JP5575118B2 - Organosilicon compound, and rubber composition and tire using the same - Google Patents

Description

The present invention is a rubber composition containing an organic silicon compound, an organic silicon compound, and relates to a tire using the rubber composition, in particular, with reducing the hysteresis loss of the rubber composition, to improve the wear resistance It relates to an organosilicon compound that can be used.

  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 associated with 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, rubber compositions containing inorganic fillers such as silica reduce tire rolling resistance, improve braking performance on wet road surfaces, and improve steering stability, but have high unvulcanized viscosity and multi-stage 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. The silane coupling agent is also widely used for applications other than rubber compositions such as a primer composition, a coating composition, and an adhesive.

US 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 reduces 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 .

Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a novel compound capable of greatly reducing the hysteresis loss of the rubber composition and greatly improving the wear resistance. . Another object of the present invention, rubber compositions containing such compounds, and to provide a tire using the rubber composition.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the organosilicon compound represented by a specific structural formula has a high reaction rate with an inorganic filler such as silica. by blending the rubber component with the filler, and improving the efficiency of the coupling reaction, while greatly reducing the hysteresis loss of the rubber composition, it found that are greatly improved wear resistance, the present invention It came to complete.

［式中、Ｒ¹、Ｒ²及びＲ³は、少なくとも一つが下記一般式(III)：
−Ｍ−Ｃ_lＨ_2l−Ｒ⁶ ・・・ (III)
（式中、Ｍは−Ｏ−又は−ＣＨ₂−で、Ｒ⁶は−ＮＲ⁷Ｒ⁸、−ＮＲ⁷−ＮＲ⁷Ｒ⁸、又は−Ｎ＝ＮＲ⁷で、但し、Ｒ⁷は−Ｃ_nＨ_2n+1であり、Ｒ⁸は−Ｃ_qＨ_2q+1であり、ｌ、ｎ及びｑはそれぞれ独立して０〜２０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−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍ及びｌは上記と同義である）で表される］で表わされることを特徴とする。 That is, the first organosilicon compound of the present invention has the following general formula (I):

[In the formula, at least one of R ¹ , R ² and R ³ is represented by the following general formula (III) :
-M-C _l H _2l -R ⁶ (III)
(In the formula, M is —O— or —CH ₂ — , R ⁶ is —NR ⁷ R ⁸ , —NR ⁷ —NR ⁷ R ⁸ , or —N═NR ⁷ , where R ⁷ is —C _n. H _{2n + 1} , R ⁸ is —C _q H _{2q + 1} , l 1 , n and q are each independently 0 to 20), and the others are —M—C ₁ H _{2l +1} (wherein M and l are as defined above ) , provided that at ^{least one} of R ¹ , R ² and R ³ is M is —O—,
R ⁴ is represented by —M—C ₁ H _{2 1} — (wherein M and l are as defined above).

［式中、Ｗは−ＮＲ⁷−（ここで、Ｒ⁷は−Ｃ_nＨ_2n+1で、ｎは０〜２０である）で表わされ、
Ｒ¹⁰及びＲ¹¹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０〜２０である）で表わされ、
Ｒ¹²は−Ｍ−Ｃ_lＨ_2l+1 （ここで、Ｍ及びｌは上記と同義である）或いは−（Ｍ−Ｃ_lＨ_2l）_yＣ_sＨ_2s+1（ここで、Ｍ及びｌは上記と同義であり、ｙ及びｓはそれぞれ独立して１〜２０である）で表わされ、但し、Ｒ¹⁰、Ｒ¹¹及びＲ¹²の一つ以上はＭが−Ｏ−であり、
Ｒ⁴ は−Ｍ−Ｃ_lＨ_2l−（ここで、Ｍ及びｌは上記と同義である）で表される］で表わされることを特徴とする。 The second organosilicon compound of the present invention has the following general formula (VI):

Wherein, W is -NR ⁷ - (wherein, R ⁷ is -C _n H _{2n + 1, n} is a is 0 to 20) is represented by,
R ¹⁰ and R ¹¹ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 20),
R ¹² is _{-M-C l H 2l + 1} ( wherein, M and l have the same meanings as mentioned above), or _{- (M-C l H 2l} ) y C s H 2s + 1 ( where, M and l Is as defined above, and y and s are each independently 1-20, provided that at least one of R ¹⁰ , R ¹¹ and R ¹² is M is —O—,
R ⁴ is -M-C _l H _2l - (wherein, M and l have the same meanings as mentioned above) characterized by being represented by] represented by.

  In the organosilicon compound of the present invention, the M is preferably —O—.

In the organosilicon compound represented by the above formula (I), at least one of R ¹ , R ² and R ³ is —O—C ₁ H _{2 1} —R ⁶ (where R ⁶ and 1 are as defined above). And the others are represented by —O—C ₁ H _{2l + 1} (where l is as defined above),
The R ⁴ is preferably represented by —C ₁ H _2l — (wherein l is as defined above).

In the organosilicon compound represented by the above formula (I), at least one of R ¹ , R ² and R ³ is —O—C ₁ H _{2 1} —NR ⁷ R ⁸ (where R ⁷ , R ⁸ and More preferably, l is as defined above.

