —, and R ¹⁶ represents a hydrogen atom, methyl group or It is a hydroxyl group, and R ⁴ is preferably represented by —C ₁ H _2l —, and R ¹⁷ is a linear or branched alkyl group represented by —C ₁ H _{2l + 1} , or the number of carbon atoms It is preferably a 6-20 aromatic hydrocarbon group.

On the other hand, when the W is represented by —O— or —CR ⁸ R ⁹ —, the R ¹² and R ¹³ are preferably each independently represented by —O—C ₁ H _2l —, and the R ¹⁶ is It is a hydrogen atom, a methyl group or a hydroxyl group, and R ⁴ is preferably represented by —C ₁ H _2l —, and R ¹⁷ is preferably represented by —C ₁ H _{2l + 1} .

<< Synthesis Method of Organosilicon Compound (A) Represented by Formula (X) >>
The organosilicon compound (A) represented by the formula (X) is, for example, (C _l H _{2l + 1} O) ₂ R ¹⁶ Si-A [wherein l, R ¹⁶ and A are as defined above]. Add an amine compound such as N-methyldiethanolamine or N-ethyldiethanolamine to the compound represented, and then add an acid such as p-toluenesulfonic acid or hydrochloric acid, or a titanium alkoxide such as titanium tetra-n-butoxide as a catalyst. Then, it can be synthesized by substituting two C _l H _{2l + 1} O— with a divalent group represented by —R ¹² —W—R ¹³ —.

<< Specific Example of Organosilicon Compound (A) Represented by Formula (X) >>
Specifically, as the organosilicon compound (A) represented by the formula (X), 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, bis (3- (methyl ) 1,3-Dioxa-6-methylaza-2-silacyclooctyl-propyl) disulfide, 3-octanoylthio-propyl (hydroxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, bis (3- ( Hydroxy) 1,3-dioxa-6-methylaza-2-silacyclooctyl-propyl) disulfide, 3-octanoylthio-propyl (hydro) 1,3-dioxa-6-methylaza-2-silacyclooctane, bis (3- (Hydro) 1,3-dioxa-6-methylaza-2-silacyclooctyl-propyl) disulfide, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-butylaza- 2-silacyclooctane, bis (3- (methyl) 1,3-dioxa-6-butylaza-2-silacyclooctyl-propyl) disulfide and the like.

  The content of the organosilicon compound (A) is preferably 1 to 20% by mass with respect to the amount of silica (C). When the content of the organosilicon compound (A) is less than 1% by mass of the amount of silica (C), the workability of the resulting rubber composition is improved, the hysteresis loss is reduced, and the wear resistance is improved. On the other hand, if it exceeds 20% by mass, the effect is saturated.

［式(XIII)中、ｒは平均重合度を表わす１以上の数であり；Ｒ²⁰はアルキル基、アルケニル基、アルキルアリール基又はアシル基である］で表される化合物が好ましい。式(XIII)において、ｒが３〜７で、Ｒ²⁰が炭素数８〜１８のアルキル基又はアルケニル基であるのが更に好ましい。 [Partial ester (B) of maleic anhydride and (poly) oxypropylene derivative]
The rubber composition used in the present invention contains a partial ester (B) of maleic anhydride and a (poly) oxypropylene derivative. Here, as the partial ester (B) of the maleic anhydride and the (poly) oxypropylene derivative, the following general formula (XIII):

[In the formula (XIII), r is a number of 1 or more representing the average degree of polymerization; R ²⁰ is an alkyl group, an alkenyl group, an alkylaryl group or an acyl group] is preferred. In formula (XIII), it is more preferable that r is 3 to 7 and R ²⁰ is an alkyl group or alkenyl group having 8 to 18 carbon atoms.

  The partial ester (B) can be obtained by reacting maleic anhydride with a (poly) oxypropylene derivative. Here, as the (poly) oxypropylene derivative, polyoxypropylene lauryl ether, polyoxypropylene myristyl ether, polyoxypropylene decyl ether, polyoxypropylene octyl ether, polyoxypropylene-2-ethylhexyl ether, polyoxypropylene stearyl ether And polyoxypropylene aliphatic ethers such as polyoxypropylene oleyl ether; polyoxypropylene aromatic ethers such as polyoxypropylene benzyl ether, polyoxypropylene alkylphenyl ether, polyoxypropylene benzylated phenyl ether, and the like. Among these, polyoxypropylene aliphatic ether is preferable, and polyoxypropylene lauryl ether is particularly preferable.

