Organosilicon compound-supported material and compounding agent for diene rubber

Abstract

To provide an organosilicon compound-carrying material giving a rubber composition capable of realizing desired hardness and tensile characteristics without deteriorating processability, abrasion resistance and low fuel consumption performance of the composition when added to the rubber composition.SOLUTION: An organosilicon compound-supported material in which a silanol group-containing organosilicon compound having a structure represented by the following formula (1) is supported on a carrier, wherein the amount of the silanol group-containing organosilicon compound supported on the carrier is 10% by mass or more based on the total mass of the supported material: (In the formulae, R1's each independently represent hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and wavy lines represent bonding sites.). ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organosilicon compound-supported material and a compounding agent for diene rubber. [Background technology]

[0002] Silica-filled tires have excellent performance in automotive applications, particularly in terms of wear resistance, rolling resistance, and wet grip. These performance improvements are closely related to the improvement of tire fuel efficiency, and therefore have been the subject of active research in the passenger car tire industry, particularly in the area of ​​solution-polymerized styrene-butadiene rubber (S-SBR).

[0003] Silica-filled rubber compositions reduce the rolling resistance of tires and improve wet grip performance, but have problems with workability because they have high unvulcanized viscosity and require multi-stage kneading or the like. Therefore, in rubber compositions in which inorganic fillers such as silica are simply compounded, the filler dispersion is insufficient, resulting in problems such as a significant decrease in fracture strength and abrasion resistance. Therefore, sulfur-containing organosilicon compounds are essential to improve the dispersion of the inorganic filler in the rubber and to chemically bond the filler to the rubber matrix.

[0004] As sulfur-containing organosilicon compounds used as compounding agents for rubber, compounds containing an alkoxysilyl group and a polysulfide silyl group in the molecule, such as bis-triethoxysilylpropyl tetrasulfide and bis-triethoxysilylpropyl disulfide, are known to be effective (see Patent Documents 1 to 4).

[0005] Various alkoxysilyl group-containing compounds have been developed to improve the dispersibility of silica, an inorganic filler, and thereby improve fuel economy. However, while these compounds improve fuel economy, they have the problem of not improving hardness or tensile properties. Therefore, there is a need for materials that improve hardness and tensile properties without compromising processability or fuel economy. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2004-525230 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-18511 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-145890 [Patent Document 4] Japanese Patent Application Laid-Open No. 2000-103795 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and aims to provide an organosilicon compound-supported material that, when added to a rubber composition, provides a rubber composition that can achieve desired hardness and tensile properties without deteriorating the processability, abrasion resistance, or fuel economy of the composition; a rubber composition containing this organosilicon compound-supported material; and a tire formed from this rubber composition. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above problems, the present inventors have found that an organosilicon compound-supported material, in which a specific silanol group-containing organosilicon compound is supported on a carrier, is suitable as a compounding agent for diene rubber. They have also found that tires obtained from rubber compositions containing this rubber compounding agent can achieve the desired hardness and tensile properties without deteriorating the processability, wear resistance, or fuel economy of the composition, and have completed the present invention.

