Organic silicon compound support, and compounding agent for diene rubber

Abstract

Provided is an organic silicon compound support obtained by a silanol group-containing organic silicon compound that has a structure represented by formula (1) being carried on a carrier. When the organic silicon compound support that has an amount of the silanol group-containing organic silicon compound carried on the carrier of 10 mass% or more relative to the total mass of the support is added to a rubber composition, the desired hardness and tensile properties can be achieved in the rubber composition without deteriorating processability, anti-wear performance, and low fuel consumption performance of the composition. (In the formula, each instance of R1 independently represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and the wavy line represents a binding site.)

Description

Organosilicon compound carriers and compounding agents for diene rubber

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

[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 improved fuel economy, and therefore have recently been the subject of active research, particularly in the passenger car tire industry, where solution-polymerized styrene-butadiene rubber (S-SBR) is used.

[0003] Silica-filled rubber compositions reduce tire rolling resistance and improve wet grip, but have high unvulcanized viscosities, require multi-stage mixing, and have workability issues. Therefore, rubber compositions that simply incorporate inorganic fillers such as silica suffer from insufficient filler dispersion, resulting in significant decreases in fracture strength and abrasion resistance. Therefore, sulfur-containing organosilicon compounds are essential to improve the dispersion of inorganic fillers in 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.

[0006] JP-T-2004-525230A JP-A-2004-18511 JP-A-2002-145890 JP-A-2000-103795

[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.

[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, wherein the amount of the silanol group-containing organosilicon compound supported on the carrier is 10 mass % or more based on the total mass of the support; (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 a bonding point.) 2. The organosilicon compound-supported material of 1, wherein the silanol group-containing organosilicon compound contains a compound represented by the following formula (2): (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): (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. The organosilicon compound-supported material of 3, wherein X is a structure represented by the following formula (4), (5), or (6): (In the formula, R 1has the same meaning as above, y is an integer of 1 to 20, and the wavy line represents the bonding point.) 5. 1 are each independently a methyl group or a phenyl group, 6. An organosilicon compound-supported product of 1, wherein the amount supported is 20 mass % or more and 80 mass % or less based on the total mass of the product, 7. An organosilicon compound-supported product of 1, wherein the carrier is silica, 8. A compounding agent for diene rubber comprising an organosilicon compound-supported product of any one of 1 to 7, 9. A rubber composition comprising (A) an organosilicon compound-supported product of any one of 1 to 7, and (B) a diene rubber, 10. A rubber composition of 9, comprising (C) an inorganic filler (excluding component (A)), 11. A rubber composition of 10, wherein component (C) comprises silica, 12. A 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. 9. A tire molded from the rubber composition of claim 9.

[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.

[0011] The present invention will be described in detail below. [Organosilicon Compound-Supported Material] The organosilicon compound-supported material of the present invention is 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 support, and is characterized in that 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%, based on the mass of the silanol group-containing organosilicon compound.

[0012]

[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. However, alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include benzyl and phenylethyl groups. 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]

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

[0017] In addition, in formulas (2) and (3), -R 1 -Si-R 1 When two or more - are present (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] (In formula (2), R 1 has the same meaning as above, but all R1 are not the same group at the same time, and in formula (3), R 1 has the same meaning as above, but all R 1 are not the same group at the same time, 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 a linear, branched, or cyclic structure containing a hydrocarbon skeleton or a siloxane skeleton, and a structure represented by the following formula (4), (5), or (6) is preferred.

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

[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] (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 supported amount allows for a smaller amount of the support to be added to the rubber composition. Furthermore, 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.The method for forming a chemical bond can be, for example, by placing the carrier and the silanol group-containing organosilicon compound in a mechanical kneading device or fluidized bed that is sealed under normal pressure, and mixing them at room temperature or by heat treatment (heating) under the presence of inert gas as required.Optionally, a catalyst (such as a hydrolysis promoter) can 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 the 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 comprises (A) the organosilicon compound-supported material described above and (B) a diene rubber. (A) Organosilicon Compound-Supported Material Component (A) is the organosilicon compound-supported material described above. In consideration of the physical properties of the resulting rubber and the balance between the degree of effect exerted and economic efficiency, 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.

[0031] (B) Diene Rubber As the diene rubber of component (B), any rubber that has been commonly used in various rubber compositions can be used, and specific examples thereof 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), and 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 rubbers (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 (excluding the above component (A)) as component (C). 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, it is preferable that the rubber composition of the present invention 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 those commonly used in the tire industry, such as silica prepared by a dry method (anhydrous silica) and silica prepared by a wet method (hydrated silica). Among these, silica prepared by a wet method is preferred because it contains a large number of silanol groups. In particular, silica having a nitrogen adsorption specific surface area (N2SA) of 70 m 2 / g or more is preferred, 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, moldability, and the like.

[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 at least one selected from a polysulfide group, a thioester group, and a mercapto group, and an alkoxysilyl group. Component (D) is not particularly limited as long as it is a compound having such a functional group, and 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 containing 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 containing 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) above, 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. For example, products available from Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemical Industry Co., Ltd., Flexis Corporation, Nippon Kanzuri Kogyo Co., Ltd., and Hosoi Chemical Industry Co., Ltd. can be used as the sulfur.