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

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

According to the present invention, it has a specific molecular structure containing a nitrogen atom (N) and a sulfur atom (S) and having a silicon-oxygen bond (Si-O), and greatly reduces the hysteresis loss of the rubber composition. In addition, it is possible to provide an organosilicon compound capable of greatly improving wear resistance. Further, it is possible to provide a tire using the rubber composition and the rubber composition containing such an organic silicon compound.

<Organic silicon compound>
The present invention is described in detail below. The first organosilicon compound of the present invention is represented by the above general formula (I), and the second organosilicon compound of the present invention is represented by the above general formula (VI). These organosilicon compounds of the present invention may be used singly or in combination of two or more. The organosilicon compound of the present invention contains a nitrogen-containing functional group such as an amino group, an imino group, a substituted amino group, or a substituted imino group that has a high affinity with the surface of an inorganic filler such as silica, so that the nitrogen atom is not shared. The electron pair can participate in the reaction between the organosilicon compound and the inorganic filler, and the coupling reaction rate 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.

  The organosilicon compound of the present invention preferably has 1 to 6 silicon-oxygen bonds (Si—O). When the organosilicon compound has 1 to 6 silicon-oxygen bonds (Si—O), the reactivity with an inorganic filler such as silica is high, and the coupling efficiency is further improved.

<< Compound of Formula (I) >>
In the general formula (I), at least one of R ¹ , R ² and R ³ is represented by the general formula (III), and the others are -M-C ₁ H _{2l + 1} (where M _is- O- or -CH ₂ -, l is represented by a is) 0-20. Provided that M is —O— in one or more of R ¹ , R ² and R ³ . In addition, since l is 0 to 20, -C _l H _{2l + 1} is hydrogen or an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, as a C1-C20 alkylene group, a methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group, A hexadecamethylene group, an octadecamethylene group and the like can be mentioned, and the alkylene group may be linear or branched .

In the above formula (III), M is —O— or —CH ₂ —, and 1 is 0-20 .

In the above formula (III), R ⁶ is —NR ⁷ R ⁸ , —NR ⁷ —NR ⁷ R ⁸ , or —N═NR ⁷ . Wherein, R ⁷ is _{-C n H 2n + 1, R} 8 is -C _q H _{2q + 1,} n and q are 0 to 20 independently. Note that -C _n H _{2n + 1} is hydrogen or an alkyl group having 1 to 20 carbon atoms because n is 0 to 20. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched. Further, -C _q H _{2q + 1,} since q is 0 to 20, hydrogen or an alkyl group having 1 to 20 carbon atoms. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched.

In the general formula (I), R ⁴ is represented by —M—C ₁ H _{2 1} —, and particularly preferably —C ₁ H _{2 1} —, where M is —O— or -CH ₂ - and is, l is 0 to 20. In addition, since l is 0 to 20, —C ₁ H _2l — is a single bond or an alkylene group having 1 to 20 carbon atoms. Here, as a C1-C20 alkylene group, a methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group, A hexadecamethylene group, an octadecamethylene group and the like can be mentioned, and the alkylene group may be linear or branched.

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), at least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _2l —R ⁶ , and the other is —O—C ₁ H _{2l +. 1} is preferred, and R ⁴ is preferably represented by —C ₁ H _2l —.

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 —O—C ₁ H _{2 1} —NR ⁷ R ⁸ , and R ⁴ is — C _l H _2l - is preferably represented by the.

<< Compound of Formula (VI) >>
In the general formula (VI), W is, -NR ⁷ - represented by wherein, R ⁷ is -C _n H _{2n + 1, n} is 0 to 20. Note that -C _n H _{2n + 1} is hydrogen or an alkyl group having 1 to 20 carbon atoms because n is 0 to 20. Here, as the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, a stearyl group, and the like. The alkyl group may be linear or branched.

In the general formula (VI), R ¹⁰ and R ¹¹ are each independently -M-C _l H _2l - is represented by, R ¹² is -M-C _l H _{2l + 1} or - (M-C _l H _2l ) _y C _s H _{2s + 1} , wherein M is —O— or —CH ₂ — , l is 0 to 20, y and s are each independently 1 to 20 It is. However, in one or more of R ¹⁰ , R ¹¹ and R ¹² , M is —O—. Note that -C _l H _2l -is a single bond or an alkylene group having 1 to 20 carbon atoms because l is 0 to 20, where the alkylene group having 1 to 20 carbon atoms includes a methylene group, Ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group, hexadecamethylene group, octadecamethylene group, etc., and the alkylene group May be linear or branched. -C _l H _{2l + 1} is hydrogen or an alkyl group having 1 to 20 carbon atoms because l is 0 to 20, where the alkyl group having 1 to 20 carbon atoms is a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, etc. The alkyl group may be linear or branched . Further, -C _s H _{2s + 1,} since s is 1 to 20, an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, etc., the alkyl group May be linear or branched. Further, y is a number of repetitions of the (M-C _l H _2l) units is 1-20. In addition, it is preferable that M in the (M-C ₁ H _2l ) unit is —O— (oxygen).

In the general formula (VI), R ⁴ is represented by —M—C ₁ H _{2 1} —, and particularly preferably —C ₁ H _{2 1} —, where M is —O— or -CH ₂ - and is, l is 0 to 20. In addition, -C _l H _2l- is as described above.

