Organosilicon compound, rubber composition, and rubber material

Abstract

The present invention addresses the problem of providing: an organosilicon compound which has a novel structure and which, when used in or for a rubber composition or a rubber material, can provide a rubber material excellent in terms of fuel efficiency and wear resistance; a rubber composition containing the organosilicon compound; and a rubber material obtained using the rubber composition.　It has been found that the problem can be solved by: an organosilicon compound which is represented by general formula [1] (e.g., an organosilicon compound having a sulfide bond and a thiadiazole structure, tetrazole structure, triazine structure, or benzoxazole structure) and / or a condensate including the organosilicon compound as a condensation component; a rubber composition in which the organosilicon compound and / or the condensate is used; and a rubber material which is obtained using the rubber composition.

Description

Organosilicon compound, rubber composition, and rubber material

[0001] The present invention relates to an organosilicon compound having a specific structure and a rubber composition using the same. The present invention is suitable for use in tires, belts, vibration-proof rubber, and the like, and is particularly suitable for use in tires.

[0002] In recent years, a variety of silica-blended rubber products have become popular, including silica-blended tires with excellent fuel economy and braking performance, as well as vibration-isolating rubber and various rubber rolls. However, silica-blended rubber compositions exhibit a significant increase in compound viscosity, so a common approach to alleviate this increase in viscosity is to incorporate a silane coupling agent. It is also known that silane coupling agents react with silanol groups on the silica surface to reduce the interaction between silica particles, thereby lowering the loss tangent and dynamic modulus of the rubber.

[0003] Currently, among silane coupling agents, polysulfide-based coupling agents are widely used in fuel-efficient tires (see Patent Document 1).

[0004] However, improvements in wear resistance, fuel economy, etc. are being sought, and new coupling agents are currently being developed.

[0005] Japanese Patent Application Laid-Open No. 2000-103794

[0006] In view of the above, the present invention provides an organosilicon compound having a novel structure, which, when used in a rubber composition or rubber material, enables the production of a rubber material having excellent abrasion resistance (preferably, also excellent fuel economy), a rubber composition containing the organosilicon compound, and a rubber material obtained by using the rubber composition.

[0007] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by a specific organosilicon compound (for example, an organosilicon compound having a sulfide bond and a thiadiazole structure, or a tetrazole structure, a triazine structure, or a benzoxazole structure) and / or a condensate containing the organosilicon compound as a condensation component, a rubber composition using the same, or a rubber material obtained by using the rubber composition.

[0008] The present invention can also be described as follows: Item 1: An organosilicon compound represented by the following general formula [1], and / or a condensation product containing the organosilicon compound represented by the following general formula [1] as a condensation component. (In formula [1], R 1 , R 2 , R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a hydroxy group, a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18, and R is either a polyalkylene glycol monoalkyl ether group, a carboxyl group having 2 to 18 carbon atoms, or a halogen atom. 1 , R 2 , R 3 At least one of the groups is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a hydroxy group, or a C a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18, and R is any one of a polyalkylene glycol monoalkyl ether group, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a carboxyl group having 2 to 18 carbon atoms, and a halogen atom. 4 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms which may contain a substituted or unsubstituted aromatic ring, R 5 is an organic group based on a monocyclic or fused polycyclic heterocyclic compound, n is 1 to 3, and x is 2 to 4. 5 Item 2. The organosilicon compound or condensate according to Item 1, wherein R is an organic group represented by the following general formulas [2] to [8]: (In formula [2], R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a mercapto group. (In formula [3], R 7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Term 3 In formula [1], R 1 , R 2 , R 3 are each independently a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, and R 4 Item 4. The organosilicon compound or condensate according to Item 1 or 2, wherein is a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms. Item 5. A rubber composition comprising a rubber, a silica-based filler, and the organosilicon compound or condensate according to Item 1. Item 6. The rubber composition according to Item 4, wherein the rubber is one or more rubbers selected from the group consisting of natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR), ethylene-propylene copolymer rubber (EPDM), and butyl rubber (IIR). Item 7. The silica-based filler has a BET specific surface area of ​​20 to 300 m. 2 Item 7. A rubber material obtained by using the rubber composition according to any one of items 4 to 6. Item 8. A tire, belt, or vibration-proof rubber obtained by using the rubber material according to item 7.

[0009] The present inventors have found that the use of the organosilicon compound and / or condensate of the present invention in a rubber composition makes it possible to obtain a rubber material having excellent abrasion resistance (and preferably also excellent fuel economy).

[0010] The present invention is directed to an organosilicon compound represented by the following general formula [1] and / or a condensation product containing the organosilicon compound represented by the following general formula [1] as a condensation component. (In formula [1], R 1 , R 2, R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a hydroxy group, a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18, and R is either a polyalkylene glycol monoalkyl ether group, a carboxyl group having 2 to 18 carbon atoms, or a halogen atom. 1 , R 2 , R 3 At least one of the groups is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a hydroxy group, or a C a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18, and R is any one of a polyalkylene glycol monoalkyl ether group, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a carboxyl group having 2 to 18 carbon atoms, and a halogen atom. 4 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms which may contain a substituted or unsubstituted aromatic ring, R 5 is an organic group based on a monocyclic or fused polycyclic heterocyclic compound, and is preferably an organic group represented by the following general formulas [2] to [8] (particularly, an organic group represented by the following general formulas [2] to [4] and [6] to [8]), where n is 1 to 3 and x is 2 to 4. (In formula [2], R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a mercapto group. (In formula [3], R 7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0011] In the general formula [1], R 1 , R 2 , R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a hydroxy group, a H 2a+1 O-((CH2) b O) c wherein a is 1 to 18, b is 1 to 6, and c is 1 to 18; a carboxyl group having 2 to 18 carbon atoms; and a halogen atom, which is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a siloxy group having a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a siloxy group having a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, an aminoalkoxy group having 1 to 12 carbon atoms, an alkylaminoalkoxy group having 2 to 12 carbon atoms, a dialkylaminoalkoxy group having 3 to 12 carbon atoms, C a H 2a+1 O-((CH2) b O) c where a is 4 to 18, b is 2 to 4, and c is 1 to 12, and the alkyl group is preferably any one of a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms, a siloxy group having a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a siloxy group having a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, an aminoalkoxy group having 1 to 12 carbon atoms, an alkylaminoalkoxy group having 2 to 12 carbon atoms, a dialkylaminoalkoxy group having 3 to 12 carbon atoms, and C a H 2a+1O-((CH2) b O) c wherein a is 4 to 18, b is 2 to 4, and c is 1 to 8; more preferably, it is a polyalkylene glycol monoalkyl ether group represented by the formula (I) above, where a is 4 to 18, b is 2 to 4, and c is 1 to 8; particularly preferably, it is a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms; and most preferably, it is an unsubstituted alkoxy group having 1 to 3 carbon atoms.

