JP2015113315A - Sulfur-containing organic silicon compound and method of producing the same, compounding agent for rubber, and rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sulfur-containing organic silicon compound which can significantly reduce the hysteresis loss of a rubber composition and significantly improve its abrasion resistance.SOLUTION: This invention provides use of a compounding agent for rubber comprising a sulfur-containing organic silicon compound having a hydrolyzable silyl group, a sulfide group and an amino group as a component.

Description

  The present invention relates to a sulfur-containing organosilicon compound having a hydrolyzable silyl group, sulfide group, and amino group in the molecule and effectively used in a rubber compound, a method for producing the same, and a compounding agent for rubber. A rubber composition obtained by compounding the rubber compounding agent and a tire using the rubber composition have low hysteresis loss and excellent wear resistance.

  The sulfur-containing organosilicon compound is useful as an essential component for the production of a tire comprising a silica-filled rubber composition. Silica-filled tires have improved performance in automotive applications, particularly excellent wear resistance, rolling resistance and wet grip. Such performance improvement is closely related to improvement in fuel efficiency of tires, and has been actively studied recently.

  In order to improve fuel economy, it is essential to increase the silica filling rate of the rubber composition, but the silica filled rubber composition reduces the rolling resistance of the tire and improves wet grip, but has a high unvulcanized viscosity. Multi-step kneading is required and there is a problem in workability. Therefore, in a rubber composition in which an inorganic filler such as silica is simply blended, there is a problem that the filler is insufficiently dispersed and the fracture strength and wear resistance are greatly reduced. Therefore, a sulfur-containing organosilicon compound has been indispensable for improving the dispersibility of the inorganic filler in the rubber and for chemically bonding the filler and the rubber matrix.

  As sulfur-containing organosilicon compounds, compounds containing an alkoxysilyl group and a polysulfidesilyl group in the molecule, such as bis-triethoxysilylpropyl tetrasulfide and bis-triethoxysilylpropyl disulfide, are known to be effective. .

  In addition to the above organosilicon compound having a polysulfide group, the composition obtained by transesterifying a sulfide group-containing organosilicon compound and an alkyl alcohol amine can greatly improve fuel efficiency and wear resistance. (Japanese Patent Laid-Open No. 2008-169157, International Publication No. 2009/104766).

However, the sulfur-containing organosilicon compound described in the above patent document has a problem that storage stability is poor and handling is difficult.
The background art documents related to the present invention are as follows.

Japanese Patent Publication No.51-20208 Special table 2004-525230 gazette JP 2004-18511 A JP 2005-8639 A JP 2002-145890 A JP 2008-150546 A JP 2010-132604 A Japanese Patent No. 4571125 US Provisional Patent Application No. 60 / 423,577 US Pat. No. 6,229,036 U.S. Pat. No. 6,414,061 JP 2008-169157 A International Publication No. 2009/104766

  The object of the present invention is to solve the above-mentioned problems of the prior art, to greatly reduce the hysteresis loss of the rubber composition, to greatly improve the wear resistance, and to include a good storage stability. The object is to provide a sulfur organosilicon compound and a method for producing the same. Another object is to provide a rubber compounding agent and a rubber composition containing the sulfur-containing organosilicon compound.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a rubber composition using a rubber compounding agent containing a specific sulfur-containing organosilicon compound having a hydrolyzable silyl group, sulfide group, or amino group The present invention has been found to satisfy the desired low fuel consumption tire characteristics, and has led to the present invention.

