JP2010248155A - Organosilicon compound, rubber composition using the same and tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a new compound that greatly reduces hysteresis loss and largely improves abrasion resistance without accelerating scorch of rubber composition; a rubber composition using the compound; and a tire using the rubber composition. <P>SOLUTION: The organosilicon compound contains: one or more nitrogen atoms and one or more sulfur atoms in a molecule; and one or more silicon-oxygen bonds. In the organosilicon compound, an electron withdrawing substituent is added to at least one of the nitrogen atoms or at least one of the nitrogen atoms forms an ammonium salt structure. The rubber composition is obtained by mixing a rubber component (A) composed of a natural rubber and/or a diene-based synthetic rubber with an inorganic filler (B) and the organosilicon compound (C). The tire uses the rubber composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an organosilicon compound, a rubber composition containing the organosilicon compound, and a tire using the rubber composition, and in particular, reduces hysteresis loss and wear resistance without accelerating scorching of the rubber composition. The present invention relates to an organosilicon compound capable of improving the properties.

  Recently, from the viewpoint of vehicle safety, it is required to improve the safety of tires on wet road surfaces. In addition, from the viewpoint of reducing carbon dioxide emissions due to increased interest in environmental issues, it is also required to further reduce fuel consumption of vehicles.

  In response to these demands, conventionally, as a technique for achieving both improvement in performance on a wet road surface of a tire and reduction in rolling resistance, a technique of using an inorganic filler such as silica as a filler of a rubber composition used for a tire tread is known. It is known to be effective. However, the rubber composition containing an inorganic filler such as silica reduces the rolling resistance of the tire, improves the braking performance on the wet road surface, and improves the handling stability, but has a high unvulcanized viscosity and multistage kneading. Therefore, there is a problem in workability. Therefore, in a rubber composition containing an inorganic filler such as silica, the breaking strength and wear resistance are greatly reduced, and problems such as vulcanization delay and poor filler dispersion occur. Therefore, when an inorganic filler such as silica is blended with the rubber composition for tread, the unvulcanized viscosity of the rubber composition is reduced, the modulus and wear resistance are ensured, and the hysteresis loss is further reduced. It is essential to add a silane coupling agent.

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

  However, since the silane coupling agent is expensive, the blending cost increases due to the blending of the silane coupling agent. Also, the addition of a dispersion improver decreases the unvulcanized viscosity of the rubber composition and improves workability, but also decreases the wear resistance. Furthermore, when the dispersion improver is a highly ionic compound, a decrease in workability such as roll adhesion is also observed. Furthermore, as a result of investigation by the present inventors, even when an inorganic filler such as silica is blended as a filler, even when a conventional silane coupling agent is added, the hysteresis loss of the rubber composition is reduced and the wear resistance is reduced. However, it was found that there was still room for improvement.

  On the other hand, the present inventors, as a result of intensive studies, have a functional group having a high affinity with a silanol group on the silica surface or a functional group having a high affinity with a silicon atom in the molecular structure of the silane coupling agent. It has been found that the reaction between silane and silica can be promoted by introducing, and as a result, the efficiency of the coupling reaction can be improved, and a reduction in hysteresis and an improvement in wear resistance can be achieved simultaneously. And as such a coupling agent, it discovered that a highly basic compound can accelerate | stimulate especially the reaction between silane-silica, but this compound had the problem of accelerating scorch of a rubber composition simultaneously.

  Accordingly, an object of the present invention is to provide a novel compound capable of greatly reducing hysteresis loss and greatly improving wear resistance without accelerating scorching of a rubber composition. Another object of the present invention is to provide a rubber composition containing such a compound and a tire using the rubber composition.

  As a result of diligent studies to achieve the above object, the present inventors have found that an organosilicon compound containing a nitrogen atom and a sulfur atom in the molecule and having a silicon-oxygen bond, wherein the nitrogen atom has an electron-withdrawing substitution. Organosilicon compounds with added groups or nitrogen atoms forming an ammonium salt structure have a high reaction rate with inorganic fillers such as silica, so these organosilicon compounds are blended with rubber components together with inorganic fillers. As a result, the efficiency of the coupling reaction is improved, the hysteresis loss of the rubber composition is greatly reduced, and the wear resistance is greatly improved, and the scorching of the rubber composition is not accelerated. As a result, the present invention has been completed.

That is, the organosilicon compound of the present invention contains at least one nitrogen atom and one sulfur atom in the molecule, and has at least one silicon-oxygen bond,
An electron-withdrawing substituent is added to at least one of the nitrogen atoms, or at least one of the nitrogen atoms forms an ammonium salt structure.

