WO2023032663A1 - Rubber composition and tire product - Google Patents

Rubber composition and tire product Download PDF

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Publication number
WO2023032663A1
WO2023032663A1 PCT/JP2022/031005 JP2022031005W WO2023032663A1 WO 2023032663 A1 WO2023032663 A1 WO 2023032663A1 JP 2022031005 W JP2022031005 W JP 2022031005W WO 2023032663 A1 WO2023032663 A1 WO 2023032663A1
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Prior art keywords
group
rubber
integer
carbon atoms
hydrogen atom
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PCT/JP2022/031005
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French (fr)
Japanese (ja)
Inventor
陽一 秋山
圭介 知野
誠 芦浦
将太郎 内澤
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Ｅｎｅｏｓ株式会社
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Publication of WO2023032663A1 publication Critical patent/WO2023032663A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to rubber compositions.
  • the present invention also relates to tire products manufactured using the rubber composition.
  • tires are manufactured from a rubber composition containing vulcanizing agents, fillers such as carbon black and silica, and anti-aging agents and waxes that suppress quality deterioration. has been done.
  • the cut resistance and chipping resistance of a tire are each important performance related to performance maintenance during use of the tire.
  • it is effective to increase the elongation at break and the strength at break.
  • Techniques for improving elongation at break include, for example, reducing the amount of fillers such as carbon black and silica.
  • such a method has the problem of lowering the hardness and impairing the steering stability.
  • it has been proposed to add a specific amount of carbon black or silica having a specific specific surface area to a rubber composition for tires (see Patent Document 1).
  • the present inventors have made intensive studies to solve the above problems, and as a result, surprisingly, the rubber component contains a rubber additive containing a sulfur-containing hydrocarbon polymer and an unsaturated double bond
  • the tire manufactured using the obtained rubber composition has a high tensile product, which is the product of breaking strength and breaking elongation, and as a result, cut resistance and chipping resistance It was found that the performance can be improved.
  • the present inventors have completed the present invention based on such findings.
  • the unsaturated double bond-containing silane compound has the following general formula (1): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; L is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R
  • the rubber composition according to [1], comprising a compound represented by: [3]
  • the unsaturated double bond-containing silane compound has the following formula: [In the above formulas, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom.
  • the sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur, and the unsaturated hydrocarbon contains an alicyclic unsaturated compound [1] to [4 ]
  • the rubber composition of the present invention contains at least a rubber component, a rubber additive, and an unsaturated double bond-containing silane compound, and preferably further contains a filler.
  • the content of the rubber component is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 75% by mass or less, and still more preferably 30% by mass, based on the total solid mass of the rubber composition. It is more than mass % and below 70 mass %.
  • the content of the rubber additive is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 25 parts by mass or less, and still more preferably 5 parts by mass with respect to 100 parts by mass of the rubber component.
  • the content of the unsaturated double bond-containing silane compound is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the rubber component.
  • the rubber component is not particularly limited, it preferably contains a diene rubber.
  • aromatic vinyl-conjugated diene copolymer rubber As the diene rubber, it is preferable to use at least one of aromatic vinyl-conjugated diene copolymer rubber and conjugated diene (co)polymer rubber.
  • Aromatic vinyl-conjugated diene copolymer rubbers include styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber, styrene-isoprene rubber, and styrene- ⁇ -methylstyrene-butadiene rubber.
  • Conjugated diene (co)polymer rubbers include butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), and the like.
  • diene rubbers include nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene terpolymer rubber (EPDM), butyl rubber (IIR), and the like. Modified diene rubbers of these diene rubbers can also be used. Modified diene rubbers include diene rubbers modified by modification techniques such as main chain modification, single terminal modification, both terminal modification, and hydrogenation.
  • the modified functional group of the modified synthetic diene rubber includes various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group. It may be contained in rubber.
  • the method for producing the diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization and cationic polymerization.
  • natural rubber examples include natural rubber latex, technical grade rubber (TSR), smoked sheet (RSS), gutta-percha, Eucommia-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, plant component fermented rubber, and the like.
  • modified natural rubber such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber, sulfonic acid-modified natural rubber, and zinc sulfonate-modified natural rubber, which are obtained by modifying these natural rubbers, are also included in natural rubber. .
  • the ratio of cis/trans/vinyl in the double bond portion of natural rubber and synthetic diene rubber is not particularly limited, and any ratio can be suitably used.
  • the number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, but the number average molecular weight is preferably 500 to 3,000,000 and the molecular weight distribution is preferably 1.5 to 15.
  • non-diene rubber may be blended in addition to diene rubber.
  • a wide range of known rubbers can be used as the non-diene rubber. Specific examples include olefin rubber such as ethylene/propylene rubber (EPM), chlorosulfonated polyethylene rubber (CSM), acrylic rubber (ACM), urethane rubber (U), and silicone rubber (VMQ, PVMQ, FVMQ). , fluororubber (FKM) and polysulfide rubber (T).
  • the rubber composition of the present invention can also contain an elastomer other than the above rubber components within a range that does not impair its functions.
  • Elastomers include polystyrenes such as styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), and their hydrogenated products (SEBS, SEPS, SEEPS).
  • Thermoplastic elastomers selected from the group consisting of elastomeric polymers, polyolefin-based elastomers, polyvinyl chloride-based elastomers, polyurethane-based elastomers, polyester-based elastomers, and polyamide-based elastomers.
  • the content of the diene rubber is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass, relative to the total amount of the rubber component.
  • the total content of the aromatic vinyl-conjugated diene copolymer rubber and the conjugated diene (co)polymer rubber in the rubber component is preferably 70% by mass or more, more preferably 70% by mass or more, based on the total amount of the rubber component. is 80% by mass or more, more preferably 90% by mass or more.
  • Rubber additives used in rubber compositions include the following sulfur-containing hydrocarbon polymers.
  • Sulfur-containing hydrocarbon polymers are reaction products of polymers of unsaturated hydrocarbons and sulfur.
  • the sulfur-containing hydrocarbon polymer is preferably a reaction product obtained by reacting an unsaturated bond of an unsaturated hydrocarbon polymer with sulfur.
  • the weight average molecular weight (Mw) of the sulfur-containing hydrocarbon polymer is preferably 500 or more and 4000 or less, and the lower limit is more preferably 600 or more, still more preferably 700 or more, and still more preferably 800 or more. Also, the upper limit is more preferably 3000 or less, still more preferably 2000 or less, and even more preferably 1500 or less. In particular, the weight average molecular weight (Mw) of the sulfur-containing hydrocarbon polymer is preferably 600 or more and 3000 or less, more preferably 700 or more and 2000 or less, still more preferably 800 or more and 1500 or less.
  • the sulfur-containing hydrocarbon polymer By reducing the weight average molecular weight of the sulfur-containing hydrocarbon polymer, the sulfur-containing hydrocarbon polymer is suppressed from binding to each other through sulfur, increasing the amount of sulfur that binds to the rubber component, and improving the tensile strength of the tire. product can be improved.
  • the molecular weight distribution (Mw/number average molecular weight (Mn)) of the sulfur-containing hydrocarbon polymer is preferably 1.0 or more and 5.0 or less, more preferably 1.0 or more and 4.0 or less, It is more preferably 1.0 or more and 3.0 or less, and still more preferably 1.0 or more and 2.5 or less.
  • the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) can be measured by a conventionally known GPC (gel permeation chromatography) analysis method.
  • At least a hydrocarbon having an unsaturated bond for reacting with sulfur is used as a raw material for the polymer.
  • the unsaturated hydrocarbon preferably contains an alicyclic unsaturated compound, and the alicyclic unsaturated hydrocarbon is more preferably a compound having a norbornene skeleton. This is because the double bond structure of the norbornene skeleton is distorted and has good reactivity with sulfur.
  • the unsaturated bonds of the alicyclic unsaturated compound may remain after reaction with sulfur or may be completely consumed.
  • unsaturated bonds of alicyclic unsaturated compounds there are unsaturated bonds present in the norbornene skeleton and unsaturated bonds present in the cyclopentene skeleton. More preferably, all unsaturated bonds are consumed.
  • useful compounds such as ethylene, propylene and butadiene, among fractions obtained by thermal decomposition of naphtha, are used as unsaturated hydrocarbon polymers from the viewpoint of industrial production.
  • a resin (hereinafter referred to as “petroleum resin”) obtained by polymerizing the removed remaining fraction in a mixed state can be used.
  • Petroleum resins generally include aliphatic petroleum resins (C5 petroleum resins) obtained by (co)polymerizing C5 fractions, and (co)polymerizing C9 fractions obtained by pyrolysis of naphtha.
  • Aromatic petroleum resins obtained by the above, and copolymer petroleum resins (C5/C9 petroleum resins) obtained by copolymerizing the C5 fraction and the C9 fraction.
  • the petroleum resin has different properties depending on the olefin content in the raw material, but it is a transparent pale yellow to yellowish brown resin with a molecular weight of 200 to 8000 and a softening point of 5 to 180 ° C. is.
  • alicyclic unsaturated hydrocarbon petroleum resin a petroleum resin obtained by (co)polymerizing a fraction containing an alicyclic unsaturated hydrocarbon (hereinafter referred to as "alicyclic unsaturated hydrocarbon petroleum resin") is used. use.
  • the alicyclic unsaturated hydrocarbon petroleum resin is obtained, for example, by dimerizing the cyclopentadienes contained in the C5 fraction to obtain dicyclopentadienes, separating from the other C5 fractions by distillation, and heating. Including those polymerized by the Diels-Alder reaction.
  • Cyclopentadienes include, for example, cyclopentadiene, methylcyclopentadiene, and the like.
  • the dicyclopentadienes include, for example, dicyclopentadiene (DCPD), methyldicyclopentadiene, etc. Dicyclopentadiene is particularly preferred.
  • the alicyclic unsaturated hydrocarbon petroleum resin may contain C5 fractions and C9 fractions other than cyclopentadienes.
  • the C5 fraction generally uses a fraction with a boiling point range of about 20 to 110°C among the fractions obtained by thermal cracking of petroleum.
  • Examples of C5 fractions other than cyclopentadienes include olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene. , 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.
  • the C9 fraction is generally a fraction with a boiling point range of about 100 to 280°C among the fractions obtained by thermal cracking of petroleum.
  • Examples of the C9 fraction include styrene homologues such as ⁇ -methylstyrene, ⁇ -methylstyrene and ⁇ -methylstyrene, and indene homologues such as indene and coumarone.
  • Friedel-Crafts type catalyst is added in an amount of 0.01 to 5% by weight based on the raw material oil, and the polymerization reaction is carried out. After completion of the reaction, the Friedel-Crafts-type catalyst is decomposed and removed using alkali, and finally unreacted oil and low-molecular-weight polymer are removed by distillation or the like.
  • Friedel-Crafts-type catalysts generally include, for example, aluminum trichloride, aluminum tribromide, boron trifluoride or their phenol complexes, butanol complexes, and the like.
  • the polymerization temperature is preferably 0 to 100°C, particularly preferably 0 to 80°C.
  • the catalyst amount and the polymerization time are preferably 0.1 to 10 hours when the catalyst is 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the raw material oil.
  • the reaction pressure is preferably atmospheric pressure to 1 MPa.
  • the petroleum resin may be partially polymerized with compounds having various functional groups.
  • functional groups include alcohol compounds and phenol compounds having hydroxyl groups.
  • alcohol compounds include alcohol compounds having double bonds such as allyl alcohol and 2-butene-1,4-diol.
  • phenolic compound alkylphenols such as phenol, cresol, xylenol, pt-butylphenol, p-octylphenol and p-nonylphenol can be used. These hydroxyl-containing compounds may be used alone, or two or more of them may be used in combination.
  • the hydroxyl group-containing petroleum resin can be obtained by thermally polymerizing a (meth)acrylic acid alkyl ester or the like together with a petroleum fraction to introduce an ester group into the petroleum resin, and then reducing the ester group. It can also be produced by a method of hydrating the introduced double bond.
  • the hydroxyl group-containing petroleum resin those obtained by the various methods described above can be used, but from the viewpoint of performance and production, it is preferable to use a phenol-modified petroleum resin or the like.
  • the phenol-modified petroleum resin is obtained by cationic polymerization of the C9 fraction in the presence of phenol, and is easy to modify.
  • the method of polymerization is not particularly limited, and is selected from, for example, the above-mentioned Diels-Alder reaction, a thermal polymerization reaction in which heating is performed at about 150 to 300 ° C. for about 1 to 10 hours, and the above-mentioned Friedel-Crafts-type reaction. can.
  • These resins described above preferably have a softening point of 200°C or less (measurement method: ASTM E28-58-T), more preferably 45 to 160°C.
  • a partially hydrogenated petroleum resin obtained by hydrogenating part of the double bonds in the above petroleum resin can also be used.
  • Hydrogenation conditions are arbitrary, but at least one solvent selected from saturated chain hydrocarbons, saturated alicyclic hydrocarbons and aromatic hydrocarbons having a boiling point of 140 to 280° C. at normal pressure and a petroleum resin and reaction using a general hydrogenation catalyst containing nickel, molybdenum, cobalt, palladium, platinum, etc., at a reaction temperature of 150 to 320 ° C., a reaction pressure of 3 to 30 MPa, and a reaction time of 1 to 10 hours. I do.
  • C5, C9, and C5/C9 petroleum resins having double bonds in the molecule include Neoresin EP-140 (softening point: 140°C) manufactured by ENEOS Corporation, and manufactured by Maruzen Petrochemical Co., Ltd. Marukaretsu M-890A (softening point: 105°C), Maruzen Petrochemical Co., Ltd.
  • Marukaretsu M-845A (softening point: 145°C), ENEOS T-REZ RB093 (softening point: 92°C), ENEOS ) T-REZ RB100 (softening point: 98°C), ENEOS T-REZ RC093 (softening point: 93°C), ENEOS T-REZ RC100 (softening point: 97°C), ENEOS ( T-REZ RC115 manufactured by ENEOS Corporation (softening point: 112°C), T-REZ RD104 manufactured by ENEOS Corporation (softening point: 102°C), T-REZ PR802 manufactured by ENEOS Corporation (softening point: 89°C), Japan Zeon Co., Ltd.
  • a sulfur-containing hydrocarbon polymer can be produced by reacting an unsaturated hydrocarbon with sulfur in a molten state while heating in the absence of a solvent. By conducting the heating reaction in the absence of a solvent rather than in a solvent, it is possible to reduce the weight average molecular weight of the sulfur-containing hydrocarbon polymer while reducing the variation in molecular weight.
  • the conditions for the heating reaction are not particularly limited and can be set as appropriate. is 0.5 to 10 hours, more preferably 1 to 8 hours. The weight average molecular weight of the sulfur-containing hydrocarbon polymer can be adjusted by adjusting the heating reaction conditions.
  • the amount of sulfur added to the petroleum resin is not particularly limited, but it is preferably 0.1 equivalent or more, preferably 0.3 to 5 equivalents, per unsaturated bond (double bond) of the unsaturated hydrocarbon.
  • a compound having a norbornene skeleton, particularly dicyclopentadiene, as the unsaturated alicyclic hydrocarbon it is preferable to use a compound having a norbornene skeleton, particularly dicyclopentadiene, as the unsaturated alicyclic hydrocarbon.
  • the double bond on the norbornene skeleton of the dicyclopentadiene reacts with sulfur, and more preferably only the double bond on the norbornene skeleton reacts with sulfur. It can be confirmed by 1 H-NMR that the double bond on the norbornene skeleton was consumed by reaction with sulfur.
  • a silane compound contained in the rubber composition can function as a silane coupling agent.
  • the rubber composition contains at least an unsaturated double bond-containing silane compound and may further contain other silane compounds having no unsaturated double bonds.
  • the content of the unsaturated double bond-containing silane compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, relative to the total amount of the silane compound. Moreover, it may be 100% by mass or less, preferably 100% by mass.
  • Preferred silane compounds are described below.
  • the unsaturated double bond-containing silane compound preferably has the following formula (1): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; L is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R
  • a is an integer of 0 or 1, preferably 1.
  • b is an integer of 0 or 1, preferably 1;
  • Each c is independently an integer of 0 or 1, preferably 1.
  • Each d is independently an integer of 0 or 1, preferably 1.
  • e is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably an integer of 0 or 1.
  • R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are - A crosslinked structure represented by (CH 2 ) f — may be formed.
  • f is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1.
  • R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are - A crosslinked structure represented by (CH 2 ) g — may be formed.
  • g is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1.
  • R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 or 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
  • R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 to 5 carbon atoms a group, more preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or, R 16 and R 17 are bonded together to form a 4- to 9-membered alicyclic hydrocarbon, preferably a 4- to 7-membered alicyclic
  • R 1 , R 2 and R 3 each independently represent a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom.
  • hydrocarbon groups include alkyl groups, aralkyl groups, and aryl groups.
  • alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1.
  • the aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
  • the number of carbon atoms in the aralkyl group is preferably 7-60, more preferably 7-20, even more preferably 7-14.
  • Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups.
  • the number of carbon atoms in the aryl group is preferably 6-60, more preferably 6-24, even more preferably 6-12.
  • a hydrocarbon group containing an oxygen atom or a nitrogen atom is a group having a structure in which a carbon atom in the hydrocarbon group is replaced with an oxygen atom or a nitrogen atom.
  • the hydrocarbon group which may contain an oxygen atom or a nitrogen atom for R 1 , R 2 and R 3 is an alkoxy group, an amino group substituted with one or more alkyl groups, or an alkyl group. More preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, still more preferably one or more or an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms.
  • alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy groups, among which methoxy and ethoxy groups are preferred.
  • the amino group substituted with one or more alkyl groups includes N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferred.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl group. Among them, a methyl group and an ethyl group are preferred.
  • L is a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably the number of carbon atoms in the hydrocarbon group is 1-30, more preferably 1-20, still more preferably 1-10.
  • L is particularly preferably a hydrocarbon group containing sulfur.
  • the total length of the linear portion connecting the silyl group and the alicyclic hydrocarbon portion in such a hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, as the total number of atoms of carbon, nitrogen, oxygen or sulfur. , more preferably 4-6.
  • the unsaturated double bond-containing silane compound preferably has the formula (2): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10, a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or
  • h in the compound represented by the above formula (2) is an integer of 1 to 10, preferably 1 to 8, more preferably 2 to 7, still more preferably 3 to 6, still more preferably 3 to 5 It is an integer, particularly preferably 3. Further, a to g and R 1 to R 18 are as explained in formula (1) above.
  • the unsaturated double bond-containing silane compound more preferably has the formula (3): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10, a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8
  • a to g and R 1 to R 11 are as described in the above formula (1), and h is as described in the above formula (2). is.
  • R 31 in formula (3) is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 to 5 carbon atoms, more preferably a hydrogen atom , a methyl group or an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom.
  • the unsaturated double bond-containing silane compound more preferably has the formula (4): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10, a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R
  • R 32 in formula (4) is a hydrogen atom, a methyl group or an alkyl group having 2 to 9 carbon atoms, preferably a methyl group or an alkyl group having 2 to 5 carbon atoms, more preferably a methyl group or an alkyl group having 2 to 5 carbon atoms. It is one or two alkyl groups, more preferably a methyl group.
  • the unsaturated double bond-containing silane compound more preferably has the formula (5): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10, a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R
  • x in formula (5) is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2, still more preferably 1.
  • the unsaturated double bond-containing silane compound is more preferably represented by formula (6): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ], or formula (7): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ], or formula (8): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ],or, Formula (9): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ] It is a compound represented by formula (6): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group
  • R 1 to R 3 are as explained for the above formula (1).
  • R 1 to R 3 are as explained in formula (1) above.
  • R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom.
  • the R 1 R 2 R 3 Si group is represented by the formula (10): [In the formula, each R 19 is independently an alkoxy group or an amino group substituted with one or more alkyl groups; each R 20 is independently a hydrogen atom or an alkyl group; each L 1 is independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; each j is independently an integer of 0 or 1; k is an integer from 1 to 3, An asterisk (*) indicates a site bonded to a portion other than the silyl group of the silane compound. ] and a silane compound having the chemical structure of
  • each R 19 is independently an alkoxy group or an amino group substituted with one or more alkyl groups.
  • each R 19 is independently a hydrolyzable group, an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, still more preferably an alkoxy group having 1 to 20 carbon atoms.
  • or an amino group substituted with one or more alkyl groups more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, more preferably one or more alkyl groups having 1 to 20 carbon atoms. It is a substituted amino group.
  • the alkoxy group includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc. Among these, methoxy or ethoxy is preferred.
  • the amino group substituted with one or more alkyl groups includes N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferred.
  • the alkoxy group and amino group are bonded to silicon (Si) via a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur.
  • a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur.
  • Each R 20 is independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups, among which methyl and ethyl groups are preferred.
  • each L 1 is independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen,
  • k is an integer of 1-3, preferably an integer of 2-3, more preferably 3.
  • Each j is independently an integer of 0 or 1, preferably 0.
  • the R 1 R 2 R 3 Si group is a triethoxysilyl group ((EtO) 3 Si group) or a trimethoxysilyl group in the above formulas (1) to (9).
  • Silane compounds are more preferred, and silane compounds in which the R 1 R 2 R 3 Si group is a triethoxysilyl group are even more preferred.
  • a particularly preferred embodiment of the unsaturated double bond-containing silane compound is a compound represented by the following formula.
  • the unsaturated double bond-containing silane compound is preferably its stereoisomer or any mixture of those stereoisomers.
  • unsaturated double bond-containing silane compounds have the formula (14): [In the formula, a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10
  • R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; Y is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. ] It can be produced by reacting the compound represented by.
  • R 1 to R 18 and a to g are as explained for the unsaturated double bond-containing silane compound represented by formula (1).
  • Y is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen having 1 to 30 carbon atoms.
  • a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of oxygen and sulfur more preferably nitrogen having 1 to 20 carbon atoms, at least one selected from the group consisting of oxygen and sulfur
  • It is a hydrocarbon group optionally containing a heteroatom, more preferably a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur having 1 to 10 carbon atoms.
  • Y is particularly preferably a hydrocarbon group containing sulfur.
  • the total length of the straight chain portion connecting the silyl group and the alicyclic hydrocarbon moiety in such a hydrocarbon group is preferably 3 to 8, more preferably the total number of atoms of carbon, nitrogen, oxygen or sulfur. is 4-7, more preferably 4-6.
  • the compound represented by the formula (14) and the compound represented by the formula (15) are added. It can be synthesized by subjecting it to a reaction or a condensation reaction.
  • a radical addition reaction a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like can be used, and for example, reactions similar to pericyclic reactions, hydrosilylation reactions, hydroamination reactions, etc. can.
  • the condensation reaction for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, a Friedel-Crafts reaction, or the like can be used.
  • the compound represented by the above formula (14) is a Diels-Alder reaction between the same or different conjugated diene compounds, or a conjugated diene compound and an alkene compound, based on the knowledge already known to those skilled in the art. It can be synthesized by a Diels-Alder reaction with In addition, the compound represented by formula (14) can be prepared by optionally thermally denaturing and/or optionally purifying the compound synthesized by the Diels-Alder reaction. can.
  • the unsaturated double bond-containing silane compound represented by formula (2) is obtained by combining the compound represented by formula (14) above with formula (16): [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10; ] It can be produced by reacting the compound represented by.
  • R 1 to R 18 and a to g are as explained for the unsaturated double bond-containing silane compound represented by formula (1). Furthermore, h is as explained in the compound represented by formula (2).
  • Examples of compounds represented by the above formula (16) include alkoxysilane compounds having a mercapto group.
  • Alkoxysilane compounds having a mercapto group include mercaptotrimethoxysilane, mercaptotriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyl.
  • triethoxysilane 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 4-mercaptobutyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 3-mercaptopropyltripropoxysilane Silane, 4-mercaptobutyltripropoxysilane, 2-mercaptoethylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane silane, 4-mercaptobutylmethyldiethoxysilane, and the like.
  • Examples of unsaturated double bond-containing silane compounds other than the above include vinyl group-containing silanes and (meth)acrylic group-containing silanes.
  • Vinyl group-containing silanes include, for example, vinyltriethoxysilane and vinyltrimethoxysilane.
  • (Meth)acryl group-containing silanes include, for example, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane and the like.
  • silane compounds include, for example, the following formula (11): [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; each L is independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is preferably ) is as described in .
  • preferred embodiments of each L are as described in the formula (1) above.
  • Preferred embodiments of a, b, c, d, and e are as described in formula (1) above.
  • R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, preferably a hydrogen atom.
  • the other silane compound is preferably a sulfur-containing silane compound.
  • silane compounds represented by the above formula (11) are preferably represented by formula (12):
  • each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom; h is an integer from 1 to 10, m is an integer from 1 to 10, a is an integer of 0 or 1, b is an integer of 0 or 1, c is each independently an integer of 0 or 1, d is each independently an integer of 0 or 1, e is an integer from 0 to 5, R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- , f is an integer from 1 to 5, R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 26 , R 27 and R 28 Preferred embodiments are as described in formula (11) above.
  • preferred embodiments of each L are as described in the formula (11) above.
  • preferred embodiments of a, b, c, d, and e are as described in formula (11) above.
  • preferred embodiments of h are as described in the above formula (2).
  • m is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3. be.
  • silane compounds are more preferably represented by formula (17): [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ], or formula (18): [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ] It is a compound represented by formula (17): [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ] It is a compound represented by formula (17): [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ] It is a compound represented by formula (17): [In the formula, each of R 1 , R 2 and R
  • Another more preferred embodiment of the other silane compound is a compound represented by the following formula.
  • R 1 to R 3 are as explained in formula (1) above.
  • an even more preferred embodiment of the other silane compound represented by formula (11) above is a silane compound in which the R 1 R 2 R 3 Si group has the chemical structure of formula (10) above.