[0009] That is, the present invention provides: 1. An organosilicon compound-supported material in which a silanol group-containing organosilicon compound having a structure represented by the following formula (1) is supported on a carrier, an organosilicon compound-supported material, wherein the amount of the silanol group-containing organosilicon compound supported on the support is 10 mass % or more based on the total mass of the support; [ka] (In the formula, R 1 each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and the wavy line represents the point of attachment. 2. The organosilicon compound-supported material of 1, wherein the silanol group-containing organosilicon compound comprises a compound represented by the following formula (2): [ka] (In the formula, R 1 has the same meaning as above, and m is an integer of 1 to 100. 3. The organosilicon compound-supported material of 1, wherein the silanol group-containing organosilicon compound comprises a compound represented by the following formula (3): [ka] (In the formula, R 1 has the same meaning as above, X represents an n-valent structure, m is an integer of 1 to 100, and n is an integer of 2 to 8. 4. The organosilicon compound-supported material of 3, wherein X is a structure represented by the following formula (4), (5), or (6): [ka] (In the formula, R 1 has the same meaning as above, y is an integer of 1 to 20, and the wavy line represents the bonding site. 5. The above R 1 wherein each independently represents a methyl group or a phenyl group; 6. The organosilicon compound-supported material of 1, wherein the amount of the supported material is 20% by mass or more and 80% by mass or less based on the total mass of the supported material. 7. The organosilicon compound-supported material of 1, wherein the support is silica. 8. A compounding agent for diene rubber containing an organosilicon compound-supported material according to any one of 1 to 7. 9. (A) An organosilicon compound-supported material according to any one of 1 to 7, and (B) Diene rubber A rubber composition comprising: 10. The rubber composition of 9 containing (C) an inorganic filler (excluding the component (A)). 11. The rubber composition of 10, wherein the component (C) contains silica. 12. The rubber composition of 11, comprising (D) an organosilicon compound having at least one selected from a polysulfide group, a thioester group, and a mercapto group, and an alkoxysilyl group; 13. Tire formed from the rubber composition of 9 to provide. [Effects of the Invention]

[0010] The rubber composition containing the organosilicon compound-supported material of the present invention has excellent processability, and tires formed using this rubber composition can achieve the desired hardness and tensile properties without compromising wear resistance or fuel economy. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be specifically described below. [Organosilicon Compound Supported Material] The organosilicon compound-supported material of the present invention is characterized in that a silanol group-containing organosilicon compound having a structure represented by the following formula (1) is supported on a support, and the amount of silanol group-containing organosilicon compound supported on the support is 10 mass% or more based on the total mass of the support. The content of hydroxyl groups derived from silanol structures in the silanol group-containing organosilicon compound is preferably 0.5 to 30.0 mass %, more preferably 0.6 to 20 mass %, and even more preferably 0.8 to 18 mass %, relative to the mass of the silanol group-containing organosilicon compound.

[0012] [ka]

[0013] In formula (1), R 1each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. The alkyl group may be linear, branched, or cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, tert-butyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, and n-octyl groups. An alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a benzyl group and a phenylethyl group. The aryl group is preferably an aryl group having 6 to 18 carbon atoms, and specific examples thereof include unsubstituted aryl groups such as phenyl and naphthyl groups; and alkylaryl groups having 7 to 18 carbon atoms such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl groups, with a phenyl group being preferred.

[0014] The silanol group-containing organosilicon compound preferably contains a compound represented by the following formula (2) and / or a compound represented by the following formula (3).

[0015] [ka]

[0016] In equations (2) and (3), R 1 represents the same meaning as in the above formula (1), and is preferably a methyl group or a phenyl group. m is an integer of 1 to 100, and an integer of 1 to 60 is preferred. n is an integer of 2 to 8, and an integer of 2 to 4 is preferred.

[0017] In addition, in formulas (2) and (3), -R 1 -Si-R 1When there are two or more -'s (m is 2 or more), they may be the same or different, and may be, for example, compounds represented by the following formula (2') and / or (3').

[0018] [ka] (In formula (2), R 1 means the same as above, but for all R 1 are not the same group at the same time, and in formula (3), R 1 means the same as above, but for all R 1 are not simultaneously the same group, and in each formula, m1 and m2 are each an integer of 1 or more, and m1+m2 is an integer of 2 to 100.)

[0019] X represents an n-valent structure, and examples thereof include linear, branched, or cyclic structures containing a hydrocarbon skeleton or a siloxane skeleton, and structures represented by the following formula (4), (5), or (6) are preferred.

[0020] [ka] (In the formula, R 1 has the same meaning as above, and the wavy line indicates the bond point.)

[0021] In formula (4), y is an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

[0022] Specific examples of silanol group-containing organosilicon compounds include, but are not limited to, those represented by the following formula: In the formula, Me represents a methyl group (the same applies hereinafter).

[0023] [ka] (In the formula, m, m1, and m2 have the same meanings as above.)