Accordingly, the present invention provides the following sulfur-containing organosilicon compound, a method for producing the same, a rubber compounding agent, and a rubber composition.
[1]
The following formula (1)
(R ¹ O) _(3-p) (R ² ) _p Si—R ³ —S _n —R ³ —Si (OR ¹ ) _(3-p) (R ² ) _p (1)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value of 2 ≦ n ≦ 6 And p represents 0-2.)
A sulfide group-containing organosilicon compound represented by formula (2):
R ⁴ R ⁵ R ⁶ N (2)
[Wherein R ⁴ is an aryl group having 6 to 12 carbon atoms, R ⁵ is a group represented by the following formula (3), R ⁶ is an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Or a group represented by the following formula (3).
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site.)]
A sulfur-containing organosilicon compound obtained by a transesterification reaction with an amine compound represented by the formula:
[2]
The amine compound represented by the above formula (2) is N-phenyldiethanolamine, 2- (N-methylanilino) ethanol, 2- (N-ethylanilino) ethanol, m-tolyldiethanolamine, o-tolyldiethanolamine, p-tolyldiethanolamine. N-ethyl-N-2-hydroxyethyl-m-toluidine, N-methyl-N-2-hydroxyethyl-m-toluidine, N-ethyl-N-2-hydroxyethyl-o-toluidine, N-methyl- It is selected from N-2-hydroxyethyl-o-toluidine, N-ethyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, The sulfur-containing organosilicon compound according to [1].
[3]
The amount of the amine compound represented by the above formula (2) is 1 to 200 parts by mass with respect to 100 parts by mass of the sulfide group-containing organosilicon compound represented by the above formula (1) [ The sulfur-containing organosilicon compound according to [1] or [2].
[4]
The following formula (1)
(R ¹ O) _(3-p) (R ² ) _p Si—R ³ —S _n —R ³ —Si (OR ¹ ) _(3-p) (R ² ) _p (1)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value of 2 ≦ n ≦ 6 And p represents 0-2.)
A sulfide group-containing organosilicon compound represented by formula (2):
R ⁴ R ⁵ R ⁶ N (2)
[Wherein R ⁴ is an aryl group having 6 to 12 carbon atoms, R ⁵ is a group represented by the following formula (3), R ⁶ is an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Or a group represented by the following formula (3).
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site.)]
The method for producing a sulfur-containing organosilicon compound according to [1], wherein the transesterification reaction is performed in the presence of a catalyst of the amine compound represented by the formula:
[5]
The amine compound represented by the above formula (2) is N-phenyldiethanolamine, 2- (N-methylanilino) ethanol, 2- (N-ethylanilino) ethanol, m-tolyldiethanolamine, o-tolyldiethanolamine, p-tolyldiethanolamine. N-ethyl-N-2-hydroxyethyl-m-toluidine, N-methyl-N-2-hydroxyethyl-m-toluidine, N-ethyl-N-2-hydroxyethyl-o-toluidine, N-methyl- It is selected from N-2-hydroxyethyl-o-toluidine, N-ethyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, [4] The production method according to [4].
[6]
The amount of the amine compound represented by the above formula (2) is 1 to 200 parts by mass with respect to 100 parts by mass of the sulfide group-containing organosilicon compound represented by the above formula (1) [ [4] or [5].
[7]
The production method according to any one of [4] to [6], wherein the catalyst is an acid catalyst, an alkali metal alcoholate, or an organometallic catalyst.
[8]
[1] A compounding agent for rubber comprising the sulfur-containing organosilicon compound according to any one of [3].
[9]
Furthermore, it contains at least one kind of powder, and the mass ratio of the sulfur-containing organosilicon compound (A) and the at least one kind of powder (B) is (A) / (B) = 70/30 to 5 The rubber compounding agent according to [8], which has a ratio of / 95.
[10]
A rubber composition comprising the rubber compounding agent according to [8] or [9].
[11]
[10] A tire formed using the rubber composition according to [10].

  The sulfur-containing organosilicon compound of the present invention has a hydrolyzable silyl group, an amino group, and a sulfide group, and the reactivity and dispersibility in the vicinity of silica increase due to the interaction of the amino group with silica in the rubber. Therefore, the hysteresis loss of the rubber composition can be greatly reduced, and desired low fuel consumption tire characteristics can be satisfied. Moreover, the storage stability can be improved by using an aryl group-substituted amine compound.

  Hereinafter, the present invention will be specifically described. In the present invention, the “silane coupling agent” is included in the “organosilicon compound”.

