TW201936678A - Organosilicon compound, and additive for rubber and rubber composition each including same - Google Patents

Abstract

An organosilicon compound represented by formula (1) which, when added to a rubber composition, enables the rubber composition to not only give a cured object having a greatly reduced hysteresis loss but also render fuel-saving tires having desired wet grip performance possible. (In formula (1), R1 represents an alkyl or aryl group; R2 represents an alkyl or aryl group; A represents a monovalent hydrocarbon group; X represents a single bond or one or more radicals selected from among -S-, -CO-, and -CS-; a is a number larger than 0, b is a number of 0 or larger, c is a number of 0 or larger, d is a number of 0 or larger, e is a number larger than 0, and f is a number of 0 or larger, c+d being a number larger than 0; and m is an integer of 1-3; the order of the repeating units being optional.).

Description

Organic germanium compound, rubber blending agent and rubber composition using the same

The present invention relates to an organic ruthenium compound, a rubber blending agent and a rubber composition using the same, and more particularly to an organic ruthenium compound having a polybutadiene skeleton and a skeleton containing a sulfur atom, a method for producing the same, and a method for producing the same A rubber blending agent and a rubber composition of a bismuth compound, and a tire obtained from the rubber composition.

The sulfur-containing organic cerium compound is useful as an essential component in the production of a tire made of a cerium oxide-filled rubber composition. The cerium oxide filled tire has excellent performance in automotive applications, particularly excellent in abrasion resistance, rolling resistance and wet grip. Such performance improvement is closely related to the low fuel consumption of tires, and has recently been vigorously studied.

In order to improve the fuel economy, it is necessary to increase the cerium oxide filling rate of the rubber composition. However, although the ruthenium dioxide-filled rubber composition reduces the rolling resistance of the tire and improves the wet grip property, the unvulcanized viscosity is high, and multi-stage mixing is required. There is a problem with the workability.
Therefore, in the rubber composition in which only the inorganic filler such as cerium oxide is blended, the dispersion of the filler is insufficient, and the breaking strength and the abrasion resistance are largely lowered. Therefore, in order to improve the dispersibility of the inorganic filler into the rubber while chemically bonding the filler to the rubber matrix, it is necessary to contain a sulfur-containing organic cerium compound.

As a sulfur-containing organic cerium compound used as a rubber admixture, a compound containing an alkoxy fluorenyl group and a polythioether fluorenyl group in a molecule, such as bistriethoxydecyl propyl tetrasulfide or double triethyl ethane, is known. Oxydecyl propyl disulfide or the like (see Patent Documents 1 to 4).

On the other hand, Patent Document 5 discloses a decane-modified butadiene polymer as a rubber admixture, but since the decane-modified butadiene polymer does not contain a sulfur atom, there is a case where the desired tire physical properties cannot be exhibited. .
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2004-525230
[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-18511
[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-145890
[Patent Document 4] US Patent No. 6229036
[Patent Document 5] Japanese Laid-Open Patent Publication No. 2016-191040

[Problems to be solved by the invention]

The present invention has been made in view of the above circumstances, and an object of the invention is to provide an organic ruthenium compound which, when added to a rubber composition, can greatly reduce the hysteresis loss of the cured product, and at the same time, can provide a achievable The rubber composition of the low fuel consumption tire of the desired wet grip characteristics.
Further, another object of the invention is to provide a rubber blending agent comprising the organic cerium compound, a rubber composition obtained by blending the rubber blending agent, and a tire formed of the rubber composition.

[Means for solving the problem]

In order to solve the above problems, the inventors of the present invention have intensively reviewed and found that a specific organic ruthenium compound having a polybutadiene skeleton and a unit containing a hydrolyzable thiol group and having a unit having a sulfur bond is added to the rubber composition. It can be used as a rubber blending agent, and it is found that the tire obtained from the rubber composition containing the rubber blending agent can achieve desired wet grip characteristics and low fuel consumption. The present invention was completed.