[0012] Also R 1 , R 2 , R 3 At least one of the groups is a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a hydroxy group, or a C a H 2a+1 O-((CH2) b O) c where a is 2 to 18, b is 2 to 6, and c is 2 to 18; a polyalkylene glycol monoalkyl ether group; an aminoalkoxy group having 2 to 12 carbon atoms; an alkylaminoalkoxy group having 2 to 12 carbon atoms; or a dialkylaminoalkoxy group having 3 to 12 carbon atoms; a H 2a+1 O-((CH2) b O) c wherein a is 4 to 18, b is 2 to 6, and c is 2 to 18, more preferably any one of a polyalkylene glycol monoalkyl ether group, an aminoalkoxy group having 2 to 12 carbon atoms, an alkylaminoalkoxy group having 3 to 12 carbon atoms, and a dialkylaminoalkoxy group having 4 to 12 carbon atoms, particularly preferably a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, and most preferably an unsubstituted alkoxy group having 1 to 3 carbon atoms.

[0013] In the general formula [1], R 4 R may contain a substituted or unsubstituted aromatic ring, is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group, still more preferably a substituted or unsubstituted divalent alkylene group, and particularly preferably a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms. 4Examples of the aromatic ring in include a divalent aromatic hydrocarbon ring such as a phenylene group and a divalent aromatic heterocyclic ring. The aromatic ring preferably has 6 to 10 atoms constituting the ring.

[0014] In the general formula [1], examples of the substituent that can be substituted include alkyl groups such as methyl, ethyl, and isopropyl, aryl groups such as phenyl, aralkyl groups such as benzyl, unsaturated hydrocarbon groups such as vinyl, halogeno groups such as fluoro, chloro, bromo, and iodo, amino, and nitro groups. 1 ~R 4 The number of substituents that can be substituted in R may be one or two or more. When there are two or more substituents, the multiple substituents may be the same or different. However, 1 ~R 4 In the formula (I), when the substituent contains carbon atoms, the "number of carbon atoms" includes the number of carbon atoms contained in the substituent.

[0015] In the general formula [1], R 5 is an organic group based on a monocyclic or fused polycyclic heterocyclic compound (i.e., a monocyclic or fused polycyclic heterocyclic compound). The term "organic group based on a monocyclic or fused polycyclic heterocyclic compound" refers to a monovalent organic group having the heterocyclic compound, which is converted to S in the general formula [1]. x The term "a" refers to a residue obtained by removing S from the ring of the heterocyclic compound of the general formula [1], and examples thereof include a residue obtained by removing a mercapto group in a monocyclic or fused polycyclic heterocyclic compound having a mercapto group, which will be described later. x The atoms constituting the ring of the heterocyclic compound preferably have a sulfur atom and / or a nitrogen atom as a heteroatom, and more preferably the heteroatom is a sulfur atom and / or a nitrogen atom. The structure of the heterocyclic compound is preferably a 5-membered ring structure or a 6-membered ring structure. The heterocyclic compound is preferably a 5-membered ring structure or a 6-membered ring structure. 1 ~R 4R may have a substituent such as any of the substituents exemplified above as the substituent that R may have, or an alkyl group such as a methyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, an unsaturated hydrocarbon group such as a vinyl group, an alkoxy group such as a methoxy group, or an alkylthio group such as a methylthio group. 5 is more preferably an organic group represented by the following general formulas [2] to [8], and particularly preferably an organic group represented by the following general formulas [2] to [4] and [6] to [8]. (In formula [2], R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (preferably an alkyl group having 1 to 2 carbon atoms), or a mercapto group. (In formula [3], R 7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (preferably an alkyl group having 1 to 2 carbon atoms), or a phenyl group.

[0016] In the general formula [1], n is 1 to 3. In the general formula [1], n is R 5 indicates the number of monovalent groups surrounded by [ ] that bond to the above. Note that in the case of formula [2] and formula [3], n is 1 in the case of formula [4], n is 2 in the case of formula [5], n is 2 in the case of formula [6], n is 1 in the case of formula [7], and n is 1 in the case of formula [8]. When n is 2 or 3, the monovalent groups surrounded by [ ] may be the same or different.

[0017] In the general formula [1], x is 2 to 4, preferably 2 to 3, and may be 2.

[0018] The organosilicon compound of the present invention may be a condensate (oligomer) obtained by hydrolyzing an organosilicon compound represented by general formula [1] followed by a condensation reaction, or may be a condensate (oligomer) obtained by condensing with other components. Examples of other components include divalent or higher C alkyl polyols having 1 to 60 carbon atoms and optionally containing a nitrogen atom in the molecule and / or divalent or higher C (poly)alkyl ether polyols having 2 to 60 carbon atoms and optionally containing a nitrogen atom in the molecule, with alkyl polyols having 2 to 60 carbon atoms and / or (poly)alkyl ether polyols having 2 to 60 carbon atoms being preferred, and alkyl polyols having 2 to 30 carbon atoms and / or (poly)alkyl ether polyols having 2 to 30 carbon atoms being more preferred.