[Sulfur-containing organosilicon compound (silane coupling agent)]
The sulfur-containing organosilicon compound of the present invention has the following formula (1)
(R ¹ O) _(3-p) (R ² ) _p Si—R ³ —S _n —R ³ —Si (OR ¹ ) _(3-p) (R ² ) _p (1)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value of 2 ≦ n ≦ 6 And p represents 0-2.)
A sulfide group-containing organosilicon compound represented by formula (2):
R ⁴ R ⁵ R ⁶ N (2)
[Wherein R ⁴ is an aryl group having 6 to 12 carbon atoms, R ⁵ is a group represented by the following formula (3), R ⁶ is an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Or a group represented by the following formula (3).
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site.)]
Is a sulfur-containing organosilicon compound obtained by a transesterification reaction in the presence of a catalyst.

In the above formula (1), R ¹ and R ² each represent a monovalent hydrocarbon group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n Examples include alkyl groups such as -butyl group, i-butyl group, t-butyl group, vinyl group, allyl group, and methallyl group, and alkenyl groups. R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, specifically, methylene group, ethylene group, propylene group, n-butylene group, i-butylene group, hexylene group, decylene group, phenylene group, Examples thereof include an alkylene group such as a methylphenylethylene group, an arylene group, an alkenylene group, and a group in which these groups are bonded. n represents a number of 2 ≦ n ≦ 6 as an average value, and preferably an average value of 2 ≦ n ≦ 4 is used. p is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

Examples of such compounds represented by the above formula (1) include the following, but are not limited to those exemplified here.
_{(CH 3 O) 3 Si- (} CH 2) 3 -S 4 - (CH 2) 3 -Si (OCH 3) 3
_{(CH 3 O) 3 Si- (} CH 2) 3 -S 3 - (CH 2) 3 -Si (OCH 3) 3
_{(CH 3 O) 3 Si- (} CH 2) 3 -S 2 - (CH 2) 3 -Si (OCH 3) 3
_{(CH 3 CH 2 O) 3} Si- (CH 2) 3 -S 4 - (CH 2) 3 -Si (OCH 2 CH 3) 3
_{(CH 3 CH 2 O) 3} Si- (CH 2) 3 -S 3 - (CH 2) 3 -Si (OCH 2 CH 3) 3
_{(CH 3 CH 2 O) 3} Si- (CH 2) 3 -S 2 - (CH 2) 3 -Si (OCH 2 CH 3) 3

In the above formula (2), R ⁴ represents an aryl group having 6 to 12 carbon atoms, and specific examples include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and an ethylphenyl group.

R ⁵ is the following formula (3)
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site (hereinafter the same).
Specific examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a decylene group, and a dodecylene group. Examples of the alkylene group of 1 to 10 include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, and a decylene group.

R ⁶ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a group represented by the above formula (3). Specifically, as the alkyl group having 1 to 12 carbon atoms, methyl Group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, and aryl groups having 6 to 12 carbon atoms include phenyl group, naphthyl group, tolyl group, xylyl group, ethyl group And a group of the above formula (3) includes * —CH ₂ —OH, * —C ₂ H ₄ —OH, * —C ₃ H ₆ —OH, * —C ₂ H ₄ —O—. _{C 2 H 4 -OH, * -} (CH 2 CH 2 O) 2 -C 2 H 4 -OH, * - (CH 2 CH 2 O) 3 -C 2 H 4 -OH, * - (CH 2 CH 2 _{O) 4 -C 2 H 4 -OH} , * - ( those _{CH 2 CH 2 O) 5 -C} 2 H 4 -OH While the like, exemplified here No et al.

  More specifically, the amine compound represented by the above formula (2) is N-phenyldiethanolamine, 2- (N-methylanilino) ethanol, 2- (N-ethylanilino) ethanol, m-tolyldiethanolamine, o-tolyldiethanolamine, p-tolyldiethanolamine, N-ethyl-N-2-hydroxyethyl-m-toluidine, N-methyl-N-2-hydroxyethyl-m-toluidine, N-ethyl-N-2-hydroxyethyl-o-toluidine, N-methyl-N-2-hydroxyethyl-o-toluidine, N-ethyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine From the viewpoint of N-phenyldiethanolamine, 2- (N-methylanilino) ethanol 2-(N-ethylanilino) ethanol are preferred.