That is, the present invention provides:
An organic hydrazine compound represented by the following formula (1);

(wherein R ¹ independently of each other represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms; A, A represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a single bond or a group of one or more selected from -S-, -CO- and -CS-; a represents a value greater than 0. Number, b represents a number above 0, c represents a number above 0, d represents a number above 0, e represents a number greater than 0, f represents a number above 0, but c+d represents a number greater than 0; m represents 1 An integer of ～3; however, the order of each repeating unit is arbitrary).
2. The organofluorene compound according to 1, wherein the functional group represented by -XA is a functional group represented by the following formula (2);

(In the formula, the A system is the same as described above; * means the bonding key).
3. A method for producing an organic phosphonium compound according to 1, characterized in that an organic phosphonium compound represented by the following formula (3) is reacted with a compound represented by the following formula (4);

(wherein R ¹ , R ² , a, b, c, d, e, f, and m are the same as described above)

(In the formula, A and X are the same as described above).
4. The production method according to 3, wherein the compound represented by the above formula (4) is a compound represented by the following formula (5);

(In the formula, the A system is the same as described above).
A rubber blending agent comprising the organic ruthenium compound according to 1 or 2.
A rubber composition comprising the rubber blending agent as described in 5.
A tire obtained by molding a rubber composition as described in 6.

[Effects of the Invention]

The organic ruthenium compound of the present invention has a polybutadiene skeleton, a sulfur bond, and a hydrolyzable thiol group, and the tire formed by using the rubber composition of the rubber-containing admixture containing the organic ruthenium compound can satisfy the desired wet grip. Ground characteristics and low fuel consumption tire characteristics.

[Formation of the Invention]

Hereinafter, the present invention will be specifically described.
[Organic bismuth compound]
The organic hydrazine compound of the present invention is represented by the following formula (1). Further, in the formula (1), the order of each repeating unit is arbitrary.

In the formula, R ¹ independently represents a carbon number of 1 to 10, preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents a carbon number of 1 to 10, preferably Is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and X represents a single bond or a group of one or more selected from -S-, -CO-, and -CS-; and a represents a value greater than 0. Number, b represents a number above 0, c represents a number above 0, d represents a number above 0, e represents a number greater than 0, f represents a number above 0, but c+d represents a number greater than 0; m represents 1 An integer of ~3.

Here, the alkyl group having 1 to 10 carbon atoms of R ¹ and R ² may be any of a linear chain, a branched chain, and a cyclic ring, and specific examples thereof include a methyl group, an ethyl group, and a positive electrode. Propyl, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, cyclopropyl, cyclobutane Base, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
Specific examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, an a-naphthyl group, and a β-naphthyl group.

Among these, R ^{1 is} preferably a linear alkyl group, more preferably a methyl group or an ethyl group.
Further, R ^{2 is} preferably a linear alkyl group, more preferably a methyl group or an ethyl group.

The monovalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted by A is preferably a carbon number of 1 to 10, and examples thereof include a linear, branched or cyclic alkyl group, an aryl group and an aralkyl group. Base. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-butyl group, a tert-butyl group, a pentyl group, a 2-pentyl group, a 3-pentyl group, a neopentyl group, and the like. Third amyl, hexyl, 2-hexyl, 3-hexyl, isohexyl, tert-hexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, decyl, decyl, eleven Base, dodecyl, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, cyclopentyl, cyclohexyl, cycloheptyl, a linear, branched or cyclic alkyl group such as a cyclohexyl group or a tributylcyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a trimethylphenyl group; a benzyl group or a phenethyl group; An aralkyl group such as 3-phenylpropyl group. In addition, examples of the substituted hydrocarbon group include a hetero atom such as nitrogen, oxygen, sulfur, or a ruthenium atom, and specific examples thereof include trimethoxydecylpropyl group and triethoxymethoxypropyl group. An alkoxyfluorenyl-containing alkyl group; benzimidazolyl, imidazolyl, benzothiazolyl, benzo a heterocyclic group such as an azole group, a pyrimidinyl group, a fluorenyl group, a triazolyl group or a pyridyl group.

X represents at least one linking group selected from a single bond, a sulfur atom (-S-), a carbonyl bond (-CO-), and a thiocarbonyl bond (-CS-), preferably -CO-. By having such a sulphur grease structure, it is possible to improve tire physical properties such as low fuel consumption and wet grip.