[0019] Examples of the divalent or higher alkyl polyols having 1 to 60 carbon atoms and which may contain a nitrogen atom in the molecule include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, diethanolamine, methyldiethanolamine, butyldiethanolamine, triethanolamine, etc. Examples of divalent or higher (poly)alkyl ether polyols having 2 to 60 carbon atoms and which may contain a nitrogen atom in the molecule include diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, etc.

[0020] In the organosilicon compound of the present invention, in the general formula [1], R 1 , R 2 , R 3 are each independently a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, and R 4 is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms, and R 1 , R 2 , R 3 are each independently selected from a methoxy group and an ethoxy group; R 4 is particularly preferably a trimethylene group.

[0021] The method for producing the organosilicon compound of the present invention is not particularly limited, but can be produced by referring to, for example, a method described in a literature (Angew. Chem. Int. Ed. 2022, 61, e202209044). That is, a production method can be exemplified by reacting a mercaptosilane with a monocyclic or fused polycyclic heterocyclic compound having a mercapto group using a peroxide in the presence of a quaternary ammonium salt.

[0022] Specific examples of mercaptosilane include, but are not limited to, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, and the like. One or more of these mercaptosilanes may be used.

[0023] Examples of the monocyclic or fused polycyclic heterocyclic compounds having a mercapto group include 2-mercapto-1,3,4-thiadiazole, 2-mercapto-5-methyl-1,3,4-thiadiazole, 2-ethyl-5-mercapto-1,3,4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 2-mercapto-5-methylthio-1,3,4-thiadiazole, 2-ethylthio-5-mercapto-1,3,4-thiadiazole, 2-mercapto-5-methoxy-1, Examples of the mercapto group-containing monocyclic or fused polycyclic heterocyclic compound include, but are not limited to, 3,4-thiadiazole, 2-ethoxy-5-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 5-mercapto-1H-tetrazole, 5-mercapto-1-methyl-1H-tetrazole, 5-mercapto-1-phenyl-1H-tetrazole, 2,4,6-trimercapto-s-triazine, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole. The mercapto group-containing monocyclic or fused polycyclic heterocyclic compound may be one or more of these.

[0024] The amount of the monocyclic or fused polycyclic heterocyclic compound having a mercapto group used is preferably 0.3 to 5.0 molar equivalents, more preferably 0.5 to 3.0 molar equivalents, and particularly preferably 0.6 to 2.5 molar equivalents, relative to the amount of the mercaptosilane.

[0025] Examples of quaternary ammonium salts include tetraalkylammonium chloride salts such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, trioctylmethylammonium chloride, tridecylmethylammonium chloride, trioctylethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tridodecylmethylammonium chloride, trihexadecylmethylammonium chloride, trioctadecylmethylammonium chloride, lauryltripropylammonium chloride, hexadecyltripropylammonium chloride, octadecyltripropylammonium chloride, dodecyltributylammonium chloride, hexadecyltributylammonium chloride, octadecyltributylammonium chloride, didodecyldimethylammonium chloride, dihexadecyldimethylammonium chloride, and dioctadecyldimethylammonium chloride; tetraalkylammonium fluoride salts in which the chloride ions in the tetraalkylammonium chloride salts are replaced with fluorine ions; and tetraalkylammonium bromide salts in which the chloride ions in the tetraalkylammonium chloride salts are replaced with bromine ions. Tetraalkylammonium iodide salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced by iodide ions; tetraalkylammonium hydroxide salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced by hydroxide ions; tetraalkylammonium sulfate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced by sulfate ions; tetraalkylammonium hydrogen sulfate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced by hydrogen sulfate ions; tetraalkylammonium methyl sulfate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced by methyl sulfate ions; tetraalkylammonium tetrafluoroborate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced by tetrafluoroborate ions;Examples thereof include tetraalkylammonium hexafluorophosphate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced with hexafluorophosphate ions, tetraalkylammonium perchlorate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced with perchlorate ions, tetraalkylammonium acetate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced with acetate ions, and tetraalkylammonium p-toluenesulfonate salts in which the chloride ions constituting the tetraalkylammonium chloride salts are replaced with p-toluenesulfonate ions.

[0026] Phenyltrialkylammonium chloride salts such as phenyltrimethylammonium chloride, phenyltriethylammonium chloride, phenyltripropylammonium chloride, phenyltributylammonium chloride, and phenyltrioctylammonium chloride; phenyltrialkylammonium fluoride salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with fluoride ions; phenyltrialkylammonium bromide salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with bromine ions; phenyltrialkylammonium iodide salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with iodide ions; phenyltrialkylammonium hydroxide salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with hydroxide ions; phenyltrialkylammonium sulfate salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with sulfate ions; phenyltrialkylammonium hydrogensulfate salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with hydrogensulfate ions; phenyltrialkylammonium methylsulfate salts in which the chloride ions in the phenyltrialkylammonium chloride salts are replaced with methylsulfate ions; Examples of the phenyltrialkylammonium tetrafluoroborate salt include a phenyltrialkylammonium tetrafluoroborate salt in which the chloride ion constituting the phenyltrialkylammonium chloride salt is replaced with a tetrafluoroborate ion; a phenyltrialkylammonium hexafluorophosphate salt in which the chloride ion constituting the phenyltrialkylammonium chloride salt is replaced with a hexafluorophosphate ion; a phenyltrialkylammonium perchlorate salt in which the chloride ion constituting the phenyltrialkylammonium chloride salt is replaced with a perchlorate ion; a phenyltrialkylammonium acetate salt in which the chloride ion constituting the phenyltrialkylammonium chloride salt is replaced with an acetate ion; and a phenyltrialkylammonium p-toluenesulfonate salt in which the chloride ion constituting the phenyltrialkylammonium chloride salt is replaced with a p-toluenesulfonate ion.