  • the other silane compound is more preferably a silane compound in which the R 1 R 2 R 3 Si group is a triethoxysilyl group or a trimethoxysilyl group, and a silane compound in which the R 1 R 2 R 3 Si group is a triethoxysilyl group.
  • Compounds are even more preferred.
  • Particularly preferred embodiments of other silane compounds include compounds represented by the following formulas.
  • the other silane compound is preferably its stereoisomer or any mixture of those stereoisomers.
  • the compound represented by the above formula (14) and the compound represented by the above formula (15) can be synthesized by subjecting them to an addition reaction or a condensation reaction.
  • an addition reaction here, a radical addition reaction, a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like can be used, and for example, reactions similar to pericyclic reactions, hydrosilylation reactions, hydroamination reactions, etc. can.
  • the condensation reaction for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, a Friedel-Crafts reaction, or the like can be used.
  • the compound represented by the above formula (14) is a Diels-Alder reaction between the same or different conjugated diene compounds, or a conjugated diene compound and an alkene compound, based on the knowledge already known to those skilled in the art. It can be synthesized by a Diels-Alder reaction with In addition, the compound represented by the above formula (14) is prepared by thermally denaturing the compound synthesized by the Diels-Alder reaction, if necessary, and/or by purifying it, if necessary. can be done.
  • silane compounds can be produced by reacting the compound represented by the above formula (14) with the compound represented by the above formula (16).
  • Preferred embodiments of the above formula (16) are as described for the unsaturated double bond-containing silane compound.
  • silane compounds include the following formula (19): [In the formula, at least one or all of R 31 , R 32 and R 33 is —O—(R 35 —O) m —R 36 (R 35 is a divalent hydrocarbon group having 1 to 30 carbon atoms, R 36 is an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and m is an integer of 1 to 30.
  • R 31 , R 32 and R 33 are the above —O—(R 35 —O) m —R 36
  • the remaining groups are alkyl groups having 1 to 12 carbon atoms, —O —R 37 (R 37 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
  • R 31 , R 32 and R 33 may be the same or different;
  • R 34 is a divalent hydrocarbon group having 1 to 30 carbon atoms. ] can also be used.
  • the divalent hydrocarbon groups having 1 to 30 carbon atoms represented by R 34 and R 35 include, for example, aliphatic aromatic hydrocarbon groups; and combinations thereof.
  • alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms represented by R 36 and R 37 include: alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and phenethyl group.
  • m is preferably an integer of 1-20, more preferably an integer of 2-15, even more preferably 3-10.
  • R 1 , R 2 and R 3 are the above -O-(R 35 -O) m -R 36 , the remaining group is an alkyl group having 1 to 12 carbon atoms, carbon Examples of aryl groups of numbers 6 to 30 include alkyl groups such as methyl group and ethyl group; and aryl groups such as phenyl group and tolyl group.
  • a preferred embodiment of the above formula (19) is that two of R 31 , R 32 and R 33 are —O—(C 2 H 4 —O) n —C 13 H 27 and the rest are —O—C 2 H 5 , the average number of n is 5, and R 34 is a trimethylene group.
  • Examples of the compound represented by formula (19) include Evonik's product name "Si363".
  • silane compounds include, for example, formula (13): [In the formula, t and v are each independently an integer from 0 to 10; u is an integer from 2 to 10, q and r are each independently an integer from 1 to 3; w and z are each independently an integer of 0 or 1; L 2 and L 3 are each independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur; R 21 and R 23 are each independently an alkoxy group or an amino group substituted with one or more alkyl groups; R22 and R24 are each independently a hydrogen atom or an alkyl group. ]
  • a compound represented by can be used.
  • t and v are each independently an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 1 to 3, more preferably 2 is.
  • u is an integer of 2 to 10, more preferably an integer of 2 to 8.
  • q and r are each independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
  • w and z are each independently an integer of 0 or 1, preferably 0.
  • L 2 and L 3 are each independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen, oxygen and A hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of sulfur, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur
  • R 21 and R 23 are each independently a hydrolyzable group, an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, still more preferably an alkoxy group having 1 to 20 carbon atoms, or 1 an amino group substituted with one or more alkyl groups, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, more preferably one or more alkyl groups having 1 to 20 carbon atoms. It is an amino group.
  • the alkoxy group includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc. Among these, methoxy or ethoxy is preferred.
  • the amino group substituted with one or more alkyl groups includes N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferred.
  • the alkoxy group and amino group are bonded to silicon (Si) via a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. good too.
  • R 22 and R 24 are each independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, still more preferably an alkyl group having 1 to 20 carbon atoms, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups, among which methyl and ethyl groups are preferred.
  • silane compounds in addition to the compounds represented by the above formula (13), compounds represented by the above formula (16), particularly silane compounds having the following structures can be used.
  • R 41 is a hydrogen atom or a monovalent hydrocarbon group containing up to 18 carbon atoms
  • R42 is a divalent hydrocarbon group containing up to 12 carbon atoms
  • Each of X 2 and X 3 is independently selected from the group consisting of the elements listed for R 44 and X 1 , wherein R 44 is a monovalent hydrocarbon group of up to 6 carbon atoms is).
  • a compound represented by can be used.
  • R 41 are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, benzyl and phenethyl. including.
  • R 42 include methylene, ethylene, propylene, isopropylene, butylene, hexylene, octylene, decylene, cyclohexylene and phenylene.
  • R 43 are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, benzyl, phenethyl , 3-oxabutyl and 4,7-dioxaoctyl.
  • R 44 include hydrogen, methyl, ethyl, propyl, isopropyl, butyl and phenyl.
  • representative, non-limiting examples of X 1 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy and acetoxy.
  • Representative examples of X 2 and X 3 include methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl and cyclohexyl, as well as the representative examples of X 1 given above.
  • R 41 is an alkyl group containing 5 to 9 carbon atoms and is attached via a primary carbon atom to the carbonyl group and R 42 is methylene, ethylene or is propylene, X 1 is methoxy, ethoxy or propoxy, and X 2 and X 3 individually include representative examples of X 1 and methyl.
  • silane compound represented by the above formula (20) examples include triethoxysilylmethylthioformate, 2-triethoxysilylethylthioacetate, 3-triethoxysilylpropylthiopropanoate, 3-triethoxysilylpropylthio hexanoate, 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate), 3-diethoxymethylsilylpropylthiooctanoate, 3-ethoxydimethylsilylpropylthiooctanoate, 3-triethoxysilylpropylthiododecanoate, 3-triethoxysilylpropylthiooctadodecanoate, 3-trimethoxysilylpropylthiooctanoate, 3-triacetoxysilylpropylthioacetate, 3-dipropoxymethylsilyl
  • 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate), 3-diethoxymethylsilylpropylthiooctanoate, and 3-ethoxydimethylsilylpropylthiooctano is preferred, and 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate) is more preferred.
  • Examples of the compound represented by (3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate)) include NXT silane (trade name) manufactured by Momentive.
  • a condensate of the silane compound represented by formula (20) may be used in place of the silane compound represented by formula (20) or together with the silane compound represented by formula (20).
  • Condensates of other silane compounds described above include, for example, the following formula (23): [In the formula, x:y is 1:99 to 99:1. ] It is a condensate represented by. Commercially available products may be used as such condensates. For example, NXT Z45 silane available from Momentive.
  • fillers examples include silica, carbon black, barium sulfate, calcium carbonate, titanium oxide, clay and talc. At least one of silica and carbon black is preferably used, and silica is more preferably used.
  • the content of the filler is preferably 1 part by mass or more and less than 300 parts by mass, more preferably 5 parts by mass or more and 200 parts by mass or less, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. 180 parts by mass or less, more preferably 15 parts by mass or more and 160 parts by mass or less, particularly preferably 20 parts by mass or more and 160 parts by mass or less, and particularly preferably 30 parts by mass or more and 130 parts by mass or less. , and most preferably 40 parts by mass or more and 110 parts by mass or less.
  • silica examples include, but are not limited to, dry process silica, wet process silica, colloidal silica, and precipitated silica. Among these, wet-process silica containing hydrous silicic acid as a main component is preferable. These silicas can be used alone or in combination of two or more.
  • the specific surface area of silica is not particularly limited, but the nitrogen adsorption specific surface area (BET method) is usually in the range of 10 to 400 m 2 /g, preferably 20 to 300 m 2 /g, more preferably 120 to 190 m 2 /g. . If the specific surface area of silica is within the above numerical range, mechanical properties and the like can be improved.
  • the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.
  • the rubber composition of the present invention contains a vulcanizing agent, a vulcanization accelerator, an auxiliary vulcanization accelerator, an anti-aging agent, a softening agent, an antioxidant, a silanization reaction accelerator, and a coloring agent as long as the functions of the rubber composition are not impaired. agents, and other processing aids such as inorganic materials other than silica.
  • Vulcanizing agents include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, zinc oxide, magnesium oxide, litharge, p -quinonedioxime, p-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenol resin, brominated alkylphenol resin, chlorinated alkylphenol resin and the like.
  • the content of the vulcanizing agent is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • Vulcanization accelerators include thiuram-based agents such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetramethylthiuram monosulfide (TMTM), aldehyde/ammonia-based agents such as hexamethylenetetramine, and diphenylguanidine (DPG).
  • TMTD tetramethylthiuram disulfide
  • TETD tetraethylthiuram disulfide
  • TMTM tetramethylthiuram monosulfide
  • DPG diphenylguanidine
  • guanidines such as 2-mercaptobenzothiazole (MBT), thiazoles such as dibenzothiazyldisulfide (DM), N-cyclohexyl-2-benzothiazylsulfenamide (CBS), Nt-butyl-2 -Sulfenamides such as benzothiazylsulfenamide (BBS), and dithiocarbamates such as zinc dimethyldithiocarbamate (ZnPDC).
  • the content of the vulcanization accelerator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • vulcanization accelerators include fatty acids such as acetic acid, propionic acid, butyric acid, stearic acid, acrylic acid and maleic acid, zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, zinc maleate and the like.
  • Fatty acid zincs, fatty acid zinc salts which are salts thereof, zinc oxide, and the like can be mentioned.
  • the content of the vulcanization accelerator aid is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • anti-aging agents examples include compounds such as aliphatic and aromatic hindered amines and hindered phenols.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • antioxidants examples include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
  • BHT butylhydroxytoluene
  • BHA butylhydroxyanisole
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • the softening agent conventionally known ones can be used, and it is not particularly limited, but petroleum-based softening agents such as aroma oil, paraffin oil, naphthenic oil, palm oil, castor oil, cottonseed oil, soybean oil, etc. and the like. At the time of use, one of these may be used singly or two or more may be appropriately selected and used.
  • a softening agent is contained, from the viewpoint of ease of handling, among the above softening agents, those that are liquid at room temperature such as 25 ° C., for example, petroleum softening agents such as aroma oil, paraffin oil, naphthenic oil is preferably contained, and aromatic oils are particularly preferred.
  • the softener content is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass, per 100 parts by mass of the rubber component.
  • silanization reaction accelerator Any silanization reaction accelerator may be used as long as it promotes the silanization reaction between silica and the silane coupling agent (the above silane compound).
  • the silanization reaction accelerator include carbamide compounds such as urea derivatives and thiourea; guanidine compounds such as guanidine hydrochloride, guanidinium thiocyanate, guanidine and diphenylguanidine. Any one type of these silanization reaction accelerators may be used, or two or more types may be used in combination.
  • Urea derivatives include, for example, urea, methylurea, ethylurea, propylurea, butylurea, pentylurea, hexylurea, cyclohexylurea, N,N'-dimethylurea, N,N'-diethylurea, N,N,N ',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, diethylurea, dipropylurea, dibutylurea, dipentylurea, dihexylurea and salts thereof.
  • urea is excellent.
  • coloring agents include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, azo pigments, and copper phthalocyanine pigments.
  • the content of the coloring agent is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
  • processing aids can be kneaded with the rubber component using a known rubber kneader, such as a roll, Banbury mixer, kneader, etc., vulcanized under arbitrary conditions, and used as a rubber composition.
  • the amount of other processing aids to be added can be a conventional general content as long as it does not contradict the object of the present invention.
  • the method for producing the rubber composition of the present invention comprises at least the step of kneading the above rubber component, the above rubber additive, and the above unsaturated double bond-containing silane compound.
  • the method for producing the rubber composition may preferably further comprise the step of kneading the vulcanizing agent. More preferably, it may further comprise a step of kneading the vulcanizing agent and the vulcanization accelerator.
  • the other processing aids described above can be appropriately blended and kneaded within a range that does not impair the functions of the rubber composition.
  • a conventionally known kneading device can be used for the production of the rubber composition, and the kneading temperature, time, mixing order, etc. can be appropriately selected.
  • tire products can be produced by conventionally known methods and common technical knowledge widely known to those skilled in the art.
  • Tire products include tires and other related components.
  • the rubber composition is extruded, then molded using a tire molding machine, and then heated and pressurized using a vulcanizer to form crosslinks, whereby a tire can be manufactured.
  • a tire manufactured using the rubber composition of the present invention is excellent in tensile product.
  • tires for passenger cars there are no particular restrictions on the use of tires, and examples include tires for passenger cars, tires for heavy loads, tires for motorcycles (motorcycles), and studless tires. Among these, it can be suitably used for tires for passenger cars.
  • the shape, structure, size and material of the tire are not particularly limited and can be selected as appropriate according to the purpose.
  • the rubber composition of the present invention can be applied to each part of a tire.
  • the applicable portion of the tire is not particularly limited, and may be appropriately selected from the tread, carcass, sidewall, inner liner, undertread, belt portion, etc. of the tire according to the purpose.
  • Rubber product The rubber composition of the present invention can also be used to produce rubber products other than tire products.
  • Rubber products other than tires include automobile rubber parts (exterior, interior, weather strips, boots, mounts, seals, sealers, gaskets), hoses, belts, sheets, anti-vibration rubber, rollers, linings. , rubberized cloth, sealing materials, gloves, fenders, medical rubber (syringe gaskets, tubes, catheters), gaskets (for home appliances, construction), asphalt modifiers, grips, toys, shoes, sandals, keys Pads, gears, PET bottle cap liners and the like are included.
  • VNB 2-vinylnorbornene
  • the connection was sealed with silicon grease, the needle tip of the gas-tight syringe was introduced into the flask through the septum, the flask was immersed in an oil bath, and the bath temperature was gradually increased until the internal temperature reached 50°C. At that time, the metering pump was operated and mercaptopropyltriethoxysilane was added dropwise for reaction. Two hours after the dropping of the entire amount was completed, the flask was taken out from the oil bath and allowed to stand to room temperature. Excess VNB was then distilled off under reduced pressure to obtain 37.4 g of the target colorless and transparent liquid compound (VNB-SSi).
  • the obtained silane compound (VNB-SSi) was confirmed to have a silane introduction rate of 100% by 1 H-NMR measurement and 13 C-NMR measurement, and the double bond of the norbornene ring had disappeared. bottom.
  • the obtained silane compound (VNB-SSi) is a mixture of silane compounds (1A, 1B) represented by the following reaction formula.
  • mercaptopropyltriethoxysilane was added twice (first time: 0.10 g (0.85 mmol), second time: 0.26 g (2.13 mmol)), each at 70°C for 5 hours. After reacting for a period of time, the mixture was allowed to cool to room temperature to obtain 25.0 g of the objective colorless to pale yellow clear liquid.
  • the obtained silane compound (VNB-2SSi) is a mixture of silane compounds (2A, 2B) represented by the following reaction formula.
  • a syringe was then used to inject 11.9 g (0.0498 mol) of 3-mercaptopropyltriethoxysilane. Finally, 0.123 g (0.746 mmol) was added to azobisisobutyronitrile while flowing nitrogen, and nitrogen bubbling was performed for 20 minutes. The flask was immersed in an oil bath, and the temperature of the bath was gradually raised to 70° C. for reaction. Six hours after reaching 70°C, the flask was removed from the oil bath and allowed to stand until it reached room temperature (25°C).
  • Example 1 Each of the following components was kneaded using a 250 mL kneader (Laboplastomill manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. Details of the kneading operation performed are as follows (i) to (iii). (i) Mixer kneading: Put the rubber component into a closed pressure kneader heated to 130°C, masticate at 30 rpm for 1 minute, and then mix 1 of silica, zinc oxide, stearic acid, and anti-aging agent.
  • Example 2 A rubber composition was obtained in the same manner as in Example 1, except that 5.6 parts by mass of 3-acryloxypropyltriethoxysilane was added as the silane coupling agent instead of vinyltriethoxysilane.
  • Example 3 A rubber composition was obtained in the same manner as in Example 1, except that 5.6 parts by mass of an unsaturated double bond-containing silane compound A (VNB-SSi) was added as a silane coupling agent instead of vinyltriethoxysilane. .
  • VNB-SSi unsaturated double bond-containing silane compound A
  • Example 4 A rubber composition was obtained in the same manner as in Example 1, except that 5.6 parts by mass of the unsaturated double bond-containing silane compound C (ENB-SSi) was added as the silane coupling agent instead of vinyltriethoxysilane. .
  • Example 3 A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of hydrocarbon polymer E was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 3 parts by mass.
  • Example 5 Example 3 except that the amount of sulfur-containing hydrocarbon polymer A added was changed to 1.5 parts by mass, the amount of hydrocarbon polymer E added was 13.5 parts by mass, and the amount of sulfur added was changed to 3 parts by mass. A rubber composition was obtained in the same manner.
  • Example 6 Examples except that the amount of sulfur-containing hydrocarbon polymer A added was changed to 7.5 parts by mass, the amount of hydrocarbon polymer E added was changed to 7.5 parts by mass, and the amount of sulfur added was changed to 2.5 parts by mass A rubber composition was obtained in the same manner as in 3.
  • Example 7 Example 3 except that 0.8 parts by mass of the unsaturated double bond-containing silane compound A (VNB-SSi) as the silane coupling agent was replaced with the unsaturated double bond-containing silane compound B (VNB-2SSi) A rubber composition was obtained in the same manner as.
  • dumbbell-shaped test piece was punched out from each rubber sheet, and a tensile test was performed at a tensile speed of 500 mm / min in accordance with JIS K6251 (published in 2010), and 100% modulus [MPa] at room temperature (25 ° C.) measured by
  • the 100% modulus value which is an index of the crosslink density of each rubber sheet, was adjusted so as to be approximately close to each other, and then other physical properties were confirmed.
  • Table 1 shows the above measurement results.
  • the tensile product (index (%)) results of Examples 1 to 7 and Comparative Examples 2 and 3 are shown as relative values when each value in Comparative Example 1 is set to 100.
  • Example 8 A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of the sulfur-containing hydrocarbon polymer B was added instead of the sulfur-containing hydrocarbon polymer A.
  • Example 9 A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of sulfur-containing hydrocarbon polymer C was added instead of sulfur-containing hydrocarbon polymer A.
  • Example 10 A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of sulfur-containing hydrocarbon polymer D was added instead of sulfur-containing hydrocarbon polymer A.

Abstract

[Problem] To provide a rubber composition that can improve the cut resistance and chipping resistance of the tire. [Solution] This rubber composition includes a rubber component, a rubber additive that contains a sulfur-containing hydrocarbon polymer, and a silane compounds that contains an unsaturated double bond.

Description

ゴム組成物およびタイヤ製品Rubber compositions and tire products
　本発明は、ゴム組成物に関する。また、本発明は、該ゴム組成物を用いて製造されたタイヤ製品に関する。 The present invention relates to rubber compositions. The present invention also relates to tire products manufactured using the rubber composition.
　従来、タイヤは、加硫を担う加硫剤、カーボンブラックやシリカなどの充填剤、品質劣化を抑制する老化防止剤やワックスなどを含むゴム組成物から製造されており、それぞれの成分について改良がなされてきた。 Conventionally, tires are manufactured from a rubber composition containing vulcanizing agents, fillers such as carbon black and silica, and anti-aging agents and waxes that suppress quality deterioration. has been done.
　近年、タイヤには様々な性能が求められている。例えば、タイヤの耐カット性、耐チッピング性はそれぞれ、タイヤ使用時における性能維持に関する重要な性能である。タイヤの耐カット性、耐チッピング性を向上させるためには、破断伸び、破断強度を高めることが有効である。破断伸びを向上させるための手法としては、例えば、カーボンブラックやシリカのような充填剤の量を減らすことが挙げられる。しかし、このような手法では硬度が低下し、操縦安定性を損なうという課題がある。このような課題に対して、タイヤ用ゴム組成物に特定の比表面積を有するカーボンブラックやシリカを特定量で配合することが提案されている（特許文献１参照）。また、破断強度を高めるための手法としては、シリカを増量することが有効であるが、シリカの増量はシリカの分散不良を招き、好ましくない。シリカの分散性を改善するためにはシランカップリング剤の増量や架橋密度を上げる手法が有効であるが、シランカップリング剤の増量は破断伸びを悪化させる一因となる。このような課題に対して、タイヤ用ゴム組成物にシリカ、特定のテトラジン化合物、亜鉛または亜鉛化合物を特定量で配合することが提案されている（特許文献２参照）。しかし、依然として、タイヤの耐カット性、耐チッピング性を向上できる破断伸び、破断強度を高めたゴム組成物が求められている。 In recent years, various performances have been required for tires. For example, the cut resistance and chipping resistance of a tire are each important performance related to performance maintenance during use of the tire. In order to improve the cut resistance and chipping resistance of a tire, it is effective to increase the elongation at break and the strength at break. Techniques for improving elongation at break include, for example, reducing the amount of fillers such as carbon black and silica. However, such a method has the problem of lowering the hardness and impairing the steering stability. In order to solve such problems, it has been proposed to add a specific amount of carbon black or silica having a specific specific surface area to a rubber composition for tires (see Patent Document 1). As a technique for increasing the breaking strength, it is effective to increase the amount of silica, but increasing the amount of silica causes poor dispersion of silica, which is not preferable. In order to improve the dispersibility of silica, it is effective to increase the amount of the silane coupling agent or to increase the crosslink density, but the increase in the amount of the silane coupling agent is one of the causes of deterioration of elongation at break. In order to solve such problems, it has been proposed to add a specific amount of silica, a specific tetrazine compound, zinc or a zinc compound to a rubber composition for tires (see Patent Document 2). However, there is still a demand for a rubber composition with improved breaking elongation and breaking strength that can improve the cut resistance and chipping resistance of tires.
特開２０２１－７０７７８号公報Japanese Patent Application Laid-Open No. 2021-70778 特開２０２０－１７６２２９号公報JP 2020-176229 A
　そこで、本発明者らは、上記課題を解決するために鋭意検討を行った結果、驚くべきことに、ゴム成分に、含硫黄炭化水素重合体を含むゴム用添加剤と、不飽和二重結合含有シラン化合物とを配合することで、得られたゴム組成物を用いて製造したタイヤは、破断強度と破断伸びとの積である抗張積が高くなり、その結果、耐カット性、耐チッピング性を向上できることを知見した。本発明者らは、かかる知見に基づいて、本発明を完成するに至った。 Therefore, the present inventors have made intensive studies to solve the above problems, and as a result, surprisingly, the rubber component contains a rubber additive containing a sulfur-containing hydrocarbon polymer and an unsaturated double bond By blending the containing silane compound, the tire manufactured using the obtained rubber composition has a high tensile product, which is the product of breaking strength and breaking elongation, and as a result, cut resistance and chipping resistance It was found that the performance can be improved. The present inventors have completed the present invention based on such findings.
　すなわち、本発明によれば、以下の発明が提供される。
［１］　ゴム成分と、
　含硫黄炭化水素重合体を含むゴム用添加剤と、
　不飽和二重結合含有シラン化合物と、
を含む、ゴム組成物。
［２］　前記不飽和二重結合含有シラン化合物が、下記一般式（１）：
Figure JPOXMLDOC01-appb-C000003
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　Ｌは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９とＲ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ１６は、水素原子、メチル基または炭素数２～８のアルキル基であり、かつ、Ｒ１７は、水素原子、メチル基または炭素数２～１０のアルキル基であり、ここで、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成し、かつ、Ｒ１４、Ｒ１５およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、若しくは、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、
　または、
　Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素を形成してもよく、ここで、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基である。］
で表される化合物を含む、［１］に記載のゴム組成物。
［３］　前記不飽和二重結合含有シラン化合物が、ノルボルネン骨格を有する化合物を含む、［１］または［２］に記載のゴム組成物。
［４］　前記不飽和二重結合含有シラン化合物が、下記式：
Figure JPOXMLDOC01-appb-C000004
 ［上記各式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］
で表される化合物の少なくとも１種を含む、［１］～［３］のいずれかに記載のゴム組成物。
［５］　前記含硫黄炭化水素重合体が、不飽和炭化水素の重合体と硫黄との反応生成物であり、前記不飽和炭化水素が脂環式不飽和化合物を含む、［１］～［４］のいずれかに記載のゴム組成物。
［６］　前記含硫黄炭化水素重合体の重量平均分子量が５００以上４０００以下である、［１］～［５］のいずれかに記載のゴム組成物。
［７］　前記ゴム成分が、芳香族ビニル－共役ジエン共重合体ゴムおよび共役ジエン（共）重合体ゴムからなる群から選択される少なくとも１種である、［１］～［６］のいずれかに記載のゴム組成物。
［８］　前記ゴム成分が、スチレン－ブタジエンゴム、ブタジエンゴム、天然ゴム、およびイソプレンゴムからなる群から選択される少なくとも１種を含む、［１］～［７］のいずれかに記載のゴム組成物。
［９］　充填剤をさらに含む、［１］～［８］のいずれかに記載のゴム組成物。
［１０］　前記充填剤が、シリカおよびカーボンブラックからなる群から選択される少なくとも１種を含む、［９］に記載のゴム組成物。
［１１］　タイヤ製品用である、［１］～［１０］のいずれかに記載のゴム組成物。
［１２］　［１］～［１１］のいずれかに記載のゴム組成物を用いて製造されたタイヤ製品。 That is, according to the present invention, the following inventions are provided.
