WO1999051674A1 - Conjugated diene rubber composition - Google Patents

Abstract

A conjugated diene rubber composition comprising the following ingredients (a) to (e): (a) a rubber ingredient consisting mainly of a conjugated diene rubber having polar groups, (b) a reinforcement comprising silica, (c) an ether polymer, (d) a silane coupling agent, and (e) a silylating agent. The rubber composition is excellent in the dispersion of the silica, cross-links at a high rate, is less apt to scorch, has excellent strength properties, is less apt to be electrostatically charged, and is effective in reducing fuel consumption when used in a tire material.

Description

 Specification

 Conjugated gen rubber composition

' Technical field

 TECHNICAL FIELD The present invention relates to a rubber composition which provides an automobile tire which has a high crosslinking speed, hardly generates scorch, has excellent strength properties, and has excellent fuel efficiency. Background technology

 In recent years, with the emphasis on resource saving and environmental measures, the demand for lower fuel consumption of automobiles has become more severe. Contribution to lower fuel consumption of automobile tires by reducing rolling resistance Is required. In order to reduce the rolling resistance of a tire, a rubber material that can provide low heat build-up and heat rubber is generally used as a rubber material for a tire.

 Hitherto, it has been proposed to reduce the heat build-up by using a rubber composition obtained by combining conjugated gen rubber as a rubber material for tires and silica instead of carbon black as a reinforcing agent. However, the rubber composition containing silica has a problem in that sufficient abrasion resistance and tensile strength cannot be obtained as compared with the rubber composition containing carbon black. It is believed that the third reason is that silica has a lower affinity for conjugated gen rubber than carbon black, and thus cannot exhibit a sufficient reinforcing effect.

 Conventionally, a method using a silane coupling agent has been proposed in order to increase the affinity between silica and a conjugated gen rubber (Japanese Patent Application Laid-Open Nos. 3-252524, 3-252). 433 publication). This method requires the use of large amounts of expensive silane coupling agents to achieve a satisfactory effect.

As another improvement method, the use of conjugated genomics in which a substituent having affinity for silicity is introduced is being studied. For example, a conjugated gen rubber polymerized by an emulsion polymerization method is a conjugated gen rubber having a tertiary amino group introduced therein (Japanese Patent Application Laid-Open No. 11-134344, etc.), and a conjugated gen rubber obtained by an anion polymerization method is alkylsilyl. Group (Japanese Patent Application Laid-Open No. Hei 1-188501, etc.) and a halogenated silyl group (Japanese Patent Application Laid-Open Conjugated gen rubbers into which a substituted amino group (eg, Japanese Patent Application Laid-Open No. 286/86) or a substituted amino group (eg, Japanese Patent Application Laid-Open No. Sho 62-22940) has been proposed.

 However, many of the conjugated gen rubbers with these substituents are poorly processable, have low heat build-up, bow I tensile strength and abrasion resistance because when mixed with silica, they are strongly agglomerated with silica and cause poor dispersion. It has the disadvantage that the properties such as properties are not sufficiently improved.

 In order to disperse silica well and improve properties such as processability, low heat build-up, tensile strength, and abrasion resistance, it has been proposed to use a conjugated diene rubber copolymerized with a monomer containing a polar group. . However, since the main structure contains a polar group, stability over time is insufficient, gelation occurs, and Mooney viscosity increases at high temperatures. For this reason, there was a problem that handling was difficult, for example, the reinforcing agent such as silica was not kneaded well when compounding the reinforcing agent by kneading, and the workability was reduced due to the high viscosity.

 In addition, conjugated gen-aromatic vinyl copolymer rubber containing silica has a low crosslinking rate. Therefore, in general, sulfenamide crosslinking accelerators such as N-cyclohexyl-12-benzothiazolesulfenamide and diphenamide are generally used. The cross-linking speed is increased by using a guanidine cross-linking accelerator such as luguanidine. However, the cross-linking using this cross-linking accelerator in combination has a problem that scorch is generated.

Recently, a silica-containing rubber is compounded with a silylating agent to increase the water repellency by hydrophobizing the hydrophilic portion of the rubber composition having active hydrogen such as hydroxyl, amino, and carboxyl groups. In addition, it has been proposed to improve the dispersibility of silica (for example, Japanese Patent Application Laid-Open Nos. Hei 7-118452, Hei 9-197915). Furthermore, silica is non-conductive, whereas carbon black, which is a typical packing material, is conductive. For this reason, the silica-containing rubber product has a problem that static electricity generated by friction or the like is easily charged. As a solution, it has been proposed to mix both silica and an ether polymer with the conjugated rubber to impart conductivity to the crosslinked product of the conjugated conjugated rubber composition and prevent electrification (for example, W097Z390555, etc.). However, there is no known example in which a silylating agent is blended with this silica-containing conjugated genogen composition. It was not known what bridges would be obtained when the bridge was bridged.

 It is an object of the present invention to provide a rubber capable of producing a tire which disperses silica well, has a high crosslinking speed, hardly generates scorch, has excellent strength characteristics, is hardly charged, and has excellent fuel efficiency when used as a tire material. It is to provide a composition. Disclosure of the invention

 The present inventors have conducted intensive studies to overcome the above-mentioned problems of the prior art. As a result, a polar group-containing conjugated rubber, silica, an ether polymer, a rubber containing a silane coupling agent and a silylating agent The composition is found to be excellent in silica dispersibility, fast in crosslinking rate, hard to generate scorch, excellent in strength strength, hard to be charged, and excellent in fuel efficiency when used in tire materials. The present invention has been completed.

 According to the present invention, (a) a rubber component containing a conjugated diene rubber containing a polar group as a main component, (b) a reinforcing agent containing silica, (c) an ether polymer, and (d) a silane coupling agent And (e) a conjugated rubber composition containing a silylating agent. BEST MODE FOR CARRYING OUT THE INVENTION

 (Polar group-containing conjugated diene rubber)

 The polar group-containing conjugated rubber used in the present invention includes a conjugated diene monomer, a polar group-containing monomer copolymerizable with a conjugated diene monomer, and a polar group copolymerizable with these monomers as necessary. Is a copolymer rubber of a resin monomer containing no.

 Examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-11,3-butadiene, 2,3-dimethinole-1,3-butadiene, 2-chlorobuta-1,3-butadiene, 1 , 3-pentagen and the like. Among these, 1,3-butadiene, 2-methyl-1,3-butadiene and the like are preferable, and 1,3-butadiene is more preferable. These conjugated gens can be used alone or in combination of two or more.

The polar group-containing monomer copolymerizable with the conjugated diene monomer is not particularly limited, Examples thereof include polar group-containing vinyl monomers having atoms drawn from groups 5B and 6B of the second to fourth periods of the periodic table. Examples of atoms selected from Groups 5B and 6B of the second to fourth periods of the periodic table include, for example, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Among these, a nitrogen atom and an oxygen atom are preferable, and a nitrogen atom is particularly preferable. Specific examples of the polar group having an atom selected from Groups 5B and 6B of the Periodic Tables 2 to 4 include a hydroxyl group, an oxy group, an epoxy group, a carboxy group, a carbonyl group, Oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfininole group, thiocarbonyl group, imino group, amino group, nitrile group, ammonium group, imido group, amide group, hydrazo group, azozo And diazo groups. Among these, a hydroxyl group, an oxy group, an epoxy group, a sulfide group, a disulfide group, an imino group, an amino group, and the like are preferable, a hydroxyl group, an amino group, an oxy group, and the like are more preferable, and an amino group is more preferable. preferable.

 Examples of the polar group-containing monomer having an atom selected from Group 5B and Group 6B of the Periodic Tables 2 to 4 include, for example, an amino group-containing vinyl monomer and a hydroxyl group-containing Examples thereof include a vinyl monomer and an oxy group-containing vinyl monomer. Among these, a hydroxyl group-containing vinyl monomer and an amino group-containing vinyl monomer are preferable, and an amino group-containing vinyl monomer is particularly preferable. Masure, These polar group-containing butyl monomers can be used alone or in combination of two or more.

 Examples of the amino group-containing vinyl monomer include polymerizable monomers having at least one amino group selected from primary, secondary and tertiary amino groups in one molecule. Among these, a tertiary amino group-containing vinyl monomer is particularly preferred. Examples of the primary amino group-containing vinyl monomer include acrylamide, methacrylamide, p-aminostyrene, aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, and aminobutyl acrylate. Rate, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminobutyl methacrylate and the like.

Examples of the secondary amino group-containing vinyl monomer include, for example, anilinostyrene; Linofenyl butadiene; N-methyl acrylamide, N-ethyl acrylamide, N-methylol acrylamide, etc. N-monosubstituted acrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, N-monosubstituted methacrylamides such as N-methylol acrylamide, N- (4-anilinophenyl) methacrylamide; and the like.

 Examples of the tertiary amino group-containing vinyl monomer include, for example, N, N-disubstituted aminoalkyl acrylate, N, N-disubstituted aminoalkylacrylamide, N, N-disubstituted aminoaromatic biel monomer And a monomer having a pyridyl group. Of these, N, N-disubstituted aminoalkyl acrylates and N, N-disubstituted aminoalkyl acrylamides are preferred.

Examples of the N, N-disubstituted aminoacrylate include N, N-dimethylaminomethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl phthalate, N, N-dimethyl Aminobutyl acrylate, N, N-Getylaminoethyl acrylate, N, N-Getylaminopropyl pinoleacrylate, N, N-Getinoleaminobutynoleate tallate, N-Methinole-N-ethyl Aminoethyl acrylate, N, N-dipropylaminoethyl acrylate, N, N-dibutynoleaminoethyl acrylate, N, N-dibutynoleaminopropyl acrylate, N, N-dibutylaminobutyl acrylate Creatrate, N, N-Dihexylaminoethyl acrylate, N, N-Dioctylaminoethyl acrylate, N, N-Dimethyl Laminomethyl methacrylate, N, N-Dimethylaminoethyl methacrylate, N, N-Dimethylaminopropyl methacrylate, N, N-Dimethinoleaminobutynolemethacrylate, N, N-Jethylaminoethynole methacrylate, N, N-Jetinoleaminopropinole methacrylate, N, N-Diethyl / reaminobutyl methacrylate, N-Methyl-N-ethylaminoethyl methacrylate, N, N-Dipropynole Aminoethynolemethacrylate, N, N-dibutylaminoethyl methacrylate, N, N-dibutylaminopropyl methacrylate, N, N-dibutylaminobutyl methacrylate, N, N-dihexylaminoethyl methacrylate Acrylic acid such as N, N-dioctylaminoethyl methacrylate, acryloylmorpholine Or methacrylic acid ester No. Among these, N, N dimethylaminoethyl acrylate, N, N dimethylaminoethyl acrylate, N, N dipropylaminoethyl acrylate, N, N dimethylaminoethyl acrylate, N methyl N-ethylaminoethyl acrylate, N, N dimethylaminoethyl methacrylate, N, N dimethylaminoethyl methacrylate, N, N dipropylaminoethyl methacrylate, N, N dimethylaminoethyl methacrylate Methacrylate and N-methyl-N-ethylaminoethyl methacrylate are preferred.