[0027] benzyltrialkylammonium chloride salts such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, benzyllauryldimethylammonium chloride, benzylcetyldimethylammonium chloride, and benzylstearyldimethylammonium chloride; benzyltrialkylammonium fluoride salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced with fluoride ions; benzyltrialkylammonium bromide salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced with bromide ions; benzyltrialkylammonium iodide salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced with iodide ions; benzyltrialkylammonium hydroxide salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced with hydroxide ions; benzyltrialkylammonium sulfate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced with sulfate ions; benzyltrialkylammonium hydrogensulfate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced with hydrogensulfate ions; benzyltrialkylammonium methylsulfate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced by methylsulfate ions; benzyltrialkylammonium tetrafluoroborate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced by tetrafluoroborate ions; benzyltrialkylammonium hexafluorophosphate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced by hexafluorophosphate ions; benzyltrialkylammonium perchlorate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced by perchlorate ions; benzyltrialkylammonium acetate salts in which the chloride ions in the benzyltrialkylammonium chloride salts are replaced by acetate ions;Examples include benzyltrialkylammonium p-toluenesulfonate salts in which the chloride ions constituting the benzyltrialkylammonium chloride salts are replaced with p-toluenesulfonate ions, and benzalkonium chloride. One or more of these quaternary ammonium salts may be used as the quaternary ammonium salt.

[0028] The amount of the quaternary ammonium salt used is preferably 0.0001 to 10 molar equivalents, and more preferably 0.001 to 1.0 molar equivalents, relative to the mercaptosilane.

[0029] Examples of peroxides include hydrogen peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(tert-butylperoxyisopropyl)-benzene, peroxyketals such as tert-butylperoxybenzoate and 1,1-di-tert-butylperoxycyclohexane, α-cumylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy Examples of the peroxycarbonate include, but are not limited to, alkyl peresters such as di-2-ethylhexanoate, tert-amylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, and tert-amylperoxybenzoate; peroxycarbonates such as di-2-ethylhexylperoxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butylperoxyisopropyl carbonate, and 1,6-bis(tert-butylperoxycarbonyloxy)hexane; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyoctoate, and lauroyl peroxide. These peroxycarbonates may be used alone or in combination.

[0030] The amount of the peroxide used is preferably 0.1 to 20 molar equivalents, more preferably 0.5 to 5.0 molar equivalents, relative to the mercaptosilane.

[0031] The reaction between mercaptosilane and a monocyclic or fused polycyclic heterocyclic compound having a mercapto group is preferably carried out in a solvent. Examples of the solvent include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, and xylene; amide solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide, and N-methylpyrrolidone; and water. One or more of these solvents may be used.

[0032] The amount of the solvent used is preferably 0.3 to 100 times by mass, more preferably 0.5 to 40 times by mass, relative to the amount of the mercaptosilane.

[0033] There are no limitations on the reaction conditions, but the reaction temperature is usually 0 to 60°C and the reaction time is preferably about 1 to 24 hours.

[0034] The organosilicon compound represented by the general formula [1] and / or the condensate containing the organosilicon compound represented by the following general formula [1] as a condensation component can be used not only for tires but also for rubbers such as vibration-proof rubber, rubber flooring, rolls, packings, sealing materials, and O-rings, and further for parts of electronic devices such as semiconductor encapsulants.

[0035] The rubber composition of the present invention contains a rubber, a silica-based filler, and an organosilicon compound represented by general formula [1] of the present invention, and / or a condensate containing an organosilicon compound represented by general formula [1] as a condensation component.

[0036] [Rubber, Silica-Based Filler] The rubber used in the rubber composition of the present invention is not particularly limited, but examples thereof include natural rubber (NR), polyisoprene rubber (IR), various styrene-butadiene copolymer rubbers (SBR), polybutadiene rubber (BR), various acrylonitrile-butadiene copolymer rubbers (NBR), chloroprene rubber (CR), various ethylene-propylene copolymer rubbers (EPDM), and butyl rubber (IIR). Diene-based rubbers are preferred. Rubbers may also include those whose terminals or main chains have been modified as needed (e.g., terminally modified SBR) or those modified to impart desired properties (e.g., modified NR). The rubbers may be used alone or in any blend. NR, IR, and SBR are particularly preferred. In the case of blends, rubbers selected from NR, IR, and SBR may be contained as the rubber component in an amount of 10 to 90% by mass based on a total of 100% by mass of the rubber components.

[0037] The silica-based filler used in the rubber composition of the present invention has a BET specific surface area of ​​10 to 400 m 2 / g, and wet silica and dry silica having a BET specific surface area of ​​20 to 300 m 2 / g, and a BET specific surface area of ​​50 to 300 m 2 / g, and a BET specific surface area of ​​30 to 250 m 2 The BET specific surface area can be measured using a Shimadzu Tristar II 3020 measuring device according to the protocol attached to the device.

[0038] The silica-based filler used in the rubber composition of the present invention preferably contains 10 to 150 parts by mass, more preferably 20 to 150 parts by mass, even more preferably 20 to 120 parts by mass, still more preferably 40 to 120 parts by mass, and particularly preferably 60 to 120 parts by mass of the silica-based filler per 100 parts by mass of rubber.

[0039] [Organosilicon Compound Represented by General Formula [1] and / or Condensate Containing Organosilicon Compound Represented by General Formula [1] as a Condensation Component] The rubber composition of the present invention contains, as the organosilicon compound, an organosilicon compound represented by the general formula [1] and / or a condensate containing an organosilicon compound represented by the general formula [1] as a condensation component.

[0040] The organosilicon compound represented by general formula [1] and / or the condensate containing the organosilicon compound represented by general formula [1] as a condensation component used in the rubber composition of the present invention preferably contains 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and particularly preferably 3 to 15 parts by mass, per 100 parts by mass of rubber.