  Further, it is more preferable that the degree of polymerization of the oxypropylene unit is 3 to 7, particularly 5, and the alkyl group or alkenyl group has 8 to 18 carbon atoms. Specifically, if polyoxypropylene is abbreviated as POP (r) and r is an average degree of polymerization, POP (3) octyl ether, POP (4) 2-ethylhexyl ether, POP (3) decyl ether, POP (5) Decyl ether, POP (3) lauryl ether, POP (5) lauryl ether, POP (8) lauryl ether, POP (1) stearyl ether, POP (5) myristyl ether and the like. The above (poly) oxypropylene derivatives may be used alone or in combination of two or more.

  The partial ester (B) of the maleic anhydride and the (poly) oxypropylene derivative may contain raw material maleic anhydride. In this case, the content of maleic anhydride is preferably 10% by mass or less, and more preferably 5% by mass or less. Further, the partial ester (B) of maleic anhydride and a (poly) oxypropylene derivative may contain a raw material (poly) oxypropylene derivative. In this case, the content of the (poly) oxypropylene derivative is preferably 40% by mass or less, and more preferably 20% by mass or less.

  The blending amount of the partial ester (B) of the maleic anhydride and the (poly) oxypropylene derivative is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount of the partial ester (B) of maleic anhydride and (poly) oxypropylene derivative is less than 1 part by mass with respect to 100 parts by mass of the rubber component, the effect of reducing the viscosity when unvulcanized is small, 30 masses If it exceeds the part, the cost becomes high.

[Silica (C)]
Furthermore, the rubber composition used in the present invention contains silica (C). Here, the compounding amount of the silica (C) is preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the rubber component. When the compounding amount of silica (C) is less than 10 parts by mass with respect to 100 parts by mass of the rubber component, the effect of reducing the rolling resistance of the tire and the effect of improving the braking performance and driving stability on wet road surfaces are low, and 200 parts by mass. If it exceeds 1, the unvulcanized viscosity of the rubber composition may increase and workability may decrease. The silica (C) used in the rubber composition used in the present invention is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate and the like. Among these, wet silica is most preferable because it has the most remarkable effects of improving the fracture resistance, braking performance on wet road surfaces, steering stability (wet grip properties), and low rolling resistance. The silica (C) preferably has a BET surface area of 40 to 350 m ² / g. Silica having a BET surface area within this range has an advantage that both rubber reinforcement and dispersibility in the rubber component can be achieved. From this viewpoint, silica having a BET surface area in the range of 80 to 300 m ² / g is more preferable. When the BET surface area of the silica (C) is less than 40 m ² / g, may wear resistance is greatly reduced for the particle size of the silica is too large, also, BET surface area of the silica (C) is 350 meters ² / When it exceeds g, since the particle diameter of the silica is too small, the hysteresis loss is greatly increased.

[Other compounding agents in rubber composition]
In addition to the rubber component, organosilicon compound (A), partial ester (B) of maleic anhydride and (poly) oxypropylene derivative, silica (C), the rubber composition used in the present invention is used in the rubber industry. Commonly used compounding agents such as carbon black, softening agent, vulcanizing agent, vulcanization accelerator, anti-aging agent, zinc white, stearic acid and the like can be appropriately compounded according to the purpose. As these compounding agents, commercially available products can be suitably used. The rubber composition was appropriately selected as necessary together with the organosilicon compound (A), the partial ester (B) of maleic anhydride and (poly) oxypropylene derivative, and silica (C) as the rubber component. It can be produced by blending various compounding agents, kneading, heating, extruding and the like.