In the compound of the above formula (VI), 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.

<< 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 -Add amine compounds such as methyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, and further add acid such as p-toluenesulfonic acid and hydrochloric acid as a catalyst, and titanium alkoxide such as titanium tetra-n-butoxide, and heat. , R ¹ , R ² and R ³ are substituted with a monovalent nitrogen-containing group represented by formula (II) or formula (III), or R ¹ and R ² are —R ¹⁰ —W—R ¹¹ - It can be synthesized by substituting a bivalent nitrogen-containing group. Further, optionally, an alcohol compound such as 2- (2-butoxyethoxy) ethanol is added and heated to _convert one or more of R ¹ , R ² and R ³ _to- (M-C ₁ H _{2 l} ) _y C A monovalent group represented by _s H _{2s + 1} may be substituted.

<< Specific Examples of Organosilicon Compounds >>
Specific examples of the organosilicon compound of the present invention include (3-mercaptopropyl) (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (methyl) 1,3- Dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (ethyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (butyl) 1,3- Dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (octyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (decyl) 1,3- Dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyl) 1,3-dioxa- -Methylaza-2-silacyclooctane, (3-mercaptopropyl) (octyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (2-ethylhexyloxy) 1,3 -Dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (decyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyloxy) 1, 3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (octadecyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (2- ( Butoxyethoxy) ethoxy) 1,3-dioxa-6-methylaza-2-sila Crooctane, (3-mercaptopentyl) (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopentyl) (methyl) 1,3-dioxa-6-methylaza-2-silacyclo Octane, (3-mercaptopentyl) (ethyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopentyl) (butyl) 1,3-dioxa-6-methylaza-2-silacyclo Octane, (3-mercaptopentyl) (octyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopentyl) (decyl) 1,3-dioxa-6-methylaza-2-silacyclo Octane, (3-mercaptopentyl) (dodecyl) 1,3-dioxa-6-methylaza-2-silashic Looctane, (3-mercaptopentyl) (octyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopentyl) (2-ethylhexyloxy) 1,3-dioxa-6-methylaza- 2-silacyclooctane, (3-mercaptopentyl) (decyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopentyl) (dodecyloxy) 1,3-dioxa-6-methylaza 2-silacyclooctane, (3-mercaptopentyl) (octadecyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopentyl) (2- (butoxyethoxy) ethoxy) 1, 3-dioxa-6-methylaza-2-silacyclooctane, (3-merca Todecyl) (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptodecyl) (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercapto Decyl) (ethyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptodecyl) (butyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercapto (Decyl) (octyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptodecyl) (decyl) 1,3-dioxa-6-methylaza-2-silacyclooctane,
(3-mercaptodecyl) (dodecyl) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptodecyl) (octyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane , (3-mercaptodecyl) (2-ethylhexyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptodecyl) (decyloxy) 1,3-dioxa-6-methylaza-2- Silacyclooctane, (3-mercaptodecyl) (dodecyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane, (3-mercaptodecyl) (octadecyloxy) 1,3-dioxa-6-methylaza- 2-Silacyclooctane, (3-mercaptodecyl) (2- (butoxyethoxy) ethoxy) , 3-Dioxa-6-methylaza-2-silacyclooctane, (3-mercaptopropyl) (ethoxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (methyl) 1 , 3-Dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (ethyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (butyl) 1 , 3-Dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (octyl) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (decyl) 1 , 3-Dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyl) 1 3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (octyloxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (2-ethylhexyl) Oxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (decyloxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) ( Dodecyloxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) (octadecyloxy) 1,3-dioxa-6-ethylaza-2-silacyclooctane, (3-mercaptopropyl) ) (2- (Butoxyethoxy) ethoxy) 1,3-dioxa-6-ethyl Aza-2-silacyclooctane, (3-mercaptopropyl) (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (methyl) 1,3-dioxa-6 Butylaza-2-silacyclooctane, (3-mercaptopropyl) (ethyl) 1,3-dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (butyl) 1,3-dioxa-6 Butylaza-2-silacyclooctane, (3-mercaptopropyl) (octyl) 1,3-dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (decyl) 1,3-dioxa-6 Butylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyl) 1,3-dioxa-6-butyla 2-silacyclooctane, (3-mercaptopropyl) (octyloxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (2-ethylhexyloxy) 1,3-dioxa -6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (decyloxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyloxy) 1,3- Dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (octadecyloxy) 1,3-dioxa-6-butylaza-2-silacyclooctane,