[0041] [Other Organosilicon Compounds] The rubber composition of the present invention may contain at least one organosilicon compound other than the organosilicon compound represented by the general formula [1] and the condensate containing the organosilicon compound represented by the general formula [1] as a condensation component, selected from the group consisting of vinyl-based organosilicon compounds, amino-based organosilicon compounds, alkyl-based organosilicon compounds, epoxy-based organosilicon compounds, methacrylic-based organosilicon compounds, (protected) mercapto-based organosilicon compounds, (poly)sulfide-based organosilicon compounds, and condensates thereof (hereinafter, these organosilicon compounds may be collectively referred to as "other organosilicon compounds"). These may also be contained as by-products during the synthesis of the organosilicon compound represented by the general formula [1].

[0042] In the rubber composition of the present invention, when other organosilicon compounds are contained, that is, at least one selected from vinyl-based organosilicon compounds, amino-based organosilicon compounds, alkyl-based organosilicon compounds, epoxy-based organosilicon compounds, methacrylic-based organosilicon compounds, (protected) mercapto-based organosilicon compounds, (poly)sulfide-based organosilicon compounds, and condensates thereof, the amount of the other organosilicon compounds may be 0.1 to 20 parts by mass, 0.2 to 15 parts by mass, 0.3 to 10 parts by mass, or 0.3 to 5.0 parts by mass per 100 parts by mass of the silica-based filler.

[0043] Examples of the vinyl-based organosilicon compound of the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, triethoxyvinylsilane, and the like.

[0044] Examples of the amino-based organosilicon compound of the present invention include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and 3-(N-phenyl)aminopropyltrimethoxysilane.

[0045] Examples of the alkyl-based organosilicon compound of the present invention include methyltrimethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, and hexamethyldisilazane.

[0046] Examples of the epoxy-based organosilicon compound of the present invention include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane.

[0047] Examples of the methacrylic organosilicon compound of the present invention include 3-methacryloxypropyltriethoxysilane and 3-methacryloxypropyltrimethoxysilane.

[0048] The (poly)sulfide-based organosilicon compound of the present invention is exemplified by a polysulfide-based silane coupling agent represented by the general formula [9], and bis(3-triethoxysilylpropyl) disulfide and bis(3-triethoxysilylpropyl) tetrasulfide are particularly preferred. (R 8 -O) 3-m (R 8 ) m -Si-R 9 -S l -R 9 -Si-(R 8 )m' (O-R 8' ) 3-m' ...[9] (In formula [9], R 8 are independently alkyl groups having 1 to 18 carbon atoms; a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18; R 9 represents an alkylene group having 1 to 9 carbon atoms or a divalent phenyl group, l represents 1 to 9, and m and m' are the same or different and represent an integer of 0, 1, or 2.

[0049] Examples of the (protected) mercapto-based organosilicon compound of the present invention include mercapto-based organosilicon compounds having a mercapto group as a compound, such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, and protected mercapto-based organosilicon compounds that do not have a mercapto group as a compound (the mercapto group is protected), such as 3-octanoylthio-1-propyltriethoxysilane and 3-propionylthiopropyltrimethoxysilane, which subsequently acquire a mercapto group by application of heat, chemicals, etc. The (protected) mercapto-based organosilicon compound of the present invention is preferably a compound represented by the following formula

[10] : R 10 n (R 11 ) 3-n -Si-R 12 -SH...

[10] R 10 are each independently a hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. 11 are each independently an alkoxy group, preferably an alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms. 12 is a divalent hydrocarbon group, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, and preferably an alkylene group having 1 to 4 carbon atoms. n is 0, 1 or 2.

[0050] Specific examples of other organosilicon compounds that can be used in combination include, but are not limited to, Kabras-2 and Kabras-4 manufactured by Osaka Soda Co., Ltd., which correspond to the compound represented by the general formula [9] above, S330 manufactured by JNC Corporation, which is 3-aminopropyltriethoxysilane, Si-75 manufactured by Evonik, which corresponds to the Kabras-2 type, Si-69, which corresponds to the Kabras-4 type, Si-363 represented by the following formula

[11] , A-1289 manufactured by Momentive, which corresponds to the Kabras-4 type, A-189 which is 3-mercaptopropyltrimethoxysilane, A-1891 which is 3-mercaptopropyltriethoxysilane, NXT which is 3-octanoylthio-1-propyltriethoxysilane, NXT-LowV represented by the following formula

[12] , and KBE-846 manufactured by Shin-Etsu Chemical Co., Ltd., which corresponds to the Kabras-4 type. These compounds can also be used alone or in combination.

[0051] It is also preferred that the total mass of at least one of the organosilicon compounds of the present invention, vinyl organosilicon compounds, amino organosilicon compounds, alkyl organosilicon compounds, epoxy organosilicon compounds, methacrylic organosilicon compounds, (protected) mercapto organosilicon compounds, (poly)sulfide organosilicon compounds, and condensates thereof does not exceed 30 parts by mass per 100 parts by mass of the silica-based filler.

[0052] In producing the rubber composition of the present invention, kneading is preferably carried out at 80 to 250° C., more preferably at 80 to 200° C. The kneading time is not particularly limited, but is, for example, 1 minute to 1 hour.

[0053] In the present invention, it is preferable that the composition further contains a crosslinking agent, and it is particularly preferable that the crosslinking agent is at least one selected from sulfur, selenium, organic peroxides, morpholine disulfide, thiuram compounds, and oxime compounds, but the crosslinking agent is not limited to these.

[0054] The content of the crosslinking agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass, per 100 parts by mass of rubber.

[0055] The composition (rubber composition for crosslinking) obtained by adding the crosslinking agent to the rubber composition of the present invention is preferably kneaded at 100° C. or less. The kneading time is not particularly limited, but is, for example, 1 minute to 1 hour.