  The amount of the amine compound represented by the above formula (2) is 1 to 200 parts by mass, preferably 2 to 100 parts per 100 parts by mass of the sulfide group-containing organosilicon compound represented by the above formula (1). It is a mass part, More preferably, it is 10-50 mass parts.

  The catalyst used in the transesterification reaction of the organosilicon compound of the above formula (1) and the amine compound of the above formula (2) is preferably an acid catalyst, an alkali metal alcoholate, or an organometallic catalyst. Examples of the acid catalyst include organic acids such as trifluoromethanesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, camphorsulfonic acid, and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. Examples of the alkali metal alcoholate include sodium methoxide, sodium ethoxide, potassium ethoxide, potassium methoxide, and lithium ethoxide. Examples of organometallic catalysts include titanium catalysts such as tetramethoxy titanium, tetraethoxy titanium, tetrabutoxy titanium and tetrapropoxy titanium, and tin catalysts such as dibutyl tin oxide, methyl phenyl tin oxide, tetraethyl tin and hexaethyl tin oxide. It is done.

  Although there is no restriction | limiting in particular about the usage-amount of the said catalyst, 0.0001-10 mass% with respect to the sulfide group containing organosilicon compound represented by the above Formula (1) which is a raw material, Preferably it is 0.0001-1 mass. %.

  The sulfur-containing organosilicon compound of the present invention is a transesterification product of a sulfide group-containing organosilicon compound of the formula (1) and a phenyl group-substituted amine-containing alcohol of the formula (2), and is produced depending on the valence of the alcohol used. The sulfur-containing organosilicon compound is different. Moreover, although the sulfur-containing organosilicon compound of this invention may be a mixture containing the several organosilicon compound shown below, it is not limited to the organosilicon compound shown below.

  Examples of the reaction between a trialkoxysilyl group-containing organosilicon compound and a monohydric alcohol are: an unreacted sulfide group-containing organosilicon compound, a reaction product obtained by transesterifying one alkoxysilyl group, and two alkoxysilyl groups. A transesterified reaction product, a reaction product obtained by transesterification of three alkoxysilyl groups, a reaction product obtained by transesterification of four alkoxysilyl groups, a reaction product obtained by transesterification of five alkoxysilyl groups, and a reaction product obtained by transesterifying six alkoxysilyl groups. It is conceivable that exchanged reactants are formed. The product is not limited to the organosilicon compounds shown below.

（式中、Ｒ¹は上記の通り。Ａは式（２）で示されるＯＨ基を１個有するアミン化合物の残基、ｘは平均値として２≦ｘ≦６の数である。）

(Wherein R ¹ is as described above, A is a residue of an amine compound having one OH group represented by formula (2), and x is an average value of 2 ≦ x ≦ 6.)

  Examples of the reaction between a trialkoxysilyl group-containing organosilicon compound and a divalent alcohol will be given. Unreacted sulfide group-containing organosilicon compound, reaction product obtained by transesterification of two alcohols in the molecule, reaction product obtained by transesterification of two alcohols between molecules, reaction product cross-linked by dialcohols across multiple molecules A reaction product in which two alcohols are transesterified in the molecule and a reaction product in which a sulfide group-containing organosilicon compound is crosslinked by a dialcohol body, a reaction product in which two alcohols are transesterified in the molecule, and a sulfide group-containing organosilicon A reaction product in which a compound is cross-linked with a dialcohol compound over multiple molecules is considered. The product is not limited to the organosilicon compounds shown below.

（式中、Ｒ¹は上記の通り。Ｂは式（２）で示されるＯＨ基を２個有するアミン化合物の残基、ｘは平均値として２≦ｘ≦６の数である。）

(In the formula, R ¹ is as described above. B is a residue of an amine compound having two OH groups represented by formula (2), and x is an average value of 2 ≦ x ≦ 6.)