[0024] In the organosilicon compound-supported material of the present invention, the amount of silanol group-containing organosilicon compound supported on the carrier is 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total mass of the support. A larger amount of support allows for a smaller amount of support to be added to the rubber composition. From the viewpoint of workability, the support is preferably in the form of a powder. If the amount of silanol group-containing organosilicon compound supported is too high, the support will become paste-like; therefore, the amount of silanol group-containing organosilicon compound supported is preferably 80% by mass or less, based on the total mass of the support.

[0025] Examples of the carrier for the organosilicon compound-supported material of the present invention include silica, carbon black, talc, calcium carbonate, stearic acid, aluminum hydroxide, alumina, magnesium hydroxide, etc., with silica being preferred.

[0026] In the organosilicon compound-supported material of the present invention, the carrier and the silanol group-containing organosilicon compound may form a chemical bond.As a method for forming a chemical bond, for example, the carrier and the silanol group-containing organosilicon compound are placed in a mechanical kneading device or fluidized bed sealed at normal pressure, and if necessary, in the presence of an inert gas, they are mixed at room temperature or by heat treatment (heating).In some cases, a catalyst (such as a hydrolysis promoter) may be used to promote the reaction between the carrier and the silanol group-containing organosilicon compound.

[0027] In the organosilicon compound-supported material of the present invention, in addition to the silanol group-containing organosilicon compound, a silane coupling agent having an alkoxysilyl group and one or more groups selected from a polysulfide group, a thioester group, and a mercapto group may be supported on the carrier.

[0028] Specific examples of the silane coupling agent include polysulfide-based organosilicon compounds such as bis-(3-bistriethoxysilylpropyl)-tetrasulfide and bis-(3-bistriethoxysilylpropyl)-disulfide; mercapto-based organosilicon compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; and thioester-based organosilicon compounds such as 3-octanoylthiopropyltriethoxysilane and 3-propionylthiopropyltrimethoxysilane. Also usable are reaction products of the above-mentioned organosilicon compounds having sulfur atoms with alcohols containing polyether groups, hydrolysis condensates of these organosilicon compounds, and co-hydrolysis condensates of these organosilicon compounds with other organosilicon compounds having alkoxysilyl groups.

[0029] When the organosilicon compound-supported material of the present invention contains the silane coupling agent, the amount of the silane coupling agent is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the support. If the amount of silane coupling agent is too large, the support will become pasty, so the total amount of the silanol group-containing organosilicon compound and silane coupling agent supported is preferably 80% by mass or less, based on the total mass of the support.

[0030] [Rubber composition] The rubber composition of the present invention contains (A) the organosilicon compound-supported material and (B) a diene rubber. (A) Organosilicon Compound Support Component (A) is the organosilicon compound-supported material described above. The amount of component (A) in the rubber composition of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, per 100 parts by mass of component (B), which will be described in detail later, taking into consideration the physical properties of the resulting rubber and the balance between the degree of effect exerted and economic efficiency.

[0031] (B) Diene rubber The diene rubber of component (B) can be any rubber that has been commonly used in various rubber compositions. Specific examples include diene rubbers such as various isoprene rubbers (IR) such as natural rubber, various styrene-butadiene copolymer rubbers (SBR), various polybutadiene rubbers (BR), and acrylonitrile-butadiene copolymer rubbers (NBR). These may be used alone or in combination of two or more. In addition to the diene rubber, non-diene rubbers such as butyl rubber (IIR) and ethylene-propylene copolymer rubber (EPR, EPDM) may also be used in combination.

[0032] (C) Inorganic filler In addition to the above components, the rubber composition of the present invention may contain an inorganic filler as component (C) (excluding the above component (A)). Examples of inorganic fillers include those commonly used in the tire industry, such as silica, carbon black, aluminum hydroxide, alumina (aluminum oxide), calcium carbonate, talc, and clay. These may be used alone or in combination of two or more. Among these, the rubber composition of the present invention preferably contains silica and carbon black.