[tire]
Thus, the tire of the present invention is characterized by using the above-mentioned rubber composition, and it is preferable that the above-mentioned rubber composition is further used for the tread. The tire of the present invention is excellent in wear resistance. The tire of the present invention has a conventionally known structure and is not particularly limited, and can be produced by a normal method. In addition, when the tire of the present invention is a pneumatic tire, the gas filled in the tire may be normal or air with adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium. .

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Production Example of Organosilicon Compound X]
In a 500 mL four-necked eggplant flask, 3-ethanoylthio-propyltriethoxysilane [represented by the formula (I), A ¹ is the formula (III), R ¹ is —O—CH ₂ CH ₃ , R ₂ is —O—CH ₂ CH ₃ , R ³ is —O—CH ₂ CH ₃ , R ⁴ is —CH ₂ CH ₂ CH ₂ —, R ⁵ is —CH ₃ , and x is 1. A certain compound] 46 g, N-methyldiethanolamine 20 g, titanium tetra n-butoxide 0.8 g and toluene 220 mL were weighed. Next, while stirring with a mechanical stirrer and flowing dry nitrogen (0.2 L / min), the flask was heated in an oil bath, a Dimroth condenser was attached, and reflux was performed for 11 hours. Thereafter, the solvent is removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components are removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol) to obtain 56 g of a yellow transparent liquid. Obtained. When the obtained organosilicon compound X was analyzed by ¹ H-NMR, 0.7 (t; 2H), 1.0 (s; 3H), 1.6 (m; 2H), 2.4 (m; 3H), 2.5 (m; 4H ), 2.8 (t; 2H), 3.8 (m; 4H), represented by formula (VIII), A ² is formula (III), W is -N (CH ₃ )-, R ¹² Is —O—CH ₂ CH ₂ — (where the O side is linked to Si), R ₁₃ is —O—CH ₂ CH ₂ — (where the O side is linked to Si), and R ¹⁴ is —O—CH _2. It was found to be a compound in which CH ₃ , R ⁴ is —CH ₂ CH ₂ CH ₂ —, R ⁵ is —CH ₃ , and x is 1.

[Example 1]
100 parts by mass of emulsion polymerization SBR is kneaded with a mixer at 65 rpm and a starting temperature of 105 ° C. for 30 seconds. After mixing and kneading in the amount shown in 1, the kneaded product was discharged and formed into a sheet with a roll. Next, the obtained sheet-like kneaded product was kneaded with a mixer at 65 rpm and a start temperature of 105 ° C., and the kneaded product was discharged and formed into a sheet again with a roll.

  After sufficiently cooling the sheet-like kneaded material obtained as described above at room temperature, mono [POP (5) lauryl ether] maleic acid ester, zinc white, vulcanization accelerator A, vulcanization accelerator B, Sulfur accelerator C and sulfur were added in the amounts shown in Table 1, and a rubber composition was obtained by kneading with a mixer at 50 rpm and starting temperature of 80 ° C.

[Comparative Example 1]
In Example 1, a rubber composition was obtained in the same manner as in Example 1 except that mono [POP (5) lauryl ether] maleic acid ester was not blended.

[Comparative Example 2]
In Example 1, instead of the organosilicon compound X, the silane compound of the kind and amount shown in Table 1 was added, and the mono [POP (5) lauryl ether] maleic acid ester was not blended. A rubber composition was obtained in the same manner.

[Comparative Example 3]
In Example 1, instead of the organosilicon compound X, a rubber composition was obtained in the same manner as in Example 1 except that the types and amounts of silane compounds shown in Table 1 were added.

[Comparative Example 4]
In Example 1, instead of the organosilicon compound X, the silane compound of the kind and amount shown in Table 1 was added, and the mono [POP (5) lauryl ether] maleic acid ester was not blended. A rubber composition was obtained in the same manner.
Next, the Mooney viscosity and abrasion resistance of the obtained rubber composition were measured by the following methods. The results are shown in Table 1.

<Mooney viscosity>
In accordance with JIS K6300-1994, Mooney viscosity ML _{1 + 4} (130 ° C.) was measured at 130 ° C., and the value of Comparative Example 2 was set to 100 and displayed as an index. A smaller index value indicates a lower Mooney viscosity (unvulcanized viscosity) and better workability.