(3-mercaptopropyl) (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane, (3-mercaptopropyl) (ethoxy) 1,3-dioxa-6-decylaza- 2-silacyclooctane, (3-mercaptopropyl) (methyl) 1,3-dioxa-6-decylaza-2-silacyclooctane, (3-mercaptopropyl) (ethyl) 1,3-dioxa-6-decylaza- 2-silacyclooctane, (3-mercaptopropyl) (butyl) 1,3-dioxa-6-decylaza-2-silacyclooctane, (3-mercaptopropyl) (octyl) 1,3-dioxa-6-decylaza- 2-Silacyclooctane, (3-mercaptopropyl) (decyl) 1,3-dioxa-6-decylaza-2 Silacyclooctane, (3-mercaptopropyl) (dodecyl) 1,3-dioxa-6-decylaza-2-silacyclooctane, (3-mercaptopropyl) (octyloxy) 1,3-dioxa-6-decylaza-2 -Silacyclooctane, (3-mercaptopropyl) (2-ethylhexyloxy) 1,3-dioxa-6-decylaza-2-silacyclooctane, (3-mercaptopropyl) (decyloxy) 1,3-dioxa-6 Decylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyloxy) 1,3-dioxa-6-decylaza-2-silacyclooctane, (3-mercaptopropyl) (octadecyloxy) 1,3-dioxa- 6-decylaza-2-silacyclooctane, (3-mercaptopropyl) 2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-decylaza-2-silacyclooctane, (3-mercaptopropyl) (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, ( 3-mercaptopropyl) (methyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (ethyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, ( 3-mercaptopropyl) (butyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (octyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, 3-mercaptopropyl) (decyl) 1,3-dioxa-6-dodecylaza-2-silacyclooct Tan, (3-mercaptopropyl) (dodecyl) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (octyloxy) 1,3-dioxa-6-dodecylaza-2-sila Cyclooctane, (3-mercaptopropyl) (2-ethylhexyloxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (decyloxy) 1,3-dioxa-6-dodecylaza- 2-silacyclooctane, (3-mercaptopropyl) (dodecyloxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (octadecyloxy) 1,3-dioxa-6 Dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (2 (Butoxyethoxy) ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane, (3-mercaptopropyl) (ethoxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3 -Mercaptopropyl) (methyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (ethyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (butyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (octyl) 1,3-dioxa-6-octadecylaza-2-silacyclo Octane,
(3-mercaptopropyl) (decyl) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyl) 1,3-dioxa-6-octadecylaza-2-silacyclo Octane, (3-mercaptopropyl) (octyloxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (2-ethylhexyloxy) 1,3-dioxa-6-octadecyl Aza-2-silacyclooctane, (3-mercaptopropyl) (decyloxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (dodecyloxy) 1,3-dioxa- 6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl (Octadecyloxy) 1,3-dioxa-6-octadecylaza-2-silacyclooctane, (3-mercaptopropyl) (2- (butoxyethoxy) ethoxy) 1,3-dioxa-6-octadecylaza-2-sila Cyclooctane, (3-mercaptopropyl) di (dimethylaminoethoxy) ethoxysilane, (3-mercaptopropyl) di (dimethylaminoethoxy) methylsilane, (3-mercaptopropyl) di (dimethylaminoethoxy) ethylsilane, (3-mercapto (Propyl) di (dimethylaminoethoxy) butylsilane, (3-mercaptopropyl) di (dimethylaminoethoxy) octylsilane, (3-mercaptopropyl) di (dimethylaminoethoxy) decylsilane, (3-mercaptopropyl) di (dimethyla) Noethoxy) dodecylsilane, (3-mercaptopropyl) di (dimethylaminoethoxy) octyloxysilane, (3-mercaptopropyl) di (dimethylaminoethoxy) 2-ethylhexyloxysilane, (3-mercaptopropyl) di (dimethylaminoethoxy) ) Decyloxysilane, (3-mercaptopropyl) di (dimethylaminoethoxy) dodecyloxysilane, (3-mercaptopropyl) di (dimethylaminoethoxy) octadecyloxysilane ,
(3-mercaptopropyl) (dimethylaminoethoxy) diethoxysilane, (3-mercaptopropyl) (dimethylaminoethoxy) dimethylsilane, (3-mercaptopropyl) di (dimethylaminoethoxy) ethylsilane, (3-mercaptopropyl) ( (Dimethylaminoethoxy) dibutylsilane, (3-mercaptopropyl) (dimethylaminoethoxy) dioctylsilane, (3-mercaptopropyl) (dimethylaminoethoxy) didecylsilane, (3-mercaptopropyl) (dimethylaminoethoxy) didodecylsilane, ( 3-mercaptopropyl) (dimethylaminoethoxy) dioctyloxysilane, (3-mercaptopropyl) (dimethylaminoethoxy) di (2-ethylhexyloxy) silane, (3-mercaptopropyl Pill) (dimethylaminoethoxy) didecyl silane, (3-mercaptopropyl) (dimethylaminoethoxy) didodecyl silane, (3-mercaptopropyl) (dimethylaminoethoxy) dioctadecyl silane,
(3-mercaptopentyl) di (dimethylaminoethoxy) ethoxysilane, (3-mercaptopentyl) di (dimethylaminoethoxy) methylsilane, (3-mercaptopentyl) di (dimethylaminoethoxy) ethylsilane, (3-mercaptopentyl) di (Dimethylaminoethoxy) butylsilane, (3-mercaptopentyl) di (dimethylaminoethoxy) octylsilane, (3-mercaptopentyl) di (dimethylaminoethoxy) decylsilane,
(3-mercaptopentyl) di (dimethylaminoethoxy) dodecylsilane, (3-mercaptopentyl) di (dimethylaminoethoxy) octyloxysilane, (3-mercaptopentyl) di (dimethylaminoethoxy) 2-ethylhexyloxysilane, 3-mercaptopentyl) di (dimethylaminoethoxy) decyloxysilane, (3-mercaptopentyl) di (dimethylaminoethoxy) dodecyloxysilane, (3-mercaptopentyl) di (dimethylaminoethoxy) octadecyloxysilane ,