［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、ｌ、ｍ及びｎはそれぞれ独立して０〜１０で、ＸはＦ、Ｃｌ、Ｂｒ、Ｉ、ＢＦ₄、ＰＦ₆、Ｒ⁷ＣＯ₂又はＲ⁷ＳＯ₃で、Ｒ⁶は下記式(VI)：

（式中、Ａ²はＣ、Ｎ、Ｓ又はＰで、Ｚは＝Ｏ又は＝ＮＲ⁷で、Ｙ¹は−Ｏ−、−ＮＲ⁷−又は−Ｓ−で、ｌは０〜１０で、Ａ²がＣの場合、ｐは０〜１、ｑは１〜３、２ｐ＋ｑは３で、Ａ²がＮの場合、ｐは０〜１、ｑは０〜２、２ｐ＋ｑは２で、Ａ²がＳの場合、ｐは０〜２、ｑは１で、２ｐ＋ｑは１〜５で、Ａ²がＰの場合、ｐは０〜２、ｑは０〜４、２ｐ＋ｑは４である）で表わされ、但し、Ｒ⁷は水素原子又は炭素数１〜１２の直鎖若しくは分岐鎖アルキル基である}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、
式(I)及び式(II)中のＲ⁴は−Ｙ²−Ｃ_lＨ_2l−（ここで、Ｙ²は−Ｏ−、−ＮＲ⁶−、−Ｎ⁺(Ｃ_mＨ_2m+1)₂・Ｘ^-−、−ＣＨ₂−又は単結合で、但し、Ｒ⁶、Ｘ、ｌ及びｍは上記と同義である）で表わされ、
式(III)中のＲ⁵は−Ｙ³−Ｃ_lＨ_2l+1（ここで、Ｙ³は−Ｏ−、−Ｓ−、−Ｎ(Ｃ_mＨ_2m+1)−又は−ＣＨ₂−で、但し、ｌ及びｍは上記と同義である）で表わされ、
ｘは１〜６である］で表わされる有機ケイ素化合物が好ましい。ここで、前記Ｒ⁶が下記式(a)〜(g)：

［式中、ｌ及びｍはそれぞれ独立して０〜１０である］のいずれかで表わされ、前記Ｒ⁴が−Ｃ_lＨ_2l−［式中、ｌは０〜１０である］で表わされることが特に好ましい。 As the organosilicon compound of the present invention, 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 —, l, m and n are each independently 0 to 10, and X is F, Cl, Br, I, BF ₄ , PF ₆ , R ⁷ CO ₂ or R ⁷ SO ₃ , R ⁶ is the following formula (VI):

(Wherein A ² is C, N, S or P, Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, and l is 0 to 10, When A ² is C, p is 0 to 1, q is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, A ² Table If is S, p is 0 to 2, q is 1, 2p + q is 1-5, when a ² is P, p is 0 to 2, q is 0~4,2p + q is 4) Provided that R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms}, and the others are -M-C ₁ H _{2l + 1} (where M and 1 Are as defined above, provided that one or more of R ¹ , R ² and R ³ is M is —O—,
R ^{4 in} formula (I) and formula (II) is —Y ² —C ₁ H _2l — (where Y ² is —O—, —NR ⁶ —, —N ⁺ (C _m H _{2m + 1} )). ₂ · X ⁻ —, —CH ₂ — or a single bond, wherein R ⁶ , X, l and m are as defined above,
R ⁵ in formula (III) is —Y ³ —C ₁ H _{2l + 1} (where Y ³ is —O—, —S—, —N (C _m H _{2m + 1} ) — or —CH ₂ —). Where l and m are as defined above),
x is 1 to 6] is preferred. Here, R ⁶ represents the following formulas (a) to (g):

[Wherein l and m are each independently 0 to 10], and R ⁴ is represented by —C ₁ H _2l — [wherein l is 0 to 10]. It is particularly preferred that

［式中、Ａ³は、下記一般式(VIII)又は式(III)：

で表わされ、
式(VII)及び式(VIII)中のＷは−ＮＲ⁶−{ここで、Ｒ⁶は下記式(VI)：

（式中、Ａ²はＣ、Ｎ、Ｓ又はＰで、Ｚは＝Ｏ又は＝ＮＲ⁷で、Ｙ¹は−Ｏ−、−ＮＲ⁷−又は−Ｓ−で、ｌは０〜１０で、Ａ²がＣの場合、ｐは０〜１、ｑは１〜３、２ｐ＋ｑは３で、Ａ²がＮの場合、ｐは０〜１、ｑは０〜２、２ｐ＋ｑは２で、Ａ²がＳの場合、ｐは０〜２、ｑは１で、２ｐ＋ｑは１〜５で、Ａ²がＰの場合、ｐは０〜２、ｑは０〜４、２ｐ＋ｑは４である）で表わされる}又は下記式(IX)若しくは式(X)：

（式中、Ｒ⁶は上記と同義で、ＸはＦ、Ｃｌ、Ｂｒ、Ｉ、ＢＦ₄、ＰＦ₆、Ｒ⁷ＣＯ₂又はＲ⁷ＳＯ₃で、ｌ、ｍ及びｎはそれぞれ独立して０〜１０である）で表わされ、
式(VII)及び式(VIII)中のＲ⁸及びＲ⁹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、Ｒ¹⁰は−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、Ｒ⁸、Ｒ⁹及びＲ¹⁰の一つ以上はＭが−Ｏ−であり、
式(VII)及び式(VIII)中のＲ¹¹は−Ｙ⁴−Ｃ_lＨ_2l−（ここで、Ｙ⁴は−Ｏ−、−ＣＨ₂−又は単結合で、但し、ｌは上記と同義である）で表わされ、
式(III)中のＲ⁵は−Ｙ³−Ｃ_lＨ_2l+1（ここで、Ｙ³は−Ｏ−、−Ｓ−、−Ｎ(Ｃ_mＨ_2m+1)−又は−ＣＨ₂−で、但し、ｌ及びｍは上記と同義である）で表わされ、
ｘは１〜６である］で表わされる有機ケイ素化合物も好ましい。ここで、前記Ｒ⁶が下記式(a)〜(g)：