[Method for producing sulfur-containing organosilicon compound (silane coupling agent)]
As described above, the sulfur-containing organosilicon compound of the present invention has the following formula (1):
(R ¹ O) _(3-p) (R ² ) _p Si—R ³ —S _n —R ³ —Si (OR ¹ ) _(3-p) (R ² ) _p (1)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value of 2 ≦ n ≦ 6 And p represents 0-2.)
A sulfide group-containing organosilicon compound represented by formula (2):
R ⁴ R ⁵ R ⁶ N (2)
[Wherein R ⁴ is an aryl group having 6 to 12 carbon atoms, R ⁵ is a group represented by the following formula (3), R ⁶ is an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Or a group represented by the following formula (3).
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site.)]
Is obtained by transesterification in the presence of a catalyst, and a solvent may be used as necessary when producing the organosilicon compound of the present invention. The solvent is not particularly limited as long as it is non-reactive with the sulfide group-containing organosilicon compound and amine compound as raw materials, but specifically, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, decane, benzene, toluene, Aromatic hydrocarbon solvents such as xylene, ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and the like can be mentioned.

  Although the reaction temperature in the case of manufacturing the organosilicon compound of this invention will not be specifically limited if reaction has advanced, Preferably it is 20-150 degreeC, More preferably, it is about 60-120 degreeC. Although reaction time will not be specifically limited if reaction is complete | finished, Preferably it is 10 minutes-24 hours, More preferably, it is about 1-15 hours.

  The rubber compounding agent of the present invention contains the sulfur-containing organosilicon compound (A) of the present invention, and a mixture of the sulfur-containing organosilicon compound (A) and at least one powder (B) previously used for rubber. It can also be used as a compounding agent. Examples of the powder (B) include carbon black, talc, calcium carbonate, stearic acid, silica, aluminum hydroxide, alumina, and magnesium hydroxide. From the viewpoint of reinforcing properties, silica and aluminum hydroxide are preferable, and silica is particularly preferable.

  The blending amount of the powder (B) is 70/30 to 5/95, more preferably 60/40 to 10/90 in terms of the mass ratio of the component (A) / (B). If the amount of the powder (B) is too small, the rubber compounding agent becomes liquid, and it may be difficult to prepare the rubber kneader. When there is too much quantity of powder (B), the whole quantity will increase with respect to the effective quantity of the compounding agent for rubber | gum, and transportation cost may become high.

  The rubber compounding agent of the present invention is mixed with an organic polymer such as fatty acid, fatty acid salt, polyethylene, polypropylene, polyoxyalkylene, polyester, polyurethane, polystyrene, polybutadiene, polyisoprene, natural rubber, styrene-butadiene copolymer, or rubber. It is generally blended for tires such as vulcanizing agents, crosslinking agents, vulcanization accelerators, crosslinking accelerators, various oils, anti-aging agents, fillers, plasticizers, and other general rubbers. Various additives may be blended, and the form may be liquid or solid, further diluted with an organic solvent, or emulsified.

The rubber compounding agent of the present invention is suitably used for a rubber composition containing silica.
In this case, the addition amount of the rubber compounding agent is 0.2 to 30 parts by mass, particularly preferably 1 to 20 parts by mass of the organosilicon compound of the present invention with respect to 100 parts by mass of the filler compounded in the rubber composition. It is desirable to do. If the amount of the organosilicon compound added is too small, desired rubber properties cannot be obtained. On the contrary, if the amount is too large, the effect is saturated with respect to the amount added, which is uneconomical.

  Here, as rubber blended as a main component in the rubber composition using the rubber compounding agent according to the present invention, any rubber conventionally blended in various rubber compositions, for example, natural rubber (NR) Diene rubbers such as isoprene rubber (IR), various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), acrylonitrile-butadiene copolymer rubbers (NBR), butyl rubber (IIR), and ethylene-propylene Copolymer rubber (EPR, EPDM) or the like can be used alone or as any blend. Examples of the filler to be blended include silica, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and titanium oxide.

  In addition to the essential components described above, the rubber composition using the rubber compounding agent according to the present invention includes carbon black, vulcanizing agent, crosslinking agent, vulcanization accelerator, crosslinking accelerator, various oils, anti-aging agent, and filling. Various additives generally blended for tires such as an agent and a plasticizer and other general rubbers can be blended. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated.