(3-mercaptodecyl) di (dimethylaminoethoxy) ethoxysilane, (3-mercaptodecyl) di (dimethylaminoethoxy) methylsilane, (3-mercaptodecyl) di (dimethylaminoethoxy) ethylsilane, (3-mercaptodecyl) di (Dimethylaminoethoxy) butylsilane, (3-mercaptodecyl) di (dimethylaminoethoxy) octylsilane, (3-mercaptodecyl) di (dimethylaminoethoxy) decylsilane, (3-mercaptodecyl) di (dimethylaminoethoxy) dodecylsilane , (3-mercaptodecyl) di (dimethylaminoethoxy) octyloxysilane, (3-mercaptodecyl) di (dimethylaminoethoxy) 2-ethylhexyloxysilane, (3-mercaptodecyl) di (dimethylamino) Ethoxy) decyl silane, (3-mercaptopropyl-decyl) di (dimethylaminoethoxy) dodecyloxy silane, (3-mercaptopropyl-decyl) di (dimethylaminoethoxy) octadecyl silane,
(3-mercaptopropyl) di (dibutylaminoethoxy) ethoxysilane, (3-mercaptopropyl) di (dibutylaminoethoxy) methylsilane, (3-mercaptopropyl) di (dibutylaminoethoxy) ethylsilane, (3-mercaptopropyl) di (Dibutylaminoethoxy) butylsilane, (3-mercaptopropyl) di (dibutylaminoethoxy) octylsilane, (3-mercaptopropyl) di (dibutylaminoethoxy) decylsilane, (3-mercaptopropyl) di (dibutylaminoethoxy) dodecylsilane (3-mercaptopropyl) di (dibutylaminoethoxy) octyloxysilane, (3-mercaptopropyl) di (dibutylaminoethoxy) 2-ethylhexyloxysilane, (3-mercaptopropi ) Di (dibutyl aminoethoxy) decyl silane, (3-mercaptopropyl) di (dibutyl aminoethoxy) dodecyloxy silane, (3-mercaptopropyl) di (dibutyl aminoethoxy) octadecyl silane,
(3-mercaptopropyl) (dibutylaminoethoxy) diethoxysilane, (3-mercaptopropyl) (dibutylaminoethoxy) dimethylsilane, (3-mercaptopropyl) (dibutylaminoethoxy) diethylsilane, (3-mercaptopropyl) ( Dibutylaminoethoxy) dibutylsilane, (3-mercaptopropyl) (dibutylaminoethoxy) dioctylsilane, (3-mercaptopropyl) (dibutylaminoethoxy) didecylsilane, (3-mercaptopropyl) (dibutylaminoethoxy) didodecylsilane, ( 3-mercaptopropyl) (dibutylaminoethoxy) dioctyloxysilane, (3-mercaptopropyl) (dibutylaminoethoxy) di (2-ethylhexyloxy) silane, (3-mercaptotop Pill) (dibutyl-amino ethoxy) didecyl silane, (3-mercaptopropyl) (dibutyl-amino ethoxy) didodecyl silane, (3-mercaptopropyl) (dibutyl-amino ethoxy) dioctadecyl silane,
(3-mercaptopropyl) di (didecylaminoethoxy) ethoxysilane, (3-mercaptopropyl) di (didecylaminoethoxy) methylsilane, (3-mercaptopropyl) di (didecylaminoethoxy) ethylsilane, (3-mercapto Propyl) di (didecylaminoethoxy) butylsilane,
(3-mercaptopropyl) di (didecylaminoethoxy) octylsilane, (3-mercaptopropyl) di (didecylaminoethoxy) decylsilane, (3-mercaptopropyl) di (didecylaminoethoxy) dodecylsilane, (3- Mercaptopropyl) di (didecylaminoethoxy) octyloxysilane, (3-mercaptopropyl) di (didecylaminoethoxy) 2-ethylhexyloxysilane, (3-mercaptopropyl) di (didecylaminoethoxy) decyloxysilane, (3-mercaptopropyl) di (didecylaminoethoxy) dodecyloxysilane, (3-mercaptopropyl) di (didecylaminoethoxy) octadecyloxysilane ,
(3-mercaptopropyl) (didecylaminoethoxy) diethoxysilane, (3-mercaptopropyl) (didecylaminoethoxy) dimethylsilane, (3-mercaptopropyl) (didecylaminoethoxy) diethylsilane, (3-mercapto Propyl) (didecylaminoethoxy) dibutylsilane, (3-mercaptopropyl) (didecylaminoethoxy) dioctylsilane, (3-mercaptopropyl) (didecylaminoethoxy) didecylsilane, (3-mercaptopropyl) (didecylamino) Ethoxy) didodecylsilane, (3-mercaptopropyl) (didecylaminoethoxy) dioctyloxysilane, (3-mercaptopropyl) (didecylaminoethoxy) di (2-ethylhexyloxy) silane, (3-mercaptop) Pill) (didecyl aminoethoxy) didecyl silane, (3-mercaptopropyl) (didecyl aminoethoxy) didodecyl silane, (3-mercaptopropyl) (didecyl aminoethoxy) dioctadecyl silane,
(3-mercaptopropyl) di (didodecylaminoethoxy) ethoxysilane, (3-mercaptopropyl) di (didodecylaminoethoxy) methylsilane, (3-mercaptopropyl) di (didodecylaminoethoxy) ethylsilane, (3-mercapto Propyl) di (didodecylaminoethoxy) butylsilane, (3-mercaptopropyl) di (didodecylaminoethoxy) octylsilane, (3-mercaptopropyl) di (didodecylaminoethoxy) decylsilane, (3-mercaptopropyl) di ( Didodecylaminoethoxy) dodecylsilane, (3-mercaptopropyl) di (didodecylaminoethoxy) octyloxysilane, (3-mercaptopropyl) di (didodecylaminoethoxy) 2-ethylhexyloxysilane, (3 Mercaptopropyl) di (dodecyl-amino ethoxy) decyl silane, (3-mercaptopropyl) di (dodecyl-amino ethoxy) dodecyloxy silane, (3-mercaptopropyl) di (dodecyl-amino ethoxy) octadecyl silane,
(3-mercaptopropyl) (didodecylaminoethoxy) diethoxysilane, (3-mercaptopropyl) (didodecylaminoethoxy) dimethylsilane, (3-mercaptopropyl) (didodecylaminoethoxy) diethylsilane, (3-mercapto Propyl) (didodecylaminoethoxy) dibutylsilane, (3-mercaptopropyl) (didodecylaminoethoxy) dioctylsilane, (3-mercaptopropyl) (didodecylaminoethoxy) didecylsilane, (3-mercaptopropyl) (didodecylamino) Ethoxy) didodecylsilane, (3-mercaptopropyl) (didodecylaminoethoxy) dioctyloxysilane, (3-mercaptopropyl) (didodecylaminoethoxy) di (2-ethylhexyloxy) silane, 3-mercaptopropyl) (didodecyl aminoethoxy) didecyl silane, (3-mercaptopropyl) (didodecyl aminoethoxy) didodecyl silane, (3-mercaptopropyl) is (didodecyl aminoethoxy) dioctadecyl silane Can be mentioned.