Examples of the N, N disubstituted aminoalkyl acrylamide include N, N dimethylaminomethyl acrylamide, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminopropynoleacrylamide. N, N-dimethylaminobutyl acrylamide, N, N getylaminoethyl acrylamide, N, N getylaminopropyl acrylamide, N, N Jethylaminobutyl acrylamide, N Methyl-N-ethylaminoethyl acrylamide, N, N-dipropylaminoethyl acrylamide, N, N dibutyltinaminoethyl acrylamide, N, N dibutylaminopropyl acrylamide N, N dibutylaminobutylacrylamide, N, N_dihexylaminoethylacrylamide, N, N-dihexylaminopropylacrylamide Examples of N, N-dimethylaminomethylmethacrylamide, N, N-dimethylaminomethylmethacrylamide, N, N-dimethylaminoaminomethacrylamide include N, N-dimethylaminomethylmethacrylamide and N, N-dimethylaminomethylmethacrylamide. Amid, N, N dimethylaminopropyl methacrylamide, N, N-dimethylaminobutyl methacrylamide, N, N getylaminoethyl methacrylamide, N, N-Jethylaminopropyl methacrylamide N, N dimethylaminobutyl methacrylamide, N methyl-Nethyl aminoethyl methacrylamide, N, N dipropylaminoethyl methacrylamide, N, N-dibutylaminoethyl methacrylamide, N, N dibutylamino methacrylate Propyl methacrylamide, N, N dibutylaminobutyl methacrylamide Acrylamide monomers such as N, N dihexylaminopropyl methacrylamide, N, N dihexylaminopropyl methacrylamide, N, N dioctylaminopropyl methacrylamide; Or methacrylamide monomers, etc. Can be Among these, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dioctylaminopropyl acrylamide, N, N-dimethylaminopropyl acrylamide Methacrylamide, N, N-getylaminopropyl methacrylamide, N, N-dioctylaminopropyl methacrylamide, etc. are preferred.

 Examples of N, N-disubstituted amino aromatic butyl monomers include N, N-dimethylaminoethyl styrene, N, N-getylaminoethyl styrene, N, N-dipropynoleaminoethyl styrene, Styrene derivatives such as N, N-dioctynoleaminoethynolestyrene are exemplified.

 Examples of the vinyl monomer having a pyridyl group include 2-butylpyridin, 4-vinylinolepyridine, 5-methyl-12-bierpyridine, 5-ethyl-2-bulpyridine and the like. Among these, 2-vinylinpyridine, 4-vinyl / leviridine and the like are preferred.

 Examples of the hydroxyl group-containing vinyl monomer include a polymerizable monomer having at least one primary, secondary or tertiary hydroxyl group in one molecule. Such hydroxyl group-containing vinyl monomers include, for example, unsaturated carboxylic acid monomers, butyl ether monomers, and vinyl ketone monomers each containing a hydroxyl group. Preferred is a hydroxyl group-containing unsaturated carboxylic acid monomer. Examples of the hydroxyl group-containing unsaturated carboxylic acid monomer include, for example, esters such as atalilic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, derivatives such as amides and anhydrides, and preferably acrylic acid, It is an ester monomer such as methacrylic acid.

Examples of hydroxyl group-containing vinyl monomers include, for example, hydroxymethyl acrylate, 2-hydroxypropynoleate acrylate, 2-hydroxypropinoleate acrylate, 3-hydroxypropinolate acrylate, 3 —Chloro 1-hydroxypropyl acrylate, 3-phenoxy 1-2—hydroxypropinorea acrylate, glycerone monoacrylate, hydroxybutyl acrylate, 2-chloro-3-hydroxypropinorea Acrylate, hydroxyhexyl acrylate, hydroxy octyl acrylate, hydroxymethyl acrylamide, 2-hydroxy Propylacrylamide, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2—hydroxypropyl methacrylate, 3—hydroxypropyl methacrylate, 3—chloro-2—hydroxypropyl methacrylate, 3-phenoxy 2 — hydroxypropynolemethacrylate, glyceronolemethacrylate, hydroxybutynolemethacrylate, 2 —chloro-3 —hydroxypropyl methacrylate, hydroxyhexynomethacrylate, hydroxyoctyl methacrylate , Hydroxymethyl methacrylamide, 2-hydroxypropyl methacrylamide, 3-hydroxypropyl methacrylamide, 3-hydroxypropyl acrylamide, di (ethylene glycol) Conate, Jiichi

(Propylene glycol) itaconate, bis (2-hydroxypropinole) itaconate, bis (2-hydroxypropynole) itaconate, bis (2-hydroxyethylenole) fumarate, bis (2-hydroxypropynole) malate, 2-hydroxy Examples thereof include hydroxyethyl vinylinole ether, hydroxymethyl vinyl ketone, and aryl alcohol. Among these, hydroxymethyl acrylate, 2-hydroxyshetyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 3-phenoxy-1-hydroxypropyl acrylate Crylate, glycerose monoacrylate, hydroxybutynoacrylate, hydroxyhexyl acrylate, hydroxyoctynoacrylate, hydroxymethylinoacrylate acrylamide, 2-hydroxypropyla Crylamide, 3—hydroxypropyl acrylamide, hydroxymethyl methacrylate, 2-hydroxyl methacrylate, 2—hydroxypropyl methacrylate, 3—hydroxypropyl methacrylate, 3— Phenoxy-1-hydroxypropyl methacrylate, Lyceronole monomethacrylate, hydroxyptylate / remethacrylate, hydroxyhexynolemethacrylate, hydroxyoctynolemethacrylate, hydroxymethyl methacrylamide, 2-hydroxypropyl methacrylamide, 3—hi Droxypropyl methacrylamide is preferred.

Examples of the vinyl group-containing vinyl monomers include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, 6-trimethoxysilyl 1,2-hexene, p-trimethoxysilylstyrene, and 3-trimethoxysilyl methacrylate. Propyl, Examples thereof include alkoxysilyl group-containing vinyl monomers such as 3-triethoxysilylpropyl acrylate.

 Examples of the monomer having no polar group that can be copolymerized with both the conjugated diene monomer and the monomer copolymerizable with the conjugated diene monomer include an aromatic vinyl monomer having no polar group ( Hereinafter, these compounds will be referred to as aromatic butyl monomers. Specific examples thereof include styrene, α-methinolestyrene, 2-methynolestyrene, 3-methynolestyrene, 4-methynolestyrene, and 2,2. Includes 4-diisopropynolestyrene, 2,4-dimethynolethylene, 4-tert-butynolestyrene, 5-tert-butyl-2-methynolethylene, monochlorostyrene, dichlorostyrene, monophnolerostyrene. Among them, styrene is preferred. Two or more aromatic vinyl monomers may be used in combination.