  In these rubber compositions, the organosilicon compound of the present invention can be used in place of a known silane coupling agent, but the addition of other silane coupling agents is optional, and silica has conventionally been used. You may add the arbitrary silane coupling agents used together with a filler. Typical examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, β-aminoethyl-γ. -Aminopropyltrimethoxysilane, β-aminoethyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Triethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, bis-triethoxysilylpropyl tetrasulfide, bis-triethoxysilylpropyl disulfide, etc. It can gel.

  The rubber composition obtained by compounding the rubber compounding agent of the present invention can be used after kneading, vulcanizing or crosslinking by a general method.

  The tire of the present invention is characterized by using the above rubber composition, and the above rubber composition is preferably used for a 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, an inert gas such as nitrogen, argon, helium, etc. can be used as the gas filled in the tire, in addition to normal or adjusted oxygen partial pressure.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in more detail, this invention is not limited to these Examples. In the following examples, the viscosity is based on measurement at 25 ° C. with a capillary kinematic viscometer. Moreover, a part shows a mass part.

[Example 1]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) N-phenyldiethanolamine 90.6 g (0.5 mol) and xylene 500 g were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.03 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 580.5 g of the reaction product obtained by concentration under reduced pressure using a rotary evaporator is a brown transparent liquid having a viscosity of 73 mm ² / s, and the obtained sulfur-containing organosilicon compound is converted into an organosilicon compound (1). And

[Example 2]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) Then, 181.2 g (1.0 mol) of N-phenyldiethanolamine and 500 g of xylene were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.05 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 625.9 g of the reaction product obtained by concentration under reduced pressure on a rotary evaporator is a brown transparent liquid having a viscosity of 1080 mm ² / s, and the obtained sulfur-containing organosilicon compound is converted into an organosilicon compound (2). And

[Example 3]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) N-phenyldiethanolamine 90.6 g (0.5 mol) and xylene 500 g were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.6 g of trifluoromethanesulfonic acid was added, and the mixture was heated and stirred at 120 ° C. for 10 hours. Thereafter, 6.0 g of KYOWARD 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at room temperature for 2 hours. The reaction product of 578.8 g obtained by concentrating and filtering under reduced pressure using a rotary evaporator is a brown transparent liquid having a viscosity of 70 mm ² / s, and the resulting sulfur-containing organosilicon compound is converted to an organosilicon compound (3). And

[Example 4]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) Then, 181.2 g (1.0 mol) of N-phenyldiethanolamine and 500 g of xylene were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.6 g of trifluoromethanesulfonic acid was added, and the mixture was heated and stirred at 120 ° C. for 10 hours. Thereafter, 6.0 g of KYOWARD 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at room temperature for 2 hours. 620.9 g of the reaction product obtained by concentration under reduced pressure and filtration with a rotary evaporator is a brown transparent liquid having a viscosity of 990 mm ² / s, and the resulting sulfur-containing organosilicon compound is converted to an organosilicon compound (4). And

[Example 5]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) Then, 97.7 g (0.5 mol) of p-tolyldiethanolamine and 500 g of xylene were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.03 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 588.8 g of the reaction product obtained by concentration under reduced pressure on a rotary evaporator is a brown transparent liquid having a viscosity of 89 mm ² / s, and the obtained sulfur-containing organosilicon compound is combined with the organosilicon compound (5). To do.

[Example 6]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) 2- (N-methylanilino) ethanol 75.6 g (0.5 mol) and xylene 500 g were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.03 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 587.5 g of the reaction product obtained by concentration under reduced pressure on a rotary evaporator is a brown transparent liquid having a viscosity of 58 mm ² / s, and the obtained sulfur-containing organosilicon compound is combined with the organosilicon compound (6). To do.

[Example 7]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) 2- (N-ethylanilino) ethanol 82.6 g (0.5 mol) and xylene 500 g were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.03 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 591.6 g of the reaction product obtained by concentration under reduced pressure using a rotary evaporator is a brown transparent liquid having a viscosity of 58 mm ² / s. The obtained sulfur-containing organosilicon compound is combined with the organosilicon compound (7). To do.