[0033] Examples of carbon black include those commonly used in the tire industry, such as GPF, FEF, HAF, ISAF, and SAF. Examples of silica include silica prepared by a dry method (anhydrous silica) and silica prepared by a wet method (hydrated silica), which are commonly used in the tire industry. Among these, silica prepared by a wet method is preferred because it contains a large number of silanol groups. In particular, silica has a nitrogen adsorption specific surface area (N2SA) of 70m 2 / g or more is preferable, and 100m 2 The upper limit of N2SA is not particularly limited, but from the viewpoint of ease of handling, it is preferably 500 m 2 / g or less is preferable, and 400m 2 / g or less is more preferable.

[0034] The amount of component (C) in the rubber composition of the present invention is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 20 to 130 parts by mass, per 100 parts by mass of component (B), from the viewpoints of dispersibility, fuel economy, molding processability, etc.

[0035] (D) Silane coupling agent In addition to the above components, the rubber compounding agent of the present invention can contain (D) a silane coupling agent having an alkoxysilyl group and one or more selected from a polysulfide group, a thioester group, and a mercapto group. Component (D) is not particularly limited as long as it is a compound having such a functional group. For example, any conventionally known silane coupling agent compounded in rubber compositions for applications such as tires can be used. Furthermore, part or all of component (D) may be previously contained in component (A) in the form of being supported on the carrier.

[0036] Specific examples of the silane coupling agent include polysulfide-based organosilicon compounds such as bis-(3-bistriethoxysilylpropyl)-tetrasulfide and bis-(3-bistriethoxysilylpropyl)-disulfide; mercapto-based organosilicon compounds such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; and thioester-based organosilicon compounds such as 3-octanoylthiopropyltriethoxysilane and 3-propionylthiopropyltrimethoxysilane. Also usable are reaction products of the above-mentioned organosilicon compounds having sulfur atoms with alcohols containing polyether groups, hydrolysis condensates of these organosilicon compounds, and co-hydrolysis condensates of these organosilicon compounds with other organosilicon compounds having alkoxysilyl groups. The component (D) may be used alone or in combination of two or more types.

[0037] When the rubber composition of the present invention contains the component (D), the compounding amount thereof is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the component (B).

[0038] In addition to the components (A) to (D), the rubber composition of the present invention may contain various additives that are generally compounded in tires and other rubbers, such as sulfur, crosslinking agents, vulcanization accelerators, crosslinking accelerators, various oils, antioxidants, plasticizers, various resins, wax, zinc oxide, etc. The amounts of these additives may be conventional amounts as long as they do not deviate from the object of the present invention.

[0039] Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, and soluble sulfur, which are commonly used in the rubber industry. These may be used alone or in combination of two or more. These sulfurs may be available from, for example, Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemical Industry Co., Ltd., Flexis Corporation, Nippon Kanzuri Kogyo Co., Ltd., Hosoi Chemical Industry Co., Ltd., etc.

[0040] When sulfur is added, the amount added is preferably 0.1 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass, and even more preferably 0.5 to 2.0 parts by mass, per 100 parts by mass of component (B). Within this range, a good balance between tensile properties and abrasion resistance is achieved.

[0041] [Rubber products (tires)] The rubber composition of the present invention can be used for producing rubber products such as tires by preparing a composition from the above-mentioned components (A) and (B), as well as the optional components (C), (D), and other components, in a conventional manner and vulcanizing or crosslinking the composition. In particular, when producing tires, it is preferable to use the rubber composition of the present invention in the tread. A tire obtained using the rubber composition of the present invention has reduced rolling resistance and improved wear resistance, and therefore can achieve the desired low fuel consumption. The tire structure may be a conventionally known structure, and the manufacturing method may be a conventionally known manufacturing method. In the case of a gas-filled tire, the gas to be filled in the tire may be air, air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium. [Example]

[0042] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0043] [Example 1-1] Silica [BET specific surface area: 160 m] was added to a 5 L Henschel mixer (manufactured by Nippon Coke Engineering Co., Ltd.; the same applies hereinafter). 2 1,000 g of [Nipsil AQ (Tosoh Silica Corporation)] was placed in the container, and 112 g of an organosilicon compound (hydroxyl group content: 10.0% by mass) represented by the following formula (7) was sprayed onto the container and stirred at 25°C for 10 minutes. The container was then removed from the Henschel mixer to obtain organosilicon compound-supported material (A-1).