The functional group represented by -XA is particularly preferably a group represented by the following formula (2).

(In the formula, the A system is the same as described above; * means the bonding key).

a is a number greater than 0, preferably greater than 5, and more preferably an integer of 10 to 100.
b is a number of 0 or more, preferably an integer of 0 to 50, more preferably an integer of 0 to 5.
c is a number of 0 or more, d is a number of 0 or more, and c+d is a number greater than 0, preferably more than 2, more preferably an integer of 3 to 50.
e is a number greater than 0, preferably greater than 2, and more preferably greater than 3 to 50.
f is a number of 0 or more, but when a unit containing f is used, it is preferably more than 2, more preferably an integer of 3 to 50.
m is an integer of 1 to 3.

The organic ruthenium compound represented by the formula (1) can be obtained by reacting an organic ruthenium compound represented by the following formula (3) with a sulfur atom-containing compound represented by the following formula (4).

(wherein R ¹ , R ² , a, b, c, d, e, f, A, X and m are the same as described above.)

Examples of the sulfur atom-containing compound represented by the above formula (4) include an alkylthiol compound, an alkoxyfluorenyl group-containing mercapto compound, a heterocyclic mercapto compound, and a thio acid compound. The sulfur atom-containing compound is particularly preferably a thio acid compound represented by the following formula (5).

(In the formula, the A system is the same as above.)

Specific examples of the compound having a sulfur atom represented by the above formula (4) include an alkyl group such as propanethiol, butanol, hexyl mercaptan, pentyl mercaptan, octyl mercaptan or decyl mercaptan. a mercaptan compound; an alkoxyfluorenyl-containing mercapto compound such as 3-mercaptopropyltrimethoxydecane or 3-mercaptopropyltriethoxydecane; mercaptobenzimidazole, mercapto imidazole, mercaptobenzothiazole, 2 - mercaptobenzo a heterocyclic mercapto compound such as azole, 2-mercaptopyrimidine, 6-fluorenylpurine, 1H-1,2,4-triazole-3-thiol or 4-mercaptopyridine; thioacetic acid, thiobenzoic acid, etc. A thio acid compound or the like. Among these, thioacetic acid is preferred from the viewpoint of improving the physical properties of the rubber in which the organic ruthenium compound is blended.

In the above reaction, a catalyst can be used as needed. The catalyst is preferably a radical generator, and examples thereof include an azo compound, an organic peroxide, and the like, and those which generate radicals due to heat or generate radicals by light irradiation. Specific examples of the azo compound include azobisisobutyronitrile (AIBN) and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN). Examples of the organic peroxide include di-tert-butyl peroxide, tert-butyl hydroperoxide, benzammonium peroxide, methyl ethyl ketone peroxide, and tert-butyl peroxygen. 2-ethylhexanoate or the like.

Further, the above reaction may be carried out without a solvent, but a solvent may also be used.
Specific examples of the usable solvent include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; diethyl ether, tetrahydrofuran, and An ether solvent such as an alkane; an ester solvent such as ethyl acetate or butyl acetate; an aprotic polar solvent such as N,N-dimethylformamide; a chlorinated hydrocarbon solvent such as dichloromethane or chloroform; The solvent may be used singly or in combination of two or more.

The reaction temperature of the above reaction is not particularly limited, and it can be carried out at 0 ° C to heating, preferably 40 to 150 ° C.
In order to obtain a moderate reaction rate, it is preferred to carry out the reaction under heating. From such a viewpoint, the reaction temperature is preferably from 40 to 130 ° C, more preferably from 50 to 120 ° C.
Further, the reaction time is not particularly limited, but is usually about 1 to 60 hours, preferably 1 to 30 hours, more preferably 1 to 20 hours.

[Adhesive for rubber]
The rubber blending agent of the present invention contains the organic hydrazine compound represented by the above formula (1).
In this case, in consideration of viscosity, workability, and the like, the number average molecular weight of the above organic cerium compound used for the rubber binder is preferably 100,000 or less, more preferably 40,000 or less, and still more preferably 1,000 to 20,000. Further, in the present invention, the number average molecular weight is a polystyrene-converted value of gel permeation chromatography.