[Comparative Example 1]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) N-methyldiethanolamine 59.6 g (0.5 mol) and xylene 500 g were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.03 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 545.1 g of a reaction product obtained by concentration under reduced pressure on a rotary evaporator is a brown transparent liquid having a viscosity of 42 mm ² / s. The obtained sulfur-containing organosilicon compound is combined with the organosilicon compound (8). To do.

[Comparative Example 2]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 539.0 g (1.0 mol) of bis (triethoxysilylpropyl) tetrasulfide (KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd.) Then, 74.6 g (0.5 mol) of triethanolamine and 500 g of xylene were placed and heated to 120 ° C. in an oil bath. Thereafter, 0.03 g of tetrabutoxy titanium was added, and the mixture was heated and stirred at 120 ° C. for 5 hours. Thereafter, 538.5 g of a reaction product obtained by concentration under reduced pressure using a rotary evaporator is a brown transparent liquid having a viscosity of 122 mm ² / s, and the obtained sulfur-containing organosilicon compound is combined with the organosilicon compound (9). To do.

[Examples 8 to 14, Comparative Examples 3 and 4]
The storage stability of the sulfur-containing organosilicon compounds synthesized in Examples 1 to 7 and Comparative Examples 1 and 2 was measured by the following method. The results are shown in Table 1.
[Measurement condition]
20 g of a sulfur-containing organosilicon compound was placed in a 50 g glass container and stored in a constant temperature and humidity chamber at 40 ° C. and 50 RH% in an open system, and the state after 1 week and 1 month was evaluated.
[Evaluation criteria]
○: No change (maintains liquid state)
Δ: partially solidified ×: completely solidified (gelation)

  As shown in Table 1, it was shown that the reaction product with alkyl alcohol amine has poor wet heat stability, whereas the sulfur-containing organosilicon compound of the present invention has excellent wet heat stability and can be stored for a long time. .

[Examples 15 to 21, Comparative Examples 5 to 9]
Oil-extended emulsion polymerization SBR (# 1712 manufactured by JSR Corporation) 110 parts, NR (general RSS # 3 grade) 20 parts, carbon black (general N234 grade) 20 parts, silica (Nippon Silica Industry Co., Ltd.) Nipsil AQ) 50 parts, sulfur-containing organosilicon compounds of Examples 1 to 7 or comparative compounds A to C 6.5 parts shown below, stearic acid 1 part, anti-aging agent 6C (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) A masterbatch was prepared by blending 1 part of Nocrack 6C). To this, 3 parts of zinc white, 0.5 parts of vulcanization accelerator DM (dibenzothiazyl disulfide), 1 part of vulcanization accelerator NS (Nt-butyl-2-benzothiazolylsulfenamide), sulfur 1. 5 parts was added and kneaded to obtain a rubber composition.
Next, the unvulcanized or vulcanized physical properties of the rubber composition were measured by the following method. The results are shown in Tables 2 and 3.

[Unvulcanized properties]
(1) Mooney viscosity Measured according to JIS K 6300, with a residual heat of 1 minute, a measurement of 4 minutes, and a temperature of 130 ° C. The smaller the index value, the lower the Mooney viscosity and the better the workability.
[Vulcanized properties]
(2) Dynamic viscoelasticity Using a viscoelasticity measuring device (Rheometrix Co., Ltd.), dynamic viscoelasticity was measured under conditions of tensile dynamic strain 5%, frequency 15 Hz, 60 ° C. In addition, the test piece used the sheet | seat of thickness 0.2cm and width 0.5cm, the initial load was 160 g with the distance between use nippings 2 cm. The value of tan δ was expressed as an index with Comparative Example 7 as 100. The smaller the index value, the smaller the hysteresis loss and the lower the heat buildup.
(3) Abrasion resistance In accordance with JIS K 6264-2: 2005, a test was performed at room temperature and a slip rate of 25% using a Lambone type abrasion tester, and the reciprocal of the abrasion amount of Comparative Example 7 was set to 100. The index was displayed. The larger the index value, the smaller the amount of wear and the better the wear resistance.

  As shown in Tables 2 and 3, it was shown that the organosilicon compound of the present invention significantly reduces the hysteresis loss and greatly improves the wear resistance.