[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 wear resistance is achieved.

[0041] [Rubber Products (Tires)] The rubber composition of the present invention can be used for the production of 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, using a conventional method, and then vulcanizing or crosslinking the composition. In particular, when producing tires, the rubber composition of the present invention is preferably used in the tread. Tires obtained using the rubber composition of the present invention have reduced rolling resistance and improved wear resistance, thereby achieving desired fuel economy. The tire structure can be a conventionally known structure, and the manufacturing method thereof may also be a conventionally known manufacturing method. In addition, in the case of gas-filled tires, the gas to be filled in the tire can usually be air, air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium.

[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 and Engineering Co., Ltd., the same applies hereinafter). 2 / g, Nipsil AQ (manufactured by Tosoh Silica Corporation), the same applies hereinafter.) was placed in a container, and 112 g of an organosilicon compound (hydroxyl group content 10.0% by mass) represented by the following formula (7) was sprayed thereinto, followed by stirring for 10 minutes at 25° C. The container was then removed from the Henschel mixer to obtain organosilicon compound-supported material (A-1).

[0044]

[0045] [Example 1-2] The same procedure as in Example 1-1 was carried out, except that the amount of the organosilicon compound represented by the above formula (7) was changed to 333 g, to obtain an organosilicon compound-supported material (A-2).

[0046] [Example 1-3] The same procedure as in Example 1-1 was carried out, except that the amount of the organosilicon compound represented by the above formula (7) was changed to 1000 g, to obtain an organosilicon compound-supported material (A-3).

[0047] Example 1-4 An organosilicon compound-supported material (A-4) was obtained by the same procedure as in Example 1-1, except that the organosilicon compound represented by the above formula (7) was replaced with 1,000 g of an organosilicon compound represented by the following formula (8) (hydroxyl group content: 2.2% by mass).

[0048]

[0049] Example 1-5 An organosilicon compound-supported material (A-5) was obtained by the same procedure as in Example 1-1, except that the organosilicon compound represented by the above formula (7) was replaced with 1,000 g of an organosilicon compound represented by the following formula (9) (hydroxyl group content: 1.1% by mass):

[0050]

[0051] Example 1-6 An organosilicon compound-supported material (A-6) was obtained by the same procedure as in Example 1-1, except that the organosilicon compound represented by the above formula (7) was replaced with 1,000 g of an organosilicon compound represented by the following formula (10) (hydroxyl group content: 0.8% by mass):

[0052]

[0053] Example 1-7 An organosilicon compound-supported material (A-7) was obtained by the same procedure as in Example 1-1, except that the organosilicon compound represented by the above formula (7) was replaced with 1,000 g of an organosilicon compound represented by the following formula (11) (hydroxyl group content: 5.9% by mass):

[0054]

[0055] Example 1-8 An organosilicon compound-supported material (A-8) was obtained by the same procedure as in Example 1-1, except that the organosilicon compound represented by the above formula (7) was replaced with 1,000 g of an organosilicon compound represented by the following formula (12) (hydroxyl group content: 15.7% by mass).

[0056]

[0057] Example 1-9 An organosilicon compound-supported material (A-9) was obtained by the same procedure as in Example 1-1, except that the organosilicon compound represented by the above formula (7) was replaced with 1,000 g of an organosilicon compound represented by the following formula (13) (hydroxyl group content: 4.4% by mass).

[0058]

[0059] Examples 2-1 to 2-9, Comparative Example 2-1 Using a 4 L internal mixer (MIXTRON, manufactured by Kobe Steel, Ltd.), a natural rubber listed in Table 1 was kneaded for 60 seconds. Next, carbon black, silica, the organosilicon compound-supported materials produced in Examples 1-1 to 1-9 (no organosilicon compound-supported material was added to Comparative Example 2-1), stearic acid, antioxidant, resin, and wax listed in Table 1 were added, and the internal temperature was raised to 150°C and the mixture was discharged. It was then stretched using a roll. 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 a roll. 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 (manufactured by 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 Example 1-3 (A-4): Organosilicon compound-supported material obtained in Example 1-4 (A-5): Organosilicon compound-supported material obtained in Example 1-5 (A-6): Organosilicon compound-supported material obtained in Example 1-6 (A-7): Organosilicon compound-supported material obtained in Example 1-7 (A-8): Organosilicon compound-supported material obtained in Example 1-8 (A-9): Organosilicon compound-supported material obtained in Example 1-9 Stearic acid: industrial stearic acid (manufactured by Kao Corporation) Antioxidant: Nocrac 6C (manufactured by 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 and 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 (manufactured by 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 Measured in accordance with JIS K 6300-1:2013 with 1 minute of preheating, 4 minutes of measurement, and at a temperature of 130°C, and expressed as an index with Comparative Example 2-1 as 100. The smaller the index value, the lower the Mooney viscosity and the better the processability. [Vulcanized physical 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 as 100. The larger the index value, the higher the hardness and the better the performance. (3) Tensile properties JIS No. 3 dumbbell-shaped test pieces were punched out, and a tensile test was carried out in accordance with JIS K6251 at a tensile speed of 500 mm / min to measure the 300% modulus (M 300 ) [MPa] was measured at room temperature. The results were expressed as an index, with Comparative Example 2-1 being 100. A larger index value indicates a higher modulus and better tensile properties. (4) Dynamic Viscoelasticity (Temperature Dispersion) Measurements were performed using a viscoelasticity measuring device (manufactured by Metrabib) under conditions of a tensile dynamic strain of 1% and a frequency of 55 Hz. The test specimen was a sheet with a thickness of 0.2 cm and a width of 0.5 cm, with a clamp distance of 2 cm and an initial load of 1 N. The tan δ (60°C) value was expressed as an index, with Comparative Example 2-1 being 100. A smaller index value for tan δ (60°C) indicates better rolling resistance. (5) Abrasion Resistance Tests were performed using an FPS testing machine (manufactured by Ueshima Seisakusho Co., Ltd.) under conditions of a sample speed of 200 m / min, a load of 20 N, a road surface temperature of 30°C, and slip ratios of 5% and 20%. The results obtained were expressed as an index, with Comparative Example 2-1 being set at 100. A larger index value indicates a smaller amount of wear and better wear resistance.