[0056] In addition to the above, the rubber composition of the present invention can use compounding agents that are commonly used in the rubber industry, as long as they do not deviate from the spirit of the present invention. For example, crosslinking accelerators (auxiliaries) such as guanidine-based crosslinking accelerators, sulfenamide-based crosslinking accelerators, thiazole-based crosslinking accelerators, and zinc oxide (zinc oxide), processing aids such as stearic acid, titanate-based coupling agents, antioxidants such as phenyl-α-naphthylamine and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, fillers such as carbon black and calcium carbonate, reinforcing agents, softeners, plasticizers, tackifiers, and scorch inhibitors can be used.

[0057] Examples of the guanidine crosslinking accelerator include 1,3-diphenylguanidine and 1,3-di-o-tolylguanidine.

[0058] Examples of the sulfenamide crosslinking accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-tert-butyl-2-benzothiazolylsulfenamide, and N-tert-butylbis(1,3-benzothiazole-2-sulfen)imide.

[0059] Examples of the thiazole-based crosslinking accelerator include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc, and 2-(morpholinodithio)benzothiazole.

[0060] The amount of crosslinking accelerator (auxiliary) compounded in the rubber composition of the present invention is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 3 to 9 parts by mass, per 100 parts by mass of rubber. The amount of crosslinking accelerator (auxiliary) compounded is the total amount of crosslinking accelerator and crosslinking accelerator auxiliary, and when both a crosslinking accelerator and a crosslinking accelerator auxiliary are used, it represents the total amount of these.

[0061] Examples of processing aids include higher fatty acids such as stearic acid, oleic acid, palmitic acid, and lauric acid; higher fatty acid amides such as stearic acid amide and oleic acid amide; higher fatty acid esters such as ethyl oleate; and higher aliphatic amines such as stearylamine and oleylamine.

[0062] The amount of processing aid in the rubber composition of the present invention is, for example, 300 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 10 parts by mass or less, per 100 parts by mass of rubber.

[0063] Examples of softeners include petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as vaseline, paraffin and naphthene; and silicone oils.

[0064] The amount of softener in the rubber composition of the present invention is, for example, 300 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, per 100 parts by mass of rubber.

[0065] The amount of antioxidant mixed in the rubber composition of the present invention is, for example, 30 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of rubber.

[0066] The rubber composition of the present invention may further contain carbon black. Examples of carbon black include, but are not limited to, carbon blacks of various classes such as SRF, FEF, HAF, ISAF, and SAF.

[0067] The amount of carbon black to be compounded is preferably 0.5 to 100 parts by mass, more preferably 1 to 90 parts by mass, and particularly preferably 2 to 80 parts by mass, per 100 parts by mass of rubber.

[0068] The rubber composition (rubber composition for crosslinking) of the present invention can be kneaded using various mixing machines commonly used in the rubber industry, such as rolls, pressure kneaders, intermixers, and Banbury mixers.

[0069] The rubber composition for crosslinking thus prepared is molded into an intended shape using an extruder, a calendar roll, or a press, and then heated preferably at 120 to 230°C for 1 minute to 3 hours to obtain a crosslinked product. A mold may also be used for crosslinking.

[0070] The rubber composition of the present invention preferably has a ratio of tan δ at 0°C to tan δ at 60°C [tan δ at 0°C / tan δ at 60°C] of 1.6 or more, more preferably 2.2 or more, and even more preferably 2.5 or more.

[0071] A rubber material using the rubber composition of the present invention can be suitably used in rubber parts that are used dynamically, such as tires (particularly tread portions), belts, and vibration-isolating rubber, and the rubber material is preferably a crosslinked product obtained by crosslinking the rubber composition of the present invention.

[0072] The present invention will be specifically explained below with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as it does not deviate from the gist of the invention. Modifications can be made within the scope of the above and below-mentioned aims, and all such modifications are included within the technical scope of the present invention. In the chemical formula, Et represents an ethyl group.

[0073] Synthesis of disulfide-type triethoxysilane (organosilicon compound 1) having a 2-mercapto-5-methyl-1,3,4-thiadiazole residue: 36.1 g (151.3 mmol) of 3-mercaptopropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd.), 20.0 g (151.3 mmol) of 2-mercapto-5-methyl-1,3,4-thiadiazole (Tokyo Chemical Industry Co., Ltd.), 2.2 g (6.1 mmol) of tetrabutylammonium iodide (Tokyo Chemical Industry Co., Ltd.), and 600 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 1000 mL three-neck flask equipped with a thermometer and a magnetic stirrer. 39.0 g (302.9 mmol) of a 70% tert-butyl hydroperoxide solution (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise while stirring the contents of the flask with a magnetic stirrer, and the mixture was then stirred at room temperature for 2 hours. After the reaction was completed, the organic layer obtained by separation was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain 61.2 g of organosilicon compound 1 (formula

[13] ) as a brown liquid. The physical properties are shown below. 1 H NMR (400MHz, CDCl3) δ3.8 (q, J = 6.8Hz, 6H), 2.9 (t, J = 7.2Hz, 2H), 2.7 (s, 3H), 1.9-1.8 (m, 2H), 1.2 (t, J=6.8Hz, 9H), 0.8-0.7 (m, 2H)

[0074] Synthesis of disulfide-type triethoxysilane (organosilicon compound 2) having a 5-mercapto-1-methyl-1H-tetrazole residue: 20.5 g (86.1 mmol) of 3-mercaptopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 g (86.1 mmol) of 5-mercapto-1-methyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.3 g (3.4 mmol) of tetrabutylammonium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 170 mL of dichloromethane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 500 mL three-neck flask equipped with a thermometer and a magnetic stirrer. 14.1 g (109.5 mmol) of a 70% tert-butyl hydroperoxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise while stirring the contents of the flask with a magnetic stirrer, and the mixture was then stirred at room temperature for 1 hour. After the reaction was completed, the organic layer obtained by separation was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain 33.0 g of organosilicon compound 2 (formula