Claims (11)

The following formula (1)
(R ¹ O) _(3-p) (R ² ) _p Si—R ³ —S _n —R ³ —Si (OR ¹ ) _(3-p) (R ² ) _p (1)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value of 2 ≦ n ≦ 6 And p represents 0-2.)
A sulfide group-containing organosilicon compound represented by formula (2):
R ⁴ R ⁵ R ⁶ N (2)
[Wherein R ⁴ is an aryl group having 6 to 12 carbon atoms, R ⁵ is a group represented by the following formula (3), R ⁶ is an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Or a group represented by the following formula (3).
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site.)]
A sulfur-containing organosilicon compound obtained by a transesterification reaction with an amine compound represented by the formula:   The amine compound represented by the above formula (2) is N-phenyldiethanolamine, 2- (N-methylanilino) ethanol, 2- (N-ethylanilino) ethanol, m-tolyldiethanolamine, o-tolyldiethanolamine, p-tolyldiethanolamine. N-ethyl-N-2-hydroxyethyl-m-toluidine, N-methyl-N-2-hydroxyethyl-m-toluidine, N-ethyl-N-2-hydroxyethyl-o-toluidine, N-methyl- It is selected from N-2-hydroxyethyl-o-toluidine, N-ethyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, The sulfur-containing organosilicon compound according to claim 1.   The amount of the amine compound represented by the above formula (2) is 1 to 200 parts by mass with respect to 100 parts by mass of the sulfide group-containing organosilicon compound represented by the above formula (1). Item 3. The sulfur-containing organosilicon compound according to Item 1 or 2. The following formula (1)
(R ¹ O) _(3-p) (R ² ) _p Si—R ³ —S _n —R ³ —Si (OR ¹ ) _(3-p) (R ² ) _p (1)
Wherein R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is an average value of 2 ≦ n ≦ 6 And p represents 0-2.)
A sulfide group-containing organosilicon compound represented by formula (2):
R ⁴ R ⁵ R ⁶ N (2)
[Wherein R ⁴ is an aryl group having 6 to 12 carbon atoms, R ⁵ is a group represented by the following formula (3), R ⁶ is an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. Or a group represented by the following formula (3).
_{* - (CH 2) s -R} 7 -OH (3)
Wherein R ⁷ is an alkylene group having 1 to 12 carbon atoms or * —O— (Y—O) _m —Y— *, Y is an alkylene group having 1 to 10 carbon atoms, and m is 1 -40, and s represents 0 to 12. * represents a binding site.)]
The method for producing a sulfur-containing organosilicon compound according to claim 1, wherein the transesterification reaction is performed in the presence of a catalyst.   The amine compound represented by the above formula (2) is N-phenyldiethanolamine, 2- (N-methylanilino) ethanol, 2- (N-ethylanilino) ethanol, m-tolyldiethanolamine, o-tolyldiethanolamine, p-tolyldiethanolamine. N-ethyl-N-2-hydroxyethyl-m-toluidine, N-methyl-N-2-hydroxyethyl-m-toluidine, N-ethyl-N-2-hydroxyethyl-o-toluidine, N-methyl- It is selected from N-2-hydroxyethyl-o-toluidine, N-ethyl-N-2-hydroxyethyl-p-toluidine, N-methyl-N-2-hydroxyethyl-p-toluidine, The manufacturing method of Claim 4.   The amount of the amine compound represented by the above formula (2) is 1 to 200 parts by mass with respect to 100 parts by mass of the sulfide group-containing organosilicon compound represented by the above formula (1). Item 6. The method according to Item 4 or 5.   The method according to any one of claims 4 to 6, wherein the catalyst is an acid catalyst, an alkali metal alcoholate, or an organometallic catalyst.   The compounding agent for rubber | gum which comprises the sulfur-containing organosilicon compound of any one of Claims 1-3.   Furthermore, it contains at least one kind of powder, and the mass ratio of the sulfur-containing organosilicon compound (A) and the at least one kind of powder (B) is (A) / (B) = 70/30 to 5 The compounding agent for rubber according to claim 8, which has a ratio of / 95.   A rubber composition comprising the rubber compounding agent according to claim 8 or 9.   A tire formed using the rubber composition according to claim 10.