［式中、ｌ及びｍはそれぞれ独立して０〜１０である］のいずれかで表わされ、前記Ｒ¹¹が−Ｃ_lＨ_2l−［式中、ｌは０〜１０である］で表わされることが特に好ましい。 The organosilicon compound of the present invention includes the following general formula (VII):

Wherein, A ³ is represented by the following general formula (VIII) or formula (III):

Represented by
In formula (VII) and formula (VIII), W represents —NR ⁶ — {where R ⁶ represents the following formula (VI):

(Wherein A ² is C, N, S or P, Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, and l is 0 to 10, When A ² is C, p is 0 to 1, q is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, A ² If is S, p is 0 to 2, q is 1, 2p + q is 1-5, when a ² is P, p is 0 to 2, q is represented by 0~4,2p + q is 4) Or the following formula (IX) or formula (X):

Wherein R ⁶ is as defined above, X is F, Cl, Br, I, BF ₄ , PF ₆ , R ⁷ CO ₂ or R ⁷ SO ₃ , and l, m and n are each independently 0 10)
R ⁸ and R ^{9 in} formula (VII) and formula (VIII) are each independently —M—C ₁ H _{2 1} — (where M is —O— or —CH ₂ —, and 1 is 0 to 10 R ¹⁰ is represented by -M-C _l H _{2l + 1} (where M and l are as defined above), provided that R ⁸ , R ⁹ and R ¹⁰ are One or more M is -O-;
R ^{11 in} formula (VII) and formula (VIII) is —Y ⁴ —C ₁ H _2l — (where Y ⁴ is —O—, —CH ₂ — or a single bond, where l is as defined above. It is expressed by
R ⁵ in formula (III) is —Y ³ —C ₁ H _{2l + 1} (where Y ³ is —O—, —S—, —N (C _m H _{2m + 1} ) — or —CH ₂ —). Where l and m are as defined above),
An organosilicon compound represented by x is 1 to 6] is also preferable. Wherein said R ⁶ is represented by the following formula (a) ~ (g):

Wherein, l and m are each independently from 0 to 10] represented by any one of the R ¹¹ is -C _l H _2l - represented by [wherein, l is 0-10] It is particularly preferred that

  In the preferred organosilicon compound, M is preferably —O—.

  Moreover, the rubber composition of the present invention comprises an inorganic filler (B) and the above organosilicon compound (C) in a rubber component (A) made of natural rubber and / or a diene synthetic rubber. It is characterized by becoming.

The rubber composition of the present invention is obtained by blending 5 to 140 parts by mass of the inorganic filler (B) with respect to 100 parts by mass of the rubber component (A) composed of the natural rubber and / or the diene synthetic rubber.
Furthermore, it is preferable that 1-20 mass% of the compounding quantity of the said inorganic filler (B) is included for the said organosilicon compound (C).

  In the rubber composition of the present invention, the organosilicon compound (C) preferably has a purity of 80% or more.

In a preferred example of the rubber composition of the present invention, the inorganic filler (B) is silica or aluminum hydroxide. Wherein the silica is preferably BET surface area of 40~350 m ² / g.

  The tire of the present invention is characterized by using the above rubber composition.

  According to the present invention, it contains a nitrogen atom (N) and a sulfur atom (S), has a silicon-oxygen bond (Si-O), and an electron-withdrawing substituent is added to the nitrogen atom (N). Or has a specific molecular structure in which the nitrogen atom (N) forms an ammonium salt structure, significantly lowering the hysteresis loss and speeding up the wear resistance without accelerating the scorching of the rubber composition An organosilicon compound that can be produced can be provided. Moreover, the rubber composition containing this organosilicon compound and the tire using this rubber composition can be provided.

<Organic silicon compound>
The present invention is described in detail below. The organosilicon compound of the present invention contains at least one nitrogen atom (N) and one sulfur atom (S) in the molecule, and at least one silicon-oxygen bond (Si-O). An electron-withdrawing substituent is added to at least one of the nitrogen atoms (N), or at least one of the nitrogen atoms (N) forms an ammonium salt structure. In the organosilicon compound, an unshared electron pair of a nitrogen atom in a molecular structure can participate in a reaction between a silane coupling agent and an inorganic filler such as silica, and the speed of the coupling reaction is high. Therefore, by adding the organosilicon compound of the present invention to the inorganic filler-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 reduced. It is possible to greatly improve the wear resistance while greatly reducing. In addition, since the organosilicon compound of the present invention has high addition efficiency, a high effect can be obtained even in a small amount, and it contributes to reduction of the blending cost. Furthermore, the organosilicon compound of the present invention has an electron-withdrawing substituent added to at least one of the nitrogen atoms (N), or at least one of the nitrogen atoms (N) forms an ammonium salt structure, Although the polarity is high but the basicity is low, the scorch time of the rubber composition is not shortened.