The conjugated diene rubber having a polar group used in the present invention preferably contains 40 to 99.99% by weight, more preferably 45 to 90% by weight, and particularly preferably 50 to 85% by weight of a conjugated diene monomer unit. / ₀ , more preferably 55 to 80% by weight, preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, particularly preferably 0.1 to 10% by weight of the polar group-containing vinyl unit. The polymerizable polar group-free monomer unit is preferably 0 to 59.99% by weight, more preferably 9.95 to 54.95% by weight, and particularly preferably 14.9 to 49.9%. %, More preferably 19.9 to 44.9% by weight.

 The content of each monomer unit in the polar group-containing conjugated rubber can be appropriately selected from the above ranges in consideration of the low heat generation property, abrasion resistance, and strength characteristics of the tire.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the conjugated diene rubber having a polar group is in the range of 20 to 200, preferably 30 to 150, more preferably 50 to 120. If the Mooney viscosity of the polar group-containing conjugated gen rubber is low, it is easy to manufacture, but it is difficult to obtain sufficient heat generation characteristics 摩 耗 abrasion resistance, etc. Conversely, if it is large, it is excellent in abrasion resistance, etc. The viscosity of the material becomes too high, resulting in poor processability.

 (Method for producing conjugated gen rubber containing polar group)

The method for producing the conjugated diene rubber having a polar group used in the present invention is not particularly limited, but usually an emulsion polymerization method is employed. The emulsion polymerization method is not particularly limited. And a method of polymerizing with a radical polymerization initiator.

 The emulsifier used in the emulsion polymerization method is not particularly limited, but the use of an emulsifier having a carboxyl group can further improve the problem of mold contamination in the resulting copolymer at high temperature and short time crosslinking. .

 Examples of the emulsifier having a carboxyl group include fatty acid soap and rosin soap. Examples of the fatty acid soap include long-chain aliphatic carboxylic acids having 12 to 18 carbon atoms, sodium salts of these mixed aliphatic carboxylic acids, and mixed aliphatic carboxylic acid salt salts. . Examples of the long-chain aliphatic carboxylic acid having 12 to 18 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. Examples of the rosin acid soap include sodium salts and potassium salts obtained by disproportionation of natural rosin, and sodium salts and potassium salts obtained by hydrogenating natural rosin. Examples of the natural rosin include abietic acid, levopimaric acid, parastolic acid, dehydroabietic acid, tetrahydroabietic acid, and neoabietic acid, and examples thereof include gum rosin, wood rosin, and tall oil rosin. The amount of the emulsifier is not particularly limited, but is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the monomer.

 Examples of the radical polymerization initiator include a persulfate such as ammonium persulfate and potassium persulfate; a combination of ammonium persulfate and ferric sulfate; a combination of an organic peroxide and ferric sulfate; and Redox initiators such as a combination of hydrogen peroxide and ferric sulfate; and the like. The radical polymerization initiator to be used is not particularly limited, but usually, an organic peroxide, a redox polymerization initiator, an azo compound, a persulfate, or the like is used. The amount of the polymerization initiator to be used is preferably 0.005 to 3 parts by weight per 100 parts by weight of the monomer.

The as of the emulsion polymerization can be appropriately selected depending on the kind of the radical polymerization initiator used, but is preferably 0 to 100 ° C, more preferably 0 to 60 ° C. The polymerization mode may be any mode such as continuous polymerization or batch polymerization. As the conversion of emulsion polymerization increases, a tendency to gel is observed. Therefore, heavy The conversion is preferably suppressed to 90% or less, and particularly preferably, the polymerization is stopped within the range of 50 to 80%. The termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached. As the polymerization terminator, for example, an amine compound such as getyl hydroxyloleamine / hydroxylamine, a quinone compound such as hydroquinone or benzoquinone, a compound such as sodium nitrite and sodium dithiocarbamate are used.

 After the termination of the emulsion polymerization reaction, unreacted monomers are removed from the obtained polymer latex, if necessary, and then, if necessary, an acid such as nitric acid or sulfuric acid is added and mixed to adjust the pH of the latex to a predetermined value. After adjusting to a value, salts such as sodium chloride, calcium chloride, and chlorinated lime are added and mixed as a coagulant, and the polymer is coagulated as crumb. The crumb can be washed, dehydrated, and dried with a band drier to obtain a conjugated diene rubber.

 (Rubber component)

 The rubber component used in the present invention is mainly composed of a conjugated diene rubber having a polar group. In addition to the polar group-containing conjugated rubber, other rubbers may be blended within a range that does not impair the effects and objects of the present invention.

The other rubber is not particularly limited, and a conjugated rubber other than the polar group-containing conjugated rubber is usually used. Examples of such conjugated rubbers include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, and solution-polymerized random styrene-butadiene copolymer rubber (for example, styrene unit of 5 to 50% by weight). _^0/0, 1, 2-bond unit quantity 1 0-8 0% of the butadiene units), high trans' styrene-butadiene copolymer rubber (e.g., 1 in butadiene units, 4 one trans bond units of 7 0 to 95%), low cis polybutadiene rubber, high cis butadiene rubber, high trans butadiene rubber (for example, 70 to 95% of 1,4 trans-bond units in butadiene unit), styrene monoisoprene copolymer rubber, Buta-gen-soprene copolymer rubber, solution-polymerized random styrene-butadiene-soprene copolymer rubber, emulsion-polymerized styrene-butadiene One isoprene copolymer rubber, emulsion-polymerized styrene one acrylonitrile one butadiene copolymer rubber, Akuriro nitrile over butadiene copolymer rubber, high Bulle 'styrene-butadiene copolymer Examples include a low-butyl-styrene-butadiene copolymer block copolymer rubber, a polystyrene-polybutadiene-polystyrene block copolymer rubber, and the like, which can be appropriately selected according to required characteristics. Of these, natural rubber, butadiene rubber, isoprene rubber, styrene-butadiene copolymer rubber, and styrene-isoprene butadiene copolymer rubber are particularly preferred.

 Further, as the rubber other than the conjugated gen rubber, for example, butyl rubber, halogenated butizole rubber, ethylene-propylene-gen terpolymer rubber, epichloronohydrin rubber and the like can be used.

These rubbers can be used alone or in combination of two or more. When a polar group-containing conjugated gen rubber and another rubber are used together as a rubber component, the proportion of each rubber is appropriately selected according to the application and purpose, but among the rubber components, a polar group-containing conjugated gen rubber is preferable. 5 0 weight _^0/0 or more, and more preferable properly 7 0 wt% or more, particularly preferably 9 0 wt% or more.