<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.

  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), ethylene-propylene copolymer, and the like. 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 preferably has a BET surface area of 40 to 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 blending amount of the inorganic filler (B) is preferably in the range of 5 to 140 parts by mass with respect to 100 parts by mass of the rubber component (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.

で表わされる３−メルカプトプロピル（エトキシ）１，３−ジオキサ−６−メチルアザ−２−シラシクロオクタン［有機ケイ素化合物（Ｃ−１）］24.0gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 2.6(t;4H), 2.5(m;2H), 2.4(s;3H), 1.6(m;2H), 0.8(t;3H), 0.6(t;2H) <Production Example 1 of Organosilicon Compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercaptopropyltriethoxysilane, 11.9 g of N-methyldiethanolamine and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

24.0 g of 3-mercaptopropyl (ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane [organosilicon compound (C-1)] represented by The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (s; 3H), 1.6 (m; 2H), 0.8 (t; 3H), 0.6 (t; 2H)

で表わされる３−メルカプトプロピル（メチル）１，３−ジオキサ−６−メチルアザ−２−シラシクロオクタン［有機ケイ素化合物（Ｃ−２）］21.5gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;4H), 2.6(t;4H), 2.5(m;2H), 2.4(s;3H), 1.6(m;2H), 0.6(t;2H), 0.1(s;3H) <Production Example 2 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 18.0 g of 3-mercaptopropyldimethoxymethylsilane, 11.9 g of N-methyldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

21.5 g of 3-mercaptopropyl (methyl) 1,3-dioxa-6-methylaza-2-silacyclooctane [organosilicon compound (C-2)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 4H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (s; 3H), 1.6 (m; 2H), 0.6 (t; 2H), 0.1 (s; 3H)

で表わされる３−メルカプトプロピル（エトキシ）１，３−ジオキサ−６−ブチルアザ−２−シラシクロオクタン［有機ケイ素化合物（Ｃ−３）］28.7gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 2.6(t;4H), 2.5(m;2H), 2.4(m;2H), 1.6(m;2H), 1.4(m;2H), 1.3(m;2H), 0.9(t;3H), 0.8(t;3H), 0.6(t;2H) <Production Example 3 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercaptopropyltriethoxysilane, 16.1 g of N-butyldiethanolamine and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

28.7 g of 3-mercaptopropyl (ethoxy) 1,3-dioxa-6-butylaza-2-silacyclooctane [organosilicon compound (C-3)] represented by The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (m; 2H), 1.6 (m; 2H), 1.4 (m; 2H), 1.3 (m; 2H), 0.9 (t; 3H), 0.8 (t; 3H), 0.6 (t; 2H)

で表わされる３−メルカプトプロピル（エトキシ）１，３−ジオキサ−６−ドデシルアザ−２−シラシクロオクタン［有機ケイ素化合物（Ｃ−４）］40.0gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 2.6(t;4H), 2.5(m;2H), 2.4(m;2H), 1.6(m;2H), 1.4(m;2H), 1.3(m;18H), 0.9(t;3H), 0.8(t;3H), 0.6(t;2H) <Production Example 4 of organosilicon compound>
Under a nitrogen atmosphere, 23.8 g of 3-mercaptopropyltriethoxysilane, 27.3 g of N-lauryldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a 500 mL four-necked eggplant flask. The temperature was raised to 150 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