Here, examples of the electron-withdrawing substituent added to the nitrogen atom (N) include a substituent represented by the above formula (VI). In the formula (VI), A ² represents C, N, S or P. Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, l is 0 to 10, and when A ² is C, p is 0 to 1, q Is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, and when A ² is S, p is 0 to 2, q is 1 2p + q is 1-5, and when A ² is P, p is 0-2, q is 0-4, and 2p + q is 4. Here, R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and examples of the linear or branched alkyl group 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, a decyl group, a dodecyl group, etc. are mentioned. 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.

The ammonium salt structure formed by the nitrogen atom (N) is not particularly limited, and examples thereof include a structure in which an ammonium ion and an arbitrary anion are ionically bonded. Here, examples of the anion include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , R ⁷ CO ₂ ⁻ or R ⁷ SO ₃ ⁻ . R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, heptyl group, octyl group, decyl group, dodecyl group and the like.

  More specifically, the organosilicon compound of the present invention is preferably a compound represented by the above general formula (I) and a compound represented by the above general formula (VII). These organosilicon compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

<< Compound of Formula (I) >>
In the above general formula (I), A ¹ is represented by the above general formula (II) or formula (III), and x is 1-6. 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 ₁ 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 (V), m is 0 to 10, and n is 0 to 10. Here, l, m, and n may be the same or different. Note that −C _l H _{2l + 1} is as described above. Further, -C _m H _{2m + 1} and -C _n H _{2n + 1} is, for m and n 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. Moreover, since l is 0 to 10, -C _l 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 formula (IV), R ⁶ is represented by the above formula (VI). In the formula (VI), A ² is C, N, S or P, Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, and l is 0 to 10 When A ² is C, p is 0 to 1, q is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, When A ² is S, p is 0 to 2, q is 1, 2p + q is 1 to 5, and when A ² is P, p is 0 to 2, q is 0 to 4, and 2p + q is 4. Here, R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and examples of the linear or branched alkyl group 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, a decyl group, a dodecyl group, etc. are mentioned. Note that −C _l H _{2l + 1} is as described above.

In the above formula (V), X is F, Cl, Br, I, BF ₄ , PF ₆ , R ⁷ CO ₂ or R ⁷ SO ₃ . R ⁷ is as described above.

In the above formula (I) and formula (II), R ⁴ is represented by —Y ² —C ₁ H _2l —. Here, Y ² is —O—, —NR ⁶ —, —N ⁺ (C _m H _{2m + 1} ) ₂ .X ⁻ —, —CH ₂ — or a single bond, and l and m are each independently 0 to 10, and R ⁶ and X are as described above. Incidentally, -C _l H _2l - is as described above and -C _m H _{2m + 1.}

In the above formula (III), R ⁵ is represented by —Y ³ —C ₁ H _{2l + 1} . Here, Y ³ is —O—, —S—, —N (C _m H _{2m + 1} ) — or —CH ₂ —, wherein l is 0 to 10 and m is 0 to 10. In addition, -C _l H _{2l + 1} and -C _m H _{2m + 1} are as described above.

In the compound of the above formula (I), M is preferably —O— (oxygen). In this case, M is -CH ₂ - are highly reactive with an inorganic filler such as silica as compared to compounds wherein.

In the compound of the above formula (I), R ⁶ is preferably represented by any one of the above formulas (a) to (g). Here, l and m are 0 independently, are as described above -C _l H _{2l + 1} and -C _m H _{2m + 1.}

In the compound of the above formula (I), R ⁴ is preferably represented by —C ₁ H _2l —. Here, l is 0~10, -C _l H _2l - is as described above.

<< Compound of Formula (VII) >>
In the general formula (VII), A ³ is represented by the general formula (VIII) or the formula (III), and x is 1-6. Here, x is preferably in the range of 2 to 4 from the viewpoint of achieving both the effect of preventing early vulcanization and sufficient reactivity with the polymer.

In the above formulas (VII) and (VIII), W is represented by —NR ⁶ —, or the above formula (IX) or formula (X), where R ⁶ is represented by the above formula (VI). . In the formula (VI), A ² is C, N, S or P, Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, and l is 0 to 10 When A ² is C, p is 0 to 1, q is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, When A ² is S, p is 0 to 2, q is 1, 2p + q is 1 to 5, and when A ² is P, p is 0 to 2, q is 0 to 4, and 2p + q is 4. R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Group, heptyl group, octyl group, decyl group, dodecyl group and the like.

In the above formulas (IX) and (X), X is F, Cl, Br, I, BF ₄ , PF ₆ , R ⁷ CO ₂ or R ⁷ SO ₃ . R ⁷ is as described above.

In the above formulas (IX) and (X), l is 0 to 10 and m is 0 to 10. Here, l and m may be the same or different. Note that -C _l H _{2l + 1} and -C _m H _{2m + 1} are hydrogen or an alkyl group having 1 to 10 carbon atoms because l and m are 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.

R ⁶ in the above formula (X) is represented by the above formula (VI), and A ² , Z, Y ¹ , l, p, q and —C ₁ H _{2l + 1} in the formula (VI) are the same as those described above. It is as follows.