 (Reinforcing agent)

 The reinforcing agent used in the present invention contains silica as an essential component, and optionally contains other reinforcing agents.

 The silica is not particularly limited, but examples thereof include dry white carbon, wet white carbon, colloidal silica, and precipitated silica. Among these, wet-process white carbon containing hydrous caustic acid as a main component is particularly preferred. These silicas can be used alone or in combination of two or more.

The specific surface area of silica is not particularly limited, a nitrogen adsorption specific surface area (BET method), preferably ^{5 0~ 4 0 0 m 2 Z} g, more preferably ^{1 0 0~ 2 5 0 m 2} g, in particular preferably ^{1 2 0~1 9 O m 2 Z} g. When the specific surface area of the silica is within this range, improvements such as reinforcement, abrasion resistance and low heat build-up are sufficiently achieved, which is preferable. Here, the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D330-81.

The reinforcing agent other than silica is not particularly limited, but usually carbon black is used. Examples of carbon black include furnace black and acetylene Racks, thermal black, channel black, graphite, and the like can be used. Among them, furnace black is particularly preferable, and specific examples thereof include various types such as SAF, ISAF, ISAF—HS, ISAF—LS, II SAF—HS, HAF, HAF—HS, HAF—LS, and FEF. Grades. These carbon blacks can be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (NSA) of Ripbon Black is not particularly limited, but is preferably 5 to 200ιη ² ^, more preferably 50 to: L 50 m ² / g, and particularly preferably 80 to 130 m It is in the range of ² Zg. When the nitrogen adsorption specific surface area of carbon black is within this range, the tensile strength / abrasion resistance is improved at a high level, which is preferable. The amount of DBP adsorbed by the carbon black is not particularly limited, but is preferably in the range of 5 to 300 ml of ZOO g, more preferably 50 to 200 ml / 100 g, and particularly preferably in the range of 80 to 160 ml of ZOO g. When the DBP adsorption amount of the carbon black is within this range, the bow I tensile strength / abrasion resistance is improved at a high level, which is preferable.

As the carbon black, the adsorption of cetyltrimethylammonium ammonium Niu arm bromide My de (CTAB) specific surface area at a pressure of 24, O OO psi at 1 10~170m ² Zg

Abrasion resistance can be further improved by using high-structure carbon black having an adsorption amount of DBP (24MDBP) of 110 to 130 ml / 100 g after being repeatedly compressed four times.

The content of silica in the reinforcing agent is preferably 10 to 100 weight _^0/0, more preferably

30 to 100% by weight, particularly preferably 50 to 100% by weight. / ₀ , more preferably 7

0 to 100% by weight.

 (Ether polymer)

As the ether polymer, a polymer having an ether bond (-C-0-C-I) in a main chain is used without any particular limitation. As the ether polymer, preferably, an oxysilane monomer such as an alkylene oxide monomer, an epihydric hydrin monomer, an unsaturated epoxide monomer, or the like, alone or in combination of two or more, is added in a block or random manner. A polymerized product is used. Specific examples of the ether polymer obtained by addition-polymerizing an oxysilane monomer alone or in combination of two or more thereof include, for example, a homopolymer of an alkylene oxide monomer and a copolymer of two or more alkylene oxide monomers. Polymer, copolymer of alkylene oxide monomer and epihalohydrin monomer, copolymer of alkylene oxide monomer and unsaturated epoxide monomer, alkylene oxide monomer and epihalohydrin Copolymer of dolin monomer and unsaturated epoxide monomer, homopolymer of ephalohydrin monomer, copolymer of two or more ephalohydrin monomers, monomeric ephalohydrin monomer and unsaturated epoxide monomer And a homopolymer of an unsaturated epoxide monomer, and a copolymer of two or more unsaturated epoxide monomers. Among these, a copolymer of two or more alkylene oxide monomers or a copolymer of an alkylene oxide monomer and an unsaturated epoxide monomer is preferable, and an alkylene oxide monomer and an unsaturated epoxide are preferable. Copolymers with monomers are particularly preferred.

 Examples of the alkylene oxide monomer include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxymonoisobutane, 2,3-epoxybutane, 1,2-epoxyhexene, 2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-1 Epoxy-1-pentylpropane, 1,2-epoxy-1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane, and the like. Of these, lower anolexylene oxides such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and amylene oxide are preferred, and ethylene oxide-propylene oxide is particularly preferred.

 Epiha hydrin monomers include, for example, epichlorohydrin, epibromohydrin, epiohydrin, 2,3-epoxy-1 1,1,1 tripropenolepropane, 1,2-epoxy-1H, 1 H, 2 H, 3 H, 3 H-heptadecafluoroundecane and the like, and usually epichlorohydrin is used.

There is no particular limitation on the unsaturated epoxide monomer as long as it has at least one carbon-carbon unsaturated bond and at least one epoxy group in the molecule. Alkenyl daricidyl ether monomers such as arylglycidyl ether, butenyldaricidyl ether, and octenyldaricidyl ether; to 3,4-epoxy-1-butene, 1,2-epoxy-1-5 Kisen, 1, 2-epoxy

Alkenyl epoxide monomers such as 9-decene; aryl epoxide monomers such as styrene epoxide and glycidyl phenyl ether; and the like. Of these, alkenyl dalicidyl ether monomers are preferred, and aryl glycidyl / ether is particularly preferred.

 Other oxysilane monomers include, for example, 1,2-epoxy-1-methoxy-2-methylpropane, 2- (3,4-epoxycyclohexyl) ethynoletrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane And so on.

 These oxysilane monomers can be used alone or in combination of two or more.