《Abrasion resistance》
A vulcanized rubber obtained by vulcanizing the above rubber composition at 160 ° C. for 20 minutes is compliant with JIS K 6264-2: 2005, and has a slip rate of 60% at room temperature using a Lambone type wear tester. The test was performed under the conditions, and the index was displayed with the reciprocal of the wear amount of Comparative Example 2 as 100. The larger the index value, the smaller the wear amount and the better the wear resistance.

* 1: Emulsion polymerization SBR, # 1500, manufactured by JSR
* 2: Nippon Silica Kogyo Co., Ltd., nip seal AQ, BET surface area = 220 m ² / g
* 3: Bis (3-triethoxysilylpropyl) disulfide * 4: Shin-Etsu Chemical Co., Ltd., 3-mercaptopropyltriethoxysilane * 5: Ouchi Shinsei Chemical Co., Ltd., NOCRACK 6C
* 6: Nocrack 224, manufactured by Ouchi Shinsei Chemical Industries, Ltd.
* 7: Sunseller D, manufactured by Sanshin Chemical Industry
* 8: Sunsell DM, manufactured by Sanshin Chemical Industry
* 9: Sunseller NS, manufactured by Sanshin Chemical Industry

  According to Table 1, in place of the conventional silane coupling agent (3-mercaptopropylethoxysilane), the organosilicon compound X and the partial ester (B) of maleic anhydride and (poly) oxypropylene derivative are silica. It can be seen that by blending with the contained rubber composition, the unvulcanized viscosity can be greatly reduced and workability can be greatly improved while the wear resistance is equally secured.

  On the other hand, when other conventional silane coupling agents are used (comparative example 4) in order to improve the wear resistance than when the conventional silane coupling agent is used (Comparative Example 2), the improvement of the wear resistance is It can be seen that the Mooney viscosity is very high, but the workability deteriorates. When the partial ester (B) was added to this (Comparative Example 3), the Mooney viscosity decreased to some extent, but was still not at a level showing good workability.

  Here, when the organosilicon compound X was used (Comparative Example 1), the wear resistance was improved as in Comparative Example 4, but the Mooney viscosity was high and the workability was deteriorated. However, as shown in Example 1, by combining the organosilicon compound X and the partial ester (B), the Mooney viscosity was lowered and more excellent than Comparative Example 2 using a conventional silane coupling agent. It was found to exhibit wear resistance.

Claims (23)

  Organosilicon compound having one or more silicon-oxygen bonds and one or more sulfur atoms in the molecule, and having one or more nitrogen atoms at a position 3 to 8 atoms away from the silicon atoms ( A tire comprising a rubber composition comprising A), a partial ester (B) of maleic anhydride and a (poly) oxypropylene derivative, and silica (C).   The tire according to claim 1, wherein the organosilicon compound (A) has 1 to 6 silicon-oxygen bonds and 1 to 10 sulfur atoms in the molecule. The organosilicon compound (A) is represented by the following general formula (I):

[Wherein A ¹ represents the following general formula (II) or formula (III):

Represented by
At least one of R ¹ , R ² and R ³ in formula (I) and formula (II) is the following general formula (IV) or formula (V):

(In the formula, M is —O— or —CH ₂ —, X and Y are independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R. ⁹ or -R ⁸ , R ⁷ is -NR ⁸ R ⁹ , -NR ⁸ -NR ⁸ R ⁹ or -N = NR ⁸ , provided that R ⁸ is -C _n H _{2n + 1} , R ⁹ is a _{-C q H 2q + 1, l} , m, n and q are represented by each independently a 0-10), others _{-M-C l H 2l + 1} ( wherein, M and l is as defined above, provided that at ^{least one} of R ¹ , R ² and R ³ is M is —O—;
R ⁴ represents the following general formula (VI) or formula (VII):

(In the formula, M, X, Y, R ⁶ , l and m are as defined above, and R ¹⁰ is —NR ⁸ —, —NR ⁸ —NR ⁸ — or —N═N—, wherein R ⁸ Is as defined above) or -M-C ₁ H _2l- (wherein M and l are as defined above),
R ⁵ in formula (III) is the above general formula (IV), formula (V), or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ —NR ⁸ R ^9). -N = NR ⁸ or -M-C _m H _{2m + 1} , wherein R ⁸ , R ⁹ , M, l and m are as defined above.
The tire according to claim 1, wherein x is 1 to 10. The organosilicon compound (A) is represented by the following general formula (VIII):