[1] a rubber component;
a rubber additive comprising a sulfur-containing hydrocarbon polymer;
an unsaturated double bond-containing silane compound;
A rubber composition comprising:
[2] The unsaturated double bond-containing silane compound has the following general formula (1):
Figure JPOXMLDOC01-appb-C000003
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
L is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms,
or,
R 16 and R 17 may be joined together to form a 4- to 9-membered alicyclic hydrocarbon, wherein R 14 and R 15 are joined together to form a double bond, and , R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
The rubber composition according to [1], comprising a compound represented by:
[3] The rubber composition according to [1] or [2], wherein the unsaturated double bond-containing silane compound contains a compound having a norbornene skeleton.
[4] The unsaturated double bond-containing silane compound has the following formula:
Figure JPOXMLDOC01-appb-C000004
 [In the above formulas, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ]
The rubber composition according to any one of [1] to [3], comprising at least one compound represented by
[5] The sulfur-containing hydrocarbon polymer is a reaction product of an unsaturated hydrocarbon polymer and sulfur, and the unsaturated hydrocarbon contains an alicyclic unsaturated compound [1] to [4 ] The rubber composition according to any one of the above.
[6] The rubber composition according to any one of [1] to [5], wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 500 or more and 4000 or less.
[7] Any one of [1] to [6], wherein the rubber component is at least one selected from the group consisting of aromatic vinyl-conjugated diene copolymer rubbers and conjugated diene (co)polymer rubbers. The rubber composition according to .
[8] The rubber composition according to any one of [1] to [7], wherein the rubber component contains at least one selected from the group consisting of styrene-butadiene rubber, butadiene rubber, natural rubber, and isoprene rubber. thing.
[9] The rubber composition according to any one of [1] to [8], further comprising a filler.
[10] The rubber composition according to [9], wherein the filler contains at least one selected from the group consisting of silica and carbon black.
[11] The rubber composition according to any one of [1] to [10], which is used for tire products.
[12] A tire product produced using the rubber composition according to any one of [1] to [11].
　本発明によれば、耐カット性、耐チッピング性に優れるタイヤを製造するためのゴム組成物を提供することができる。 According to the present invention, it is possible to provide a rubber composition for producing tires having excellent cut resistance and chipping resistance.
［ゴム組成物］
　本発明のゴム組成物は、少なくとも、ゴム成分と、ゴム用添加剤と、不飽和二重結合含有シラン化合物とを含み、充填剤をさらに含むことが好ましい。ゴム成分の含有量は、ゴム組成物の固形分質量全体に対して、好ましくは２０質量％以上８０質量％以下であり、より好ましくは２５質量％以上７５質量％以下であり、さらに好ましくは３０質量％以上７０質量％以下である。ゴム用添加剤の含有量は、ゴム成分１００質量部に対して、好ましくは１質量部以上３０質量部以下であり、より好ましくは３質量部以上２５質量部以下であり、さらに好ましくは５質量部以上２０質量部以下である。不飽和二重結合含有シラン化合物の含有量は、ゴム成分１００質量部に対して、好ましくは１質量部以上２０質量部以下であり、より好ましくは２質量部以上１０質量部以下である。 [Rubber composition]
The rubber composition of the present invention contains at least a rubber component, a rubber additive, and an unsaturated double bond-containing silane compound, and preferably further contains a filler. The content of the rubber component is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 75% by mass or less, and still more preferably 30% by mass, based on the total solid mass of the rubber composition. It is more than mass % and below 70 mass %. The content of the rubber additive is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 25 parts by mass or less, and still more preferably 5 parts by mass with respect to 100 parts by mass of the rubber component. parts or more and 20 parts by mass or less. The content of the unsaturated double bond-containing silane compound is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the rubber component.
（ゴム成分）
　ゴム成分としては、特に限定されないが、ジエン系ゴムを含むことが好ましい。下記の含硫黄炭化水素重合体は、一般的な不飽和炭化水素重合体である不飽和石油樹脂（硫黄を含有しないもの）に比べて、ジエン系ゴムに対する反応性が高く、ゴム分子鎖に反応し易い。そのため、ジエン系ゴムを用いることで、タイヤの破断強度や破断伸びが高くなり、抗張積（＝破断強度×破断伸び）を向上することができる。 (rubber component)
Although the rubber component is not particularly limited, it preferably contains a diene rubber. The following sulfur-containing hydrocarbon polymers have higher reactivity with diene-based rubbers than unsaturated petroleum resins (containing no sulfur), which are general unsaturated hydrocarbon polymers, and react with rubber molecular chains. easy to do Therefore, by using a diene rubber, the breaking strength and breaking elongation of the tire can be increased, and the tensile product (=breaking strength×breaking elongation) can be improved.
  ジエン系ゴムとしては、芳香族ビニル－共役ジエン共重合体ゴムおよび共役ジエン（共）重合体ゴムの少なくとも１種を用いることが好ましい。芳香族ビニル－共役ジエン共重合体ゴムとしては、スチレン－ブタジエンゴム（ＳＢＲ）、スチレン－イソプレン－ブタジエンゴム、スチレン－イソプレンゴム、およびスチレン－α－メチルスチレン－ブタジエンゴム等が挙げられる。共役ジエン（共）重合体ゴムとしては、ブタジエンゴム（ＢＲ）、天然ゴム（ＮＲ）、およびイソプレンゴム（ＩＲ）等が挙げられる。また、これら以外のジエン系ゴムとしては、ニトリルゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、エチレン－プロピレン－ジエン三元共重合体ゴム（ＥＰＤＭ）、ブチルゴム（ＩＩＲ）等が挙げられる。さらに、これらのジエン系ゴムの変性ジエン系ゴムを用いることもできる。変性ジエン系ゴムには、主鎖変性、片末端変性、両末端変性、水素添加等の変性手法によるジエン系ゴムが包含される。ここで、変性合成ジエン系ゴムの変性官能基としては、エポキシ基、アミノ基、アルコキシシリル基、水酸基等の各種官能基が挙げられ、これら官能基は１種又は２種以上が変性合成ジエン系ゴムに含まれていてもよい。これらの中でも、スチレン－ブタジエンゴム、ブタジエンゴム、天然ゴム、およびイソプレンゴムからなる群から選択される少なくとも１種を用いることが好ましく、スチレン－ブタジエンゴムおよびブタジエンゴムの１種以上を用いることがより好ましい。 As the diene rubber, it is preferable to use at least one of aromatic vinyl-conjugated diene copolymer rubber and conjugated diene (co)polymer rubber. Aromatic vinyl-conjugated diene copolymer rubbers include styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber, styrene-isoprene rubber, and styrene-α-methylstyrene-butadiene rubber. Conjugated diene (co)polymer rubbers include butadiene rubber (BR), natural rubber (NR), isoprene rubber (IR), and the like. Other diene rubbers include nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene terpolymer rubber (EPDM), butyl rubber (IIR), and the like. Modified diene rubbers of these diene rubbers can also be used. Modified diene rubbers include diene rubbers modified by modification techniques such as main chain modification, single terminal modification, both terminal modification, and hydrogenation. Here, the modified functional group of the modified synthetic diene rubber includes various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group. It may be contained in rubber. Among these, it is preferable to use at least one selected from the group consisting of styrene-butadiene rubber, butadiene rubber, natural rubber, and isoprene rubber, and more preferably one or more of styrene-butadiene rubber and butadiene rubber. preferable.
  ジエン系ゴムの製造方法は、特に制限はなく、乳化重合、溶液重合、ラジカル重合、アニオン重合、カチオン重合等が挙げられる。 The method for producing the diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization and cationic polymerization.
  天然ゴムとしては、天然ゴムラテックス、技術的格付けゴム（ＴＳＲ）、スモークドシート（ＲＳＳ）、ガタパーチャ、杜仲由来天然ゴム、グアユール由来天然ゴム、ロシアンタンポポ由来天然ゴム、植物成分発酵ゴム等が挙げられる。さらにこれらの天然ゴムを変性した、エポキシ化天然ゴム、メタクリル酸変性天然ゴム、スチレン変性天然ゴム、スルホン酸変性天然ゴム、スルホン酸亜鉛変性天然ゴム等の変性天然ゴム等も、天然ゴムに含まれる。 Examples of natural rubber include natural rubber latex, technical grade rubber (TSR), smoked sheet (RSS), gutta-percha, Eucommia-derived natural rubber, guayule-derived natural rubber, Russian dandelion-derived natural rubber, plant component fermented rubber, and the like. Furthermore, modified natural rubber such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber, sulfonic acid-modified natural rubber, and zinc sulfonate-modified natural rubber, which are obtained by modifying these natural rubbers, are also included in natural rubber. .
  また、天然ゴムおよび合成ジエン系ゴムの二重結合部のシス／トランス／ビニルの比率は、特に制限はなく、いずれの比率においても好適に用いることができる。また、ジエン系ゴムの数平均分子量および分子量分布は、特に制限はないが、数平均分子量は５００～３００００００、分子量分布は１．５～１５が好ましい。 Moreover, the ratio of cis/trans/vinyl in the double bond portion of natural rubber and synthetic diene rubber is not particularly limited, and any ratio can be suitably used. The number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, but the number average molecular weight is preferably 500 to 3,000,000 and the molecular weight distribution is preferably 1.5 to 15.
　ゴム成分としては、ジエン系ゴム以外にも非ジエン系ゴムを配合してもよい。非ジエン系ゴムとしては、公知のものを広く使用することができる。具体的な例としては、エチレン・プロピレンゴム（ＥＰＭ）等のオレフィン系ゴム、クロロスルホン化ポリエチレンゴム（ＣＳＭ）、アクリルゴム（ＡＣＭ）、ウレタンゴム（Ｕ）、シリコーンゴム（ＶＭＱ、ＰＶＭＱ、ＦＶＭＱ）、フッ素ゴム（ＦＫＭ）、多硫化ゴム（Ｔ）が挙げられる。 As the rubber component, non-diene rubber may be blended in addition to diene rubber. A wide range of known rubbers can be used as the non-diene rubber. Specific examples include olefin rubber such as ethylene/propylene rubber (EPM), chlorosulfonated polyethylene rubber (CSM), acrylic rubber (ACM), urethane rubber (U), and silicone rubber (VMQ, PVMQ, FVMQ). , fluororubber (FKM) and polysulfide rubber (T).
　また、本発明のゴム組成物には、その機能を損なわない範囲で、上記のゴム成分以外にもエラストマーを配合することもできる。エラストマーとしては、スチレン－イソプレン－スチレン三元ブロック共重合体（ＳＩＳ）、スチレン－ブタジエン－スチレン三元ブロック共重合体（ＳＢＳ）、それらの水添物（ＳＥＢＳ，ＳＥＰＳ，ＳＥＥＰＳ）等のポリスチレン系エラストマー性ポリマー、ポリオレフィン系エラストマー、ポリ塩化ビニル系エラストマー、ポリウレタン系エラストマー、ポリエステル系エラストマー、及び、ポリアミド系エラストマーのからなる群より選択される熱可塑性エラストマーが挙げられる。 In addition, the rubber composition of the present invention can also contain an elastomer other than the above rubber components within a range that does not impair its functions. Elastomers include polystyrenes such as styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), and their hydrogenated products (SEBS, SEPS, SEEPS). Thermoplastic elastomers selected from the group consisting of elastomeric polymers, polyolefin-based elastomers, polyvinyl chloride-based elastomers, polyurethane-based elastomers, polyester-based elastomers, and polyamide-based elastomers.
  ジエン系ゴムの含有量は、ゴム成分の全量に対して、好ましくは１０質量％以上であり、より好ましくは３０質量％以上であり、さらに好ましくは５０質量％である。特に、ゴム成分中の芳香族ビニル－共役ジエン共重合体ゴムおよび共役ジエン（共）重合体ゴムの合計含有量は、ゴム成分の全量に対して、好ましくは７０質量％以上であり、より好ましくは８０質量％以上であり、さらに好ましくは９０質量％以上である。 The content of the diene rubber is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass, relative to the total amount of the rubber component. In particular, the total content of the aromatic vinyl-conjugated diene copolymer rubber and the conjugated diene (co)polymer rubber in the rubber component is preferably 70% by mass or more, more preferably 70% by mass or more, based on the total amount of the rubber component. is 80% by mass or more, more preferably 90% by mass or more.
（ゴム用添加剤）
　ゴム組成物に用いるゴム用添加剤は、下記の含硫黄炭化水素重合体を含む。本発明においては、ゴム成分に、下記の含硫黄炭化水素重合体を含むゴム用添加剤と、不飽和二重結合含有シラン化合物とを配合して得られたゴム組成物を用いて製造したタイヤは、抗張積（＝破断強度×破断伸び）が高くなり、その結果、耐カット性、耐チッピング性を向上することができる。 (Additive for rubber)
Rubber additives used in rubber compositions include the following sulfur-containing hydrocarbon polymers. In the present invention, a tire produced using a rubber composition obtained by blending a rubber component with a rubber additive containing the following sulfur-containing hydrocarbon polymer and a silane compound containing an unsaturated double bond. , the tensile product (=breaking strength×breaking elongation) is increased, and as a result, cut resistance and chipping resistance can be improved.
（含硫黄炭化水素重合体）
　含硫黄炭化水素重合体は、不飽和炭化水素の重合体と硫黄との反応生成物である。具体的には、含硫黄炭化水素重合体は、不飽和炭化水素の重合体の不飽和結合に硫黄を反応させて得た反応生成物であることが好ましい。 (Sulfur-containing hydrocarbon polymer)
Sulfur-containing hydrocarbon polymers are reaction products of polymers of unsaturated hydrocarbons and sulfur. Specifically, the sulfur-containing hydrocarbon polymer is preferably a reaction product obtained by reacting an unsaturated bond of an unsaturated hydrocarbon polymer with sulfur.
　含硫黄炭化水素重合体の重量平均分子量（Ｍｗ）は、好ましくは５００以上４０００以下であり、下限値はより好ましくは６００以上であり、さらに好ましくは７００以上であり、さらにより好ましくは８００以上であり、また、上限値はより好ましくは３０００以下であり、さらに好ましくは２０００以下であり、さらにより好ましくは１５００以下である。特に、含硫黄炭化水素重合体の重量平均分子量（Ｍｗ）は、好ましくは６００以上３０００以下であり、より好ましくは７００以上２０００以下であり、さらに好ましくは８００以上１５００以下である。含硫黄炭化水素重合体の重量平均分子量を小さくすることで、含硫黄炭化水素重合体同士が硫黄を介して結合するのを抑制し、ゴム成分と結合する硫黄量を増大させ、タイヤの抗張積をより向上させることができる。
　また、含硫黄炭化水素重合体の分子量分布（Ｍｗ／数平均分子量（Ｍｎ））は、好ましくは１．０以上５．０以下であり、より好ましくは１．０以上４．０以下であり、さらに好ましくは１．０以上３．０以下であり、さらにより好ましくは１．０以上２．５以下である。
　なお、重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）は、従来公知のＧＰＣ（ゲルパーミエーションクロマトグラフィー）解析の方法によって測定することができる。 The weight average molecular weight (Mw) of the sulfur-containing hydrocarbon polymer is preferably 500 or more and 4000 or less, and the lower limit is more preferably 600 or more, still more preferably 700 or more, and still more preferably 800 or more. Also, the upper limit is more preferably 3000 or less, still more preferably 2000 or less, and even more preferably 1500 or less. In particular, the weight average molecular weight (Mw) of the sulfur-containing hydrocarbon polymer is preferably 600 or more and 3000 or less, more preferably 700 or more and 2000 or less, still more preferably 800 or more and 1500 or less. By reducing the weight average molecular weight of the sulfur-containing hydrocarbon polymer, the sulfur-containing hydrocarbon polymer is suppressed from binding to each other through sulfur, increasing the amount of sulfur that binds to the rubber component, and improving the tensile strength of the tire. product can be improved.
Further, the molecular weight distribution (Mw/number average molecular weight (Mn)) of the sulfur-containing hydrocarbon polymer is preferably 1.0 or more and 5.0 or less, more preferably 1.0 or more and 4.0 or less, It is more preferably 1.0 or more and 3.0 or less, and still more preferably 1.0 or more and 2.5 or less.
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) can be measured by a conventionally known GPC (gel permeation chromatography) analysis method.
　本発明においては、重合体の原料として、少なくとも、硫黄と反応させるための不飽和結合を有する炭化水素を用いる。不飽和炭化水素は脂環式不飽和化合物を含むものが好ましく、脂環式不飽和炭化水素はノルボルネン骨格を有する化合物であることがより好ましい。ノルボルネン骨格の二重結合の構造がひずみを持ち、硫黄との反応性が良いためである。脂環式不飽和化合物の不飽和結合は硫黄との反応後に残存してもよく、全て消費されてもよい。脂環式不飽和化合物の不飽和結合としては、ノルボルネン骨格に存在する不飽和結合とシクロペンテン骨格に存在する不飽和結合があるが、タイヤ用ゴムの抗張積向上の観点からは、ノルボルネン骨格の不飽和結合は全て消費されていることがより好ましい。 In the present invention, at least a hydrocarbon having an unsaturated bond for reacting with sulfur is used as a raw material for the polymer. The unsaturated hydrocarbon preferably contains an alicyclic unsaturated compound, and the alicyclic unsaturated hydrocarbon is more preferably a compound having a norbornene skeleton. This is because the double bond structure of the norbornene skeleton is distorted and has good reactivity with sulfur. The unsaturated bonds of the alicyclic unsaturated compound may remain after reaction with sulfur or may be completely consumed. As unsaturated bonds of alicyclic unsaturated compounds, there are unsaturated bonds present in the norbornene skeleton and unsaturated bonds present in the cyclopentene skeleton. More preferably, all unsaturated bonds are consumed.
　本発明の一実施形態においては、不飽和炭化水素の重合体として、工業的な製造の観点から、ナフサを熱分解して得た留分のうち、エチレン、プロピレンおよびブタジエン等の有用な化合物を取り去った残りの留分を、混合状態のまま重合して得られた樹脂（以下、「石油樹脂」という）を用いることができる。石油樹脂としては、一般的には、Ｃ５留分を（共）重合して得られる脂肪族系石油樹脂（Ｃ５系石油樹脂）、ナフサの熱分解によって得られるＣ９留分を（共）重合して得られる芳香族系石油樹脂（Ｃ９系石油樹脂）、前記Ｃ５留分とＣ９留分を共重合して得られる共重合系石油樹脂（Ｃ５／Ｃ９系石油樹脂）が挙げられる。なお、石油樹脂は、原料中のオレフィン含有量によって生成する樹脂の性質が異なるが、分子量２００～８０００、軟化点５～１８０℃の透明な淡黄色ないし黄褐色の松脂（まつやに）状の樹脂である。 In one embodiment of the present invention, useful compounds such as ethylene, propylene and butadiene, among fractions obtained by thermal decomposition of naphtha, are used as unsaturated hydrocarbon polymers from the viewpoint of industrial production. A resin (hereinafter referred to as “petroleum resin”) obtained by polymerizing the removed remaining fraction in a mixed state can be used. Petroleum resins generally include aliphatic petroleum resins (C5 petroleum resins) obtained by (co)polymerizing C5 fractions, and (co)polymerizing C9 fractions obtained by pyrolysis of naphtha. Aromatic petroleum resins (C9 petroleum resins) obtained by the above, and copolymer petroleum resins (C5/C9 petroleum resins) obtained by copolymerizing the C5 fraction and the C9 fraction. The petroleum resin has different properties depending on the olefin content in the raw material, but it is a transparent pale yellow to yellowish brown resin with a molecular weight of 200 to 8000 and a softening point of 5 to 180 ° C. is.
　本発明においては、石油樹脂の中でも、脂環式不飽和炭化水素を含む留分を（共）重合して得られる石油樹脂（以下、「脂環式不飽和炭化水素系石油樹脂」という）を用いる。脂環式不飽和炭化水素系石油樹脂は、例えば、Ｃ５留分中に含まれるシクロペンタジエン類を２量体化してジシクロペンタジエン類とし、蒸留して他のＣ５留分と分離し、加熱してディールス・アルダー反応により重合させたものを含む。シクロペンタジエン類とは、例えば、シクロペンタジエン、メチルシクロペンタジエン等が挙げられる。また、ジシクロペンタジエン類とは、例えば、ジシクロペンタジエン（ＤＣＰＤ）、メチルジシクロペンタジエン等があげられ、特にジシクロペンタジエンが好ましい。 In the present invention, among petroleum resins, a petroleum resin obtained by (co)polymerizing a fraction containing an alicyclic unsaturated hydrocarbon (hereinafter referred to as "alicyclic unsaturated hydrocarbon petroleum resin") is used. use. The alicyclic unsaturated hydrocarbon petroleum resin is obtained, for example, by dimerizing the cyclopentadienes contained in the C5 fraction to obtain dicyclopentadienes, separating from the other C5 fractions by distillation, and heating. Including those polymerized by the Diels-Alder reaction. Cyclopentadienes include, for example, cyclopentadiene, methylcyclopentadiene, and the like. The dicyclopentadienes include, for example, dicyclopentadiene (DCPD), methyldicyclopentadiene, etc. Dicyclopentadiene is particularly preferred.
　脂環式不飽和炭化水素系石油樹脂には、シクロペンタジエン類以外のＣ５留分やＣ９留分が含まれていてもよい。 The alicyclic unsaturated hydrocarbon petroleum resin may contain C5 fractions and C9 fractions other than cyclopentadienes.
　Ｃ５留分は、一般的には、石油類の熱分解により得られる留分のうち、沸点範囲が２０～１１０℃程度の留分が用いられる。シクロペンタジエン類以外のＣ５留分としては、例えば、１－ペンテン、２－ペンテン、２－メチル－１－ブテン、２－メチル－２－ブテン、３－メチル－１－ブテン等のオレフィン系炭化水素、２－メチル－１，３－ブタジエン、１，２－ペンタジエン、１，３－ペンタジエン、３－メチル－１，２－ブタジエン等のジオレフィン系炭化水素が挙げられる。 The C5 fraction generally uses a fraction with a boiling point range of about 20 to 110°C among the fractions obtained by thermal cracking of petroleum. Examples of C5 fractions other than cyclopentadienes include olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene. , 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene.
　Ｃ９留分は、一般的には、石油類の熱分解により得られる留分のうち、沸点範囲が１００～２８０℃程度の留分が用いられる。Ｃ９留分としては、例えば、α－メチルスチレン、β－メチルスチレン、γ－メチルスチレン等のスチレン同族体やインデン、クマロン等のインデン同族体等が挙げられる。 The C9 fraction is generally a fraction with a boiling point range of about 100 to 280°C among the fractions obtained by thermal cracking of petroleum. Examples of the C9 fraction include styrene homologues such as α-methylstyrene, β-methylstyrene and γ-methylstyrene, and indene homologues such as indene and coumarone.
　一般的なＣ５系石油樹脂、Ｃ９系石油樹脂、Ｃ５／Ｃ９系石油樹脂の製造方法は以下の通りである。原料油に対して０．０１～５重量％のフリーデルクラフツ型触媒を添加し、重合反応を行う。反応終了後、アルカリを用いてフリーデルクラフツ型触媒を分解除去し、最後に蒸留等により未反応油および低分子重合物を除去する。一般的にフリーデルクラフツ型触媒としては、例えば三塩化アルミニウム、三臭化アルミニウム、三フッ化ホウ素あるいはそのフェノール錯体、ブタノール錯体等が挙げられる。中でも三塩化アルミニウム、三フッ化ホウ素のフェノール錯体、三フッ化ホウ素のブタノール錯体が好ましい。重合温度は０～１００℃が好ましく、特に好ましくは０～８０℃である。また、触媒量及び重合時間は、原料油１００質量部に対して触媒０．１～２．０質量部のとき、０．１～１０時間であること好ましい。反応圧力は大気圧～１ＭＰａが好ましい。 General methods for producing C5-based petroleum resin, C9-based petroleum resin, and C5/C9-based petroleum resin are as follows. A Friedel-Crafts type catalyst is added in an amount of 0.01 to 5% by weight based on the raw material oil, and the polymerization reaction is carried out. After completion of the reaction, the Friedel-Crafts-type catalyst is decomposed and removed using alkali, and finally unreacted oil and low-molecular-weight polymer are removed by distillation or the like. Friedel-Crafts-type catalysts generally include, for example, aluminum trichloride, aluminum tribromide, boron trifluoride or their phenol complexes, butanol complexes, and the like. Among them, aluminum trichloride, a phenol complex of boron trifluoride, and a butanol complex of boron trifluoride are preferable. The polymerization temperature is preferably 0 to 100°C, particularly preferably 0 to 80°C. Further, the catalyst amount and the polymerization time are preferably 0.1 to 10 hours when the catalyst is 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the raw material oil. The reaction pressure is preferably atmospheric pressure to 1 MPa.
　石油樹脂は一部に種々の官能基を有する化合物が重合していてもよい。官能基の例としては、水酸基を有するアルコール化合物やフェノール化合物が挙げられる。アルコール化合物の具体例としては、アリルアルコール、２－ブテン－１，４－ジオール等の二重結合を有するアルコール化合物が挙げられる。フェノール化合物としては、フェノール、クレゾール、キシレノール、ｐ－ｔ－ブチルフェノール、ｐ－オクチルフェノール、ｐ－ノニルフェノール等のアルキルフェノール類を使用できる。これらの水酸基を有する化合物は、単独で用いてもよく、二種以上を併用してもよい。 The petroleum resin may be partially polymerized with compounds having various functional groups. Examples of functional groups include alcohol compounds and phenol compounds having hydroxyl groups. Specific examples of alcohol compounds include alcohol compounds having double bonds such as allyl alcohol and 2-butene-1,4-diol. As the phenolic compound, alkylphenols such as phenol, cresol, xylenol, pt-butylphenol, p-octylphenol and p-nonylphenol can be used. These hydroxyl-containing compounds may be used alone, or two or more of them may be used in combination.