40.0 g of 3-mercaptopropyl (ethoxy) 1,3-dioxa-6-dodecylaza-2-silacyclooctane [organosilicon compound (C-4)] represented by The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (m; 2H), 1.6 (m; 2H), 1.4 (m; 2H), 1.3 (m; 18H), 0.9 (t; 3H), 0.8 (t; 3H), 0.6 (t; 2H)

で表わされる３−メルカプトプロピル（デシルオキシ）１，３−ジオキサ−６−メチルアザ−２−シラシクロオクタン［有機ケイ素化合物（Ｃ−５）］35.0gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 2.6(t;4H), 2.5(m;2H), 2.4(s;3H), 1.6(m;2H), 1.5(m;2H), 1.3(m;14H), 0.8(t;3H), 0.6(t;2H) <Production Example 5 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercaptopropyltrimethoxysilane, 11.9 g of N-methyldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Subsequently, 15.8 g of decyl alcohol was added dropwise and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

35.0 g of 3-mercaptopropyl (decyloxy) 1,3-dioxa-6-methylaza-2-silacyclooctane [organosilicon compound (C-5)] represented by The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (s; 3H), 1.6 (m; 2H), 1.5 (m; 2H), 1.3 (m; 14H), 0.8 (t; 3H), 0.6 (t; 2H)

で表わされる３−メルカプトプロピル（２−（２−ブトキシエトキシ）エトキシ）１，３-ジオキサ−６−メチルアザ−２−シラシクロオクタン［有機ケイ素化合物（Ｃ−６）］35.5gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 3.5(m;8H), 2.6(t;4H), 2.5(m;2H), 2.4(s;3H), 1.6(m;2H), 1.5(m;2H), 1.3(m;2H), 0.8(t;3H), 0.6(t;2H) <Production Example 6 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercapto-propyltriethoxysilane, 11.9 g of N-methyldiethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 150 ° C. and stirred for 6 hours. Subsequently, 16.2 g of 2- (2-butoxyethoxy) ethanol was added dropwise and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

35.5 g of 3-mercaptopropyl (2- (2-butoxyethoxy) ethoxy) 1,3-dioxa-6-methylaza-2-silacyclooctane [organosilicon compound (C-6)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 3.5 (m; 8H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (s; 3H), 1.6 (m; 2H), 1.5 (m; 2H), 1.3 (m; 2H), 0.8 (t; 3H), 0.6 (t; 2H)

で表わされる３−メルカプトプロピル ジ（ジメチルアミノエトキシ）エトキシシラン［有機ケイ素化合物（Ｃ−７）］30.0gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 2.6(t;4H), 2.5(m;2H), 2.4(s;12H), 1.6(m;2H), 0.8(t;3H), 0.6(t;2H) <Production Example 7 of Organosilicon Compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercaptopropyltriethoxysilane, 17.8 g of dimethylethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene under a nitrogen atmosphere. The temperature was raised to 130 ° C. and stirred for 6 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

30.0 g of 3-mercaptopropyl di (dimethylaminoethoxy) ethoxysilane [organosilicon compound (C-7)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (s; 12H), 1.6 (m; 2H), 0.8 (t; 3H), 0.6 (t; 2H)

で表わされる３−メルカプトプロピル ジ（ジメチルアミノエトキシ）デシルオキシシラン［有機ケイ素化合物（Ｃ−８）］39.2gを得た。生成物の¹Ｈ−ＮＭＲでの分析結果を以下に示す。
¹Ｈ−ＮＭＲ（CDCl₃, 700MHz, δ;ppm）= 3.7(m;6H), 2.6(t;4H), 2.5(m;2H), 2.4(s;12H), 1.6(m;2H), 1.5(m;2H), 1.3(m;14H), 0.8(t;3H), 0.6(t;2H) <Production Example 8 of organosilicon compound>
In a 500 mL four-necked eggplant flask, 23.8 g of 3-mercaptopropyltrimethoxysilane, 17.8 g of dimethylethanolamine, and 0.05 g of titanium tetra-n-butoxide were dissolved in 200 mL of xylene in a nitrogen atmosphere. The temperature was raised to 130 ° C. and stirred for 6 hours. Subsequently, 15.8 g of decyl alcohol was added dropwise and stirred for 2 hours. Thereafter, the solvent was removed by a rotary evaporator at 20 hPa / 40 ° C., and then the remaining volatile components were removed by a rotary pump (10 Pa) and a cold trap (dry ice + ethanol).

39.2 g of 3-mercaptopropyl di (dimethylaminoethoxy) decyloxysilane [organosilicon compound (C-8)] represented by the formula: The results of ¹ H-NMR analysis of the product are shown below.
¹ H-NMR (CDCl ₃ , 700 MHz, δ; ppm) = 3.7 (m; 6H), 2.6 (t; 4H), 2.5 (m; 2H), 2.4 (s; 12H), 1.6 (m; 2H), 1.5 (m; 2H), 1.3 (m; 14H), 0.8 (t; 3H), 0.6 (t; 2H)

<Preparation and evaluation of rubber composition>
The rubber composition of the mixing | blending prescription according to Tables 1-6 was knead | mixed and prepared with the Banbury mixer. Next, the vulcanization physical property of the obtained rubber composition was measured by the following method. The results are shown in Tables 1-6.