[In the formula, A ² represents the following general formula (IX) or formula (III):

Represented by
W in formula (VIII) and formula (IX) is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ ; However, R ⁷ is -NR ⁸ R ^9, a -NR ⁸ -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is -C _q H _{2q + 1} M, n and q are each independently 0 to 10),
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 10),
R ¹⁴ is -M-C _l H _{2l + 1} or ^{_{-M-C l H 2l -R 7}} ( wherein, M, R ⁷ and l has the same meaning as mentioned above) is represented by, where, R ^12, One or more of R ¹³ and R ¹⁴ is M is —O—;
R ⁴ represents the following general formula (VI) or formula (VII):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are as defined above), or -MC _l H _2l- (wherein M and l are as defined above),
R ⁵ in the formula (III) is the following general formula (IV) or formula (V):

(Wherein, M, X, Y, R ⁶ , R ⁷ , l and m are as defined above) or —C ₁ H _2l —R ¹¹ (where R ¹¹ is —NR ⁸ R ⁹ , —NR ⁸ -NR ⁸ R ⁹ , -N = NR ⁸ or -M-C _m H _{2m + 1} , wherein R ⁸ , R ⁹ , M, l and m are as defined above.
The tire according to claim 1, wherein x is 1 to 10.   The tire according to claim 3 or 4, wherein in the organosilicon compound (A), the M is -O-. In the organosilicon compound (A), at least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —R ⁷ (where R ⁷ and 1 are as defined above). And the others are represented by -O-C _l H _{2l + 1} (where l is as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The tire according to claim 3 or 5, wherein R ⁵ is represented by -C _l H _2l -R ¹¹ (wherein R ¹¹ and l are as defined above). In the organosilicon compound (A), at least one of the R ¹ , R ² and R ³ is —O—C ₁ H _{2 1} —NR ⁸ R ⁹ (where R ⁸ , R ⁹ and 1 are as defined above). It is expressed by
The tire according to claim 3, 5 or 6, wherein R ⁵ is represented by -C _l H _{2l + 1} (where l is as defined above). In the organosilicon compound (A), the W is represented by —NR ⁸ — (wherein R ⁸ is as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁴ is represented by —O— _Cl H _2l —R ⁷ (wherein R ⁷ and l are as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The tire according to claim 4 or 5, wherein R ⁵ is represented by -C _l H _{2l + 1} (where l is as defined above). In the organosilicon compound (A), the W is represented by —O— or —CR ⁸ R ⁹ — (wherein R ⁸ and R ⁹ are as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁴ is represented by —O—C ₁ H _{2 1} —NR ⁸ R ⁹ (wherein R ⁸ , R ⁹ and l are as defined above),
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The tire according to claim 4 or 5, wherein R ⁵ is represented by -C _l H _{2l + 1} (where l is as defined above).   The organosilicon compound (A) has a site in the molecule having a cyclic structure containing a nitrogen atom and a silicon atom, and one or more groups having small steric hindrance bonded to the silicon atom. The tire according to claim 1 or 2.   11. The tire according to claim 10, wherein in the organosilicon compound (A), the group having a small steric hindrance is at least one selected from the group consisting of a hydrogen atom, a methyl group, and a hydroxyl group. The organosilicon compound (A) is represented by the following general formula (X):