　また、水酸基含有石油樹脂は、石油留分と共に（メタ）アクリル酸アルキルエステル等を熱重合して石油樹脂中にエステル基を導入した後、該エステル基を還元する方法、石油樹脂中に残存又は導入した二重結合を水和する方法等によっても製造できる。本発明では、水酸基含有石油樹脂として、上記のような各種方法により得られるものが使用できるが、性能及び製造の観点から、フェノール変性石油樹脂等を使用するのが好ましい。 In addition, the hydroxyl group-containing petroleum resin can be obtained by thermally polymerizing a (meth)acrylic acid alkyl ester or the like together with a petroleum fraction to introduce an ester group into the petroleum resin, and then reducing the ester group. It can also be produced by a method of hydrating the introduced double bond. In the present invention, as the hydroxyl group-containing petroleum resin, those obtained by the various methods described above can be used, but from the viewpoint of performance and production, it is preferable to use a phenol-modified petroleum resin or the like.
　該フェノール変性石油樹脂は、Ｃ９留分をフェノールの存在下でカチオン重合して得られ、変性が容易である。 The phenol-modified petroleum resin is obtained by cationic polymerization of the C9 fraction in the presence of phenol, and is easy to modify.
　重合の方法は、特に限定されず、例えば、上述のディールス・アルダー反応等の１５０～３００℃程度で１～１０時間程度の加熱を行う熱重合反応や、上述のフリーデルクラフツ型反応などから選択できる。 The method of polymerization is not particularly limited, and is selected from, for example, the above-mentioned Diels-Alder reaction, a thermal polymerization reaction in which heating is performed at about 150 to 300 ° C. for about 1 to 10 hours, and the above-mentioned Friedel-Crafts-type reaction. can.
　上述のこれらの樹脂は、軟化点が２００℃以下（測定法：ＡＳＴＭ　Ｅ２８－５８－Ｔ）であることが好ましく、更に好ましくは、４５～１６０℃が望ましい。 These resins described above preferably have a softening point of 200°C or less (measurement method: ASTM E28-58-T), more preferably 45 to 160°C.
　本発明においては、上述の石油樹脂中の二重結合の一部を水素添加した部分水添石油樹脂を使用することもできる。水素添加の条件は任意であるが、常圧での沸点が１４０～２８０℃の飽和鎖状炭化水素、飽和脂環式炭化水素、芳香族炭化水素より選ばれた１種以上の溶剤と石油樹脂とを混合し、ニッケル、モリブデン、コバルト、パラジウム、白金等を含む一般的な水素化触媒を使用し、反応温度１５０～３２０℃、反応圧力３～３０ＭＰａ、反応時間１～１０時間の条件で反応を行う。 In the present invention, a partially hydrogenated petroleum resin obtained by hydrogenating part of the double bonds in the above petroleum resin can also be used. Hydrogenation conditions are arbitrary, but at least one solvent selected from saturated chain hydrocarbons, saturated alicyclic hydrocarbons and aromatic hydrocarbons having a boiling point of 140 to 280° C. at normal pressure and a petroleum resin and reaction using a general hydrogenation catalyst containing nickel, molybdenum, cobalt, palladium, platinum, etc., at a reaction temperature of 150 to 320 ° C., a reaction pressure of 3 to 30 MPa, and a reaction time of 1 to 10 hours. I do.
　分子内に二重結合を有するＣ５系、Ｃ９系、Ｃ５／Ｃ９系石油樹脂の市販品としては、ＥＮＥＯＳ（株）製ネオレジンＥＰ－１４０　（軟化点：１４０℃）、丸善石油化学（株）製マルカレッツＭ－８９０Ａ　（軟化点：１０５℃）、丸善石油化学（株）製マルカレッツＭ－８４５Ａ　（軟化点：１４５℃）ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＲＢ０９３（軟化点：９２℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＲＢ１００（軟化点：９８℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＲＣ０９３（軟化点：９３℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＲＣ１００（軟化点：９７℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＲＣ１１５（軟化点：１１２℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＲＤ１０４（軟化点：１０２℃）、ＥＮＥＯＳ（株）製Ｔ－ＲＥＺ　ＰＲ８０２（軟化点：８９℃）、日本ゼオン（株）製　Ｑｕｉｎｔｏｎｅ　Ｂ１７０（軟化点：７０℃）、日本ゼオン（株）製　Ｑｕｉｎｔｏｎｅ　Ｍ１００（軟化点：９５℃）、日本ゼオン（株）製　Ｑｕｉｎｔｏｎｅ　Ｒ１００（軟化点：９６℃）、日本ゼオン（株）製　Ｑｕｉｎｔｏｎｅ　Ａ１００（軟化点：１００℃）、日本ゼオン（株）製　Ｑｕｉｎｔｏｎｅ　ＲＸ１１０（軟化点：１１０℃）、Ｅｘｘｏｎ　Ｍｏｂｉｌ　Ｃｈｅｍｉｃａｌ製　Ｅｓｃｏｒｅｚ　１１０２（軟化点：１００℃）、Ｅｘｘｏｎ　Ｍｏｂｉｌ　Ｃｈｅｍｉｃａｌ製　Ｅｓｃｏｒｅｚ　１３０４（軟化点：９４℃）、Ｅｘｘｏｎ　Ｍｏｂｉｌ　Ｃｈｅｍｉｃａｌ製　Ｅｓｃｏｒｅｚ　１３１０ＬＣ（軟化点：１００℃）、Ｅｘｘｏｎ　Ｍｏｂｉｌ　Ｃｈｅｍｉｃａｌ製　Ｅｓｃｏｒｅｚ　１３１５（軟化点：１１５℃）、ＫＯＬＯＮ　Ｉｎｄｕｔｒｉｅｓ製　ＨＩＫＯＲＥＺ　Ａ－１１００（軟化点：９８℃）、ＫＯＬＯＮ　Ｉｎｄｕｔｒｉｅｓ製　ＨＩＫＯＲＥＺ　Ａ－１１１５（軟化点：１１２℃）、ＫＯＬＯＮ　Ｉｎｄｕｔｒｉｅｓ製　ＨＩＫＯＲＥＺ　Ａ－２１１５（軟化点：１１２℃）、ＫＯＬＯＮ　Ｉｎｄｕｔｒｉｅｓ製　ＨＩＫＯＲＥＺ　Ｃ－１１００（軟化点：９８℃）等が挙げられる。 Commercially available C5, C9, and C5/C9 petroleum resins having double bonds in the molecule include Neoresin EP-140 (softening point: 140°C) manufactured by ENEOS Corporation, and manufactured by Maruzen Petrochemical Co., Ltd. Marukaretsu M-890A (softening point: 105°C), Maruzen Petrochemical Co., Ltd. Marukaretsu M-845A (softening point: 145°C), ENEOS T-REZ RB093 (softening point: 92°C), ENEOS ) T-REZ RB100 (softening point: 98°C), ENEOS T-REZ RC093 (softening point: 93°C), ENEOS T-REZ RC100 (softening point: 97°C), ENEOS ( T-REZ RC115 manufactured by ENEOS Corporation (softening point: 112°C), T-REZ RD104 manufactured by ENEOS Corporation (softening point: 102°C), T-REZ PR802 manufactured by ENEOS Corporation (softening point: 89°C), Japan Zeon Co., Ltd. Quintone B170 (softening point: 70°C), Nippon Zeon Co., Ltd. Quintone M100 (softening point: 95°C), Zeon Co., Ltd. Quintone R100 (softening point: 96°C), Nippon Zeon ( Co., Ltd. Quintone A100 (softening point: 100°C), Nippon Zeon Co., Ltd. Quintone RX110 (softening point: 110°C), Exxon Mobil Chemical Escorez 1102 (softening point: 100°C), Exxon Mobil Chemical Escorez 1304 ( Softening point: 94°C), Exxon Mobil Chemical Escorez 1310LC (softening point: 100°C), Exxon Mobil Chemical Escorez 1315 (softening point: 115°C), KOLON Industries HIKOREZ A-1100 (softening point: 98°C), HIKOREZ A-1115 manufactured by KOLON Industries (softening point: 112°C), HIKOREZ A-2115 manufactured by KOLON Industries (softening point: 112°C), HIKOREZ C-1100 manufactured by KOLON Industries (softening point: 98°C), and the like.
（含硫黄炭化水素重合体の製造方法）
　含硫黄炭化水素重合体は、不飽和炭化水素を無溶媒下で加熱しながら溶融状態で硫黄と反応させることにより製造することができる。加熱反応を溶媒中ではなく無溶媒下で行うことで、含硫黄炭化水素重合体の重量平均分子量を小さくしながら、分子量のばらつきを小さくすることができる。また、加熱反応の条件は、特に限定されず適宜設定することができるが、好ましくは９０～１６０℃で、より好ましくは１００～１５０℃で、さらに好ましくは１００～１４０℃で、反応時間は好ましくは０．５～１０時間、より好ましくは１～８時間である。なお、加熱反応の条件を調節することで、含硫黄炭化水素重合体の重量平均分子量を調節することができる。 (Method for producing sulfur-containing hydrocarbon polymer)
A sulfur-containing hydrocarbon polymer can be produced by reacting an unsaturated hydrocarbon with sulfur in a molten state while heating in the absence of a solvent. By conducting the heating reaction in the absence of a solvent rather than in a solvent, it is possible to reduce the weight average molecular weight of the sulfur-containing hydrocarbon polymer while reducing the variation in molecular weight. In addition, the conditions for the heating reaction are not particularly limited and can be set as appropriate. is 0.5 to 10 hours, more preferably 1 to 8 hours. The weight average molecular weight of the sulfur-containing hydrocarbon polymer can be adjusted by adjusting the heating reaction conditions.
　上記の製造方法によれば、副反応を抑制することができるため、含硫黄炭化水素重合体の収率が向上し、精製工程を経ずにそのままゴム用組成物に配合することができる。 According to the above production method, side reactions can be suppressed, so the yield of the sulfur-containing hydrocarbon polymer is improved, and it can be blended into the rubber composition as it is without going through a purification process.
　石油樹脂に対する硫黄の添加量は特に限定されないが、不飽和炭化水素の不飽和結合（二重結合）当たり、０．１当量以上、好ましくは０．３～５当量の割合であることが好ましい。 The amount of sulfur added to the petroleum resin is not particularly limited, but it is preferably 0.1 equivalent or more, preferably 0.3 to 5 equivalents, per unsaturated bond (double bond) of the unsaturated hydrocarbon.
　本発明においては、不飽和脂環式炭化水素としてノルボルネン骨格を有する化合物、特にジシクロペンタジエンを用いることが好ましい。さらに、ジシクロペンタジエンのノルボルネン骨格上の二重結合が硫黄と反応することが好ましく、ノルボルネン骨格上の二重結合のみが硫黄と反応することがより好ましい。ノルボルネン骨格上の二重結合が硫黄と反応して消費されたことは、１Ｈ－ＮＭＲにより確認することができる。 In the present invention, it is preferable to use a compound having a norbornene skeleton, particularly dicyclopentadiene, as the unsaturated alicyclic hydrocarbon. Furthermore, it is preferred that the double bond on the norbornene skeleton of the dicyclopentadiene reacts with sulfur, and more preferably only the double bond on the norbornene skeleton reacts with sulfur. It can be confirmed by 1 H-NMR that the double bond on the norbornene skeleton was consumed by reaction with sulfur.
（シラン化合物）
　ゴム組成物に含まれるシラン化合物は、シランカップリング剤としての機能を果たすことができる。ゴム組成物は、少なくとも、不飽和二重結合含有シラン化合物を含み、不飽和二重結合を有さないその他のシラン化合物をさらに含んでもよい。不飽和二重結合含有シラン化合物の含有量は、シラン化合物の全量に対して、好ましくは５０質量％以上であり、より好ましくは７０質量％以上であり、さらに好ましくは８０質量％以上である。また、１００質量％以下であり、好ましくは１００質量％であってもよい。以下、好適なシラン化合物について説明する。 (Silane compound)
A silane compound contained in the rubber composition can function as a silane coupling agent. The rubber composition contains at least an unsaturated double bond-containing silane compound and may further contain other silane compounds having no unsaturated double bonds. The content of the unsaturated double bond-containing silane compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more, relative to the total amount of the silane compound. Moreover, it may be 100% by mass or less, preferably 100% by mass. Preferred silane compounds are described below.
（不飽和二重結合含有シラン化合物）
　不飽和二重結合含有シラン化合物は、好ましくは、下記の式（１）： 
Figure JPOXMLDOC01-appb-C000005
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　Ｌは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ１６は、水素原子、メチル基または炭素数２～８のアルキル基であり、かつ、Ｒ１７は、水素原子、メチル基または炭素数２～１０のアルキル基であり、ここで、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成し、かつ、Ｒ１４、Ｒ１５およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、若しくは、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、
　または、
　Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素を形成してもよく、ここで、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基である。］
で表される化合物である。 (Unsaturated double bond-containing silane compound)
The unsaturated double bond-containing silane compound preferably has the following formula (1):
Figure JPOXMLDOC01-appb-C000005
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
L is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms,
or,
R 16 and R 17 may be joined together to form a 4- to 9-membered alicyclic hydrocarbon, wherein R 14 and R 15 are joined together to form a double bond, and , R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
It is a compound represented by
　上記式（１）において、ａは、０か１の整数であり、好ましくは１である。
　また、ｂは、０か１の整数であり、好ましくは１である。
　また、ｃは、それぞれ独立して、０か１の整数であり、好ましくは１である。
　また、ｄは、それぞれ独立して、０か１の整数であり、好ましくは１である。
　また、ｅは、０～５の整数であり、好ましくは０～３の整数、より好ましくは０～２の整数、さらに好ましくは０または１の整数である。
　また、Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよい。
　また、ｆは、１～５の整数であり、好ましくは１～４の整数、より好ましくは１～３の整数、さらに好ましくは１である。
　また、Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよい。
　また、ｇは、１～５の整数であり、好ましくは１～４の整数、より好ましくは１～３の整数、さらに好ましくは１である。
　また、Ｒ１６は、水素原子、メチル基または炭素数２～８のアルキル基であり、好ましくは、水素原子、メチル基または炭素数２または３のアルキル基、より好ましくは、水素原子またはメチル基、さらにより好ましくは、水素原子であり、かつ、Ｒ１７は、水素原子、メチル基または炭素数２～１０のアルキル基であり、好ましくは、水素原子、メチル基または炭素数２～５のアルキル基、より好ましくは、水素原子またはメチル基、さらにより好ましくは、水素原子であり、ここで、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成し、かつ、Ｒ１４、Ｒ１５およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、若しくは、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、
　または、
　Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素、好ましくは４～７員の脂環式炭化水素、より好ましくは５員または６員の脂環式炭化水素、さらに好ましくは５員の脂環式炭化水素を形成してもよく、ここで、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基である。 In the above formula (1), a is an integer of 0 or 1, preferably 1.
b is an integer of 0 or 1, preferably 1;
Each c is independently an integer of 0 or 1, preferably 1.
Each d is independently an integer of 0 or 1, preferably 1.
Also, e is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably an integer of 0 or 1.
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are - A crosslinked structure represented by (CH 2 ) f — may be formed.
In addition, f is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1.
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are - A crosslinked structure represented by (CH 2 ) g — may be formed.
Also, g is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1.
R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 or 3 carbon atoms, more preferably a hydrogen atom or a methyl group. , still more preferably a hydrogen atom, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 to 5 carbon atoms a group, more preferably a hydrogen atom or a methyl group, still more preferably a hydrogen atom, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms,
or,
R 16 and R 17 are bonded together to form a 4- to 9-membered alicyclic hydrocarbon, preferably a 4- to 7-membered alicyclic hydrocarbon, more preferably a 5- or 6-membered alicyclic hydrocarbon; More preferably, it may form a 5-membered alicyclic hydrocarbon, wherein R 14 and R 15 are joined together to form a double bond, and R 12 , R 13 and R 18 are It is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms.
　また、上記式（１）において、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。炭化水素基は、例えば、アルキル基、アラルキル基またはアリール基などが挙げられる。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、ｔｅｒｔ－ブチル基、２－エチルヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられ、アルキル基の炭素原子数は１～６０が好ましく、１～３０がより好ましく、中でもメチル基またはエチル基であることが好ましい。
　アラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素原子数は７～６０が好ましく、７～２０がより好ましく、７～１４がさらに好ましい。
　アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素原子数は６～６０が好ましく、６～２４がより好ましく、６～１２がさらに好ましい。
　酸素原子または窒素原子を含む炭化水素基とは、炭化水素基中の炭素原子が酸素原子または窒素原子で置き換えられた構造を有する基である。 In formula (1) above, R 1 , R 2 and R 3 each independently represent a hydrocarbon group which may contain an oxygen atom or a nitrogen atom, or a hydrogen atom. Examples of hydrocarbon groups include alkyl groups, aralkyl groups, and aryl groups.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1. ~60 is preferable, 1 to 30 is more preferable, and a methyl group or an ethyl group is particularly preferable.
The aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms in the aralkyl group is preferably 7-60, more preferably 7-20, even more preferably 7-14.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-60, more preferably 6-24, even more preferably 6-12.
A hydrocarbon group containing an oxygen atom or a nitrogen atom is a group having a structure in which a carbon atom in the hydrocarbon group is replaced with an oxygen atom or a nitrogen atom.
　本発明のさらに好ましい実施態様において、上記Ｒ１、Ｒ２およびＲ３における酸素原子または窒素原子を含んでいてもよい炭化水素基は、アルコキシ基、１以上のアルキル基で置換されたアミノ基、またはアルキル基である。より好ましくは炭素数１～３０のアルコキシ基、さらに好ましくは炭素数１～２０のアルコキシ基、より好ましくは１以上の炭素数１～３０のアルキル基で置換されたアミノ基、さらに好ましくは１以上の炭素数１～２０のアルキル基で置換されたアミノ基、あるいは、より好ましくは炭素数１～３０のアルキル基、さらに好ましくは炭素数１～２０のアルキル基である。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基およびイソブトキシ基等が挙げられ、これらの中でも、メトキシ基またはエトキシ基が好ましい。また、１以上のアルキル基で置換されたアミノ基としては、Ｎ－メチルアミノ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ－エチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基およびＮ－イソプロピルアミノ基等が挙げられ、これらの中でも、Ｎ－メチルアミノ基またはＮ－エチルアミノ基が好ましい。また、アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、シクロペンチル基、へキシル基およびシクロへキシル基等が挙げられ、これらの中でも、メチル基およびエチル基が好ましい。 In a further preferred embodiment of the present invention, the hydrocarbon group which may contain an oxygen atom or a nitrogen atom for R 1 , R 2 and R 3 is an alkoxy group, an amino group substituted with one or more alkyl groups, or an alkyl group. more preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, still more preferably one or more or an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy groups, among which methoxy and ethoxy groups are preferred. Further, the amino group substituted with one or more alkyl groups includes N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferred. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group and cyclohexyl group. Among them, a methyl group and an ethyl group are preferred.
　また、上記式（１）において、Ｌは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、好ましくは、炭化水素基の炭素数は１～３０、より好ましくは、１～２０、さらに好ましくは、１～１０である。その中でも、Ｌは、硫黄を含む炭化水素基であることが特に好ましい。かかる炭化水素基におけるシリル基と脂環式炭化水素部分をつなぐ直鎖部分の長さが、炭素、窒素、酸素または硫黄の原子数の総和として、好ましくは３～８、より好ましくは４～７、さらに好ましくは４～６である。 In the above formula (1), L is a hydrocarbon group that may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably the number of carbon atoms in the hydrocarbon group is 1-30, more preferably 1-20, still more preferably 1-10. Among them, L is particularly preferably a hydrocarbon group containing sulfur. The total length of the linear portion connecting the silyl group and the alicyclic hydrocarbon portion in such a hydrocarbon group is preferably 3 to 8, more preferably 4 to 7, as the total number of atoms of carbon, nitrogen, oxygen or sulfur. , more preferably 4-6.
　不飽和二重結合含有シラン化合物は、好ましくは、式（２）：
Figure JPOXMLDOC01-appb-C000006
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　ｈは、１～１０の整数であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ１６は、水素原子、メチル基または炭素数２～８のアルキル基であり、かつ、Ｒ１７は、水素原子、メチル基または炭素数２～１０のアルキル基であり、ここで、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成し、かつ、Ｒ１４、Ｒ１５およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、若しくは、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、
　または、
　Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素を形成してもよく、ここで、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基である。］
で表される化合物である。 The unsaturated double bond-containing silane compound preferably has the formula (2):
Figure JPOXMLDOC01-appb-C000006
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
h is an integer from 1 to 10,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms,
or,
R 16 and R 17 may be joined together to form a 4- to 9-membered alicyclic hydrocarbon, wherein R 14 and R 15 are joined together to form a double bond, and , R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
It is a compound represented by
　上記式（２）で表される化合物におけるｈは、１～１０の整数であり、好ましくは１～８、より好ましくは２～７、さらに好ましくは３～６、さらにより好ましくは３～５の整数であり、特に好ましくは３である。また、ａ～ｇおよびＲ１～Ｒ１８については、上記式（１）において説明した通りである。 h in the compound represented by the above formula (2) is an integer of 1 to 10, preferably 1 to 8, more preferably 2 to 7, still more preferably 3 to 6, still more preferably 3 to 5 It is an integer, particularly preferably 3. Further, a to g and R 1 to R 18 are as explained in formula (1) above.
　不飽和二重結合含有シラン化合物は、より好ましくは、式（３）：
Figure JPOXMLDOC01-appb-C000007
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　ｈは、１～１０の整数であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ３１は、水素原子、メチル基または炭素数２～８のアルキル基である。］
で表される化合物である。 The unsaturated double bond-containing silane compound more preferably has the formula (3):
Figure JPOXMLDOC01-appb-C000007
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
h is an integer from 1 to 10,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 31 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms. ]
It is a compound represented by
　上記式（３）で表される化合物のうち、a～ｇおよびＲ１～Ｒ１１については、上記式（１）において説明した通りであり、ｈについては、上記式（２）で説明した通りである。 Among the compounds represented by the above formula (3), a to g and R 1 to R 11 are as described in the above formula (1), and h is as described in the above formula (2). is.
　式（３）におけるＲ３１は、水素原子、メチル基または炭素数２～８のアルキル基であり、好ましくは、水素原子、メチル基または炭素数２～５のアルキル基、より好ましくは、水素原子、メチル基または炭素数１または２のアルキル基であり、さらに好ましくは水素原子である。 R 31 in formula (3) is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, preferably a hydrogen atom, a methyl group or an alkyl group having 2 to 5 carbon atoms, more preferably a hydrogen atom , a methyl group or an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom.
　不飽和二重結合含有シラン化合物は、より好ましくは、式（４）：
Figure JPOXMLDOC01-appb-C000008
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　ｈは、１～１０の整数であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ３２は、水素原子、メチル基または炭素数２～９のアルキル基である。］
で表される化合物である。 The unsaturated double bond-containing silane compound more preferably has the formula (4):
Figure JPOXMLDOC01-appb-C000008
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
h is an integer from 1 to 10,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 32 is a hydrogen atom, a methyl group or an alkyl group having 2 to 9 carbon atoms. ]
It is a compound represented by
　上記式（４）で表される化合物のうち、a～ｇおよびＲ１～Ｒ１１については、上記式（１）において説明した通りであり、ｈについては、上記式（２）で説明した通りである。 Among the compounds represented by the above formula (4), a to g and R 1 to R 11 are as described in the above formula (1), and h is as described in the above formula (2). is.
　式（４）におけるＲ３２は、水素原子、メチル基または炭素数２～９のアルキル基であり、好ましくは、メチル基または炭素数２～５のアルキル基、より好ましくは、メチル基または炭素数１または２のアルキル基であり、さらに好ましくはメチル基である。 R 32 in formula (4) is a hydrogen atom, a methyl group or an alkyl group having 2 to 9 carbon atoms, preferably a methyl group or an alkyl group having 2 to 5 carbon atoms, more preferably a methyl group or an alkyl group having 2 to 5 carbon atoms. It is one or two alkyl groups, more preferably a methyl group.
　不飽和二重結合含有シラン化合物は、より好ましくは、式（５）：
Figure JPOXMLDOC01-appb-C000009
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　ｈは、１～１０の整数であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　ｘは、０～５の整数である。］
で表される化合物である。 The unsaturated double bond-containing silane compound more preferably has the formula (5):
Figure JPOXMLDOC01-appb-C000009
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
h is an integer from 1 to 10,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
x is an integer from 0 to 5; ]
It is a compound represented by
　上記式（５）で表される化合物のうち、a～ｇおよびＲ１～Ｒ１１については、上記式（１）において説明した通りであり、ｈについては、上記式（２）で説明した通りである。 Among the compounds represented by the above formula (5), a to g and R 1 to R 11 are as described in the above formula (1), and h is as described in the above formula (2). is.
　式（５）におけるｘは、０～５の整数であり、好ましくは０～３の整数、より好ましくは１または２、さらに好ましくは１である。 x in formula (5) is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 1 or 2, still more preferably 1.