In the above formulas (VII) and (VIII), R ⁸ and R ⁹ are each independently represented by —M—C ₁ H _2l —, and R ¹⁰ is represented by —M—C ₁ H _{2l + 1.} Where M is —O— or —CH ₂ — and l is 0-10. Provided that M is —O— in one or more of R ⁸ , R ⁹ and R ¹⁰ . 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.

In the above formulas (VII) and (VIII), R ¹¹ is represented by —Y ⁴ —C ₁ H _2l —. Here, Y ⁴ is -O -, - CH ₂ -, or a single bond, l is 0-10. In addition, -C _l H _2l- is as described above.

In the above formula (III), R ⁵ is represented by —Y ³ —C ₁ H _{2l + 1} . Here, Y ³ is —O—, —S—, —N (C _m H _{2m + 1} ) — or —CH ₂ —, wherein l is 0 to 10 and m is 0 to 10. In addition, -C _l H _{2l + 1} and -C _m H _{2m + 1} are as described above.

In the compound of the above formula (VII), M is preferably —O— (oxygen). In this case, M is -CH ₂ - are highly reactive with an inorganic filler such as silica as compared to compounds wherein.

In the compound of formula (VII), R ⁶ is preferably represented by any one of formulas (a) to (g). Here, l and m are 0 independently, are as described above -C _l H _{2l + 1} and -C _m H _{2m + 1.}

Further, in the compound of formula (VII), the R ¹¹ is -C _l H _2l - is preferably represented by the. Here, l is 0~10, -C _l H _2l - is as described above.

<< Synthesis Method of Organosilicon Compound >>
The organosilicon compound of the present invention is represented, for example, by the above general formula (I), R ¹ , R ² and R ³ are represented by -M-C ₁ H _{2 1 + 1} , and R ¹ , R ² and For compounds in which one or more of M in R ³ is —O—, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, 2- (dimethylamino) propanol, 2- (diethylamino) propanol, N An amine compound such as -methyldiethanolamine is added, and an acid such as p-toluenesulfonic acid and hydrochloric acid as a catalyst, and a titanium alkoxide such as titanium tetra-n-butoxide are added and heated, and R ¹ , R ² and R ³ One or more are substituted with a monovalent nitrogen-containing group, or R ¹ and R ² are substituted with a divalent nitrogen-containing group represented by —R ⁸ —W—R ⁹ —. Furthermore, it can be synthesized by adding an iodomethane, methyl bromide, methyl chloride, hydrogen chloride, carboxylic acids, sulfonic acids and the like to form an ammonium salt. Also, instead of the above amine compounds, 2-acetamidoethanol, 3-acetamidopropanol, N- (2-hydroxymethyl) propionamide, N- (2-hydroxyethyl) propionamide, N- (2-hydroxybutyl) propion A compound having an electron-withdrawing group on nitrogen such as amide and N-acetyldiethanol can also be used in the same procedure.

<< Specific Examples of Organosilicon Compounds >>
Specifically, as the organosilicon compound of the present invention, 3-octanoylthio-propyl (monoacetylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (diacetylaminoethoxy) monoethoxysilane, 3-octanoylthio-propyltriacetylamino Ethoxysilane, 3-octanoylthio-propyl (monoiodotrimethylaminoethoxy) diethoxysilane, 3-octanoylthio-propyl (monoiodotrimethylaminopropyloxy) diethoxysilane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa- 5-Dimethyliodoaza-2-silacyclohexane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-dimethyliodoaza-2-silacyclooctane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa -5-Acet Luaza-2-silacyclohexane, 3-octanoylthio-propyl (ethoxy) 1,3-dioxa-6-acetylaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-5-dimethyliodoaza -2-Silacyclohexane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-dimethyliodoaza-2-silacyclooctane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-5-acetylaza- 2-silacyclohexane, 3-octanoylthio-propyl (methyl) 1,3-dioxa-6-acetylaza-2-silacyclooctane, bis (3- (monoacetylaminoethoxy) diethoxysilyl-propyl) disulfide, bis (3 -(Diacetylaminoethoxy) monoethoxysilyl-propyl) disulfide, bis (3- (monodimethyliodoaminoethoxy) ) Diethoxysilyl-propyl) disulfide, bis (3- (didimethyliodoaminoethoxy) monoethoxysilyl-propyl) disulfide, bis (3- (monoacetylaminoethoxy) monoethoxymonomethylsilyl-propyl) disulfide, bis (3 -(Diacetylaminoethoxy) monomethylsilyl-propyl) disulfide, bis (3- (monodimethyliodoaminoethoxy) monoethoxymonomethylsilyl-propyl) disulfide, bis (3- (didimethyliodoaminoethoxy) monomethylsilyl-propyl) disulfide Bis (3- (monoacetylaminoethoxy) diethoxysilyl-propyl) tetrasulfide, bis (3- (diacetylaminoethoxy) monoethoxysilyl-propyl) tetrasulfide, bis (3- (monodimethyliodoaminoethoxy) disulfide Ethoxysilyl-pro Pyr) tetrasulfide, bis (3- (didimethyliodoaminoethoxy) monoethoxysilyl-propyl) tetrasulfide, bis (3- (monoacetylaminoethoxy) monoethoxymonomethylsilyl-propyl) tetrasulfide, bis (3- ( Diacetylaminoethoxy) monomethylsilyl-propyl) tetrasulfide, bis (3- (monodimethyliodoaminoethoxy) monoethoxymonomethylsilyl-propyl) tetrasulfide, bis (3- (didimethyliodoaminoethoxy) monomethylsilyl-propyl) tetra And sulfide.