In the present invention, when the organic ruthenium compound used for the rubber compounding agent is considered to have improved properties of the obtained rubber composition, the unit having a hydrolyzable thiol group preferably contains 2 mol% or more per unit. Therefore, in the formula (1), it is preferable to satisfy 0.02 ≦e / (a + b + c + d + h + e + f) < 0.9. In particular, the unit having a hydrolyzable mercapto group preferably contains 3 mol% or more per unit.

Further, in the present invention, the organic ruthenium compound used for the rubber blending agent preferably has a unit cell having a sulfur atom in an amount of 1 mol% or more per unit, in consideration of improving the properties of the obtained rubber composition and the like. Therefore, in the formula (1), it is preferable to satisfy 0.01 ≦(c+d)/(a+b+c+d+h+e+f)<1.0.
In particular, the unit unit having a sulfur atom preferably contains 2 mol% or more per unit.

Further, the rubber admixture of the present invention may contain a thioether group-containing organic hydrazine compound.
The thioether group-containing organic hydrazine compound is not particularly limited, and specific examples thereof include bis(trimethoxydecylpropyl)tetrasulfide and bis(triethoxymethylpropyl)tetrasulfide. , bis(trimethoxydecylpropyl) disulfide, bis(triethoxymethylpropyl) disulfide, and the like.

The blend ratio of the above organic cerium compound to the thioether group-containing organic cerium compound in the rubber admixture is preferably an organic hydrazine compound: thioether decane = 5:95 to 80:20, more preferably by mass ratio. It is 10:90 to 50:50.

Further, an organic cerium compound of the present invention and an organic cerium compound containing a thioether group and at least one kind of powder may be used as a rubber admixture.
Specific examples of the powder include carbon black, talc, calcium carbonate, stearic acid, cerium oxide, aluminum hydroxide, aluminum oxide, and magnesium hydroxide.
Among these, from the viewpoint of reinforcing properties, cerium oxide and aluminum hydroxide are preferred, and cerium oxide is more preferred.

When the blending amount of the powder is considered, the total amount of the powder (Y) and the total amount of the organic cerium compound and the thioether group-containing organic cerium compound (X) are considered in consideration of the handleability of the rubber binder or the transportation cost. The mass ratio ((X)/(Y)) is preferably 70/30 to 5/95, more preferably 60/40 to 10/90.

Furthermore, the rubber admixture of the present invention may also be combined with a fatty acid, a fatty acid salt, a polyethylene, a polypropylene, a polyoxyalkylene, a polyester, a polyurethane, a polystyrene, a polybutadiene, and a polyisoprene. Mixing organic polymer or rubber such as olefin, natural rubber, styrene-butadiene copolymer, etc., or blending vulcanizing agent, crosslinking agent, vulcanization accelerator, crosslinking accelerator, various oils, anti-aging agent, filling For the use of tires, plasticizers, etc., and other additives commonly used in general rubber.
Further, the form may be liquid or solid, and may be diluted in an organic solvent or may be an emulsifier.

[Rubber composition]
In the present invention, as the rubber which is a main component of the rubber composition to which the rubber binder is added, any rubber which is generally used in various rubber compositions can be used. Specific examples thereof include natural rubber (NR). : Isoprene rubber (IR), various styrene-butadiene copolymer rubber (SBR), various polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), etc. A non-diene rubber such as a butyl rubber (IIR) or an ethylene-propylene copolymer rubber (EPR or EPDM) may be used alone or in combination of two or more.
In addition, the blending amount of the rubber in the rubber composition is not particularly limited, and may be 20 to 80% by mass in the conventional general range.

The rubber admixture of the present invention is suitable as a blending agent for a filler-containing rubber composition. As the filler, the same as the above powder may be used, and examples thereof include cerium oxide, talc, clay, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and titanium oxide. Among these, the rubber admixture of the present invention is more preferably used as a blending agent of a rubber composition containing cerium oxide.
Further, the content of the filler in the rubber composition may be a conventional general blending amount as long as it does not contradict the object of the present invention.