The type and content of the oxysilane monomer in the ether polymer are appropriately selected depending on the purpose of use. For example, in order to achieve a high balance between low heat build-up and tensile strength, an ether polymer (A) obtained by copolymerizing an alkylene oxide monomer and an unsaturated epoxide monomer is generally used. the content of the alkylene O sulfoxide monomer unit in this case is preferably 8 5-9 9. 9 wt ⁰ I, more preferably 9 0-9 9 wt. /. The content of unsaturated epoxide monomer units is preferably 15 to 0.1% by weight, more preferably 10 to 1% by weight, particularly preferably 95 to 99% by weight. Preferably it is in the range of 5 to 1% by weight. Further, in order to highly improve processability are alkylene O sulfoxide monomer units is preferably 5 0 weight ⁰ /. As described above, the ether polymer (B) containing more preferably 70% by weight or more, particularly preferably 90% by weight or more is suitably used. Furthermore, in addition to low heat build-up, tensile strength and workability, antistatic properties are required. ^ As an alkylene oxide monomer unit, ethylene oxide units are 50% by weight or more, preferably 60% by weight. % Or more, more preferably 70% by weight or more of the ether polymer (C) is suitably used. In order to achieve a high balance of all the properties of low heat generation, tensile strength, workability and antistatic property, the alkylene oxide monomer unit in the above ether polymer (A) should be Chirenokishido units preferably 5 0: 1 0 0 wt _^0/0, more preferably 6 0 9 9 wt%, particularly preferably a 7 0 9 7 wt%, propylene O carboxymethyl properly 5 0 preferred are de units % To 0% by weight, more preferably 40% to 1% by weight, and particularly preferably 30% to 3% by weight. Preferred copolymers are Echire Nokishido unit 5 0-9 9 wt _^0/0, propylene O sulfoxide units 0-4 9 wt _^0/0, Contact and § Li glycidyl ether unit:! It is a copolymer consisting of up to 15% by weight. In order to highly balance all properties of low heat build-up, tensile strength, workability and antistatic property, among ether polymers, (1) 50 to 98.9% by weight of ethylene oxide unit, preferably 60 to 97.5% by weight, more preferably 70 to 96% by weight, (2) propylene oxide unit 1 to ³⁵ % by weight. Preferably 2-30 weight ⁰ /. , Yo Ri preferably 3-2 5% by weight, and (3) unsaturated Epokishido monomer units from 0.1 to 1 5% by weight, preferably from 0.5 to 1 0 weight ⁰ /. , More preferably Echirenokishido Propylene O sulfoxide-unsaturated epoxide monomer terpolymer having a respective coupling amount of from 1 to 5 weight _^0/0 are particularly preferred. In the terpolymer, the unsaturated epoxide monomer is particularly preferably an alkenyl daricidyl ether monomer such as aryl glycidyl ether.

 The (co) polymer of an oxysilane monomer containing the above terpolymer can be usually obtained by a solution polymerization method or a solvent slurry polymerization method. Examples of the catalyst include a catalyst obtained by reacting water and acetylaceton with organoaluminum; a catalyst obtained by reacting phosphoric acid and triethylamine with triisobutylaluminum; a phosphoric acid obtained by reacting triisobutylaluminum; and an organic acid salt of diazabiacycloundecene. A homogeneous catalyst such as a catalyst obtained by the reaction of a compound; a catalyst comprising a partially hydrolyzed product of anolemminium alkoxide and an organic zinc compound; a catalyst comprising an organic zinc conjugate and a polyhydric alcohol; And a heterogeneous catalyst such as a catalyst comprising water. When the solvent slurry polymerization method is used, a catalyst previously treated with both a monomer that gives a polymer soluble in the polymerization solution and a monomer that gives a polymer insoluble in the polymerization solvent is used. It is preferable to use it from the viewpoint of the stability of the polymerization reaction system.

Examples of the solvent include aromatic hydrocarbons such as toluene; linear hydrocarbons such as n-pentane and n-hexane; alicyclic hydrocarbons such as cyclopentane; You.

 When a solvent slurry polymerization method is employed using a solvent such as n-pentane, n-hexane, or cyclopentane, for example, ethylene oxide that gives a polymer that is insoluble in the solvent and a polymer that is soluble in the solvent are used. Force to treat the catalyst in advance with propylene oxide to give the following: \ As described above, it is preferable from the viewpoint of the stability of the polymerization reaction system. In the treatment of the catalyst, the catalyst component and a small amount of each monomer are mixed, and the mixture is preferably aged at a temperature of 0 to L 0 ° C, more preferably 30 to 50 ° C. .

In the polymerization reaction, a monomer component, a catalyst component, a polymerization solution, etc. are charged into a reactor, and the temperature is 0 to 100 ° C, preferably 30 to 70 ° C, and is a batch type, a semi-batch type, or a continuous type. Any method can be used. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ether polymer is preferably 70 to 150, more preferably 80 to 140, and particularly preferably 85 to 120. . When the Mooney viscosity of the ether polymer is within this range, low heat build-up, tensile strength and workability are highly balanced, which is preferable.

These ether polymers can be used alone or in combination of two or more. The amount of the ether polymer to be used is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 3 parts by weight, based on 100 parts by weight of the conjugated gen rubber selected as appropriate according to the intended use. 0 parts by weight, particularly preferably 3 to 15 parts by weight. If the amount of the ether polymer is excessively small, the effect of improving the low heat build-up, tensile strength and workability is not sufficient, and if it is excessively large, the low heat build-up is insufficient. Not preferred. The silane coupling agent is not particularly limited, but includes, for example, butyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxy-1-ethoxy) silane, β- (3,4-epoxycyclohexinole) -ethynoletrimethoxysilane, γ —Dalicidoxypropyltrimethyoxysilane, γ-methacryloxypropinoletrimethyoxysilane,] —] 3 (aminoethyl) γ-aminopropyltrimethyoxysilane, Ν— i3 (aminoethyl) γ-aminopropylmethyldimethoxysilane , Ν-phenyl y-aminopropyl trimethyoxysilane, γ-cloth provirt trimethoxysilane, γ mercaptoprovir trimethyoxysilane, γ aminop Mouth pilltriethoxysilane, bis (3- (triethoxysilinole) propinole) tetrasulfide, γ-trimethoxysilylpropyldimethylthio-capillate rubamyl tetrasulfide, γ-trimethoxysilylpropyl benzothiazyltetrasulfide And the like.