[0044] [ka]

[0045] [Example 1-2] An organosilicon compound-supported material (A-2) was obtained in the same manner as in Example 1-1, except that the amount of the organosilicon compound represented by the above formula (7) was changed to 333 g.

[0046] [Examples 1-3] An organosilicon compound-supported material (A-3) was obtained in the same manner as in Example 1-1, except that the amount of the organosilicon compound represented by the above formula (7) was changed to 1000 g.

[0047] [Examples 1-4] In Example 1-1, the same procedure as in Example 1-1 was carried out, except that 112 g of the organosilicon compound represented by the above formula (7) was changed to 1000 g of an organosilicon compound (hydroxyl group content 2.2% by mass) represented by the following formula (8), to obtain an organosilicon compound-supported material (A-4).

[0048] [ka]

[0049] [Examples 1-5] In Example 1-1, the same procedure as in Example 1-1 was carried out, except that 112 g of the organosilicon compound represented by the above formula (7) was changed to 1000 g of an organosilicon compound (hydroxyl group content 1.1% by mass) represented by the following formula (9), to obtain an organosilicon compound-supported material (A-5).

[0050] [ka]

[0051] [Examples 1-6] In Example 1-1, the same procedure as in Example 1-1 was carried out, except that 112 g of the organosilicon compound represented by the above formula (7) was changed to 1000 g of an organosilicon compound (hydroxyl group content 0.8% by mass) represented by the following formula (10), to obtain an organosilicon compound-supported material (A-6).

[0052] [ka]

[0053] [Examples 1-7] In Example 1-1, the same procedure as in Example 1-1 was carried out, except that 112 g of the organosilicon compound represented by the above formula (7) was changed to 1000 g of an organosilicon compound (hydroxyl group content 5.9% by mass) represented by the following formula (11), to obtain an organosilicon compound-supported material (A-7).

[0054] [ka]

[0055] [Examples 1-8] In Example 1-1, the same operation as in Example 1-1 was carried out, except that 112 g of the organosilicon compound represented by the above formula (7) was changed to 1000 g of an organosilicon compound (hydroxyl group content 15.7% by mass) represented by the following formula (12), to obtain an organosilicon compound-supported material (A-8).

[0056] [ka]

[0057] [Examples 1-9] In Example 1-1, the same procedure as in Example 1-1 was carried out, except that 112 g of the organosilicon compound represented by the above formula (7) was changed to 1000 g of an organosilicon compound (hydroxyl group content 4.4% by mass) represented by the following formula (13), to obtain an organosilicon compound-supported material (A-9).

[0058] [ka]

[0059] [Examples 2-1 to 2-9, Comparative Example 2-1] The natural rubber shown in Table 1 was kneaded for 60 seconds using a 4 L internal mixer (MIXTRON, manufactured by Kobe Steel, Ltd.). Next, carbon black, silica, the organosilicon compound-supported materials produced in Examples 1-1 to 1-9 (no organosilicon compound-supported material was added for Comparative Example 2-1), stearic acid, antioxidant, resin, and wax listed in Table 1 were added, the internal temperature was raised to 150°C, and the mixture was discharged. It was then stretched using rolls. The resulting rubber composition was again kneaded using an internal mixer (MIXTRON, manufactured by Kobe Steel, Ltd.) until the internal temperature reached 145°C, discharged, and then stretched using rolls. Zinc oxide, vulcanization accelerator, and sulfur listed in Table 1 were added to the mixture and kneaded to obtain a rubber composition.