<Rubber composition>
The rubber composition of the present invention is obtained by blending an inorganic filler (B) and the above-mentioned organosilicon compound (C) with a rubber component (A) made of natural rubber and / or a diene synthetic rubber. Preferably, the rubber component (A) composed of natural rubber and / or diene synthetic rubber is blended with 5 to 140 parts by weight of the inorganic filler (B), and the above organic The silicon compound (C) is blended in an amount of 1 to 20% by mass based on the blending amount of the inorganic filler (B).

  Here, when the content of the organosilicon compound (C) is less than 1% by mass of the blending amount of the inorganic filler (B), the effect of reducing the hysteresis loss of the rubber composition and the effect of improving the wear resistance are ineffective. On the other hand, if it exceeds 20% by mass, the effect is saturated.

  Further, the organosilicon compound (C) to be blended preferably has a purity of 80% or more, and by blending a compound having a purity of 80% or more, a rubber composition that can be expected to have a desired scorch improving effect is obtained. Can do.

  The rubber component (A) of the rubber composition of the present invention comprises natural rubber and / or a diene synthetic rubber. Here, examples of the diene synthetic rubber include styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber (IIR), and ethylene-propylene copolymer. These rubber components (A) may be used alone or in a blend of two or more.

  Examples of the inorganic filler (B) used in the rubber composition of the present invention include silica, aluminum hydroxide, alumina, clay, calcium carbonate, etc. Among these, silica and aluminum hydroxide are preferable from the viewpoint of reinforcement. Silica is preferred and particularly preferred. When the inorganic filler (B) is silica, the organosilicon compound (C) has a functional group having a high affinity for the silanol group on the silica surface and / or a functional group having a high affinity for the silicon atom (Si). For this reason, the coupling efficiency is greatly improved, the hysteresis loss of the rubber composition is reduced, and the effect of improving the wear resistance becomes more remarkable. In addition, there is no restriction | limiting in particular as silica, Wet silica (hydrous silicic acid), dry-type silica (anhydrous silicic acid), etc. can be used, On the other hand, as aluminum hydroxide, Heidilite (registered trademark, Showa Denko) Are preferably used.

The silica is preferably BET surface area of 40~350 m ² / g. When the BET surface area of silica is 40 m ² / g or less, the particle size of the silica is too large and wear resistance is greatly reduced. When the BET surface area of silica is 350 m ² / g or more, Since the particle diameter of the silica is too small, hysteresis loss is greatly increased.

  The compounding quantity of the said inorganic filler (B) is the range of 5-140 mass parts with respect to 100 mass parts of said rubber components (A). If the blending amount of the inorganic filler (B) is less than 5 parts by mass with respect to 100 parts by mass of the rubber component (A), the effect of reducing the hysteresis is insufficient, while if it exceeds 140 parts by mass, the workability is increased. This is because of the remarkable deterioration.

  In addition to the rubber component (A), inorganic filler (B), and organosilicon compound (C), the rubber composition of the present invention contains compounding agents commonly used in the rubber industry, such as carbon black, softeners. Vulcanizing agents, vulcanization accelerators, anti-aging agents, zinc white, stearic acid and the like can be appropriately blended depending on the purpose. As these compounding agents, commercially available products can be suitably used. In addition, the rubber composition of the present invention is blended with the rubber component (A), together with the inorganic filler (B) and the organosilicon compound (C), and various compounding agents appropriately selected as necessary. It can be produced by hot-pressing, extruding or the like.

<Tire>
The tire of the present invention is characterized by using the above rubber composition, and the above rubber composition is preferably used for the tread. In the tire of the present invention, the rolling resistance is greatly reduced, and the wear resistance is also greatly improved. 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. .

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Production Example 1 of Organosilicon Compound>
In a 100 mL two-necked eggplant flask, 6 g of 3-octanoylthio-propyltriethoxysilane and 0.08 g of titanium tetra-n-butoxide were weighed and stirred with a magnetic stirrer. This was heated to 150 ° C. with an oil bath, and the inside of the flask was decompressed to 26 kPa with a vacuum controller. Thereto was slowly added 2 g (1.02 eq) of N-methyldiethanolamine using a dropping funnel, and bubbles resulting from ethanol were generated. After all the N-methyldiethanolamine is added, heating is continued for about 1 hour until no foaming of ethanol occurs, and 7 g of a yellow transparent compound (3-octanoylthio-propyl (ethoxy) -1,3-dioxa-6 -Methylaza-2-silacyclooctane). When 2.54 g (1.0 eq) of iodomethane was slowly added to 7 g of the obtained compound, after generation of heat, 9.5 g of an organosilicon compound (C-1) was obtained. The obtained organosilicon compound (C-1) is a yellow transparent and viscous liquid, and when analyzed by ¹ H-NMR, 0.5 (t; 2H), 0.9 (t; 3H), 1.1 to 1.5 (m; 11H), 1.6 (m; 4H), 2.4 (t; 2H), 2.8 (t; 2H), 3.6 to 4.3 (m; 13H), and 3-octanoylthio-propyl (ethoxy) -1, It was found to be 3-dioxa-6-dimethyliodoaza-2-silacyclooctane.