In this case, in consideration of the physical properties of the obtained rubber, the balance between the degree of the effect of the rubber, and the economical balance, the amount of the rubber-containing admixture is 100 parts by mass based on the filler contained in the rubber composition. The cerium compound is preferably 0.2 to 30 parts by mass, more preferably 1 to 20 parts by mass.

In the rubber composition of the present invention, in addition to the above components, sulfur, carbon black, a vulcanizing agent, a crosslinking agent, a vulcanization accelerator, a crosslinking accelerator, various oils, an anti-aging agent, a plasticizer, and the like may be blended. Various additives generally used for tires such as decane coupling agents and other general rubbers. The blending amount of such additives may be a conventional general blending amount as long as it does not contradict the object of the present invention.

[Rubber products (tires)]
The rubber composition obtained by blending the rubber-containing admixture of the present invention is kneaded by a general method to form a composition, and can be used for the production of a vulcanized or crosslinked rubber product such as a rubber product such as a tire. Particularly in the production of a tire, the rubber composition of the present invention is preferably used for a tread.
The tire obtained by using the rubber composition of the present invention can greatly improve the wet grip property and the abrasion resistance in addition to greatly reducing the rolling resistance, so that desired fuel economy can be achieved.
Furthermore, the structure of the tire can be a conventional structure, and the manufacturing method can also be carried out by a conventional method. Further, in the case of a tire filled with a gas, as the gas filled in the tire, air which is adjusted by ordinary air or oxygen partial pressure, and an inert gas such as nitrogen, argon or helium may be used.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited by the examples.
In addition, the "part" in the following means the mass part. The molecular weight is a polystyrene-equivalent number average molecular weight determined by GPC (gel permeation chromatography). The viscosity is measured at 25 ° C using a rotational viscometer. Further, in the following formula, Et represents an ethyl group.

[1] Manufacture of organic bismuth compounds
[Example 1-1] The synthesis of the organic hydrazine compound A was carried out in a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and was stored in the first embodiment described in JP-A-2016-191040. In the same manner, 300 g of an organic hydrazine compound (number average molecular weight: 3,600) represented by the following average composition formula (6), 73 g of octyl mercaptan and 400 g of toluene were produced in the same manner, and the mixture was heated to 90 °C. Thereto, 1.0 g of tert-butylperoxy 2-ethylhexanoate (Perbutyl O, manufactured by Nippon Oil & Fats Co., Ltd.) was dropped, and the mixture was stirred at 90 ° C for 2 hours.

After completion of the reaction, it was confirmed by gas chromatography that the octyl mercaptan compound disappeared.
After completion of the reaction, the mixture was concentrated under reduced pressure and filtered to give a brown transparent liquid having a viscosity of 2,000 mPa·s and a number average molecular weight of 4,500.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum is in the above formula (1), and A=-C ₈ H ₁₇ , X=single bond, a=33, b=0, ( An organogermanium compound represented by c+d)=6, e=7, and f=0. This compound was regarded as an organic hydrazine compound A.

[Example 1-2] Synthesis of the organic ruthenium compound B The reaction and the post treatment were carried out in the same manner as in Example 1-1 except that the octyl mercaptan was changed to 38 g of thioacetic acid to obtain a viscosity of 2,000 mPa·s, and the number average was obtained. A brown transparent liquid with a molecular weight of 4,100.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum is in the above formula (1), and A=-CH ₃ , X=-CO-, a=33, b=0, (c) +d) = 6, an organic ruthenium compound represented by e = 7, f = 0. This compound was regarded as an organic hydrazine compound B.

[Example 1-3] Synthesis of organic hydrazine compound C The reaction and the post-treatment were carried out in the same manner as in Example 1-2 except that the amount of the thioacetic acid was changed to 19 g, to obtain a viscosity of 1,900 mPa·s and a number average molecular weight of 3,900. Brown transparent liquid.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum is in the above formula (1), and A=-CH ₃ , X=-CO-, a=33, b=3, (c) +d) = 3, e = 7, organic oxime compound shown by f = 0. This compound was regarded as an organic hydrazine compound C.