(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%. In Tables 1 to 3, the value of tan δ of Comparative Example 1 is shown as an index as 100, in Table 4, the value of tan δ of Comparative Example 9 is shown as an index, and in Table 5, the tan δ of Comparative Example 13 is shown. In Table 6, the value of tan δ of Comparative Example 17 was set as 100 and displayed as an index. 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 conditions of room temperature and a slip rate of 25%. The reciprocal of the wear amount is displayed as an index as 100. In Table 4, the reciprocal of the wear amount of Comparative Example 9 is displayed as an index, and in Table 5, the reciprocal of the wear amount of Comparative Example 13 is displayed as an index. In FIG. 6, the reciprocal of the amount of wear in Comparative Example 17 was taken as 100 and displayed as an index. The larger the index value, the smaller the wear amount and the better the wear resistance.

* 1 JSR, emulsion polymerization SBR, # 1500
* 2 Asahi Carbon, # 80
* 3 Tosoh Silica Industry Co., Ltd., nip seal AQ, BET surface area = 220 m ² / g
* 4 Bis (3-triethoxysilylpropyl) disulfide
* 5 3-Octanoylthio-propyltriethoxysilane
* 6 Tokyo Chemical Industry Co., Ltd. (3-mercaptopropyl) triethoxysilane
* 7 Ouchi Shinsei Chemical Industry, Nocrack 6C
* 8 Ouchi Shinsei Chemical Industry, Nocrack 224
* 9 Sunseller D, manufactured by Sanshin Chemical Industry
* 10 Sanshin Chemical Industries, Sunseller DM
* 11 Sanshin Chemical Industry, Sunseller NS
* 12 JSR, Emulsion SBR, # 1712, 37.5 parts by weight of aromatic oil for 100 parts by weight of rubber component
* 13 RSS # 3
* 14 Asahi Carbon, # 78
* 15 N-cyclohexylbenzothiazole-2-sulfenamide
* 16 Ouchi Shinsei Chemical Industries, Noxeller TOT-N

  From Tables 1-6, tan δ of the rubber composition is greatly reduced by blending the organosilicon compound (C) of the present invention in place of the conventional silane coupling agents (* 4, * 5 and * 6). That is, it can be seen that the wear resistance can be significantly improved while the hysteresis loss is greatly reduced to reduce heat generation.

Claims (10)

The following general formula (I):

[In the formula, at least one of R ¹ , R ² and R ³ is represented by the following general formula (III) :
-M-C _l H _2l -R ⁶ (III)
(In the formula, M is —O— or —CH ₂ — , R ⁶ is —NR ⁷ R ⁸ , —NR ⁷ —NR ⁷ R ⁸ , or —N═NR ⁷ , where R ⁷ is —C _n. H _{2n + 1} , R ⁸ is —C _q H _{2q + 1} , l 1 , n and q are each independently 0 to 20), and the others are —M—C ₁ H _{2l +1} (wherein M and l are as defined above ) , provided that at ^{least one} of R ¹ , R ² and R ³ is M is —O—,
R ⁴ is represented by —M—C ₁ H _{2 1} — (wherein M and l are as defined above), and an organosilicon compound. The following general formula (VI):

Wherein, W is -NR ⁷ - (wherein, R ⁷ is -C _n H _{2n + 1, n} is a is 0 to 20) is represented by,
R ¹⁰ and R ¹¹ are each independently represented by —M—C ₁ H _{2 1} — (wherein M is —O— or —CH ₂ —, and 1 is 0 to 20),
R ¹² is _{-M-C l H 2l + 1} ( wherein, M and l have the same meanings as mentioned above), or _{- (M-C l H 2l} ) y C s H 2s + 1 ( where, M and l Is as defined above, and y and s are each independently 1-20, provided that at least one of R ¹⁰ , R ¹¹ and R ¹² is M is —O—,
R ⁴ is -M-C _l H _2l - (wherein, M and l have the same meanings as mentioned above) the organic silicon compound, characterized by being represented by] represented by.   The organosilicon compound according to claim 1, wherein M is —O—. At least one of R ¹ , R ^2, and R ³ is represented by —O—C ₁ H _{2 l} —R ⁶ (where R ⁶ and l are as defined above), and the others are —O—C. _l H _{2l + 1} (where l is as defined above),
4. The organosilicon compound according to claim 1, wherein R ⁴ is represented by —C ₁ H _2l — (wherein l is as defined above). At least one of R ¹ , R ² and R ³ is represented by —O—C ₁ H _{2 1} —NR ⁷ R ⁸ (wherein R ⁷ , R ⁸ and 1 are as defined above). The organosilicon compound according to claim 1, 3 or 4. An inorganic filler (B) and the organosilicon compound (C) according to any one of claims 1 to 5 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 the diene synthetic rubber, 5 to 140 parts by mass of the inorganic filler (B) are blended,
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 6 characterized by the above-mentioned. The rubber composition according to claim 6 , wherein the inorganic filler (B) is silica or aluminum hydroxide. The rubber composition according to claim 8 , 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 6 to 9 .