　不飽和二重結合含有シラン化合物は、さらに好ましくは、式（６）：
Figure JPOXMLDOC01-appb-C000010
 ［式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］、または
式（７）：
Figure JPOXMLDOC01-appb-C000011
 ［式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］、または
式（８）：
Figure JPOXMLDOC01-appb-C000012
 ［式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］、または、
式（９）：
Figure JPOXMLDOC01-appb-C000013
 ［式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］
で表される化合物である。 The unsaturated double bond-containing silane compound is more preferably represented by formula (6):
Figure JPOXMLDOC01-appb-C000010
 [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ], or formula (7):
Figure JPOXMLDOC01-appb-C000011
 [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ], or formula (8):
Figure JPOXMLDOC01-appb-C000012
 [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ],or,
Formula (9):
Figure JPOXMLDOC01-appb-C000013
 [In the formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ]
It is a compound represented by
　上記式（６）～式（９）で表される化合物において、Ｒ１～Ｒ３については、上記式（１）において説明した通りである。 In the compounds represented by the above formulas (6) to (9), R 1 to R 3 are as explained for the above formula (1).
　不飽和二重結合含有シラン化合物の別のさらに好ましい態様としては、下記式で表される化合物が挙げられる。下記式で表される化合物において、Ｒ１～Ｒ３については、上記式（１）において説明した通りである。
Figure JPOXMLDOC01-appb-C000014
 ［各式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］ Another more preferred embodiment of the unsaturated double bond-containing silane compound is a compound represented by the following formula. In the compound represented by the following formula, R 1 to R 3 are as explained in formula (1) above.
Figure JPOXMLDOC01-appb-C000014
 [In each formula, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ]
　不飽和二重結合含有シラン化合物のさらにより好ましい態様としては、上記式（１）～式（９）において、Ｒ１Ｒ２Ｒ３Ｓｉ基が、式（１０）：
Figure JPOXMLDOC01-appb-C000015
 ［式中、
　Ｒ１９は、それぞれ独立して、アルコキシ基または１以上のアルキル基で置換されたアミノ基であり、
　Ｒ２０は、それぞれ独立して、水素原子またはアルキル基であり、
　Ｌ１は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、
　ｊは、それぞれ独立して、０か１の整数であり、
　ｋは、１～３の整数であり、
　アスタリスク（＊）は、前記シラン化合物のシリル基以外の部分と結合している部位を示す。］
の化学構造を有するシラン化合物が挙げられる。 As a still more preferred embodiment of the unsaturated double bond-containing silane compound, in the above formulas (1) to (9), the R 1 R 2 R 3 Si group is represented by the formula (10):
Figure JPOXMLDOC01-appb-C000015
 [In the formula,
each R 19 is independently an alkoxy group or an amino group substituted with one or more alkyl groups;
each R 20 is independently a hydrogen atom or an alkyl group;
each L 1 is independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;
each j is independently an integer of 0 or 1;
k is an integer from 1 to 3,
An asterisk (*) indicates a site bonded to a portion other than the silyl group of the silane compound. ]
and a silane compound having the chemical structure of
　上記式（１０）において、Ｒ１９は、それぞれ独立して、アルコキシ基または１以上のアルキル基で置換されたアミノ基である。好ましい一つの実施態様としては、Ｒ１９は、それぞれ独立して、加水分解性基であり、アルコキシ基、より好ましくは炭素数１～３０のアルコキシ基、さらに好ましくは炭素数１～２０のアルコキシ基、または１以上のアルキル基で置換されたアミノ基、より好ましくは１以上の炭素数１～３０のアルキル基で置換されたアミノ基、さらに好ましくは１以上の炭素数１～２０のアルキル基で置換されたアミノ基である。具体的には、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基およびイソブトキシ基等が挙げられ、これらの中でも、メトキシ基またはエトキシ基が好ましい。また、１以上のアルキル基で置換されたアミノ基としては、Ｎ－メチルアミノ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ－エチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基およびＮ－イソプロピルアミノ基等が挙げられ、これらの中でも、Ｎ－メチルアミノ基またはＮ－エチルアミノ基が好ましい。なお、アルコキシ基およびアミノ基は、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基からなる連結基を介してケイ素（Ｓｉ）と結合してもよい。
　また、Ｒ２０は、それぞれ独立して、水素原子またはアルキル基であり、より好ましくは炭素数１～３０のアルキル基、さらに好ましくは炭素数１～２０のアルキル基であり、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、シクロペンチル基、へキシル基およびシクロへキシル基等が挙げられ、これらの中でも、メチル基およびエチル基が好ましい。 In formula (10) above, each R 19 is independently an alkoxy group or an amino group substituted with one or more alkyl groups. In one preferred embodiment, each R 19 is independently a hydrolyzable group, an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, still more preferably an alkoxy group having 1 to 20 carbon atoms. , or an amino group substituted with one or more alkyl groups, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, more preferably one or more alkyl groups having 1 to 20 carbon atoms. It is a substituted amino group. Specifically, the alkoxy group includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc. Among these, methoxy or ethoxy is preferred. Further, the amino group substituted with one or more alkyl groups includes N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferred. The alkoxy group and amino group are bonded to silicon (Si) via a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. good too.
Each R 20 is independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups, among which methyl and ethyl groups are preferred.
　上記式（１０）において、Ｌ１は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい、炭素数１～３０の炭化水素基、より好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい、炭素数１～２０の炭化水素基、さらに好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい、炭素数１～１０の炭化水素基である。 In the above formula (10), each L 1 is independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen, A hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of oxygen and sulfur, more preferably at least one selected from the group consisting of nitrogen, oxygen and sulfur A hydrocarbon group having 1 to 20 carbon atoms which may contain one heteroatom, more preferably a carbon number which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur 1 to 10 hydrocarbon groups.
　上記式（１０）において、ｋは、１～３の整数であり、好ましくは２～３の整数、より好ましくは３である。
　また、ｊは、それぞれ独立して、０か１の整数であり、好ましくは０である。 In the above formula (10), k is an integer of 1-3, preferably an integer of 2-3, more preferably 3.
Each j is independently an integer of 0 or 1, preferably 0.
　不飽和二重結合含有シラン化合物は、上記式（１）～式（９）において、Ｒ１Ｒ２Ｒ３Ｓｉ基がトリエトキシシリル基（（ＥｔＯ）３Ｓｉ基）またはトリメトキシシリル基であるシラン化合物が一層好ましく、Ｒ１Ｒ２Ｒ３Ｓｉ基がトリエトキシシリル基であるシラン化合物がより一層好ましい。 In the unsaturated double bond-containing silane compound, the R 1 R 2 R 3 Si group is a triethoxysilyl group ((EtO) 3 Si group) or a trimethoxysilyl group in the above formulas (1) to (9). Silane compounds are more preferred, and silane compounds in which the R 1 R 2 R 3 Si group is a triethoxysilyl group are even more preferred.
　不飽和二重結合含有シラン化合物の特に好ましい実施態様としては、下記式で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000016
 A particularly preferred embodiment of the unsaturated double bond-containing silane compound is a compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000016
　不飽和二重結合含有シラン化合物は、好ましくは、その立体異性体、またはそれらの立体異性体の任意の混合物である。 The unsaturated double bond-containing silane compound is preferably its stereoisomer or any mixture of those stereoisomers.
（不飽和二重結合含有シラン化合物の製造方法）
　上記式（１）で表される不飽和二重結合含有シラン化合物の製造方法の一実施形態について説明するが、以下の製造方法に限定されるものではない。例えば、不飽和二重結合含有シラン化合物は、式（１４）：
Figure JPOXMLDOC01-appb-C000017
 ［式中、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ１６は、水素原子、メチル基または炭素数２～８のアルキル基であり、かつ、Ｒ１７は、水素原子、メチル基または炭素数２～１０のアルキル基であり、ここで、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成し、かつ、Ｒ１４、Ｒ１５およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、若しくは、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、
　または、
　Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素を形成してもよく、ここで、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基である。］
で表される化合物と、式（１５）：
Figure JPOXMLDOC01-appb-C000018
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　Ｙは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基である。］
で表される化合物を反応させることにより、製造することができる。 (Method for producing unsaturated double bond-containing silane compound)
An embodiment of the method for producing the unsaturated double bond-containing silane compound represented by the above formula (1) will be described, but the production method is not limited to the following. For example, unsaturated double bond-containing silane compounds have the formula (14):
Figure JPOXMLDOC01-appb-C000017
 [In the formula,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms,
or,
R 16 and R 17 may be joined together to form a 4- to 9-membered alicyclic hydrocarbon, wherein R 14 and R 15 are joined together to form a double bond, and , R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
and a compound represented by formula (15):
Figure JPOXMLDOC01-appb-C000018
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
Y is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. ]
It can be produced by reacting the compound represented by.
　上記式（１４）および式（１５）において、Ｒ１～Ｒ１８およびａ～ｇは、式（１）で表される不飽和二重結合含有シラン化合物において説明した通りである。 In formulas (14) and (15) above, R 1 to R 18 and a to g are as explained for the unsaturated double bond-containing silane compound represented by formula (1).
　また、上記式（１５）において、Ｙは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、好ましくは炭素数１～３０の窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基、より好ましくは炭素数１～２０の窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基、さらに好ましくは炭素数１～１０の窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基である。その中でも、Ｙは、硫黄を含む炭化水素基であることが特に好ましい。かかる炭化水素基におけるシリル基と脂環式炭化水素部分に結合する箇所をつなぐ直鎖部分の長さが、炭素、窒素、酸素または硫黄の原子数の総和として、好ましくは３～８、より好ましくは４～７、さらに好ましくは４～６とされる。 In the above formula (15), Y is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen having 1 to 30 carbon atoms. , a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of oxygen and sulfur, more preferably nitrogen having 1 to 20 carbon atoms, at least one selected from the group consisting of oxygen and sulfur It is a hydrocarbon group optionally containing a heteroatom, more preferably a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur having 1 to 10 carbon atoms. Among them, Y is particularly preferably a hydrocarbon group containing sulfur. The total length of the straight chain portion connecting the silyl group and the alicyclic hydrocarbon moiety in such a hydrocarbon group is preferably 3 to 8, more preferably the total number of atoms of carbon, nitrogen, oxygen or sulfur. is 4-7, more preferably 4-6.
　ここで、上記の式（１）で表される不飽和二重結合含有シラン化合物の製造においては、式（１４）で表される化合物と、式（１５）で表される化合物とを、付加反応または縮合反応に供することで合成することができる。ここにおける付加反応として、ラジカル付加反応、共役付加反応、求核付加反応、求電子付加反応などを用いることができ、例えばペリ環状反応に類する反応、ヒドロシリル化反応、ヒドロアミノ化反応などを用いることができる。縮合反応として、例えばエステル化反応、アミド化反応、チオエステル化反応、チオアミド化反応、フリーデルクラフツ反応等を用いることができる。 Here, in the production of the unsaturated double bond-containing silane compound represented by the above formula (1), the compound represented by the formula (14) and the compound represented by the formula (15) are added. It can be synthesized by subjecting it to a reaction or a condensation reaction. As the addition reaction here, a radical addition reaction, a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like can be used, and for example, reactions similar to pericyclic reactions, hydrosilylation reactions, hydroamination reactions, etc. can. As the condensation reaction, for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, a Friedel-Crafts reaction, or the like can be used.
　なお、上記式（１４）で表される化合物は、当業者に既に知られた知識に基づいて、同一もしくは異なる共役ジエン類化合物同士によるディールズ・アルダー反応、あるいは、共役ジエン類化合物とアルケン類化合物とのディールズ・アルダー反応により合成することができる。また、式（１４）で表される化合物は、当該ディールズ・アルダー反応により合成された化合物を、必要に応じて熱変性させることにより、および／または必要に応じて精製することにより調製することができる。 In addition, the compound represented by the above formula (14) is a Diels-Alder reaction between the same or different conjugated diene compounds, or a conjugated diene compound and an alkene compound, based on the knowledge already known to those skilled in the art. It can be synthesized by a Diels-Alder reaction with In addition, the compound represented by formula (14) can be prepared by optionally thermally denaturing and/or optionally purifying the compound synthesized by the Diels-Alder reaction. can.
　式（２）で表される不飽和二重結合含有シラン化合物は、上記式（１４）で表される化合物と、式（１６）：
Figure JPOXMLDOC01-appb-C000019
 ［式中、
　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　ｈは、１～１０の整数である。］
で表される化合物を反応することにより、製造することができる。 The unsaturated double bond-containing silane compound represented by formula (2) is obtained by combining the compound represented by formula (14) above with formula (16):
Figure JPOXMLDOC01-appb-C000019
 [In the formula,
R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
h is an integer from 1 to 10; ]
It can be produced by reacting the compound represented by.
　上記式（１４）および式（１６）において、Ｒ１～Ｒ１８およびａ～ｇは、式（１）で表される不飽和二重結合含有シラン化合物において説明した通りである。さらに、ｈは、式（２）で表される化合物において説明した通りである。 In formulas (14) and (16) above, R 1 to R 18 and a to g are as explained for the unsaturated double bond-containing silane compound represented by formula (1). Furthermore, h is as explained in the compound represented by formula (2).
　上記式（１６）で表される化合物としては、たとえばメルカプト基を有するアルコキシシラン化合物が挙げられる。メルカプト基を有するアルコキシシラン化合物としては、メルカプトトリメトキシシラン、メルカプトトリエトキシシラン、メルカプトメチルトリメトキシシラン、メルカプトメチルトリエトキシシラン、メルカプトメチルトリプロポキシシラン、２－メルカプトエチルトリメトキシシラン、２－メルカプトエチルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、４－メルカプトブチルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、４－メルカプトブチルトリエトキシシラン、２－メルカプトエチルトリプロポキシシラン、３－メルカプトプロピルトリプロポキシシラン、４－メルカプトブチルトリプロポキシシラン、２－メルカプトエチルメチルジメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、４－メルカプトブチルメチルジメトキシシラン、２－メルカプトエチルメチルジエトキシシラン、３－メルカプトプロピルメチルジエトキシシラン、４－メルカプトブチルメチルジエトキシシラン等が挙げられる。 Examples of compounds represented by the above formula (16) include alkoxysilane compounds having a mercapto group. Alkoxysilane compounds having a mercapto group include mercaptotrimethoxysilane, mercaptotriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyl. triethoxysilane, 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 4-mercaptobutyltriethoxysilane, 2-mercaptoethyltripropoxysilane, 3-mercaptopropyltripropoxysilane Silane, 4-mercaptobutyltripropoxysilane, 2-mercaptoethylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 3-mercaptopropylmethyldiethoxysilane silane, 4-mercaptobutylmethyldiethoxysilane, and the like.
　上記以外の不飽和二重結合含有シラン化合物としては、例えば、ビニル基含有シランや（メタ）アクリル基含有シラン等が挙げられる。ビニル基含有シランとしては、例えば、ビニルトリエトキシシラン、ビニルトリメトキシシラン等が挙げられる。（メタ）アクリル基含有シランとしては、例えば、３－アクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン等が挙げられる。 Examples of unsaturated double bond-containing silane compounds other than the above include vinyl group-containing silanes and (meth)acrylic group-containing silanes. Vinyl group-containing silanes include, for example, vinyltriethoxysilane and vinyltrimethoxysilane. (Meth)acryl group-containing silanes include, for example, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane and the like.
（不飽和二重結合を有さないその他のシラン化合物）
　その他のシラン化合物としては、例えば、下記の式（１１）： 
Figure JPOXMLDOC01-appb-C000020
 ［式中、
　各Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、　
　各Ｌは、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ２６、Ｒ２７およびＲ２８は、それぞれ独立して、水素原子、メチル基または炭素数２～１０のアルキル基を表す。］
で表される化合物を使用することができる。 (Other silane compounds without unsaturated double bonds)
Other silane compounds include, for example, the following formula (11):
Figure JPOXMLDOC01-appb-C000020
 [In the formula,
each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
each L is independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
A compound represented by can be used.
　上記式（１１）において、各Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１の好ましい実施態様は、上記式（１）で説明した通りである。
　また、各Ｌの好ましい実施態様は、上記式（１）で説明した通りである。
　また、ａ、ｂ、ｃ、ｄ、ｅの好ましい態様は、上記式（１）で説明した通りである。
　Ｒ２６、Ｒ２７およびＲ２８は、それぞれ独立して、水素原子、メチル基または炭素数２～１０のアルキル基を表し、好ましくは水素原子である。 In the above formula (11), each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is preferably ) is as described in .
Moreover, preferred embodiments of each L are as described in the formula (1) above.
Preferred embodiments of a, b, c, d, and e are as described in formula (1) above.
R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, preferably a hydrogen atom.
　その他のシラン化合物は、好ましくは含硫黄シラン化合物である。 The other silane compound is preferably a sulfur-containing silane compound.
　上記式（１１）で表されるその他のシラン化合物は、好ましくは、式（１２）：
Figure JPOXMLDOC01-appb-C000021
 ［式中、
　各Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
　ｈは、１～１０の整数であり、
　ｍは、１～１０の整数であり、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ２６、Ｒ２７およびＲ２８は、それぞれ独立して、水素原子、メチル基または炭素数２～１０のアルキル基を表す。］
で表される化合物である。 Other silane compounds represented by the above formula (11) are preferably represented by formula (12):
Figure JPOXMLDOC01-appb-C000021
 [In the formula,
each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
h is an integer from 1 to 10,
m is an integer from 1 to 10,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 26 , R 27 and R 28 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
It is a compound represented by
　上記式（１２）において、各Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ２６、Ｒ２７およびＲ２８の好ましい実施態様は、上記式（１１）で説明した通りである。
　また、各Ｌの好ましい実施態様は、上記式（１１）で説明した通りである。
　また、ａ、ｂ、ｃ、ｄ、ｅの好ましい態様は、上記式（１１）で説明した通りである。
　また、ｈの好ましい実施態様は、上記式（２）で説明した通りである。
　また、上記式（１２）において、ｍは、１～１０の整数であり、好ましくは１～８、より好ましくは１～６、さらに好ましくは１～４、さらにより好ましくは１～３の整数である。 In the above formula (12), each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 26 , R 27 and R 28 Preferred embodiments are as described in formula (11) above.
Moreover, preferred embodiments of each L are as described in the formula (11) above.
Further, preferred embodiments of a, b, c, d, and e are as described in formula (11) above.
Moreover, preferred embodiments of h are as described in the above formula (2).
Further, in the above formula (12), m is an integer of 1 to 10, preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3. be.
　その他のシラン化合物は、さらに好ましくは、式（１７）：
Figure JPOXMLDOC01-appb-C000022
 ［式中、各Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］、または
式（１８）：
Figure JPOXMLDOC01-appb-C000023
 ［式中、各Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］
で表される化合物である。 Other silane compounds are more preferably represented by formula (17):
Figure JPOXMLDOC01-appb-C000022
 [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ], or formula (18):
Figure JPOXMLDOC01-appb-C000023
 [In the formula, each of R 1 , R 2 and R 3 independently represents a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ]
It is a compound represented by
　上記式（１７）、式（１８）で表される化合物において、各Ｒ１、Ｒ２およびＲ３については、上記式（１１）において説明した通りである。 In the compounds represented by the above formulas (17) and (18), R 1 , R 2 and R 3 are as explained for the above formula (11).
　その他のシラン化合物の別のさらに好ましい態様としては、下記式で表される化合物が挙げられる。下記式で表される化合物において、Ｒ１～Ｒ３については、上記式（１）において説明した通りである。
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
 Another more preferred embodiment of the other silane compound is a compound represented by the following formula. In the compound represented by the following formula, R 1 to R 3 are as explained in formula (1) above.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
　上記式（１１）で表されるその他のシラン化合物のさらにより好ましい態様としては、Ｒ１Ｒ２Ｒ３Ｓｉ基が、上記式（１０）の化学構造を有するシラン化合物が挙げられる。特に、その他のシラン化合物は、Ｒ１Ｒ２Ｒ３Ｓｉ基がトリエトキシシリル基またはトリメトキシシリル基であるシラン化合物が一層好ましく、Ｒ１Ｒ２Ｒ３Ｓｉ基がトリエトキシシリル基であるシラン化合物がより一層好ましい。 An even more preferred embodiment of the other silane compound represented by formula (11) above is a silane compound in which the R 1 R 2 R 3 Si group has the chemical structure of formula (10) above. In particular, the other silane compound is more preferably a silane compound in which the R 1 R 2 R 3 Si group is a triethoxysilyl group or a trimethoxysilyl group, and a silane compound in which the R 1 R 2 R 3 Si group is a triethoxysilyl group. Compounds are even more preferred.
　その他のシラン化合物の特に好ましい実施態様としては、下記式で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
 Particularly preferred embodiments of other silane compounds include compounds represented by the following formulas.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
　その他のシラン化合物は、好ましくは、その立体異性体、またはそれらの立体異性体の任意の混合物である。 The other silane compound is preferably its stereoisomer or any mixture of those stereoisomers.
（その他のシラン化合物の製造方法）
　式（１１）で表されるその他のシラン化合物の製造方法の一実施形態について説明するが、以下の製造方法に限定されるものではない。例えば、その他のシラン化合物は、下記式（１４）：
Figure JPOXMLDOC01-appb-C000028
 ［式中、
　ａは、０か１の整数であり、
　ｂは、０か１の整数であり、
　ｃは、それぞれ独立して、０か１の整数であり、
　ｄは、それぞれ独立して、０か１の整数であり、
　ｅは、０～５の整数であり、
　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
　ｆは、１～５の整数であり、
　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
　ｇは、１～５の整数であり、
　Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７およびＲ１８は、それぞれ独立して、水素原子、メチル基または炭素数２～１０のアルキル基を表し、但し、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成するか、あるいは、Ｒ１４およびＲ１５は互いに結合して二重結合を形成し、また、Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素を形成してもよい。］
で表される化合物と、上記式（１５）で表される化合物を反応させることにより、製造することができる。なお、上記式（１４）および（１５）の好ましい実施態様については、不飽和二重結合含有シラン化合物において説明した通りである。 (Method for producing other silane compounds)
An embodiment of the method for producing the other silane compound represented by formula (11) will be described, but the production method is not limited to the following. For example, other silane compounds have the following formula (14):
Figure JPOXMLDOC01-appb-C000028
 [In the formula,
a is an integer of 0 or 1,
b is an integer of 0 or 1,
c is each independently an integer of 0 or 1,
d is each independently an integer of 0 or 1,
e is an integer from 0 to 5,
R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
f is an integer from 1 to 5,
R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
g is an integer from 1 to 5,
R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, provided that R 12 and R 13 is bonded to each other to form a double bond, or R 14 and R 15 are bonded to each other to form a double bond, and R 16 and R 17 are bonded to each other to form 4 to 9 may form a membered alicyclic hydrocarbon. ]
It can be produced by reacting a compound represented by with a compound represented by the above formula (15). Preferred embodiments of the above formulas (14) and (15) are as described for the unsaturated double bond-containing silane compound.
　ここで、その他のシラン化合物の製造においては、上記式（１４）で表される化合物と、上記式（１５）で表される化合物とを、付加反応または縮合反応に供することで合成することができる。ここにおける付加反応として、ラジカル付加反応、共役付加反応、求核付加反応、求電子付加反応などを用いることができ、例えばペリ環状反応に類する反応、ヒドロシリル化反応、ヒドロアミノ化反応などを用いることができる。縮合反応として、例えばエステル化反応、アミド化反応、チオエステル化反応、チオアミド化反応、フリーデルクラフツ反応等を用いることができる。 Here, in the production of other silane compounds, the compound represented by the above formula (14) and the compound represented by the above formula (15) can be synthesized by subjecting them to an addition reaction or a condensation reaction. can. As the addition reaction here, a radical addition reaction, a conjugate addition reaction, a nucleophilic addition reaction, an electrophilic addition reaction, or the like can be used, and for example, reactions similar to pericyclic reactions, hydrosilylation reactions, hydroamination reactions, etc. can. As the condensation reaction, for example, an esterification reaction, an amidation reaction, a thioesterification reaction, a thioamidation reaction, a Friedel-Crafts reaction, or the like can be used.
　なお、上記式（１４）で表される化合物は、当業者に既に知られた知識に基づいて、同一もしくは異なる共役ジエン類化合物同士によるディールズ・アルダー反応、あるいは、共役ジエン類化合物とアルケン類化合物とのディールズ・アルダー反応により合成することができる。また、上記式（１４）で表される化合物は、当該ディールズ・アルダー反応により合成された化合物を、必要に応じて熱変性させることにより、および／または必要に応じて精製することにより調製することができる。 In addition, the compound represented by the above formula (14) is a Diels-Alder reaction between the same or different conjugated diene compounds, or a conjugated diene compound and an alkene compound, based on the knowledge already known to those skilled in the art. It can be synthesized by a Diels-Alder reaction with In addition, the compound represented by the above formula (14) is prepared by thermally denaturing the compound synthesized by the Diels-Alder reaction, if necessary, and/or by purifying it, if necessary. can be done.
　また、その他のシラン化合物は、上記式（１４）で表される化合物と、上記式（１６）で表される化合物を反応することにより、製造することができる。なお、上記式（１６）の好ましい実施態様については、不飽和二重結合含有シラン化合物において説明した通りである。 Further, other silane compounds can be produced by reacting the compound represented by the above formula (14) with the compound represented by the above formula (16). Preferred embodiments of the above formula (16) are as described for the unsaturated double bond-containing silane compound.