[0060] Natural rubber: RSS#3 Carbon black: Seast 9H (manufactured by Tokai Carbon Co., Ltd.) Silica: Nipsil AQ (manufactured by Tosoh Silica Corporation) Sulfide silane: KBE-846 (Shin-Etsu Chemical Co., Ltd., bis(triethoxysilylpropyl)tetrasulfide) (A-1): Organosilicon compound-supported material obtained in Example 1-1 (A-2): Organosilicon compound-supported material obtained in Example 1-2 (A-3): Organosilicon compound-supported material obtained in Examples 1-3 (A-4): Organosilicon compound-supported material obtained in Examples 1-4 (A-5): Organosilicon compound-supported material obtained in Examples 1-5 (A-6): Organosilicon compound-supported material obtained in Examples 1-6 (A-7): Organosilicon compound-supported material obtained in Examples 1-7 (A-8): Organosilicon compound-supported material obtained in Example 1-8 (A-9): Organosilicon compound-supported material obtained in Examples 1-9 Stearic acid: Industrial stearic acid (Kao Corporation) Antioxidant: Nocrac 6C (Ouchi Shinko Chemical Industry Co., Ltd.) Resin: T-REZ RA-100 (manufactured by ENEOS Corporation) Wax: Ozoace 0355 (manufactured by Nippon Seiro Co., Ltd.) Zinc oxide: Zinc oxide No. 3 (manufactured by Mitsui Mining & Smelting Co., Ltd.) Vulcanization accelerator (a): Noccela DM-P (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Vulcanization accelerator (b): Noccela CZ-G (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Sulfur: 5% oil-treated sulfur (Hosoi Chemical Industry Co., Ltd.)

[0061] The unvulcanized and vulcanized physical properties of the rubber compositions obtained in Examples 2-1 to 1-9 and Comparative Example 2-1 were measured by the following methods. The results are also shown in Table 1. The vulcanized physical properties were measured by press-molding the obtained rubber compositions (145°C, 30 minutes) into vulcanized rubber sheets (2 mm thick).

[0062] [Unvulcanized physical properties] (1) Mooney viscosity According to JIS K 6300-1:2013, measurements were performed with 1 minute of preheating and 4 minutes of measurement at a temperature of 130°C, and the results were expressed as an index with Comparative Example 2-1 being set at 100. The smaller the index value, the lower the Mooney viscosity and the better the processability. [Vulcanization properties] (2)Hardness Durometer (Type A) hardness was measured in accordance with JIS K 6253-3:2012 and expressed as an index with Comparative Example 2-1 being 100. The larger the index value, the higher and more excellent the hardness. (3) Tensile properties JIS No. 3 dumbbell-shaped test pieces were punched out and subjected to a tensile test at a tensile speed of 500 mm / min in accordance with JIS K6251. 300 ) [MPa] was measured at room temperature. The results were expressed as an index, with Comparative Example 2-1 being set at 100. A larger index value indicates a higher modulus and more excellent tensile properties. (4) Dynamic viscoelasticity (temperature dispersion) A viscoelasticity measuring device (manufactured by Metrabib) was used to measure under conditions of a tensile dynamic strain of 1% and a frequency of 55 Hz. The test specimen was a sheet of 0.2 cm thick and 0.5 cm wide, with a clamp distance of 2 cm and an initial load of 1 N. The value of tan δ (60°C) was expressed as an index, with Comparative Example 2-1 being 100. The smaller the index value of tan δ (60°C), the better the rolling resistance. (5) Abrasion resistance Using an FPS testing machine (manufactured by Ueshima Seisakusho Co., Ltd.), the test was conducted under conditions of a sample speed of 200 m / min, a load of 20 N, a road surface temperature of 30°C, and a slip ratio of 5% and a slip ratio of 20%. The results obtained were expressed as an index, with Comparative Example 2-1 being set at 100. A larger index value indicates less wear and better wear resistance.

[0063] [Table 1]

[0064] As shown in Table 1, the vulcanized products of the rubber compositions obtained in Examples 2-1 to 2-9 have significantly improved hardness and tensile properties while maintaining wear resistance compared to the vulcanized product of the rubber composition of Comparative Example 2-1.