<Production Example 2 of organosilicon compound>
In a 200 mL eggplant flask, 40 g of bis (3-triethoxysilylpropyl) disulfide, 17.4 g of 2- (acetylamino) ethanol, and 0.5 g of titanium tetrabutoxide were weighed and stirred with a magnetic stirrer. When this was heated in an oil bath at 165 to 175 ° C. for 18 hours while flowing dry nitrogen, a reddish brown liquid was obtained and analyzed by ¹ H-NMR. 0.6 (t; 4H), 1.2 (m; 12H) , 1.7 (t; 4H), 1.9 (s; 6H), 2.6 (t; 4H), 3.5 (m; 4H), 3.7 to 3.9 (m; 7H), and bis (3- (monoacetylaminoethoxy) Diethoxysilyl-propyl) disulfide [organosilicon compound (C-2)] was found.

<Preparation and evaluation of rubber composition>
A rubber composition having a formulation according to Table 1 was prepared by kneading with a Banbury mixer. Next, the vulcanized physical properties (dynamic viscoelasticity, abrasion resistance) and scorch time of the obtained rubber composition were measured by the following methods. The results are shown in Table 1.

(1) Dynamic viscoelasticity Using a spectrometer (dynamic viscoelasticity measuring machine) manufactured by Ueshima Seisakusho, tan δ of vulcanized rubber at a frequency of 52 Hz, initial strain of 10%, measurement temperature of 60 ° C, and dynamic strain of 1%. Measured and indicated as an index with the value of tan δ of Comparative Example 1 being 100. The smaller the index value, the lower the tan δ, indicating that the rubber composition is less exothermic.

(2) Abrasion resistance test In accordance with JIS K 6264-2: 2005, a test was performed using a Lambone-type abrasion tester under the conditions of room temperature and a slip rate of 25%. As an index. The larger the index value, the smaller the wear amount and the better the wear resistance.

(3) Scorch time In accordance with JIS K6300-1, the Mooney scorch time (t5) at 130 ° C. was measured using a Mooney viscometer, and Comparative Example 1 was indicated as 100 as an index. A larger index value indicates a longer scorch time and better workability.

* 1 JSR, emulsion polymerization SBR, # 1500
* 2 Asahi Carbon, # 80
* 3 Nippon Silica Kogyo Co., Ltd., nip seal AQ, BET surface area = 220 m ² / g
* 4 Bis (3-triethoxysilylpropyl) disulfide
* 5 3-Octanoylthio-propyl (ethoxy) -1,3-dioxa-6-methylaza-2-silacyclooctane synthesized by the following method
* 6 Nouchi 6C, manufactured by Ouchi Shinsei Chemical Industry
* 7 Ouchi Shinsei Chemical Industry, Nocrack 224
* 8 Sanshin Chemical Industry, Sunseller D
* 9 Sanshin Chemical Industry, Sunseller DM
* 10 Sanshin Chemical Industry, Sunseller NS

<Production Example of 3-Octanoylthio-propyl (ethoxy) -1,3-dioxa-6-methylaza-2-silacyclooctane>
In a 500 mL four-necked eggplant flask, 60 g of 3-octanoylthio-propyltriethoxysilane, 20 g of N-methyldiethanolamine, 0.8 g of titanium tetra-n-butoxide, and 220 mL of toluene were weighed. Next, while stirring with a mechanical stirrer and flowing dry nitrogen (0.2 L / min), the flask was heated with an oil bath, a Dimroth condenser was attached, and reflux was performed for 11 hours. Then, the solvent was removed with a rotary evaporator at 20 hPa / 40 ° C, and then the remaining volatiles were removed with a rotary pump (10 Pa) and a cold trap (dry ice + ethanol). Obtained liquid. When the obtained liquid was analyzed by ¹ H-NMR, 0.7 (t; 2H), 0.9 (t; 3H), 1.2 (t; 3H), 1.4 (m; 8H), 1.7 (m; 4H), 2.4 (s; 3H), 2.5 (m; 6H), 2.9 (t; 2H), 3.8 (m; 6H) and 3-octanoylthio-propyl (ethoxy) -1,3-dioxa-6-methylaza-2- It was found to be silacyclooctane.

  From the comparison between Comparative Examples 1 and 2 in Table 1 and Examples 1 to 4, the rubber composition was obtained by blending the organosilicon compound (C) of the present invention instead of the conventional silane coupling agent (* 4). It can be seen that tan δ can be greatly reduced, that is, the hysteresis loss can be greatly reduced, and the wear resistance can be greatly improved without accelerating the scorching of the object.