[Example 1-4] The synthesis of the organic ruthenium compound D was carried out in a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and was stored in the first embodiment described in JP-A-2017-8301. 5, 400 g of organic hydrazine compound (number average molecular weight 8,800), 38 g of thioacetic acid and 400 g of toluene represented by the following average composition formula (7) were produced in the same manner, and the mixture was heated to 90 °C. Thereto, 1.0 g of tert-butylperoxy 2-ethylhexanoate (Perbutyl O, manufactured by Nippon Oil & Fats Co., Ltd.) was dropped, and the mixture was stirred at 90 ° C for 2 hours.

After completion of the reaction, it was confirmed by gas chromatography that the octyl mercaptan compound disappeared.
After completion of the reaction, the mixture was concentrated under reduced pressure and filtered to give a brown transparent liquid having a viscosity of 14,000 mPa·s and a number average molecular weight of 9,600.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum is in the above formula (1), and A=-CH ₃ , X=-CO-, a=52, b=0, (c) +d) = 01, e = 1, 1 = f = 29 organic hydrazine compound. This compound was regarded as an organic hydrazine compound D.

[Example l-5] Synthesis of organic ruthenium compound E The reaction and the post treatment were carried out in the same manner as in Example 1-4 except that the amount of the thioacetic acid was changed to 19 g, to obtain a viscosity of 13,000 mPa·s and a number average molecular weight of 9,200. Brown transparent liquid.
The average structure obtained from the molecular weight of the product and the ¹ H-NMR spectrum is in the above formula (1), and A=-CH ₃ , X=-CO-, a=52, b=5, (c) +d) = 6, organic oxime compound represented by e = 1 and f = 29. This compound was regarded as an organic hydrazine compound E.

[2] Modulation of rubber composition
[Example 2-1]
As shown in Table 1, 110 parts of blended oil-expanded emulsion SBR (JSR (manufactured by JSR) #1812), 20 parts of NR (RSS #3 grade), 20 parts of carbon black (N234 grade), and cerium oxide (Japan II) 70 parts of Nipsil AQ) made by yttrium oxide industry, 7.0 parts of organic bismuth compound A obtained in Example 1-1, 1 part of stearic acid and 6C of anti-aging agent (Nocrac 6C manufactured by Okinawa Chemical Industry Co., Ltd.) 1 part, the masterbatch is prepared.
3 parts of zinc sulphate, 0.5 part of vulcanization accelerator DM (dibenzothiazolyl disulfide), and 1 part of vulcanization accelerator NS (N-tert-butyl-2-benzothiazolylsulfenamide) And 1.5 parts of sulfur and kneaded to obtain a rubber composition.

[Examples 2-2 to 2-5]
In the same manner as in Example 2-1 except that the organic sulfonium compound A obtained in Example 1-1 was changed to the organic fluorene compounds B to E obtained in Examples 1-2 to 1-5, respectively, as shown in Table 1. Rubber composition.

[Comparative Examples 2-1 to 2-3]
The organic ruthenium compound A obtained in Example 1-1 was changed to bis(triethoxymethyl propyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.), as shown in Table 2, A rubber composition was obtained in the same manner as in Example 2-1 except for the organic fluorene compound represented by the above average structural formula (6) or (7).

With respect to the rubber compositions obtained in the above Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3, the unvulcanized and sulfided properties were measured by the following methods. The results are shown together in Tables 1 and 2.

[unsulfided property]
(1) Muney viscosity According to JIS K 6300, the measurement was carried out at a temperature of 130 ° C, residual heat for 1 minute, and measurement for 4 minutes, and Comparative Example 2-1 was regarded as 100 and expressed by an index. The smaller the value of the index, the lower the viscosity of the Mooney and the better the processability.

[sulfide property]
(2) Dynamic viscoelasticity was measured using a viscoelasticity measuring apparatus (manufactured by RHEOMETRICS Co., Ltd.) under conditions of tensile dynamic strain of 5%, frequency of 15 Hz, 0 °C or 60 °C. Further, in the test piece, a sheet having a thickness of 0.2 cm and a width of 0.5 cm was used, and the distance between the grips was set to 2 cm, and the initial load was 160 g. The value of tand is taken as Comparative Example 2-1 as 100, expressed as an index. The larger the index value of 0 ° C, the better the wet grip performance can be evaluated. The smaller the index value at 60 ° C, the smaller the hysteresis loss and the lower the heat build-up.
(3) Abrasion resistance According to JIS K 6264-2:2005, the test was carried out under the conditions of a room temperature and a slip ratio of 25% using a Lambourn type abrasion tester. Comparative Example 2-1 was taken as 100 and expressed as an index. The larger the index value, the less the wear is, indicating that the wear resistance is better.