　その他のシラン化合物としては、下記の式（１９）： 
Figure JPOXMLDOC01-appb-C000029
 ［式中、
　Ｒ３１、Ｒ３２およびＲ３３のうちの少なくとも１つまたは全部が－Ｏ－（Ｒ３５－Ｏ）ｍ－Ｒ３６（Ｒ３５は、炭素数１～３０の２価の炭化水素基であり、Ｒ３６は炭素数１～３０のアルキル基、炭素数２～３０のアルケニル基、炭素数６～３０のアリール基または炭素数７～３０のアラルキル基であり、ｍは１～３０の整数であり、Ｒ５が複数の場合、複数のＲ５は同じかまたは異なってもよい。）であり、
　Ｒ３１、Ｒ３２およびＲ３３のうちの１つまたは２つが前記－Ｏ－（Ｒ３５－Ｏ）ｍ－Ｒ３６である場合、残りの基を、炭素数１～１２のアルキル基、－Ｏ－Ｒ３７（Ｒ３７は、水素原子、炭素数１～３０のアルキル基、炭素数２～３０のアルケニル基、炭素数６～３０のアリール基、または炭素数７～３０のアラルキル基である。）、水素原子または炭素数６～３０のアリール基とすることができ、
　Ｒ３１、Ｒ３２およびＲ３３は同じかまたは異なってもよく、
　Ｒ３４は炭素数１～３０の２価の炭化水素基である。］
で表されるものも使用することができる。 Other silane compounds include the following formula (19):
Figure JPOXMLDOC01-appb-C000029
 [In the formula,
at least one or all of R 31 , R 32 and R 33 is —O—(R 35 —O) m —R 36 (R 35 is a divalent hydrocarbon group having 1 to 30 carbon atoms, R 36 is an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and m is an integer of 1 to 30. , when there are multiple R 5 , the multiple R 5 may be the same or different),
When one or two of R 31 , R 32 and R 33 are the above —O—(R 35 —O) m —R 36 , the remaining groups are alkyl groups having 1 to 12 carbon atoms, —O —R 37 (R 37 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. ), a hydrogen atom or an aryl group having 6 to 30 carbon atoms,
R 31 , R 32 and R 33 may be the same or different;
R 34 is a divalent hydrocarbon group having 1 to 30 carbon atoms. ]
can also be used.
　上記式（１９）中、Ｒ３４、Ｒ３５で表される、炭素数１～３０の２価の炭化水素基としては、例えば、アルキレン基（例えばメチレン基、ジメチレン基、トリメチレン基）等の脂肪族炭化水素基；芳香族炭化水素基；これらの組み合わせが挙げられる。
　Ｒ３６、Ｒ３７で表される、炭素数１～３０のアルキル基、炭素数２～３０のアルケニル基、炭素数６～３０のアリール基、炭素数７～３０のアラルキル基としては、例えば、メチル基、エチル基等のアルキル基；ビニル基、アリル基等のアルケニル基；フェニル基、トリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基が挙げられる。
　ｍは、１～２０の整数であるのが好ましく、２～１５の整数であるのがより好ましく、３～１０であるのがさらに好ましい。
　Ｒ１、Ｒ２およびＲ３のうちの１つまたは２つが前記－Ｏ－（Ｒ３５－Ｏ）ｍ－Ｒ３６である場合、残りの基としての、炭素数１～１２のアルキル基、炭素数６～３０のアリール基としては、例えば、メチル基、エチル基等のアルキル基；フェニル基、トリル基等のアリール基が挙げられる。 In the above formula (19), the divalent hydrocarbon groups having 1 to 30 carbon atoms represented by R 34 and R 35 include, for example, aliphatic aromatic hydrocarbon groups; and combinations thereof.
Examples of alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms represented by R 36 and R 37 include: alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group and phenethyl group.
m is preferably an integer of 1-20, more preferably an integer of 2-15, even more preferably 3-10.
When one or two of R 1 , R 2 and R 3 are the above -O-(R 35 -O) m -R 36 , the remaining group is an alkyl group having 1 to 12 carbon atoms, carbon Examples of aryl groups of numbers 6 to 30 include alkyl groups such as methyl group and ethyl group; and aryl groups such as phenyl group and tolyl group.
　上記式（１９）の好ましい態様は、Ｒ３１、Ｒ３２およびＲ３３のうち２つは－Ｏ－（Ｃ２Ｈ４－Ｏ）ｎ－Ｃ１３Ｈ２７であり、残りは－Ｏ－Ｃ２Ｈ５であり、ｎの平均数は５であり、Ｒ３４はトリメチレン基である。このような式（１９）で表される化合物としては、エボニック社の商品名「Ｓｉ３６３」が挙げられる。 A preferred embodiment of the above formula (19) is that two of R 31 , R 32 and R 33 are —O—(C 2 H 4 —O) n —C 13 H 27 and the rest are —O—C 2 H 5 , the average number of n is 5, and R 34 is a trimethylene group. Examples of the compound represented by formula (19) include Evonik's product name "Si363".
　他のシラン化合物として、例えば、式（１３）：
Figure JPOXMLDOC01-appb-C000030
 ［式中、
　ｔおよびｖは、それぞれ独立して、０～１０の整数であり、
　ｕは、２～１０の整数であり、
　ｑおよびｒは、それぞれ独立して、１～３の整数であり、
　ｗおよびｚは、それぞれ独立して、０か１の整数であり、
　Ｌ２およびＬ３は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、
　Ｒ２１およびＲ２３は、それぞれ独立して、アルコキシ基または１以上のアルキル基で置換されたアミノ基であり、
　Ｒ２２およびＲ２４は、それぞれ独立して、水素原子またはアルキル基である。］
で表される化合物を使用することができる。 Other silane compounds include, for example, formula (13):
Figure JPOXMLDOC01-appb-C000030
 [In the formula,
t and v are each independently an integer from 0 to 10;
u is an integer from 2 to 10,
q and r are each independently an integer from 1 to 3;
w and z are each independently an integer of 0 or 1;
L 2 and L 3 are each independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;
R 21 and R 23 are each independently an alkoxy group or an amino group substituted with one or more alkyl groups;
R22 and R24 are each independently a hydrogen atom or an alkyl group. ]
A compound represented by can be used.
　上記式（１３）中、ｔおよびｖは、それぞれ独立して、０～１０の整数であり、好ましくは０～５の整数であり、より好ましくは１～３の整数であり、さらに好ましくは２である。
　また、ｕは、２～１０の整数であり、より好ましくは、２～８の整数である。
　また、ｑおよびｒは、それぞれ独立して、１～３の整数であり、好ましくは２～３の整数、より好ましくは３である。
　また、ｗおよびｚは、それぞれ独立して、０か１の整数であり、好ましくは０である。
　また、Ｌ２およびＬ３は、それぞれ独立して、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい、炭素数１～３０の炭化水素基、より好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい、炭素数１～２０の炭化水素基、さらに好ましくは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい、炭素数１～１０の炭化水素基である。
　また、Ｒ２１およびＲ２３は、それぞれ独立して、加水分解性基であり、アルコキシ基、より好ましくは炭素数１～３０のアルコキシ基、さらに好ましくは炭素数１～２０のアルコキシ基、または１以上のアルキル基で置換されたアミノ基、より好ましくは１以上の炭素数１～３０のアルキル基で置換されたアミノ基、より好ましくは１以上の炭素数１～２０のアルキル基で置換されたアミノ基である。具体的には、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基およびイソブトキシ基等が挙げられ、これらの中でも、メトキシ基またはエトキシ基が好ましい。また、１以上のアルキル基で置換されたアミノ基としては、Ｎ－メチルアミノ基、Ｎ，Ｎ－ジメチルアミノ基、Ｎ－エチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基およびＮ－イソプロピルアミノ基等が挙げられ、これらの中でも、Ｎ－メチルアミノ基またはＮ－エチルアミノ基が好ましい。なお、アルコキシ基およびアミノ基は、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基からなる連結基を介してケイ素（Ｓｉ）と結合してもよい。
　また、Ｒ２２およびＲ２４は、それぞれ独立して、水素原子またはアルキル基であり、より好ましくは炭素数１～３０のアルキル基、さらに好ましくは炭素数１～２０のアルキル基であり、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、シクロペンチル基、へキシル基およびシクロへキシル基等が挙げられ、これらの中でも、メチル基およびエチル基が好ましい。 In the above formula (13), t and v are each independently an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 1 to 3, more preferably 2 is.
Also, u is an integer of 2 to 10, more preferably an integer of 2 to 8.
Also, q and r are each independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
Also, w and z are each independently an integer of 0 or 1, preferably 0.
L 2 and L 3 are each independently a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably nitrogen, oxygen and A hydrocarbon group having 1 to 30 carbon atoms which may contain at least one heteroatom selected from the group consisting of sulfur, more preferably at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur A hydrocarbon group having 1 to 20 carbon atoms which may contain an atom, more preferably a C 1 to 20 carbon atom which may contain at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur 10 hydrocarbon groups.
R 21 and R 23 are each independently a hydrolyzable group, an alkoxy group, more preferably an alkoxy group having 1 to 30 carbon atoms, still more preferably an alkoxy group having 1 to 20 carbon atoms, or 1 an amino group substituted with one or more alkyl groups, more preferably an amino group substituted with one or more alkyl groups having 1 to 30 carbon atoms, more preferably one or more alkyl groups having 1 to 20 carbon atoms. It is an amino group. Specifically, the alkoxy group includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, etc. Among these, methoxy or ethoxy is preferred. Further, the amino group substituted with one or more alkyl groups includes N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group and N-isopropylamino group. Among these, an N-methylamino group or an N-ethylamino group is preferred. The alkoxy group and amino group are bonded to silicon (Si) via a linking group consisting of a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. good too.
In addition, R 22 and R 24 are each independently a hydrogen atom or an alkyl group, more preferably an alkyl group having 1 to 30 carbon atoms, still more preferably an alkyl group having 1 to 20 carbon atoms, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl groups, among which methyl and ethyl groups are preferred.
　上記式（１３）で表される化合物のうち、ビス［３－（トリエトキシシリル）プロピル］テトラスルフィドは、市販されているものを使用してもよい。例えば、エボニック社製のＳｉ－６９が挙げられる。また、ビス［３－（トリエトキシシリル）プロピル］ジスルフィドについても、市販されているものを使用してもよい。例えば、エボニック社製のＳｉ－７５が挙げられる。 Of the compounds represented by formula (13) above, commercially available bis[3-(triethoxysilyl)propyl]tetrasulfide may be used. For example, Si-69 manufactured by Evonik may be mentioned. Also, commercially available bis[3-(triethoxysilyl)propyl]disulfide may be used. For example, Si-75 manufactured by Evonik may be mentioned.
　他のシラン化合物として、上記式（１３）で表される化合物以外にも、上記式（１６）で表される化合物、特に以下のような構造を有するシラン化合物を使用することができる。
Figure JPOXMLDOC01-appb-C000031
 As other silane compounds, in addition to the compounds represented by the above formula (13), compounds represented by the above formula (16), particularly silane compounds having the following structures can be used.
Figure JPOXMLDOC01-appb-C000031
　他のシラン化合物として、例えば、下記式（２０）
Figure JPOXMLDOC01-appb-C000032
 ［式中、
　Ｒ４１は、水素原子または最大１８の炭素原子を含む一価の炭化水素基であり、
　Ｒ４２は、最大１２の炭素原子を含む二価の炭化水素基であり、
　Ｘ１は、Ｒ４３Ｏ－およびＲ４３Ｃ（＝Ｏ）Ｏ－からなる群より選択され（式中、Ｒ４３は、水素原子、または最大１８の炭素原子を含む一価の炭化水素基、または最大１８の炭素原子および少なくとも一つの酸素原子を含む一価の炭化水素基である）、
　Ｘ２およびＸ３の各々は、独立してＲ４４およびＸ１で挙げられている要素からなる群より選択される（式中、Ｒ４４は、最大６の炭素原子の一価の炭化水素基である）。］
で表される化合物を使用することができる。 As another silane compound, for example, the following formula (20)
Figure JPOXMLDOC01-appb-C000032
 [In the formula,
R 41 is a hydrogen atom or a monovalent hydrocarbon group containing up to 18 carbon atoms,
R42 is a divalent hydrocarbon group containing up to 12 carbon atoms,
X 1 is selected from the group consisting of R 43 O-- and R 43 C(=O)O--, wherein R 43 is a hydrogen atom or a monovalent hydrocarbon group containing up to 18 carbon atoms; or a monovalent hydrocarbon group containing up to 18 carbon atoms and at least one oxygen atom),
Each of X 2 and X 3 is independently selected from the group consisting of the elements listed for R 44 and X 1 , wherein R 44 is a monovalent hydrocarbon group of up to 6 carbon atoms is). ]
A compound represented by can be used.
　上記式（２０）において、Ｒ４１の代表的な、限定されない例示は、水素、メチル、エチル、プロピル、イソプロピル、ブチル、ヘキシル、２－エチルヘキシル、オクチル、デシル、オクタデシル、シクロヘキシル、フェニル、ベンジルおよびフェネチルを含む。 In formula (20) above, representative, non-limiting examples of R 41 are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, benzyl and phenethyl. including.
　上記式（２０）において、Ｒ４２の代表的な、限定されない例示は、メチレン、エチレン、プロピレン、イソプロピレン、ブチレン、ヘキシレン、オクチレン、デシレン、シクロヘキシレンおよびフェニレンを含む。 In formula (20) above, representative, non-limiting examples of R 42 include methylene, ethylene, propylene, isopropylene, butylene, hexylene, octylene, decylene, cyclohexylene and phenylene.
　上記式（２０）において、Ｒ４３の代表的な、限定されない例示は、水素、メチル、エチル、プロピル、イソプロピル、ブチル、ヘキシル、２－エチルヘキシル、オクチル、デシル、オクタデシル、シクロヘキシル、フェニル、ベンジル、フェネチル、３－オキサブチルおよび４，７－ジオキサオクチルを含む。 In formula (20) above, representative, non-limiting examples of R 43 are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, octyl, decyl, octadecyl, cyclohexyl, phenyl, benzyl, phenethyl , 3-oxabutyl and 4,7-dioxaoctyl.
　上記式（２０）において、Ｒ４４の代表的な、限定されない例示は、水素、メチル、エチル、プロピル、イソプロピル、ブチルおよびフェニルを含む。 In formula (20) above, representative, non-limiting examples of R 44 include hydrogen, methyl, ethyl, propyl, isopropyl, butyl and phenyl.
　上記式（２０）において、Ｘ１の代表的な、限定されない例示は、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、フェノキシ、ベンジルオキシ、ヒドロキシおよびアセトキシを含む。Ｘ２およびＸ３の代表的な例示は、メチル、エチル、プロピル、イソプロピル、ｓｅｃ－ブチル、フェニル、ビニルおよびシクロヘキシルに加えて、上記に挙げられたＸ１の代表的な例示を含む。 In formula (20) above, representative, non-limiting examples of X 1 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, benzyloxy, hydroxy and acetoxy. Representative examples of X 2 and X 3 include methyl, ethyl, propyl, isopropyl, sec-butyl, phenyl, vinyl and cyclohexyl, as well as the representative examples of X 1 given above.
　本発明の更に他の実施態様において、Ｒ４１は、５～９の炭素原子を含むアルキル基であって、第一級炭素原子を介してカルボニル基に結合し、Ｒ４２は、メチレン、エチレンまたはプロピレンであり、Ｘ１は、メトキシ、エトキシまたはプロポキシであり、そして、Ｘ２およびＸ３は、個々に、Ｘ１の代表的な例示およびメチルを含む。 In yet another embodiment of the present invention R 41 is an alkyl group containing 5 to 9 carbon atoms and is attached via a primary carbon atom to the carbonyl group and R 42 is methylene, ethylene or is propylene, X 1 is methoxy, ethoxy or propoxy, and X 2 and X 3 individually include representative examples of X 1 and methyl.
　上記式（２０）で表されるシラン化合物としては、例えば、トリエトキシシリルメチルチオホルメート、２－トリエトキシシリルエチルチオアセテート、３－トリエトキシシリルプロピルチオプロパノエート、３－トリエトキシシリルプロピルチオヘキサノエート、３－オクタノイルチオ－１－プロピルトリエトキシシラン（３－トリエトキシシリルプロピルチオオクタノエート）、３－ジエトキシメチルシリルプロピルチオオクタノエート、３－エトキシジメチルシリルプロピルチオオクタノエート、３－トリエトキシシリルプロピルチオドデカノエート、３－トリエトキシシリルプロピルチオオクタドデカノエート、３－トリメトキシシリルプロピルチオオクタノエート、３－トリアセトキシシリルプロピルチオアセテート、３－ジプロポキシメチルシリルプロピルチオプロパノエート、４－オキサ－ヘキシルオキシジメチルシリルプロピルチオオクタノエート等が挙げられる。これらの中で、３－オクタノイルチオ－１－プロピルトリエトキシシラン（３－トリエトキシシリルプロピルチオオクタノエート）、３－ジエトキシメチルシリルプロピルチオオクタノエート、および３－エトキシジメチルシリルプロピルチオオクタノエートが好ましく、３－オクタノイルチオ－１－プロピルトリエトキシシラン（３－トリエトキシシリルプロピルチオオクタノエート）がより好ましい。 Examples of the silane compound represented by the above formula (20) include triethoxysilylmethylthioformate, 2-triethoxysilylethylthioacetate, 3-triethoxysilylpropylthiopropanoate, 3-triethoxysilylpropylthio hexanoate, 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate), 3-diethoxymethylsilylpropylthiooctanoate, 3-ethoxydimethylsilylpropylthiooctanoate, 3-triethoxysilylpropylthiododecanoate, 3-triethoxysilylpropylthiooctadodecanoate, 3-trimethoxysilylpropylthiooctanoate, 3-triacetoxysilylpropylthioacetate, 3-dipropoxymethylsilylpropyl thiopropanoate, 4-oxa-hexyloxydimethylsilylpropylthiooctanoate and the like. Among these, 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate), 3-diethoxymethylsilylpropylthiooctanoate, and 3-ethoxydimethylsilylpropylthiooctano is preferred, and 3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate) is more preferred.
　上記式（２０）で表される化合物は、市販されているものを使用してもよい。例えば、下記式（２１）：
Figure JPOXMLDOC01-appb-C000033
 で表される化合物（３－オクタノイルチオ－１－プロピルトリエトキシシラン（３－トリエトキシシリルプロピルチオオクタノエート））としては、モメンティブ社製の商品名ＮＸＴシランが挙げられる。 Commercially available compounds may be used as the compound represented by the formula (20). For example, the following formula (21):
Figure JPOXMLDOC01-appb-C000033
 Examples of the compound represented by (3-octanoylthio-1-propyltriethoxysilane (3-triethoxysilylpropylthiooctanoate)) include NXT silane (trade name) manufactured by Momentive.
　他のシラン化合物としては、上記式（２０）で表されるシラン化合物に替えて、あるいは上記式（２０）で表されるシラン化合物と共に、式（２０）で表されるシラン化合物の縮合物を用いることができる。式（２０）で表されるシラン化合物の縮合物は、式（２０）で表されるシラン化合物単独で、もしくは式（２２）：
Figure JPOXMLDOC01-appb-C000034
 ［式中、Ｒ４２、Ｘ１、Ｘ２およびＸ３は上記式（２０）で定義した通りである。］
で表される化合物との共存下において、シリル基を部分的に加水分解した後、他の分子のシリル基と脱エタノールもしくは脱水を伴いながら重縮合させて、単独縮合物もしくは共縮合物として調製することができる。ただし、重縮合を起こすためには、Ｘ１、Ｘ２およびＸ３のうち、少なくとも２つ以上はＲ４３Ｏ－もしくはＲ４３Ｃ（＝Ｏ）Ｏ－でなければならない。Ｒ４３は上記式（２０）で定義した通りである。 As the other silane compound, a condensate of the silane compound represented by formula (20) may be used in place of the silane compound represented by formula (20) or together with the silane compound represented by formula (20). can be used. The condensate of the silane compound represented by formula (20) is the silane compound represented by formula (20) alone, or the formula (22):
Figure JPOXMLDOC01-appb-C000034
 [In the formula, R 42 , X 1 , X 2 and X 3 are as defined in formula (20) above. ]
After partial hydrolysis of the silyl group in the presence of the compound represented by, the silyl group of another molecule is polycondensed with ethanol removal or dehydration to prepare a homocondensate or cocondensate. can do. However, in order to cause polycondensation, at least two of X 1 , X 2 and X 3 must be R 43 O-- or R 43 C(=O)O--. R 43 is as defined in formula (20) above.
　上記の他のシラン化合物の縮合物としては、例えば、下記式（２３）：
Figure JPOXMLDOC01-appb-C000035
 ［式中、ｘ：ｙは、１：９９～９９：１である。］
で表される縮合物である。このような縮合物は、市販されているものを使用してもよい。例えば、モメンティブ社製の商品名ＮＸＴ　Ｚ４５シランが挙げられる。 Condensates of other silane compounds described above include, for example, the following formula (23):
Figure JPOXMLDOC01-appb-C000035
 [In the formula, x:y is 1:99 to 99:1. ]
It is a condensate represented by. Commercially available products may be used as such condensates. For example, NXT Z45 silane available from Momentive.
（充填剤）
　充填剤としては、シリカ、カーボンブラック、硫酸バリウム、炭酸カルシウム、酸化チタン、クレイおよびタルク等が挙げられ、シリカおよびカーボンブラックの少なくとも１種を用いることが好ましく、シリカを用いることがより好ましい。充填剤の含有量は、ゴム成分１００質量部に対して、好ましくは１質量部以上３００質量部未満であり、より好ましくは５質量部以上２００質量部以下であり、さらに好ましくは１０質量部以上１８０質量部以下であり、さらにより好ましくは１５質量部以上１６０質量部以下であり、特に好ましくは２０質量部以上１６０質量部以下であり、特により好ましくは３０質量部以上１３０質量部以下であり、最も好ましくは４０質量部以上１１０質量部以下である。 (filler)
Examples of fillers include silica, carbon black, barium sulfate, calcium carbonate, titanium oxide, clay and talc. At least one of silica and carbon black is preferably used, and silica is more preferably used. The content of the filler is preferably 1 part by mass or more and less than 300 parts by mass, more preferably 5 parts by mass or more and 200 parts by mass or less, and still more preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component. 180 parts by mass or less, more preferably 15 parts by mass or more and 160 parts by mass or less, particularly preferably 20 parts by mass or more and 160 parts by mass or less, and particularly preferably 30 parts by mass or more and 130 parts by mass or less. , and most preferably 40 parts by mass or more and 110 parts by mass or less.
（シリカ）
　シリカとしては、特に限定されないが、例えば、乾式法シリカ、湿式法シリカ、コロイダルシリカ、および沈降シリカ等が挙げられる。これらの中でも、含水ケイ酸を主成分とする湿式法シリカが好ましい。これらのシリカは、それぞれ単独でまたは２種以上を組み合わせて用いることができる。 (silica)
Examples of silica include, but are not limited to, dry process silica, wet process silica, colloidal silica, and precipitated silica. Among these, wet-process silica containing hydrous silicic acid as a main component is preferable. These silicas can be used alone or in combination of two or more.
　シリカの比表面積は、特に制限されないが、窒素吸着比表面積（ＢＥＴ法）で通常１０～４００ｍ２／ｇ、好ましくは２０～３００ｍ２／ｇ、更に好ましくは１２０～１９０ｍ２／ｇの範囲である。シリカの比表面積が上記数値範囲内であれば、機械的特性等を向上させることができる。ここで、窒素吸着比表面積は、ＡＳＴＭ　Ｄ３０３７－８１に準じ、ＢＥＴ法で測定される値である。 The specific surface area of silica is not particularly limited, but the nitrogen adsorption specific surface area (BET method) is usually in the range of 10 to 400 m 2 /g, preferably 20 to 300 m 2 /g, more preferably 120 to 190 m 2 /g. . If the specific surface area of silica is within the above numerical range, mechanical properties and the like can be improved. Here, the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.
（その他の加工助剤）
　本発明のゴム組成物は、その機能を損なわない範囲で、加硫剤、加硫促進剤、加硫促進助剤、老化防止剤、軟化剤、酸化防止剤、シラニゼーション反応促進剤、着色剤、及びシリカ以外の無機材料等のその他の加工助剤を含んでいてもよい。 (Other processing aids)
The rubber composition of the present invention contains a vulcanizing agent, a vulcanization accelerator, an auxiliary vulcanization accelerator, an anti-aging agent, a softening agent, an antioxidant, a silanization reaction accelerator, and a coloring agent as long as the functions of the rubber composition are not impaired. agents, and other processing aids such as inorganic materials other than silica.