[14] ) as a brown liquid. The physical properties are shown below. 1 H NMR (400MHz, CDCl3) δ4.1 (s, 3H), 3.8 (q, J = 6.8Hz, 6H), 2.9 (t, J = 7.2Hz, 2H), 1.9-1.8 (m, 2H), 1.2 (t, J=6.8Hz, 9H), 0.8-0.7 (m, 2H)

[0075] Synthesis of disulfide-type triethoxysilane (organosilicon compound 3) having a 2,5-dimercapto-1,3,4-thiadiazole residue: 15.9 g (66.6 mmol) of 3-mercaptopropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd.), 5.0 g (33.3 mmol) of 2,5-dimercapto-1,3,4-thiadiazole (Tokyo Chemical Industry Co., Ltd.), 0.5 g (1.3 mmol) of tetrabutylammonium iodide (Tokyo Chemical Industry Co., Ltd.), and 130 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 300 mL three-neck flask equipped with a thermometer and a magnetic stirrer. While stirring the contents of the flask with a magnetic stirrer, 17.1 g (133.1 mmol) of a 70% tert-butyl hydroperoxide solution (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise, followed by stirring at room temperature for 1 hour. After the reaction was completed, the organic layer obtained by separation was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain 21.5 g of organosilicon compound 3 (formula

[15] ) as a brown liquid. The physical properties are shown below. 1 H NMR (400MHz, CDCl3) δ3.8 (q, J = 6.8Hz, 6H), 2.9 (t, J = 7.2Hz, 2H), 1.9-1.8 (m, 2H), 1.2 (t, J = 6.8Hz, 9H), 0.8-0.7 (m, 2H)

[0076] Synthesis of disulfide-type triethoxysilane having a 2,4,6-trimercapto-s-triazine residue (organosilicon compound 4) 33.6 g (141.0 mmol) of 3-mercaptopropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd.), 5.0 g (28.2 mmol) of 2,4,6-trimercapto-s-triazine (Tokyo Chemical Industry Co., Ltd.), 1.3 g (3.4 mmol) of tetrabutylammonium iodide (Tokyo Chemical Industry Co., Ltd.), and 110 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added to a 500 mL three-neck flask equipped with a thermometer and a magnetic stirrer. While stirring the contents of the flask with a magnetic stirrer, 43.6 g (338.5 mmol) of a 70% tert-butyl hydroperoxide solution (Fujifilm Wako Pure Chemical Industries Co., Ltd.) was added dropwise, followed by stirring at room temperature for 1 hour. After the reaction was completed, the organic layer obtained by separation was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. It was then purified by silica gel chromatography (n-hexane / ethyl acetate = 95 / 5), yielding 16.1 g of organosilicon compound 4 (formula

[16] ) as a pale brown liquid. Its physical properties are shown below. 1 H NMR (400MHz, CDCl3) δ3.8 (q, J = 6.8Hz, 6H), 2.9 (t, J = 7.2Hz, 2H), 1.9-1.8 (m, 2H), 1.2 (t, J = 6.8Hz, 9H), 0.8-0.7 (m, 2H)

[0077] Synthesis of disulfide-type triethoxysilane (organosilicon compound 5) having a 2-mercaptobenzoxazole residue: 31.54 g (132.3 mmol) of 3-mercaptopropyltriethoxysilane (Tokyo Chemical Industry Co., Ltd.), 20.0 g (132.3 mmol) of 2-mercaptobenzoxazole (Tokyo Chemical Industry Co., Ltd.), 1.5 g (4.0 mmol) of tetrabutylammonium iodide (Tokyo Chemical Industry Co., Ltd.), and 530 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 1000 mL three-neck flask equipped with a thermometer and a magnetic stirrer. While stirring the contents of the flask with a magnetic stirrer, 15.0 g (132.3 mmol) of 30% aqueous hydrogen peroxide (Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise, followed by stirring at room temperature for 1 hour. After completion of the reaction, the organic layer obtained by liquid separation was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. 52.1 g of organosilicon compound 5 (formula

[17] ) was obtained as a yellow liquid. The physical properties are shown below. 1 H NMR (400MHz, DMSO-d6) δ7.7-7.6 (m, 2H), 7.4-7.3 (m, 2H), 3.7 (q, J = 7.2Hz, 6H ), 3.0 (t, J=6.8Hz, 2H), 1.9-1.8 (m, 2H), 1.1 (t, J=7.2Hz, 9H), 0.7-0.6 (m, 2H)

[0078] Preparation of Rubber Compositions: Kneading tests were conducted using a Labo Plastomill 10C100 (manufactured by Toyo Seiki Co., Ltd.) equipped with 250cc Banbury mixer-type attachments BR-250 and B-250. The equipment temperature was 100°C with oil circulation heating, and the mixer rotor rotation speed was constant at 80 rpm. Tests were conducted on a 100g rubber basis. The rubber components were masticated for 30 seconds, then the chemicals shown in formula (I) in Table 1 were added and kneaded for 3 minutes, after which the kneaded mixture was discharged. The amount of organosilicon compound in each example and comparative example was adjusted so that the silicon content in the organosilicon compound was the same in both examples and comparative examples. The discharged kneaded mixture was cooled on a 6-inch roll at room temperature, and then the crosslinking agent shown in formula (II) in Table 1 was added and kneaded for 1 minute to obtain a sheet (uncrosslinked sheet) approximately 2mm thick. The following day, the remaining compound was hot-press crosslinked at 160°C for 20 minutes to obtain a test sample (crosslinked sheet).

[0079] Dynamic viscoelasticity test 1: Test pieces measuring 4 mm wide x 25 mm long x 2 mm thick were punched out from the crosslinked sheet and measured using a Rheogel-4000 manufactured by UBM Co., Ltd. under conditions of a chuck distance of 20 mm, an initial load of 1000 mN, a tensile strain of 10 μm, and vibration of 10 Hz. The measurement temperature range was -20°C to 20°C, and the temperature was raised at a rate of 2°C / min, and tan δ at 0°C was measured.