 (Silylating agent)

 In the present invention, the silinole agent added to change the surface of the sieve to be hydrophobic is, specifically, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyl / reethoxysilane, diphenylinoresethoxysilane. , Trifeninoleethoxysilane, Triphenylmethoxysilane, ρ-Methylphenyltrimethoxysilane, ρ-Methynolephenizoletriethoxysilane, 3-Port Propinoletrimethoxysilane, 3-Port Propinoletriethoxysilane, 3, 3,3-Triphnoreo-propynoletrimethoxysilane, 3,3,3-Trifluoropropynoletriethoxysilane, 3-Ditolylpropynoletrimethoxysilane, 3-Nitrilypropynoletriethoxysilane, ρ-Bromophene Ninoretrimethoxysilane, ρ— Lomopheninoletriethoxysilane, tolyltrimethoxysilane, tonoleinoletriethoxysilane, propyltrimethoxysilane chloride, propyltriethoxysilane chloride, 1,1-difluoropropyltrimethoxysilane, 1,1-difluoropropyltriethoxysilane, cyanopro Viltrimethoxysilane, cyanopropyltriethoxysilane and the like can be mentioned. The silylating agent used in the present invention preferably has a structure represented by the following general formula 1.

General formula 1:

 A

 /

 R O— S i— B

 \

 C

Wherein R is an alkyl group, A is a phenyl group or an alkylphenyl group, B is a phenyl group, an alkylphenyl group or an alkoxy group, C is a phenyl / alkyl group, It is a kilfenino group or an alkoxy group. )

 Examples of such a silylating agent include phenyltriethoxysilane, phenyltrimethoxysilane, diphenylethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, triphenylmethoxysilane and the like. In particular, phenyltriethoxysilane is preferred.

 (Rubber composition)

 The rubber composition of the present invention comprises (a) a rubber component mainly containing a conjugated gen rubber, (b) a reinforcing agent containing silica, (c) an ether polymer, (d) a silane coupling agent, and (e) silylation. Agent.

 The amount of the reinforcing agent containing (b) silica is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, particularly preferably 100 parts by weight of the rubber component (a). 30 to 120 parts by weight. If it is too large, dispersion may not be successful. If the amount is too small, the reinforcing effect is so small that it may not meet the purpose.

 (c) The amount of the ether polymer is determined according to the application, but (a) based on 100 parts by weight of the rubber component, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, Particularly preferred is 3 to 15 parts by weight. If the amount of the ether polymer is too small, low heat build-up, tensile strength, workability, and the like may be insufficient. If the amount is too large, the low heat build-up may be insufficient.

 (d) The amount of the silane coupling agent is also determined depending on the application, but is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, particularly preferably 100 parts by weight of silica. Is 1 to 10 parts by weight. If the amount is too large, the effect is not sufficient with respect to the added amount, and the strength may be adversely affected. If the amount is too small, the effect will not be sufficiently exhibited.

 (e) The amount of the silinolelating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to: 15 parts by weight, and particularly preferably 1 to 10 parts by weight, per 100 parts by weight of the rubber. Department. If the amount of the silylating agent is too large, the hardness of the rubber composition may decrease, or may be deposited on the surface to reduce the sliding resistance of the rubber composition. If the amount of the silylating agent is too small, the effect may not be sufficiently exhibited.

(Other compounds) In addition to the above components, other necessary additives such as stabilizers, cross-linking agents, cross-linking accelerators, cross-linking activators, anti-aging agents, activators, plasticizers, lubricants, and fillers are required in accordance with the usual methods. be able to.

 The stabilizer used in the present invention is not particularly limited, and examples thereof include a phenol stabilizer, a zeolite stabilizer, and a phosphorus stabilizer.

 The phenol stabilizer used in the present invention includes, for example, 2,6-di-tert-butynole 4-methinolephenogre, 2,6-di-tert-butyl-4-butyl-ethyl phenol / re, 2,6-di tert-butynole 4-n-butyl phenol, 2,6-di-tert-butyne 4-iso-butyl phenol, 2-tert-butyl phenol 4,6-dimethynole, 2, 4 , 6-tricyclohexinolephenol, 2,6-ditert-butynole 4-methoxyphenol, 2, 6-diphenol-4, octadecyloxyphenol, n-octadecyl-3- (3 ,,

5 'di-tert-butynole 4-propoxyphene) propionate, tetrakis [methylene-1 3- (3,, 5' di-tert-butyl-14,4-hydroxy-phenyl) propionate Monomethane, 1, 3, 5 —trimethyl-2, 4,

In addition to general phenol stabilizers such as 6-tris (3,5-ditert-butyl-4-hydroxybenzinole) benzene, zeo-containing phenol stabilizers are exemplified.

 Examples of the phenol-containing phenol stabilizer include 2,4-bis (octylthiomethyl) -1-6-methinolephenol and 2,4-bis (2,, 3,1-hydroxypropynolethiomethinole). Examples thereof include 1,3,6-di-methylphenol and 2,4-bis (2,1-acetylcyclohexylthiomethyl) -1,3-dimethylphenol.

 The phosphorus stabilizers used in the present invention are also known, for example, tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecinolephosphite), tris (2,4-di-tert.) —Butylphenyl) phosphite and the like.

It may contain a stabilizer. Examples of such an iodine stabilizer include pentaerythritol-tetrakisux (1-lauryl-thio-propionate), Examples thereof include dilauryl-1,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl-1,3,3′-thiodipropionate.

 The crosslinking agent is not particularly limited. For example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halide such as sulfur monochloride and sulfur dichloride; dicumyl par Organic peroxides such as oxoxide and ditertiary butyl peroxide; quinone dioximes such as P-quinone dioxime and p, p'-dibenzoyl quinone dioxime; triethylene tetramine, hexamethylene diamine, rubamate, 4 Organic polyvalent amine compounds such as 4,4'-methylenebis-o-chloroaniline; alkyl phenol resins having methylol groups; and the like. Among these, sulfur is preferred, and powdered sulfur is particularly preferred. These crosslinking agents are used alone or in combination of two or more.