　加硫剤としては、粉末硫黄、沈降性硫黄、高分散性硫黄、表面処理硫黄、不溶性硫黄、ジモルフォリンジサルファイド、アルキルフェノールジサルファイド等の硫黄系加硫剤や酸化亜鉛、酸化マグネシウム、リサージ、ｐ－キノンジオキシム、ｐ－ジベンゾイルキノンジオキシム、テトラクロロ－ｐ－ベンゾキノン、ポリ－ｐ－ジニトロベンゼン、メチレンジアニリン、フェノール樹脂、臭素化アルキルフェノール樹脂、塩素化アルキルフェノール樹脂等が挙げられる。加硫剤の含有量は、ゴム成分１００質量部に対して好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Vulcanizing agents include sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, zinc oxide, magnesium oxide, litharge, p -quinonedioxime, p-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene, methylenedianiline, phenol resin, brominated alkylphenol resin, chlorinated alkylphenol resin and the like. The content of the vulcanizing agent is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
　加硫促進剤としては、テトラメチルチウラムジスルフィド（ＴＭＴＤ）、テトラエチルチウラムジスルフィド（ＴＥＴＤ）、テトラメチルチウラムモノスルフィド（ＴＭＴＭ）等のチウラム系、ヘキサメチレンテトラミン等のアルデヒド・アンモニア系、ジフェニルグアニジン（ＤＰＧ）等のグアニジン系、２－メルカプトベンゾチアゾール（ＭＢＴ）、ジベンゾチアジルジサルファイド（ＤＭ）等のチアゾール系、Ｎ－シクロヘキシル－２－ベンゾチアジルスルフェンアマイド（ＣＢＳ）、Ｎ－ｔ－ブチル－２－ベンゾチアジルスルフェンアマイド（ＢＢＳ）等のスルフェンアミド系、ジメチルジチオカルバミン酸亜鉛（ＺｎＰＤＣ）等のジチオカルバミン酸塩系挙げられる。加硫促進剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Vulcanization accelerators include thiuram-based agents such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetramethylthiuram monosulfide (TMTM), aldehyde/ammonia-based agents such as hexamethylenetetramine, and diphenylguanidine (DPG). guanidines such as 2-mercaptobenzothiazole (MBT), thiazoles such as dibenzothiazyldisulfide (DM), N-cyclohexyl-2-benzothiazylsulfenamide (CBS), Nt-butyl-2 -Sulfenamides such as benzothiazylsulfenamide (BBS), and dithiocarbamates such as zinc dimethyldithiocarbamate (ZnPDC). The content of the vulcanization accelerator is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
　加硫促進助剤としては、酢酸、プロピオン酸、酪酸、ステアリン酸、アクリル酸、マレイン酸等の脂肪酸、酢酸亜鉛、プロピオン酸亜鉛、酪酸亜鉛、ステアリン酸亜鉛、アクリル酸亜鉛、マレイン酸亜鉛等の脂肪酸亜鉛、およびそれらの塩である脂肪酸亜鉛塩、ならびに酸化亜鉛等が挙げられる。加硫促進助剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of vulcanization accelerators include fatty acids such as acetic acid, propionic acid, butyric acid, stearic acid, acrylic acid and maleic acid, zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, zinc maleate and the like. Fatty acid zincs, fatty acid zinc salts which are salts thereof, zinc oxide, and the like can be mentioned. The content of the vulcanization accelerator aid is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
　老化防止剤としては、例えば、脂肪族および芳香族のヒンダードアミン系、ヒンダードフェノール系等の化合物が挙げられる。老化防止剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of anti-aging agents include compounds such as aliphatic and aromatic hindered amines and hindered phenols. The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
　酸化防止剤としては、例えば、ブチルヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）等が挙げられる。酸化防止剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of antioxidants include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA). The content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
　軟化剤としては、従来公知のものを用いることができ、特に制限されるものではないが、アロマオイル、パラフィンオイル、ナフテンオイル等の石油系軟化剤や、パーム油、ひまし油、綿実油、大豆油等の植物系軟化剤等が挙げられる。使用の際にはこれらの中から１種単独で又は２種以上を適宜選択使用すればよい。軟化剤を含有する場合には、取り扱い容易性の観点から、上述した軟化剤の中でも、２５℃等の常温で液体であるもの、例えば、アロマオイル、パラフィンオイル、ナフテンオイル等の石油系軟化剤を含有することが好ましく、特にアロマオイルが好ましい。軟化剤の含有量は、ゴム成分１００質量部に対して好ましくは１０～２００質量部であり、より好ましくは２０～１００質量部である。 As the softening agent, conventionally known ones can be used, and it is not particularly limited, but petroleum-based softening agents such as aroma oil, paraffin oil, naphthenic oil, palm oil, castor oil, cottonseed oil, soybean oil, etc. and the like. At the time of use, one of these may be used singly or two or more may be appropriately selected and used. When a softening agent is contained, from the viewpoint of ease of handling, among the above softening agents, those that are liquid at room temperature such as 25 ° C., for example, petroleum softening agents such as aroma oil, paraffin oil, naphthenic oil is preferably contained, and aromatic oils are particularly preferred. The softener content is preferably 10 to 200 parts by mass, more preferably 20 to 100 parts by mass, per 100 parts by mass of the rubber component.
　シラニゼーション反応促進剤としては、シリカとシランカップリング剤（上記のシラン化合物）のシラニゼーション反応を促進するものであればいかなるものであってもよい。シラニゼーション反応促進剤としては、尿素誘導体、チオ尿素等のカルバミド類化合物；グアニジン塩酸塩、チオシアン酸グアニジウム、グアニジン、ジフェニルグアニジン等のグアニジン類化合物等が挙げられる。これらのシラニゼーション反応促進剤は、いずれか１種類を使用してもよいし、２種類以上を併用してもよい。尿素誘導体としては、例えば尿素、メチル尿素、エチル尿素、プロピル尿素、ブチル尿素、ペンチル尿素、ヘキシル尿素、シクロヘキシル尿素、Ｎ，Ｎ’－ジメチル尿素、Ｎ，Ｎ’－ジエチル尿素、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル尿素、Ｎ，Ｎ－ジメチル－Ｎ’，Ｎ’－ジフェニル尿素、ジエチル尿素、ジプロピル尿素、ジブチル尿素、ジペンチル尿素、ジヘキシル尿素およびそれらの塩等があげられる。これらの中でも、尿素が優れる。 Any silanization reaction accelerator may be used as long as it promotes the silanization reaction between silica and the silane coupling agent (the above silane compound). Examples of the silanization reaction accelerator include carbamide compounds such as urea derivatives and thiourea; guanidine compounds such as guanidine hydrochloride, guanidinium thiocyanate, guanidine and diphenylguanidine. Any one type of these silanization reaction accelerators may be used, or two or more types may be used in combination. Urea derivatives include, for example, urea, methylurea, ethylurea, propylurea, butylurea, pentylurea, hexylurea, cyclohexylurea, N,N'-dimethylurea, N,N'-diethylurea, N,N,N ',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, diethylurea, dipropylurea, dibutylurea, dipentylurea, dihexylurea and salts thereof. Among these, urea is excellent.
　着色剤としては、二酸化チタン、酸化亜鉛、群青、ベンガラ、リトポン、鉛、カドミウム、鉄、コバルト、アルミニウム、塩酸塩、硫酸塩等の無機顔料、アゾ顔料、銅フタロシアニン顔料等が挙げられる。着色剤の含有量は、ゴム成分１００質量部に対して、好ましくは０.１～１０質量部であり、より好ましくは１～５質量部である。 Examples of coloring agents include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochlorides and sulfates, azo pigments, and copper phthalocyanine pigments. The content of the coloring agent is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the rubber component.
　その他の加工助剤は、公知のゴム用混練機、例えば、ロール、バンバリーミキサー、ニーダー等でゴム成分と混練し、任意の条件で加硫してゴム組成物として使用することができる。その他の加工助剤の添加量は、本発明の目的に反しない限り、従来の一般的な含有量とすることができる。 Other processing aids can be kneaded with the rubber component using a known rubber kneader, such as a roll, Banbury mixer, kneader, etc., vulcanized under arbitrary conditions, and used as a rubber composition. The amount of other processing aids to be added can be a conventional general content as long as it does not contradict the object of the present invention.
［ゴム組成物の製造方法］
　本発明のゴム組成物の製造方法は、少なくとも、上記のゴム成分と、上記のゴム用添加剤と、上記の不飽和二重結合含有シラン化合物とを混練する工程を含んでなる。ゴム組成物の製造方法は、好ましくは、さらに上記の加硫剤を混練する工程を含んでなるものであってもよい。より好ましくは、さらに該加硫剤と上記の加硫促進剤を混練する工程を含んでなるものであってもよい。 [Method for producing rubber composition]
The method for producing the rubber composition of the present invention comprises at least the step of kneading the above rubber component, the above rubber additive, and the above unsaturated double bond-containing silane compound. The method for producing the rubber composition may preferably further comprise the step of kneading the vulcanizing agent. More preferably, it may further comprise a step of kneading the vulcanizing agent and the vulcanization accelerator.
　また、ゴム組成物の製造方法は、ゴム組成物の機能を損なわない範囲で、上記のその他の加工助剤を適宜配合して、混練することができる。 In addition, in the method for producing the rubber composition, the other processing aids described above can be appropriately blended and kneaded within a range that does not impair the functions of the rubber composition.
　ゴム組成物の製造には、従来公知の混練装置を用いることができ、混練温度や時間、配合順序等を適宜選択することができる。 A conventionally known kneading device can be used for the production of the rubber composition, and the kneading temperature, time, mixing order, etc. can be appropriately selected.
［タイヤ製品］
　本発明のゴム組成物を用いて、従来公知の方法および当業者に広く知られた技術常識によりタイヤ製品を製造することができる。タイヤ製品としては、タイヤやその他の関連部材が挙げられる。例えば、ゴム組成物を押し出し、次いで、タイヤ成型機を用いて成形した後、加硫機を用いて加熱、加圧することにより架橋が形成され、タイヤを製造することができる。本発明のゴム組成物を用いて製造したタイヤは抗張積に優れる。 [Tire products]
Using the rubber composition of the present invention, tire products can be produced by conventionally known methods and common technical knowledge widely known to those skilled in the art. Tire products include tires and other related components. For example, the rubber composition is extruded, then molded using a tire molding machine, and then heated and pressurized using a vulcanizer to form crosslinks, whereby a tire can be manufactured. A tire manufactured using the rubber composition of the present invention is excellent in tensile product.
　タイヤの用途としては、特に制限はなく、例えば、乗用車用タイヤ、重荷重用タイヤ、モーターサイクル（自動二輪車）用タイヤ、スタッドレスタイヤ等が挙げられる。これらの中でも、乗用車用タイヤに好適に使用できる。 There are no particular restrictions on the use of tires, and examples include tires for passenger cars, tires for heavy loads, tires for motorcycles (motorcycles), and studless tires. Among these, it can be suitably used for tires for passenger cars.
　タイヤの形状、構造、大きさ及び材質としては、特に制限はなく、目的に応じて適宜選択することができる。また、本発明のゴム組成物はタイヤの各部に適用することができる。タイヤの適用部としては、特に制限はなく、タイヤのトレッド、カーカス、サイドウォール、インナーライナー、アンダートレッド、ベルト部など、目的に応じて適宜選択することができる。 The shape, structure, size and material of the tire are not particularly limited and can be selected as appropriate according to the purpose. Moreover, the rubber composition of the present invention can be applied to each part of a tire. The applicable portion of the tire is not particularly limited, and may be appropriately selected from the tread, carcass, sidewall, inner liner, undertread, belt portion, etc. of the tire according to the purpose.
［ゴム製品］
　本発明のゴム組成物を用いて、タイヤ製品以外のゴム製品を製造することもできる。タイヤ以外のゴム製品としては、自動車用ゴム部品（外装、内装、ウェザーストリップ類、ブーツ類、マウント類、シール類、シーラー類、ガスケット類）、ホース、ベルト、シート、防振ゴム、ローラー、ライニング、ゴム引布、シール材、手袋、防舷材、医療用ゴム（シリンジガスケット、チューブ、カテーテル）、ガスケット（家電用、建築用）、アスファルト改質剤、グリップ類、玩具、靴、サンダル、キーパッド、ギア、ペットボトルキャプライナー等が挙げられる。 [Rubber product]
The rubber composition of the present invention can also be used to produce rubber products other than tire products. Rubber products other than tires include automobile rubber parts (exterior, interior, weather strips, boots, mounts, seals, sealers, gaskets), hoses, belts, sheets, anti-vibration rubber, rollers, linings. , rubberized cloth, sealing materials, gloves, fenders, medical rubber (syringe gaskets, tubes, catheters), gaskets (for home appliances, construction), asphalt modifiers, grips, toys, shoes, sandals, keys Pads, gears, PET bottle cap liners and the like are included.
　以下に実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
［含硫黄炭化水素重合体の調製例］
（含硫黄炭化水素重合体Ａの合成）
　３００ｍｌ二口ナスフラスコに、石油樹脂Ａ（Ｍｗ：８１０、Ｍｗ／Ｍｎ：１．７４、軟化点８５℃、ヨウ素価（ＪＩＳ　Ｋ００７０準拠）：１８５．０、ＤＣＰＤ含有不飽和炭化水素の重合体）９０ｇを入れて、１３０℃に加熱し、溶融状態とした。次に、フラスコ内に硫黄８．７ｇを入れて、３時間撹拌した。反応完了後、反応物をアルミ皿に流し出し自然放冷した。 [Preparation example of sulfur-containing hydrocarbon polymer]
(Synthesis of sulfur-containing hydrocarbon polymer A)
Petroleum resin A (Mw: 810, Mw / Mn: 1.74, softening point 85 ° C., iodine value (JIS K0070 compliant): 185.0, DCPD-containing unsaturated hydrocarbon polymer) in a 300 ml two-necked eggplant flask 90 g was added and heated to 130° C. to form a molten state. Next, 8.7 g of sulfur was put into the flask and stirred for 3 hours. After completion of the reaction, the reactant was poured into an aluminum dish and allowed to cool naturally.
　その後、得られた反応物の１Ｈ－ＮＭＲ解析を行い、５．８ｐｐｍ付近のノルボルネン骨格上の二重結合の消費を確認した。また、反応物をＧＰＣ解析した結果、Ｍｗ：１，２２０、Ｍｗ／Ｍｎ：２．１０であった。元素分析の結果、硫黄量は８．９質量％であり、ノルボルネン骨格上の二重結合量当たり３．０１個の硫黄分子の導入を確認した。 After that, 1 H-NMR analysis of the resulting reaction product was performed to confirm the consumption of the double bond on the norbornene skeleton at around 5.8 ppm. As a result of GPC analysis of the reaction product, Mw: 1,220 and Mw/Mn: 2.10. As a result of elemental analysis, the amount of sulfur was 8.9% by mass, confirming the introduction of 3.01 sulfur molecules per amount of double bonds on the norbornene skeleton.
（含硫黄炭化水素重合体Ｂの合成）
　上記の含硫黄炭化水素重合体Ａの合成において、加熱温度を１２０℃に変更し、撹拌時間を１時間に変更した以外は同様にして、反応を行った。 (Synthesis of sulfur-containing hydrocarbon polymer B)
A reaction was carried out in the same manner as in the above synthesis of sulfur-containing hydrocarbon polymer A, except that the heating temperature was changed to 120° C. and the stirring time was changed to 1 hour.
　その後、得られた反応物の１Ｈ－ＮＭＲ解析を行い、５．８ｐｐｍ付近のノルボルネン骨格上の二重結合の消費を確認した。また、反応物のＧＰＣ解析の結果、Ｍｗ：８１６、Ｍｗ／Ｍｎ：１．７３であった。元素分析から硫黄量は９．０質量％であり、ノルボルネン骨格上の二重結合量当たり３．０４個の硫黄分子の導入を確認した。 After that, 1 H-NMR analysis of the resulting reaction product was performed to confirm the consumption of the double bond on the norbornene skeleton at around 5.8 ppm. As a result of GPC analysis of the reaction product, Mw: 816 and Mw/Mn: 1.73. Elemental analysis revealed that the amount of sulfur was 9.0% by mass, and it was confirmed that 3.04 sulfur molecules were introduced per amount of double bonds on the norbornene skeleton.
（含硫黄炭化水素重合体Ｃの合成）
　上記の含硫黄炭化水素重合体Ａの合成において、加熱温度を１２０℃に変更し、撹拌時間を６時間に変更した以外は同様にして、反応を行った。 (Synthesis of sulfur-containing hydrocarbon polymer C)
A reaction was carried out in the same manner as in the above synthesis of sulfur-containing hydrocarbon polymer A, except that the heating temperature was changed to 120° C. and the stirring time was changed to 6 hours.
　その後、得られた反応物の１Ｈ－ＮＭＲ解析を行い、５．８ｐｐｍ付近のノルボルネン骨格上の二重結合の消費を確認した。また、反応物のＧＰＣ解析の結果、Ｍｗ：１，０１１、Ｍｗ／Ｍｎ：１．９０であった。元素分析から硫黄量は８．９質量％であり、ノルボルネン骨格上の二重結合量当たり３．０１個の硫黄分子の導入を確認した。 After that, 1 H-NMR analysis of the resulting reaction product was performed to confirm the consumption of the double bond on the norbornene skeleton at around 5.8 ppm. As a result of GPC analysis of the reactant, Mw: 1,011 and Mw/Mn: 1.90. Elemental analysis revealed a sulfur content of 8.9% by mass, confirming the introduction of 3.01 sulfur molecules per double bond content on the norbornene skeleton.
（含硫黄炭化水素重合体Ｄの合成）
　上記の含硫黄炭化水素重合体Ａの合成において、撹拌時間を５時間に変更した以外は同様にして、反応を行った。 (Synthesis of sulfur-containing hydrocarbon polymer D)
A reaction was carried out in the same manner as in the above synthesis of the sulfur-containing hydrocarbon polymer A, except that the stirring time was changed to 5 hours.
　その後、得られた反応物の１Ｈ－ＮＭＲ解析を行い、５．８ｐｐｍ付近のノルボルネン骨格上の二重結合の消費を確認した。また、反応物のＧＰＣ解析の結果、Ｍｗ：１，４５８、Ｍｗ／Ｍｎ：２．３２であった。元素分析から硫黄量は８．９質量％であり、ノルボルネン骨格上の二重結合量当たり３．０１個の硫黄分子の導入を確認した。 After that, 1 H-NMR analysis of the resulting reaction product was performed to confirm the consumption of the double bond on the norbornene skeleton at around 5.8 ppm. As a result of GPC analysis of the reaction product, Mw: 1,458 and Mw/Mn: 2.32. Elemental analysis revealed a sulfur content of 8.9% by mass, confirming the introduction of 3.01 sulfur molecules per double bond content on the norbornene skeleton.
（炭化水素重合体Ｅの合成）
　ナフサクラッカーから得られるＣ５留分およびＣ９留分を原料モノマーとして、酸触媒による重合工程、残触媒の中和工程、軽質分の除去工程を経て、芳香族分１２％、軟化点９０℃、Ｍｗ１３００の石油樹脂を得た。 (Synthesis of hydrocarbon polymer E)
Using the C5 fraction and C9 fraction obtained from a naphtha cracker as raw material monomers, through the polymerization process with an acid catalyst, the neutralization process of the residual catalyst, and the process of removing light components, the aromatic content is 12%, the softening point is 90 ° C., and the Mw is 1300. of petroleum resin was obtained.
［不飽和二重結合含有シラン化合物の調製例］
（不飽和二重結合含有シラン化合物Ａ（ＶＮＢ－ＳＳｉ）の合成）
　１００ｍＬの三口フラスコに玉栓、真空／ドライ窒素ラインを繋げた三方コック、セプタムを取り付けた後、スターラーバーを入れ、ドライヤーで加熱しながら、系内の脱気－窒素置換を１０回繰り返し、常圧窒素雰囲気下とした。そのフラスコ内に、シリンジを用いて２－ビニルノルボルネン（ＶＮＢ）２７．５ｇ（０．２２５ｍоｌ）を注入し、窒素雰囲気下でアゾビスイソブチロニトリル０．０７４ｇ（０．４５ｍｍоｌ）を添加した後、窒素バブリングを２０分行った。続いて、ガスタイトシリンジで１０．７ｇ（０．０４５ｍｏｌ）のメルカプトプロピルトリエトキシシランを吸引して定量ポンプに取り付け、３時間で全量が滴下されるよう設定した。最後に、シリコングリースで接続部を密閉し、ガスタイトシリンジの針先をセプタムを通じてフラスコに導入し、フラスコをオイルバスに浸漬し、バス温度を徐々に上昇させて、内温が５０℃に到達した時点で定量ポンプを作動させ、メルカプトプロピルトリエトキシシランを滴下して反応させた。全量の滴下が完了してから２時間後にフラスコをオイルバスから取り出し、室温まで放置した。次に余剰のＶＮＢを減圧留去した後、目的の無色透明の液状化合物（ＶＮＢ－ＳＳｉ）３７．４ｇを得た。 [Preparation Example of Unsaturated Double Bond-Containing Silane Compound]
(Synthesis of unsaturated double bond-containing silane compound A (VNB-SSi))
After attaching a ball stopper, a three-way cock connected to a vacuum/dry nitrogen line, and a septum to a 100 mL three-necked flask, put a stirrer bar and repeat degassing and nitrogen replacement in the system 10 times while heating with a dryer. A pressurized nitrogen atmosphere was used. 27.5 g (0.225 mol) of 2-vinylnorbornene (VNB) was injected into the flask using a syringe, and 0.074 g (0.45 mmol) of azobisisobutyronitrile was added under a nitrogen atmosphere. , nitrogen bubbling was performed for 20 minutes. Subsequently, 10.7 g (0.045 mol) of mercaptopropyltriethoxysilane was sucked with a gas-tight syringe, attached to a metering pump, and set so that the entire amount would drop in 3 hours. Finally, the connection was sealed with silicon grease, the needle tip of the gas-tight syringe was introduced into the flask through the septum, the flask was immersed in an oil bath, and the bath temperature was gradually increased until the internal temperature reached 50°C. At that time, the metering pump was operated and mercaptopropyltriethoxysilane was added dropwise for reaction. Two hours after the dropping of the entire amount was completed, the flask was taken out from the oil bath and allowed to stand to room temperature. Excess VNB was then distilled off under reduced pressure to obtain 37.4 g of the target colorless and transparent liquid compound (VNB-SSi).
　得られたシラン化合物（ＶＮＢ－ＳＳｉ）は、１Ｈ－ＮＭＲの測定および１３Ｃ－ＮＭＲの測定によりシランの導入率は１００％であり、ノルボルネン環の二重結合が消失していることを確認した。得られたシラン化合物（ＶＮＢ－ＳＳｉ）は、下記反応式で示したシラン化合物（１Ａ、１Ｂ）の混合物である。
Figure JPOXMLDOC01-appb-C000036
 The obtained silane compound (VNB-SSi) was confirmed to have a silane introduction rate of 100% by 1 H-NMR measurement and 13 C-NMR measurement, and the double bond of the norbornene ring had disappeared. bottom. The obtained silane compound (VNB-SSi) is a mixture of silane compounds (1A, 1B) represented by the following reaction formula.
Figure JPOXMLDOC01-appb-C000036
（不飽和二重結合含有シラン化合物Ｂ（ＶＮＢ－２ＳＳｉ）の合成）
　５０ｍＬの三口フラスコに玉栓、真空／ドライ窒素ラインを繋げた三方コック、セプタムを取り付けた後、スターラーバーを入れ、ドライヤーで加熱しながら、系内の脱気－窒素置換を１０回繰り返し、常圧窒素雰囲気下とした。そのフラスコ内に、シリンジを用いて２－ビニルノルボルネン（ＶＮＢ）５．２ｇ（０．０４３ｍоｌ）、メルカプトプロピルトリエトキシシラン２０．３ｇ（０．０８５ｍｏｌ）を注入し、窒素雰囲気下でアゾビスイソブチロニトリル０．１４ｇ（０．８５ｍｍоｌ）を添加した後、窒素バブリングを２０分行った。シリコングリースで接続部を密閉した後、フラスコをオイルバスに浸漬し、バス温度を５０℃まで徐々に上昇させ、１３時間反応させた後、さらに７０℃に昇温して５時間反応させた。次にメルカプトプロピルトリエトキシシランについて、計２回の追加添加（１回目：０．１０ｇ（０．８５　ｍｍｏｌ）、２回目：０．２６ｇ（２．１３　ｍｍｏｌ））を行い、それぞれ７０℃で５時間を反応させた後、室温まで放冷し、目的の無色～淡黄色澄明液体２５．０ｇを得た。 (Synthesis of unsaturated double bond-containing silane compound B (VNB-2SSi))
After attaching a ball stopper, a three-way cock connected to a vacuum/dry nitrogen line, and a septum to a 50 mL three-necked flask, put a stirrer bar and repeat degassing and nitrogen replacement in the system 10 times while heating with a dryer. A pressurized nitrogen atmosphere was used. Using a syringe, 5.2 g (0.043 mol) of 2-vinylnorbornene (VNB) and 20.3 g (0.085 mol) of mercaptopropyltriethoxysilane were injected into the flask, and azobisisobutyl was added under a nitrogen atmosphere. After adding 0.14 g (0.85 mmol) of lonitrile, nitrogen bubbling was performed for 20 minutes. After the connection was sealed with silicone grease, the flask was immersed in an oil bath, the bath temperature was gradually increased to 50°C, and the mixture was reacted for 13 hours, then further heated to 70°C and reacted for 5 hours. Next, mercaptopropyltriethoxysilane was added twice (first time: 0.10 g (0.85 mmol), second time: 0.26 g (2.13 mmol)), each at 70°C for 5 hours. After reacting for a period of time, the mixture was allowed to cool to room temperature to obtain 25.0 g of the objective colorless to pale yellow clear liquid.
　得られた化合物は、１Ｈ－ＮＭＲの測定によりシランの導入率は１００％であり、ノルボルネン環およびビニル基の両方の二重結合が消失していることを確認した。得られたシラン化合物（ＶＮＢ－２ＳＳｉ）は、下記反応式で示したシラン化合物（２Ａ、２Ｂ）の混合物である。
Figure JPOXMLDOC01-appb-C000037
 It was confirmed by 1 H-NMR measurement that the obtained compound had a silane introduction rate of 100% and that the double bonds of both the norbornene ring and the vinyl group had disappeared. The obtained silane compound (VNB-2SSi) is a mixture of silane compounds (2A, 2B) represented by the following reaction formula.