  Further, from Comparative Examples 3 and 4, a silane coupling agent containing a nitrogen-containing functional group, in which an electron-withdrawing substituent is not added to the nitrogen atom, and the nitrogen atom does not form an ammonium salt structure. It can be seen that by blending (* 5), the hysteresis loss of the rubber composition can be greatly reduced and the wear resistance can be greatly improved, but the scorch time is significantly shortened and the workability is deteriorated.

Claims (12)

Each molecule contains one or more nitrogen atoms and sulfur atoms, and has one or more silicon-oxygen bonds,
An organosilicon compound, wherein an electron-withdrawing substituent is added to at least one of the nitrogen atoms, or at least one of the nitrogen atoms forms an ammonium salt structure. 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 —, l, m and n are each independently 0 to 10, and X is F, Cl, Br, I, BF ₄ , PF ₆ , R ⁷ CO ₂ or R ⁷ SO ₃ , R ⁶ is the following formula (VI):

(Wherein A ² is C, N, S or P, Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, and l is 0 to 10, When A ² is C, p is 0 to 1, q is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, A ² Table If is S, p is 0 to 2, q is 1, 2p + q is 1-5, when a ² is P, p is 0 to 2, q is 0~4,2p + q is 4) Provided that R ⁷ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms}, and the others are -M-C ₁ H _{2l + 1} (where M and 1 Are as defined above, provided that one or more of R ¹ , R ² and R ³ is M is —O—,
R ^{4 in} formula (I) and formula (II) is —Y ² —C ₁ H _2l — (where Y ² is —O—, —NR ⁶ —, —N ⁺ (C _m H _{2m + 1} )). ₂ · X ⁻ —, —CH ₂ — or a single bond, wherein R ⁶ , X, l and m are as defined above,
R ⁵ in formula (III) _{^{-Y 3 -C l H 2l + 1}} ( wherein, Y ³ is -O -, - S -, - N (C m H 2m + 1) - or -CH ₂ - Where l and m are as defined above),
The organic silicon compound according to claim 1, wherein x is 1 to 6. R ⁶ represents the following formulas (a) to (g):

[Wherein, l and m are each independently 0 to 10],
The organosilicon compound according to claim 2, wherein R ⁴ is represented by —C ₁ H _2l — [wherein 1 is 0 to 10]. The following general formula (VII):

[Wherein A ³ represents the following general formula (VIII) or formula (III):

Represented by
In formula (VII) and formula (VIII), W represents —NR ⁶ — {where R ⁶ represents the following formula (VI):

(Wherein A ² is C, N, S or P, Z is ═O or ═NR ⁷ , Y ¹ is —O—, —NR ⁷ — or —S—, and l is 0 to 10, When A ² is C, p is 0 to 1, q is 1 to 2, 2p + q is 3, and when A ² is N, p is 0 to 1, q is 0 to 2, 2p + q is 2, A ² If is S, p is 0 to 2, q is 1, 2p + q is 1-5, when a ² is P, p is 0 to 2, q is represented by 0~4,2p + q is 4) Or the following formula (IX) or formula (X):

Wherein R ⁶ is as defined above, X is F, Cl, Br, I, BF ₄ , PF ₆ , R ⁷ CO ₂ or R ⁷ SO ₃ , and l, m and n are each independently 0 10)
R ⁸ and R ^{9 in} formula (VII) and formula (VIII) are each independently —M—C ₁ H _{2 1} — (where M is —O— or —CH ₂ —, and 1 is 0 to 10 R ¹⁰ is represented by -M-C _l H _{2l + 1} (where M and l are as defined above), provided that R ⁸ , R ⁹ and R ¹⁰ are One or more M is -O-;
R ^{11 in} formula (VII) and formula (VIII) is —Y ⁴ —C ₁ H _2l — (where Y ⁴ is —O—, —CH ₂ — or a single bond, where l is as defined above. It is expressed by
R ⁵ in formula (III) is —Y ³ —C ₁ H _{2l + 1} (where Y ³ is —O—, —S—, —N (C _m H _{2m + 1} ) — or —CH ₂ —). Where l and m are as defined above),
The organic silicon compound according to claim 1, wherein x is 1 to 6. R ⁶ represents the following formulas (a) to (g):

[Wherein, l and m are each independently 0 to 10],
The organosilicon compound according to claim 4, wherein R ¹¹ is represented by —C ₁ H _2l — [wherein 1 is 0 to 10].   The organosilicon compound according to claim 2, wherein M is —O—.   An inorganic filler (B) and the organosilicon compound (C) according to any one of claims 1 to 6 are blended with a rubber component (A) made of natural rubber and / or a diene synthetic rubber. Rubber composition. To 100 parts by mass of the rubber component (A) composed of the natural rubber and / or diene synthetic rubber, 5 to 140 parts by mass of the inorganic filler (B)
Furthermore, 1-20 mass% of the compounding quantity of the said inorganic filler (B) is included for the said organosilicon compound (C), The rubber composition of Claim 7 characterized by the above-mentioned.   The rubber composition according to claim 7, wherein the organosilicon compound (C) has a purity of 80% or more.   The rubber composition according to claim 7, wherein the inorganic filler (B) is silica or aluminum hydroxide. The rubber composition according to claim 10, wherein the silica has a BET surface area of 40 to 350 m ² / g.   A tire using the rubber composition according to any one of claims 7 to 11.