[0065] [Examples 3-1 to 3-9, Comparative Example 3-1] The SBR and BR shown in Table 2 were mixed for 30 seconds using a 4 L internal mixer (MIXTRON, manufactured by Kobe Steel, Ltd.). Next, the oil components, carbon black, silica, sulfide silane, organosilicon compound-supported materials synthesized in Examples 1 to 9 (no organosilicon compound-supported materials were added for Comparative Example 3-1), stearic acid, antioxidant, and wax listed in Table 2 were added, and the internal temperature was raised to 150°C. After holding at 150°C for 2 minutes, the mixture was discharged. It was then stretched using rolls. The resulting rubber was again kneaded using an internal mixer (MIXTRON, manufactured by Kobe Steel, Ltd.) until the internal temperature reached 140°C, discharged, and stretched using rolls. To this was added zinc oxide, a vulcanization accelerator, and sulfur as shown in Table 2, and the mixture was kneaded to obtain a rubber composition.

[0066] SBR: SLR-4602 (manufactured by Trinseo) BR: BR-01 (JSR Corporation) Oil: AC-12 (Idemitsu Kosan Co., Ltd.) Carbon black: Seast 3 (manufactured by Tokai Carbon Co., Ltd.) Silica: Nipsil AQ (manufactured by Tosoh Silica Corporation) Sulfide silane: KBE-846 (Shin-Etsu Chemical Co., Ltd., bis(triethoxysilylpropyl)tetrasulfide) (A-1): Organosilicon compound-supported material obtained in Example 1-1 (A-2): Organosilicon compound-supported material obtained in Example 1-2 (A-3): Organosilicon compound-supported material obtained in Examples 1-3 (A-4): Organosilicon compound-supported material obtained in Examples 1-4 (A-5): Organosilicon compound-supported material obtained in Examples 1-5 (A-6): Organosilicon compound-supported material obtained in Examples 1-6 (A-7): Organosilicon compound-supported material obtained in Examples 1-7 (A-8): Organosilicon compound-supported material obtained in Example 1-8 (A-9): Organosilicon compound-supported material obtained in Examples 1-9 Stearic acid: Industrial stearic acid (Kao Corporation) Antioxidant: Nocrac 6C (Ouchi Shinko Chemical Industry Co., Ltd.) Wax: Ozoace 0355 (manufactured by Nippon Seiro Co., Ltd.) Zinc oxide: Zinc oxide No. 3 (manufactured by Mitsui Mining & Smelting Co., Ltd.) Vulcanization accelerator (a): Noccela D (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Vulcanization accelerator (b): Noccela DM-P (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Vulcanization accelerator (c): Noccela CZ-G (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Sulfur: 5% oil-treated sulfur (Hosoi Chemical Industry Co., Ltd.)

[0067] The unvulcanized and vulcanized physical properties of the rubber compositions obtained in Examples 3-1 to 3-9 and Comparative Example 3-1 were measured by the following methods. The results are also shown in Table 2. Regarding the vulcanized physical properties, the obtained rubber compositions were press-molded (160°C, 10 to 40 minutes) to prepare vulcanized rubber sheets (thickness 2 mm).