[0063]

[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 abrasion 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 Using a 4 L internal mixer (MIXTRON, manufactured by Kobe Steel, Ltd.), SBR and BR listed in Table 2 were kneaded for 30 seconds. Next, the oil components, carbon black, silica, sulfide silane, organosilicon compound-supported materials synthesized in Examples 1 to 9 (no organosilicon compound-supported material was 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 a roll. 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 a roll. Zinc oxide, vulcanization accelerator, and sulfur listed in Table 2 were added and kneaded to obtain a rubber composition.

[0066] SBR: SLR-4602 (manufactured by Trinseo) BR: BR-01 (manufactured by JSR Corporation) Oil: AC-12 (manufactured by 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 (manufactured by 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 Example 1-3 (A-4): Organosilicon compound-supported material obtained in Example 1-4 (A-5): Organosilicon compound-supported material obtained in Example 1-5 (A-6): Organosilicon compound-supported material obtained in Example 1-6 (A-7): Organosilicon compound-supported material obtained in Example 1-7 (A-8): Organosilicon compound-supported material obtained in Example 1-8 (A-9): Organosilicon compound-supported material obtained in Example 1-9 Stearic acid: industrial stearic acid (Kao Corporation) Antiaging agent: Nocrac 6C (Ouchi Shinko Chemical Industry Co., Ltd.) Wax: Ozoace 0355 (Nippon Seiro Co., Ltd.) Zinc oxide: Zinc oxide No. 3 (Mitsui Mining and Smelting Co., Ltd.) Vulcanization accelerator (a): Noccela D (Ouchi Shinko Chemical Industry Co., Ltd.) Vulcanization accelerator (b): Noccela DM-P (Ouchi Shinko Chemical Industry Co., Ltd.) Vulcanization accelerator (c): Noccela CZ-G (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 Measured in accordance with JIS K 6300-1:2013 with 1 minute of preheating, 4 minutes of measurement, 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 value) was calculated. The value was 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. [Vulcanized Physical 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 set to 100. The larger the index value, the higher the hardness and the better the product. (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 100. The larger the index value, the higher the modulus and the more excellent the tensile properties. (5) Dynamic viscoelasticity (temperature dispersion) A viscoelasticity measuring device (manufactured by Metrabib) was used, and measurements were taken under conditions of a tensile dynamic strain of 1% and a frequency of 55 Hz. The test specimen was a sheet with a thickness of 0.2 cm and a width of 0.5 cm, with a clamping distance of 2 cm and an initial load of 1 N. The values ​​of tan δ (0 ° C) and tan δ (60 ° C) were expressed as an index, with Comparative Example 3-1 being 100. The larger the index value of tan δ (0 ° C), the better the wet grip performance. The smaller the index value of tan δ (60 ° C), the better the rolling resistance. (6) Abrasion Resistance Using an FPS tester (manufactured by Ueshima Seisakusho Co., Ltd.), tests were conducted under the conditions of a sample speed of 200 m / min, a load of 20 N, a road surface temperature of 30°C, a slip rate of 5% and a slip rate of 20%. The results obtained were expressed as an index, with Comparative Example 3-1 being set at 100. A larger index value indicates a smaller amount of wear and better abrasion resistance.

[0069]

[0070] As shown in Table 2, the vulcanized products 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 vulcanized product 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, wherein the amount of the silanol group-containing organosilicon compound supported on the carrier is 10 mass% or more based on the total mass of the material. (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 according to claim 1, wherein the silanol group-containing organosilicon compound comprises a compound represented by the following formula (2): (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 according to claim 1, wherein the silanol group-containing organosilicon compound comprises a compound represented by the following formula (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. The organosilicon compound-supported material according to claim 3, wherein X is a structure represented by the following formula (4), (5), or (6): (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 above 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. 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. The organosilicon compound-supported material according to claim 1, wherein said support is silica.

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

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

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

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

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

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

Images