[Wherein A ³ is a group containing a sulfur atom and reacting with a rubber component,
W is —NR ⁸ —, —O— or —CR ⁸ R ¹⁵ — (wherein R ¹⁵ is —R ⁹ or —C _m H _2m —R ⁷ , where R ⁷ is —NR ⁸ R ⁹ , -NR ⁸ is -NR ⁸ R ⁹ or -N = NR ^8, R ⁸ is _{-C n H 2n + 1, R} 9 is _{-C q H 2q + 1, m} , n and q are each independently 0 to 10)
R ¹² and R ¹³ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 10), provided that R ^At least one of ¹² and R ¹³ is M is —O—;
The tire according to claim 10, wherein R ¹⁶ is a hydrogen atom, a methyl group or a hydroxyl group. In the organosilicon compound (A), the group containing the sulfur atom and reacting with the rubber component is a polysulfide group, a thioester group, a thiol group, a dithiocarbonate group, a dithioacetal group, a hemithioacetal group, a vinylthio group, α- It includes at least one selected from the group consisting of a thiocarbonyl group, a β-thiocarbonyl group, an S—CO—CH ₂ —O moiety, an S—CO—CO moiety, and an S—CH ₂ —Si moiety. The tire according to claim 10.   The tire according to claim 13, wherein in the organosilicon compound (A), a group containing the sulfur atom and reacting with a rubber component contains at least one of a polysulfide group and a thioester group. In the organosilicon compound (A), the A ³ is represented by the following general formula (XI) or (XII):

[W, R ¹² , R ¹³ and R ¹⁶ in the formula (XI) are as defined above,
R ^{4 in} formula (XI) and formula (XII) is the following general formula (VI) or formula (VII):

Wherein M, l and m are as defined above, X and Y are each independently —O—, —NR ⁸ — or —CH ₂ —, and R ⁶ is —OR ⁸ , —NR ⁸ R ⁹ or -R ^8, R ¹⁰ is ^{-NR 8 -, - NR 8 -NR} 8 - or -N = a N-, provided that, R ⁸ and R ⁹ are as defined above) or -M-C _l H _2l- (wherein M and l are as defined above),
R ¹⁷ in formula (XII) is the following general formula (IV) or formula (V):

Wherein M, X, Y, R ⁶ , R ⁷ , l and m are as defined above, or —C ₁ H _2l —R ¹⁸ (where R ¹⁸ is —NR ⁸ R ⁹ , —NR ⁸ -NR ⁸ R ⁹ , -N = NR ⁸ or -M-C _m H _{2m + 1} or an aromatic hydrocarbon group having 6 to 20 carbon atoms, provided that R ⁸ , R ⁹ , M, l and m Is synonymous with the above),
The tire according to claim 12, wherein x in the formulas (XI) and (XII) is 1 to 10.   The tire according to claim 12 or 15, wherein in the organosilicon compound (A), the M is -O-. In the organosilicon compound (A), the W is represented by —NR ⁸ — (wherein R ⁸ is as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁶ is a hydrogen atom, a methyl group or a hydroxyl group,
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
R ¹⁷ is a linear or branched alkyl group represented by —C _l H _{2l + 1} (wherein l is as defined above), or an aromatic hydrocarbon group having 6 to 20 carbon atoms. The tire according to claim 15 or 16, wherein there is a tire. In the organosilicon compound (A), the W is represented by —O— or —CR ⁸ R ⁹ — (wherein R ⁸ and R ⁹ are as defined above),
R ¹² and R ¹³ are each independently represented by —O—C ₁ H _2l — (wherein l is as defined above),
R ¹⁶ is a hydrogen atom, a methyl group or a hydroxyl group,
R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above),
The tire according to claim 15 or 16, wherein the R ¹⁷ is represented by -C _l H _{2l + 1} (where l is as defined above).   The rubber composition comprises 1 to 30 parts by mass of a partial ester (B) of the maleic anhydride and a (poly) oxypropylene derivative, and 10 to 200 parts by mass of the silica (C) with respect to 100 parts by mass of the rubber component. The tire according to any one of claims 1 to 18, further comprising 1 to 20% by mass of the organosilicon compound (A) in an amount of the silica (C). . The tire according to any one of claims 1 to 19, wherein the silica (C) has a BET surface area of 40 to 350 m ² / g.   The tire according to claim 19, wherein the rubber component is a diene rubber.   The tire according to any one of claims 1 to 21, wherein an average degree of polymerization of an oxypropylene portion of the (poly) oxypropylene derivative is 3 to 7.   The tire according to any one of claims 1 to 22, wherein the (poly) oxypropylene derivative is polyoxypropylene lauryl ether.