[0068] [Unvulcanized physical properties] (1) Mooney viscosity Measurement was performed in accordance with JIS K 6300-1:2013, with preheating for 1 minute, measurement for 4 minutes, and at a temperature of 130°C, and expressed as an index with Comparative Example 3-1 set to 100. The smaller the index value, the lower the Mooney viscosity and the better the processability. (2) Vulcanization characteristics (T90) The vulcanization rate at 160°C was measured using a rotorless rheometer, and the minimum torque ML and maximum torque MH were determined from the vulcanization curve, and T90 (the time (minutes) required to reach 90% of the maximum torque) was calculated. The results were expressed as an index, with Comparative Example 3-1 set to 100. The smaller the index value, the faster the vulcanization rate and the better the productivity. [Vulcanization properties] (3)Hardness Durometer (Type A) hardness was measured in accordance with JIS K 6253-3:2012 and expressed as an index with Comparative Example 3-1 being 100. The larger the index value, the higher and more excellent the hardness. (4) Tensile properties JIS No. 3 dumbbell-shaped test pieces were punched out and subjected to a tensile test at a tensile speed of 500 mm / min in accordance with JIS K6251. 300 ) [MPa] was measured at room temperature. The results were expressed as an index, with Comparative Example 3-1 being set at 100. A larger index value indicates a higher modulus and more excellent tensile properties. (5) Dynamic viscoelasticity (temperature dispersion) Measurements were made using a viscoelasticity measuring device (Metrabib) under conditions of a tensile dynamic strain of 1% and a frequency of 55 Hz. The test specimen was a sheet of 0.2 cm thick and 0.5 cm wide, with a clamp distance of 2 cm and an initial load of 1 N. The values ​​of tan δ(0°C) and tan δ(60°C) are expressed as indexes with Comparative Example 3-1 being 100. A larger index value of tan δ(0°C) indicates better wet grip performance. A smaller index value of tan δ(60°C) indicates better rolling resistance. (6) Abrasion resistance Using an FPS testing machine (manufactured by Ueshima Seisakusho Co., Ltd.), the test was conducted under the conditions of a sample speed of 200 m / min, a load of 20 N, a road surface temperature of 30°C, and a slip ratio of 5% and a slip ratio of 20%. The results obtained were expressed as an index, with Comparative Example 3-1 being set at 100. A larger index value indicates less wear and better wear resistance.

[0069] [Table 2]

[0070] As shown in Table 2, the vulcanizates of the rubber compositions of Examples 3-1 to 3-9 have significantly improved hardness and tensile properties while maintaining wear resistance, compared to the vulcanizate of the rubber composition of Comparative Example 3-1.

Claims

1. An organosilicon compound-supported material in which a silanol group-containing organosilicon compound having a structure represented by the following formula (1) is supported on a carrier, The amount of the silanol group-containing organosilicon compound supported on the carrier is 10% by mass or more based on the total mass of the support. 【Chemistry 1】 (In the formula, R 1 each independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and the wavy line represents the point of attachment.

2. 2. The organosilicon compound-supported material according to claim 1, wherein the silanol group-containing organosilicon compound comprises a compound represented by the following formula (2): 【Chemistry 2】 (In the formula, R 1 has the same meaning as above, and m is an integer of 1 to 100.

3. 2. The organosilicon compound-supported material according to claim 1, wherein the silanol group-containing organosilicon compound comprises a compound represented by the following formula (3): 【Transformation 3】 (In the formula, R 1 represents the same meaning as above, X represents an n-valent structure, m is an integer of 1 to 100, and n is an integer of 2 to 8.

4. 4. The organosilicon compound-supported material according to claim 3, wherein X is a structure represented by the following formula (4), (5), or (6): 【Chemistry 4】 (In the formula, R 1 has the same meaning as above, y is an integer of 1 to 20, and the wavy line represents the bonding point.

5. The R 1 2. The organosilicon compound-supported material according to claim 1, wherein each of the groups independently represents a methyl group or a phenyl group.

6. 2. The organosilicon compound-supported material according to claim 1, wherein the amount of the supported material is 20% by mass or more and 80% by mass or less based on the total mass of the supported material.

7. 2. The organosilicon compound-supported material according to claim 1, wherein the support is silica.

8. A compounding agent for diene rubber, comprising the organosilicon compound-supported material according to any one of claims 1 to 7.

9. (A) the organosilicon compound-supported material according to any one of claims 1 to 7, and (B) Diene rubber A rubber composition comprising:

10. The rubber composition according to claim 9, further comprising (C) an inorganic filler (excluding the component (A)).

11. The rubber composition according to claim 10, wherein the component (C) contains silica.

12. The rubber composition according to claim 11, further comprising (D) an organosilicon compound having an alkoxysilyl group and at least one group selected from the group consisting of a polysulfide group, a thioester group and a mercapto group.

13. A tire formed by molding the rubber composition according to claim 9.

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