[0080] Dynamic viscoelasticity test 2: A test piece measuring 4 mm wide x 15 mm long x 2 mm thick was punched out from the crosslinked sheet, and tan δ at 60°C was measured using a Rheogel-4000 manufactured by UBM Co., Ltd. under the conditions of a chuck distance of 9 mm, an initial strain of 11%, a dynamic amplitude of 5%, and a vibration frequency of 10 Hz. The measurement temperature range was constant at 60°C.

[0081] Abrasion Test 1: Test specimens were prepared in accordance with JIS K6264 and measured at an inclination angle of 35° using an Akron abrasion tester. The load was 44.1 N, the test specimen rotation speed was 250 revolutions per minute, and the abrasion wheel was rotated 500 revolutions. The abrasion volume was measured from the weight loss and the specific gravity of the compound, and this was doubled to obtain the amount of abrasion per 1000 revolutions. The results are shown in Table 3.

[0082] Abrasion Test 2: Test specimens were prepared in accordance with JIS K6264 and measured at an inclination angle of 15° using an Akron abrasion tester. The load was 44.1 N, the test specimen rotation speed was 250 revolutions per minute, and the abrasion resistance was measured using Method A. The results are shown in Table 4.

[0083] The compounding ingredients used in the examples and comparative examples are listed below. *1 SL563 manufactured by JSR Corporation *2 Nipsil AQ (BET specific surface area 215 m) manufactured by Tosoh Silica Corporation 2 / g) *3 Sunthene 415 manufactured by Nippon Oil Corporation *4 Seast 3 (HAF) manufactured by Tokai Carbon Co., Ltd. *5 Sakura stearate manufactured by NOF Corporation *6 Nocrac 6C manufactured by Ouchi Shinko Chemical Industry Co., Ltd. *7 CABRUS-2A ((poly)sulfide-based organic silicon compound) manufactured by Osaka Soda Co., Ltd. *8 Zinc oxide type 2 manufactured by Sakai Chemical Industry Co., Ltd. *9 Noccela D manufactured by Ouchi Shinko Chemical Industry Co., Ltd. *10 Noccela CZ manufactured by Ouchi Shinko Chemical Industry Co., Ltd. *11 Colloidal sulfur manufactured by Hosoi Chemical Industry Co., Ltd.

[0084]

[0085] The test results of the Examples and Comparative Examples obtained by the above test methods are shown in Tables 2 and 3.

[0086]

[0087]

[0088]

[0089] As shown in Tables 3 and 4, Examples 1 to 5, which used the organosilicon compound of the present invention, exhibited lower wear levels and superior wear resistance compared to Comparative Example 1, which used the most commonly used polysulfide-based organosilicon compound. Furthermore, as shown in Table 2, Examples 1 to 3 and 5, which used the organosilicon compound of the present invention, exhibited larger tan δ at 0°C, suggesting superior grip performance, and smaller tan δ at 60°C, suggesting superior fuel economy, compared to Comparative Example 1, which used the most commonly used polysulfide-based organosilicon compound. Generally, as the tan δ at 60°C decreases, the tan δ at 0°C also tends to decrease. However, Examples 1 to 3 and 5, which used the organosilicon compound of the present invention, are also preferred in that they exhibit superior grip performance and fuel economy.

[0090] The use of the organosilicon compound of the present invention makes it possible to provide rubber compositions and rubber materials that are excellent in abrasion resistance (preferably, also in grip and fuel economy), and therefore are particularly suitable for the production of rubber parts that are used dynamically, such as tire treads, anti-vibration rubbers, and belts.

Claims

1. An organosilicon compound represented by the following general formula [1], and / or a condensation product containing an organosilicon compound represented by the following general formula [1] as a condensation component: (In formula [1], R 1 , R 2 , R 3 each independently represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a siloxy group having a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a hydroxy group, a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18; R is either a polyalkylene glycol monoalkyl ether group, a carboxyl group having 2 to 18 carbon atoms, or a halogen atom; 1 , R 2 , R 3 At least one of the groups is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, a hydroxy group, or a C a H 2a+1 O-((CH2) b O) c where a is 1 to 18, b is 1 to 6, and c is 1 to 18; R is any one of a polyalkylene glycol monoalkyl ether group, an aminoalkoxy group having 1 to 18 carbon atoms, an alkylaminoalkoxy group having 2 to 18 carbon atoms, a dialkylaminoalkoxy group having 3 to 18 carbon atoms, a carboxyl group having 2 to 18 carbon atoms, and a halogen atom. 4 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms which may contain a substituted or unsubstituted aromatic ring, R 5 is an organic group based on a monocyclic or fused polycyclic heterocyclic compound, n is 1 to 3, and x is 2 to 4.

2. In formula [1], R 5 The organosilicon compound or condensate according to claim 1, wherein: (In formula [2], R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a mercapto group. (In formula [3], R 7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

3. In formula [1], R 1 , R 2 , R 3 are each independently a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms; R 4 2. The organosilicon compound or condensate according to claim 1, wherein is a substituted or unsubstituted divalent hydrocarbon group having 1 to 18 carbon atoms.

4. A rubber composition comprising a rubber, a silica-based filler, and the organosilicon compound or condensate according to claim 1.

5. The rubber composition according to claim 4, wherein the rubber is one or more selected from the group consisting of natural rubber (NR), polyisoprene rubber (IR), styrene butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile butadiene copolymer rubber (NBR), chloroprene rubber (CR), ethylene propylene copolymer rubber (EPDM), and butyl rubber (IIR).

6. The silica-based filler has a BET specific surface area of ​​20 to 300 m 2 5. The rubber composition according to claim 4, wherein the wet silica is in an amount of 0.1 to 1 g.

7. A rubber material made using the rubber composition according to claim 4.

8. A tire, belt, or anti-vibration rubber made using the rubber material of claim 7.

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