As shown in Tables 1 and 2, it was found that the rubber compositions of Examples 2-1 to 2-5 had a low Muey viscosity and excellent workability as compared with the rubber compositions of Comparative Example 2-1.
Further, it is understood that the sulfide compositions of the rubber compositions of Examples 2-1 to 2-5 have excellent wet grip performance and are low in comparison with the sulfides of the rubber compositions of Comparative Examples 2-1 to 2-3. It is heat-generating and excellent in abrasion resistance.

[Example 2-6]
As shown in Table 3, 100 parts of NR (RSS #3 grade), 38 parts of processing oil, 5 parts of carbon black (N234 grade), and 105 parts of cerium oxide (Nipsil AQ manufactured by Nippon Sesame Co., Ltd.) were blended. Further, 8.4 parts of the organic hydrazine compound A obtained in Example 1-1, 2 parts of stearic acid, and 2 parts of an anti-aging agent 6C (Nocrac 6C manufactured by Okinawa Chemical Industry Co., Ltd.) were prepared to prepare a master batch.
2 parts of zinc oxide, vulcanization accelerator CZ (Nocceler CZ, N-cyclohexyl-2-benzothiazolylsulfenamide) and 2 parts of sulfur were mixed and kneaded. A rubber composition was obtained.

[Examples 2-7 to 2-10]
The rubber was obtained in the same manner as in Example 2-1 except that the organic ruthenium compound obtained in Example 1-1 was changed to the organic ruthenium compounds B to E obtained in Examples 1-2 to 1-5, respectively. Composition.

[Comparative Example 2-4 to 2-6]
The organic ruthenium compound A obtained in Example 1-1 was changed to bis(triethoxymethyl propyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.), as shown in Table 4, A rubber composition was obtained in the same manner as in Example 2-6 except for the organic hydrazine compound represented by the above average structural formula (6) or (7).

Next, the unsulfided property (Munis viscosity) and the sulfide property (dynamic viscoelasticity, abrasion resistance) of the rubber composition were measured in the same manner as above. Tables 3 and 4 together show the results of the comparison of Examples 2-4 as 100, expressed as an index.

As shown in Tables 3 and 4, it was found that the sulfide-based dynamic viscoelasticity of the rubber compositions of Examples 2-6 to 2-10 was compared with the sulfides of the rubber compositions of Comparative Examples 2-4 to 2-6. Low, that is, low hysteresis loss, low heat build-up, and excellent wear resistance.

Claims (7)

An organic hydrazine compound represented by the following formula (1); (wherein R ¹ independently of each other represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms; A, A represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X represents a single bond or a group of one or more selected from -S-, -CO- and -CS-; a represents a value greater than 0. Number, b represents a number above 0, c represents a number above 0, d represents a number above 0, e represents a number greater than 0, f represents a number above 0, but c+d represents a number greater than 0; m represents 1 An integer of ～3; however, the order of each repeating unit is arbitrary). The organogermanium compound according to claim 1, wherein the functional group represented by the above -XA is a functional group represented by the following formula (2); (In the formula, the A system is the same as described above; * means the bonding key). A method for producing an organic phosphonium compound according to claim 1, characterized in that an organic phosphonium compound represented by the following formula (3) is reacted with a compound represented by the following formula (4); (wherein R ¹ , R ² , a, b, c, d, e, f, and m are the same as described above) (In the formula, A and X are the same as described above). The method of claim 3, wherein the compound represented by the above formula (4) is a compound represented by the following formula (5); (In the formula, the A system is the same as described above). A rubber blending agent comprising the organic hydrazine compound of claim 1 or 2. A rubber composition comprising the rubber admixture of claim 5. A tire obtained by molding the rubber composition of claim 6.