Figure JPOXMLDOC01-appb-C000037
（不飽和二重結合含有シラン化合物Ｃ（ＥＮＢ－ＳＳｉ）の合成）
　１００ｍＬの２口フラスコに玉栓、および真空ラインを繋いだ３方コックを設置し、スターラーバーを入れ、真空ラインを用いて、ドライヤーで加熱しながら系内の脱気－窒素置換を１０回繰り返し、常圧窒素雰囲気下とした。そのフラスコ内に、５－エチリデン－２－ノルボルネン（ＥＮＢ）を６．７３ｇ（０．０５５１モル）を入れた後、４．３３ｇのトルエン溶媒を、シリンジを用いて注入した。その後、スターラーを用いて撹拌し溶解させた。次に、シリンジを用いて、１１．９ｇ（０．０４９８モル）の３－メルカプトプロピルトリエトキシシランを注入した。最後にアゾビスイソブチロニトリルに０．１２３ｇ（０．７４６ミリモル）を窒素を流しながら添加した後、窒素バブリングを２０分間行った。フラスコをオイルバスに浸漬し、バス温度を７０℃まで徐々に上昇させ反応させた。７０℃になってから６時間後、フラスコをオイルバスから取り出し、室温（２５℃）になるまで放置した。次に、トルエンおよび未反応の５－エチリデン－２－ノルボルネン（ＥＮＢ）を減圧留去した後、１７．１ｇ（収率９５％）の目的のシラン化合物（シラン変性５－エチリデン－２－ノルボルネン：ＥＮＢ－ＳＳｉ）を得た。ＥＮＢ－ＳＳｉは、１Ｈ－ＮＭＲおよび１３Ｃ－ＮＭＲの測定により、シランの導入率は１００％であり、ノルボルネン環の二重結合が消失していることを確認した。得られたシラン化合物（ＥＮＢ－ＳＳｉ）は、下記反応式で示した４種のシラン化合物の混合物である。
Figure JPOXMLDOC01-appb-C000038
 (Synthesis of unsaturated double bond-containing silane compound C (ENB-SSi))
A ball stopper and a 3-way cock connected to a vacuum line are placed in a 100 mL two-necked flask, a stirrer bar is placed, and the vacuum line is used to heat the system with a dryer while degassing and nitrogen replacement are repeated 10 times. , under normal pressure nitrogen atmosphere. After 6.73 g (0.0551 mol) of 5-ethylidene-2-norbornene (ENB) was placed in the flask, 4.33 g of toluene solvent was injected using a syringe. After that, it was dissolved by stirring with a stirrer. A syringe was then used to inject 11.9 g (0.0498 mol) of 3-mercaptopropyltriethoxysilane. Finally, 0.123 g (0.746 mmol) was added to azobisisobutyronitrile while flowing nitrogen, and nitrogen bubbling was performed for 20 minutes. The flask was immersed in an oil bath, and the temperature of the bath was gradually raised to 70° C. for reaction. Six hours after reaching 70°C, the flask was removed from the oil bath and allowed to stand until it reached room temperature (25°C). Next, after toluene and unreacted 5-ethylidene-2-norbornene (ENB) were distilled off under reduced pressure, 17.1 g (yield 95%) of the desired silane compound (silane-modified 5-ethylidene-2-norbornene: ENB-SSi) was obtained. ENB-SSi confirmed by 1 H-NMR and 13 C-NMR measurements that the silane introduction rate was 100% and that the double bond of the norbornene ring had disappeared. The resulting silane compound (ENB-SSi) is a mixture of four silane compounds represented by the following reaction formulas.
Figure JPOXMLDOC01-appb-C000038
［実施例１］
　以下の各成分を、２５０ｍＬニーダー（東洋精機社製ラボプラストミル）を用いて混練し、ゴム組成物を得た。実施した混練操作の詳細は以下の（ｉ）～（ｉｉｉ）の通りである。
（ｉ）ミキサー混練：１３０℃に加熱した密閉式加圧ニーダーへゴム成分を投入し、３０ｒｐｍで１分間素練りを行った後、シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物の１／２量を測り取ったものと、シランカップリング剤の全量および含硫黄炭化水素重合体Ａの全量を投入し、５０ｒｐｍに回転数を上げて１分３０秒間混練を行った。さらに残りの１／２量の前記シリカ、酸化亜鉛、ステアリン酸、および老化防止剤の混合物を加えて、５分３０秒間混練を行い、放出した。
（ｉｉ）リミル：シリカの分散をよくするために、１２０℃に加熱した密閉式加圧ニーダーへ放出して十分温度が下がった混練物を、さらに５０ｒｐｍで２分間混練を行った後、放出した。
（ｉｉｉ）ロール混練（加硫系添加）：放出して十分温度が下がった後、２本ロールで上述の混練物に硫黄、加硫促進剤等を加え、混練し、ゴム組成物を得た。
・ゴム（ＳＢＲ、旭化成社製、商品名：Ｅ５８１）　　　９６．２５質量部
　（ゴム成分７０質量部、伸展油２６．２５質量部）
・ゴム（ＢＲ、日本ゼオン社製、商品名：１２２０　）　　　　３０質量部
・シリカＡＱ（東ソー社製、商品名：ニップシールＡＱ）　　　７０質量部
・酸化亜鉛３号（東邦亜鉛社製、商品名：銀嶺Ｒ）　　　　　　　３質量部
・ステアリン酸（新日本理化製、商品名：ステアリン酸３００）　１質量部
・老化防止剤（大内新興化学社製、商品名：ノクラック６Ｃ）　　１質量部
・シランカップリング剤（ビニルトリエトキシシラン）　　　５．６質量部
・含硫黄炭化水素重合体Ａ　　　　　　　　　　　　　　　　　１５質量部
・硫黄（細井化学社製、５％油処理硫黄）　　　　　　　　　　　２質量部
・加硫促進剤（大内新興化学社製、商品名：ノクセラーＣＺ）２．３質量部
・加硫促進剤（大内新興化学社製、商品名：ノクセラーＤ）　　　１質量部 [Example 1]
Each of the following components was kneaded using a 250 mL kneader (Laboplastomill manufactured by Toyo Seiki Co., Ltd.) to obtain a rubber composition. Details of the kneading operation performed are as follows (i) to (iii).
(i) Mixer kneading: Put the rubber component into a closed pressure kneader heated to 130°C, masticate at 30 rpm for 1 minute, and then mix 1 of silica, zinc oxide, stearic acid, and anti-aging agent. /2, the total amount of the silane coupling agent, and the total amount of the sulfur-containing hydrocarbon polymer A were added, and kneaded at 50 rpm for 1 minute and 30 seconds. The remaining 1/2 amount of the mixture of silica, zinc oxide, stearic acid, and anti-aging agent was added, kneaded for 5 minutes and 30 seconds, and discharged.
(ii) Remilling: In order to improve the dispersion of silica, the kneaded material was discharged to a closed pressure kneader heated to 120° C. and the temperature was sufficiently lowered. After further kneading at 50 rpm for 2 minutes, the mixture was discharged. .
(iii) Roll kneading (addition of vulcanization system): After discharging and the temperature was sufficiently lowered, sulfur, a vulcanization accelerator, etc. were added to the above kneaded product with two rolls and kneaded to obtain a rubber composition. .
・ Rubber (SBR, manufactured by Asahi Kasei Corporation, trade name: E581) 96.25 parts by mass (rubber component 70 parts by mass, extension oil 26.25 parts by mass)
・Rubber (BR, manufactured by Zeon Corporation, trade name: 1220) 30 parts by mass ・Silica AQ (manufactured by Tosoh Corporation, trade name: Nip Seal AQ) 70 parts by mass ・Zinc oxide No. 3 (manufactured by Toho Zinc Co., Ltd., trade name: Ginrei R) 3 parts by mass ・Stearic acid (manufactured by Shin Nippon Rika, trade name: stearic acid 300) 1 part by mass ・Antiaging agent (manufactured by Ouchi Shinko Kagaku Co., Ltd., trade name: Nocrac 6C) 1 part by mass ・Silane coupling agent (Vinyltriethoxysilane) 5.6 parts by mass Sulfur-containing hydrocarbon polymer A 15 parts by mass Sulfur (manufactured by Hosoi Chemical Co., Ltd., 5% oil treated sulfur) 2 parts by mass Vulcanization accelerator (Ouchi Shinko Kagaku Co., Ltd.) Product name: Noxcellar CZ) 2.3 parts by mass Vulcanization accelerator (manufactured by Ouchi Shinko Kagaku Co., Ltd., product name: Noxcellar D) 1 part by mass
［実施例２］
　シランカップリング剤としてビニルトリエトキシシランの代わりに３－アクリロキシプロピルトリエトキシシラン５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。 [Example 2]
A rubber composition was obtained in the same manner as in Example 1, except that 5.6 parts by mass of 3-acryloxypropyltriethoxysilane was added as the silane coupling agent instead of vinyltriethoxysilane.
［比較例１］
　シランカップリング剤としてビニルトリエトキシシランの代わりにビス［３－（トリエトキシシリル）プロピル］テトラスルフィド（不飽和二重結合無し、エボニック社製、商品名：Ｓｉ６９）５．６質量部を添加し、含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｅ１５質量部を添加し、硫黄の添加量を１．５質量部に変更した以外は実施例１と同様にして、ゴム組成物を得た。 [Comparative Example 1]
As a silane coupling agent, 5.6 parts by mass of bis[3-(triethoxysilyl)propyl]tetrasulfide (no unsaturated double bond, manufactured by Evonik, trade name: Si69) was added instead of vinyltriethoxysilane. A rubber composition was obtained in the same manner as in Example 1 except that 15 parts by mass of hydrocarbon polymer E was added instead of sulfur-containing hydrocarbon polymer A and the amount of sulfur added was changed to 1.5 parts by mass. rice field.
［比較例２］
　シランカップリング剤としてビニルトリエトキシシランの代わりにビス［３－（トリエトキシシリル）プロピル］テトラスルフィド（Ｓｉ６９）５．６質量部を添加し、硫黄の添加量を１質量部に変更した以外は実施例１と同様にして、ゴム組成物を得た。 [Comparative Example 2]
Except for adding 5.6 parts by mass of bis[3-(triethoxysilyl)propyl]tetrasulfide (Si69) instead of vinyltriethoxysilane as a silane coupling agent and changing the amount of sulfur added to 1 part by mass. A rubber composition was obtained in the same manner as in Example 1.
［実施例３］
　シランカップリング剤としてビニルトリエトキシシランの代わりに不飽和二重結合含有シラン化合物Ａ（ＶＮＢ－ＳＳｉ）５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。 [Example 3]
A rubber composition was obtained in the same manner as in Example 1, except that 5.6 parts by mass of an unsaturated double bond-containing silane compound A (VNB-SSi) was added as a silane coupling agent instead of vinyltriethoxysilane. .
［実施例４］
　シランカップリング剤としてビニルトリエトキシシランの代わりに不飽和二重結合含有シラン化合物Ｃ（ＥＮＢ－ＳＳｉ）５．６質量部を添加した以外は実施例１と同様にして、ゴム組成物を得た。 [Example 4]
A rubber composition was obtained in the same manner as in Example 1, except that 5.6 parts by mass of the unsaturated double bond-containing silane compound C (ENB-SSi) was added as the silane coupling agent instead of vinyltriethoxysilane. .
［比較例３］
　含硫黄炭化水素重合体Ａの代わりに炭化水素重合体Ｅ１５質量部を添加し、硫黄の添加量を３質量部に変更した以外は実施例３と同様にして、ゴム組成物を得た。 [Comparative Example 3]
A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of hydrocarbon polymer E was added instead of sulfur-containing hydrocarbon polymer A, and the amount of sulfur added was changed to 3 parts by mass.
［実施例５］
　含硫黄炭化水素重合体Ａの添加量を１．５質量部に変更し、炭化水素重合体Ｅ１３．５質量部を添加し、硫黄の添加量を３質量部に変更した以外は実施例３と同様にして、ゴム組成物を得た。 [Example 5]
Example 3 except that the amount of sulfur-containing hydrocarbon polymer A added was changed to 1.5 parts by mass, the amount of hydrocarbon polymer E added was 13.5 parts by mass, and the amount of sulfur added was changed to 3 parts by mass. A rubber composition was obtained in the same manner.
［実施例６］
　含硫黄炭化水素重合体Ａの添加量を７．５質量部に変更し、炭化水素重合体Ｅ７．５質量部を添加し、硫黄の添加量を２．５質量部に変更した以外は実施例３と同様にして、ゴム組成物を得た。 [Example 6]
Examples except that the amount of sulfur-containing hydrocarbon polymer A added was changed to 7.5 parts by mass, the amount of hydrocarbon polymer E added was changed to 7.5 parts by mass, and the amount of sulfur added was changed to 2.5 parts by mass A rubber composition was obtained in the same manner as in 3.
［実施例７］
　シランカップリング剤として不飽和二重結合含有シラン化合物Ａ（ＶＮＢ－ＳＳｉ）の内、０．８質量部分を不飽和二重結合含有シラン化合物Ｂ（ＶＮＢ－２ＳＳｉ）で置き換えた以外は実施例３と同様にして、ゴム組成物を得た。 [Example 7]
Example 3 except that 0.8 parts by mass of the unsaturated double bond-containing silane compound A (VNB-SSi) as the silane coupling agent was replaced with the unsaturated double bond-containing silane compound B (VNB-2SSi) A rubber composition was obtained in the same manner as.
［物性評価］
　実施例１～７および比較例１～３で得られたゴム組成物を用いて、下記の測定を行った。 [Evaluation of the physical properties]
The following measurements were performed using the rubber compositions obtained in Examples 1-7 and Comparative Examples 1-3.
（引張強度）
　各ゴム組成物４２ｇを金型（１５０ｍｍ×１５０ｍｍ×１ｍｍ）に入れて、１６０℃、２０ＭＰａの条件で、４０分間加熱加圧して、１ｍｍ厚のゴムシート（厚さ１ｍｍ、縦１５０ｍｍ、横１５０ｍｍ）を得た。各ゴムシートから３号ダンベル状の試験片を打ち抜き、引張速度５００ｍｍ／分での引張試験をＪＩＳ　Ｋ６２５１（２０１０年発行）に準拠して行い、１００％モジュラス［ＭＰａ］を室温（２５℃）にて測定した。なお、各実施例および各比較例では、各ゴムシートの架橋密度の指標である１００％モジュラスの値を概ね近い値になるように調節した上で他の物性を確認した。 (tensile strength)
42 g of each rubber composition was placed in a mold (150 mm × 150 mm × 1 mm) and heated and pressed for 40 minutes at 160 ° C. and 20 MPa to form a 1 mm thick rubber sheet (thickness 1 mm, length 150 mm, width 150 mm). got A No. 3 dumbbell-shaped test piece was punched out from each rubber sheet, and a tensile test was performed at a tensile speed of 500 mm / min in accordance with JIS K6251 (published in 2010), and 100% modulus [MPa] at room temperature (25 ° C.) measured by In addition, in each example and each comparative example, the 100% modulus value, which is an index of the crosslink density of each rubber sheet, was adjusted so as to be approximately close to each other, and then other physical properties were confirmed.
（抗張積）
　上記の引張強度と同様にして、各ゴムシートから３号ダンベル状の試験片を打ち抜き、ＪＩＳ　Ｋ６２５１（２０１０年発行）に準拠して、温度２０℃、引張速度５００ｍｍ／分の条件で破断強度（ＭＰａ）および破断伸び（％）を測定した。これらの測定結果から、抗張積（＝破断強度×破断伸び）を算出した。抗張積が高い方が、タイヤの耐カット性、耐チッピング性に優れることを示す。 (tensile product)
In the same manner as for the above tensile strength, a No. 3 dumbbell-shaped test piece was punched out from each rubber sheet, and the breaking strength ( MPa) and elongation at break (%) were measured. From these measurement results, the tensile product (=breaking strength×breaking elongation) was calculated. The higher the tensile product, the better the cut resistance and chipping resistance of the tire.
　以上の測定結果を表１に表す。なお、抗張積（指数（％））の結果について、実施例１～７および比較例２～３は比較例１における各値を１００とした場合の相対値として記載した。 Table 1 shows the above measurement results. The tensile product (index (%)) results of Examples 1 to 7 and Comparative Examples 2 and 3 are shown as relative values when each value in Comparative Example 1 is set to 100.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
　実施例１～７および比較例１～３の結果から、ゴム成分に対して含硫黄炭化水素重合体を含むゴム用添加剤と、不飽和二重結合含有シラン化合物とを添加して得られたゴム組成物を用いることで、得られたゴムシートは、抗張積が優れていた。よって、本発明のゴム組成物を用いることで、耐カット性、耐チッピング性に優れたタイヤを製造できることが判明した。 From the results of Examples 1 to 7 and Comparative Examples 1 to 3, rubber additives containing a sulfur-containing hydrocarbon polymer and an unsaturated double bond-containing silane compound were added to the rubber component. By using the rubber composition, the obtained rubber sheet was excellent in tensile product. Therefore, it was found that by using the rubber composition of the present invention, a tire excellent in cut resistance and chipping resistance can be produced.
（実施例８）
　含硫黄炭化水素重合体Ａの代わりに含硫黄炭化水素重合体Ｂ１５質量部を添加した以外は実施例３と同様にして、ゴム組成物を得た。 (Example 8)
A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of the sulfur-containing hydrocarbon polymer B was added instead of the sulfur-containing hydrocarbon polymer A.
（実施例９）
　含硫黄炭化水素重合体Ａの代わりに含硫黄炭化水素重合体Ｃ１５質量部を添加した以外は実施例３と同様にして、ゴム組成物を得た。 (Example 9)
A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of sulfur-containing hydrocarbon polymer C was added instead of sulfur-containing hydrocarbon polymer A.
（実施例１０）
　含硫黄炭化水素重合体Ａの代わりに含硫黄炭化水素重合体Ｄ１５質量部を添加した以外は実施例３と同様にして、ゴム組成物を得た。 (Example 10)
A rubber composition was obtained in the same manner as in Example 3, except that 15 parts by mass of sulfur-containing hydrocarbon polymer D was added instead of sulfur-containing hydrocarbon polymer A.
［物性評価］
　実施例８～１０で得られたゴム組成物を用いて、上記と同様にして引張強度および抗張積の測定を行った。測定結果を表２に表す。その結果、実施例８～１０で得られたゴム組成物はいずれも、実施例３と同様に、耐カット性、耐チッピング性に優れたタイヤを製造できることが判明した。 [Evaluation of the physical properties]
Using the rubber compositions obtained in Examples 8 to 10, tensile strength and tensile product were measured in the same manner as described above. Table 2 shows the measurement results. As a result, it was found that all of the rubber compositions obtained in Examples 8 to 10, like Example 3, were capable of producing tires excellent in cut resistance and chipping resistance.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040

Claims (12)

  1. 　ゴム成分と、
    　含硫黄炭化水素重合体を含むゴム用添加剤と、
    　不飽和二重結合含有シラン化合物と、
    を含む、ゴム組成物。     a rubber component;
    a rubber additive comprising a sulfur-containing hydrocarbon polymer;
    an unsaturated double bond-containing silane compound;
    A rubber composition comprising:
  2. 　前記不飽和二重結合含有シラン化合物が、下記一般式（１）：
    Figure JPOXMLDOC01-appb-C000001
     ［式中、
    　Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表し、
    　Ｌは、窒素、酸素および硫黄からなる群から選択される少なくとも１つのヘテロ原子を含んでいてもよい炭化水素基であり、
    　ａは、０か１の整数であり、
    　ｂは、０か１の整数であり、
    　ｃは、それぞれ独立して、０か１の整数であり、
    　ｄは、それぞれ独立して、０か１の整数であり、
    　ｅは、０～５の整数であり、
    　Ｒ４、Ｒ５、Ｒ６およびＲ７は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ４若しくはＲ５と、Ｒ６若しくはＲ７とが、－（ＣＨ２）ｆ－で表される架橋構造を形成してもよく、
    　ｆは、１～５の整数であり、
    　Ｒ８、Ｒ９、Ｒ１０およびＲ１１は、水素原子、メチル基または炭素数２～１０のアルキル基を表し、または、Ｒ８若しくはＲ９と、Ｒ１０若しくはＲ１１とが、－（ＣＨ２）ｇ－で表される架橋構造を形成してもよく、
    　ｇは、１～５の整数であり、
    　Ｒ１６は、水素原子、メチル基または炭素数２～８のアルキル基であり、かつ、Ｒ１７は、水素原子、メチル基または炭素数２～１０のアルキル基であり、ここで、Ｒ１２およびＲ１３は、互いに結合して二重結合を形成し、かつ、Ｒ１４、Ｒ１５およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、若しくは、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基であり、
    　または、
    　Ｒ１６およびＲ１７は、互いに結合して４～９員の脂環式炭化水素を形成してもよく、ここで、Ｒ１４およびＲ１５は、互いに結合して二重結合を形成し、かつ、Ｒ１２、Ｒ１３およびＲ１８は水素原子、メチル基または炭素数２～１０のアルキル基である。］
    で表される化合物を含む、請求項１に記載のゴム組成物。     The unsaturated double bond-containing silane compound has the following general formula (1):
    Figure JPOXMLDOC01-appb-C000001
     [In the formula,
    R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom;
    L is a hydrocarbon group optionally containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur;
    a is an integer of 0 or 1,
    b is an integer of 0 or 1,
    c is each independently an integer of 0 or 1,
    d is each independently an integer of 0 or 1,
    e is an integer from 0 to 5,
    R 4 , R 5 , R 6 and R 7 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 4 or R 5 and R 6 or R 7 are —(CH 2 ) may form a crosslinked structure represented by f- ,
    f is an integer from 1 to 5,
    R 8 , R 9 , R 10 and R 11 each represent a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 8 or R 9 and R 10 or R 11 are —(CH 2 ) may form a crosslinked structure represented by g- ,
    g is an integer from 1 to 5,
    R 16 is a hydrogen atom, a methyl group or an alkyl group having 2 to 8 carbon atoms, and R 17 is a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, wherein R 12 and R 13 are bonded to each other to form a double bond, and R 14 , R 15 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms, or R 14 and R 15 are bonded to each other to form a double bond, and R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms,
    or,
    R 16 and R 17 may be joined together to form a 4- to 9-membered alicyclic hydrocarbon, wherein R 14 and R 15 are joined together to form a double bond, and , R 12 , R 13 and R 18 are a hydrogen atom, a methyl group or an alkyl group having 2 to 10 carbon atoms. ]
    The rubber composition according to claim 1, comprising a compound represented by
  3. 　前記不飽和二重結合含有シラン化合物が、ノルボルネン骨格を有する化合物を含む、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the unsaturated double bond-containing silane compound contains a compound having a norbornene skeleton.
  4. 　前記不飽和二重結合含有シラン化合物が、下記式：
    Figure JPOXMLDOC01-appb-C000002
     ［上記各式中、Ｒ１、Ｒ２およびＲ３は、それぞれ独立して、酸素原子または窒素原子を含んでいてもよい炭化水素基、あるいは水素原子を表す。］
    で表される化合物の少なくとも１種を含む、請求項１に記載のゴム組成物。     The unsaturated double bond-containing silane compound has the following formula:
    Figure JPOXMLDOC01-appb-C000002
     [In the above formulas, R 1 , R 2 and R 3 each independently represent a hydrocarbon group optionally containing an oxygen atom or a nitrogen atom, or a hydrogen atom. ]
    The rubber composition according to claim 1, comprising at least one compound represented by.
  5. 　前記含硫黄炭化水素重合体が、不飽和炭化水素の重合体と硫黄との反応生成物であり、前記不飽和炭化水素が脂環式不飽和化合物を含む、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the sulfur-containing hydrocarbon polymer is a reaction product of a polymer of unsaturated hydrocarbons and sulfur, and the unsaturated hydrocarbons contain an alicyclic unsaturated compound. .
  6. 　前記含硫黄炭化水素重合体の重量平均分子量が５００以上４０００以下である、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the sulfur-containing hydrocarbon polymer has a weight average molecular weight of 500 or more and 4000 or less.
  7. 　前記ゴム成分が、芳香族ビニル－共役ジエン共重合体ゴムおよび共役ジエン（共）重合体ゴムからなる群から選択される少なくとも１種を含み、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the rubber component contains at least one selected from the group consisting of aromatic vinyl-conjugated diene copolymer rubbers and conjugated diene (co)polymer rubbers.
  8. 　前記ゴム成分が、スチレン－ブタジエンゴム、ブタジエンゴム、天然ゴム、およびイソプレンゴムからなる群から選択される少なくとも１種を含む、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the rubber component contains at least one selected from the group consisting of styrene-butadiene rubber, butadiene rubber, natural rubber, and isoprene rubber.
  9. 　充填剤をさらに含む、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, further comprising a filler.
  10. 　前記充填剤が、シリカおよびカーボンブラックからなる群から選択される少なくとも１種を含む、請求項９に記載のゴム組成物。 The rubber composition according to claim 9, wherein the filler contains at least one selected from the group consisting of silica and carbon black.
  11. 　タイヤ製品用である、請求項１～１０のいずれか一項に記載のゴム組成物。 The rubber composition according to any one of claims 1 to 10, which is used for tire products.
  12. 　請求項１～１０のいずれか一項に記載のゴム組成物を用いて製造されたタイヤ製品。 A tire product manufactured using the rubber composition according to any one of claims 1 to 10.
PCT/JP2022/031005 2021-08-30 2022-08-17 Rubber composition and tire product WO2023032663A1 (en)

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JP2020132822A (en) * 2019-02-25 2020-08-31 Ｅｎｅｏｓ株式会社 Rubber composition containing silane compound and petroleum resin
WO2021033747A1 (en) * 2019-08-22 2021-02-25 Ｅｎｅｏｓ株式会社 Sulfur-containing unsaturated hydrocarbon polymer, method for manufacturing same, additive for rubber, rubber composition, and tire
JP2021054992A (en) * 2019-09-30 2021-04-08 Ｅｎｅｏｓ株式会社 Rubber composition for tires, and pneumatic tire

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JP2020132822A (en) * 2019-02-25 2020-08-31 Ｅｎｅｏｓ株式会社 Rubber composition containing silane compound and petroleum resin
WO2021033747A1 (en) * 2019-08-22 2021-02-25 Ｅｎｅｏｓ株式会社 Sulfur-containing unsaturated hydrocarbon polymer, method for manufacturing same, additive for rubber, rubber composition, and tire
JP2021054992A (en) * 2019-09-30 2021-04-08 Ｅｎｅｏｓ株式会社 Rubber composition for tires, and pneumatic tire

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116554560A (en) * 2023-06-27 2023-08-08 河北世派轮胎有限公司 Inflation-free tire and preparation method thereof

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