 The mixing ratio of the cross-linking agent is preferably from 0.3 to 15 parts by weight, more preferably from 0.3 to 0 parts by weight, particularly preferably from 0.3 to 100 parts by weight of the rubber component (a). It is in the range of 5 to 5 parts by weight. When the compounding ratio of the cross-linking agent is in this range, it is particularly preferable because it has excellent tensile strength and abrasion resistance, and also has excellent properties such as heat resistance and residual strain.

Examples of the cross-linking accelerator include N-cyclohexyl-12-benzothiazoles-norefenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-12-benzothiazo-l / resnolefen Ami de, N- Okishechire Hmm 2-benzothiazyl zone Roh less Honoré Fen Ami de, N, Surufen'ami de crosslinking accelerators such as N ^r over diisopropylate Honoré one 2-benzothiazole one Rusuru Fen Ami de; Jifue Nirudanijin, Jiorutotoriru Guanidine cross-linking accelerators such as guanidine and o-tolylbiguanidine; thioperia cross-linking accelerators such as thiocarboaureide, dionole tolitol thiourea, ethyl lentiolerea, getyl thiourea, and trimethyl thiourea; 2-mercaptobenzothiazole, dibenzo Thiazyl disulfide Thiazole cross-linking accelerators such as 2-menolecaptobenzothiazole zinc salt, 2-mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazolecyclohexylamine salt, and 2- (2,4-dinitrophenylthio) benzothiazole; Te , Tetramethylthiuram disulfide, tetodo and other thiram crosslinking accelerators; sodium dimethinoresitio sodium rubinate, sodium getyl dithiocanolebamate, sodium di-n-butyldithiocarbamate, dimethyldithiocarbamine &, Dimethyl dithio-potassium rubbamate, zinc getyl dithiocanolebamate, zinc di-n-butyl dithiocarbamate, pentamethylene dithio-potassium rubinate, ethyl thithio-potassium rubinate Tenorel thiocanolebamate, selenium dimethyldithiocarbamate, selenium methinoresitiocarbamate, dimethyldithiokanorebamine, iron dimethyldithiocarbamate, diethylamine getyldithiocarbamate, pentamethylenedithiocanolebamate Dithiolrubic acid crosslinking accelerators such as peridine and methylpentamethylenedithiocanolebamate pipecoline; xanthogenic acid crosslinking accelerators such as sodium isopropylxanthogenate, zinc isopropylxanthate and dumbbell butylanxanthate; And the like.

These cross-linking accelerators are used alone or in combination of two or more kinds; and those containing at least a sulfenamide cross-linking accelerator are particularly preferred. Among those containing a sulfenamide cross-linking accelerator, those having a sulfenamide cross-linking accelerator in a proportion of 30% by weight or more of all the cross-linking accelerators are preferable, and 50% by weight / ⁰ . The above compounds are more preferable, and those having 70% by weight or more are particularly preferable. The compounding ratio of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.3 to 10 parts by weight, particularly preferably 0.5 to 100 parts by weight of the solid rubber. It is in the range of ~ 5 parts by weight.

The cross-linking activator is not particularly limited, and for example, higher lubricating fatty acids such as stearic acid and zinc oxide can be used. For example, it is preferable to use zinc oxide having a high surface activity and a particle size of 5 μπι or less. As a specific example, an active material having a particle size of 0.05 to 0.2 nm is preferably used. Raw zinc white or 0.3 to 1 μm zinc white. As the zinc oxide, a zinc oxide surface-treated with an amine dispersant or a wetting agent can be used. These crosslinking activators can be used alone or in combination of two or more. The mixing ratio of the crosslinking activator is appropriately selected depending on the type of the crosslinking activator. When a higher fatty acid is used, it is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the solid rubber. Mix by weight. When zinc oxide is used, it is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the solid rubber. Mix by weight. When the compounding ratio of zinc oxide is in this range, properties such as workability, bow I tensile strength and abrasion resistance are highly balanced and suitable.

 Examples of other compounding agents include force coupling agents other than silane coupling agents; activators such as methylene glycol, polyethylene glycol, and silicone oil; fillers such as calcium carbonate, tazolex, and clay; process oils and waxes And so on.

 The rubber composition of the present invention can be obtained by blending each component according to a conventional method. For example, (a) after dispersing each component in an organic solvent in which a rubber component is dissolved or dispersed, the organic solvent is removed by a steam stripping method or a method using a hot roll, And kneading using an extruder. Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples, and Comparative Examples. Various physical properties were measured according to the following methods.

 (1) The amount of styrene unit in the conjugated gen rubber was measured according to JIS K 6383 (refractive index method).

(2) The amount of the amino group-containing monomer unit in the conjugated gen rubber can be determined by dissolving the copolymer in tetrahydrofuran, and reprecipitating and coagulating twice with methanol Zacetone (50/50/50 volume ⁰ /.). After drying in vacuo, it was measured by 500 MHz ¹ H-NMR.

(3) a hydroxyl group-containing monomer units of the conjugated Jengomu in accordance with the method described in JP-A-3 1 7 4 4 0 8 No., after the polymer was phenylene Ruisoshiana one Bok treatment, ¹³ C- It was calculated by quantifying the phenyl group of phenyl / leisocyanate by NMR spectrum.

(4) Mooney viscosity (ML _{1 + 4} , 100 ° C) measured according to JISK630 did.

(5) The monomer unit amount of the ether polymer was measured by ¹ H-NMR analysis.

(6) The Mooney scorch time (t 5) was determined by measuring the scorch time of an unvulcanized rubber composition at 160 ° C. with an oscillating 'rheometer according to the Japan Rubber Association Standard SR IS 3102. Example:! 5 to 5 and Comparative Examples 2 to 4 are indices based on the Mooney scorch time (t5) of Comparative Example 1 as 100, and are the same as those of Examples 6 to 10; The scorch time ( _t 5) is indicated by an index with 100 as the index.

 (7) Vulcanization rate △ (t 90-t 10) is 90% of the maximum torque at 160 ° C by an oscillating rheometer for unvulcanized rubber composition in accordance with Japan Rubber Association Standard SR IS 3102. The difference 時間 (t90-t10) between the time to reach (t90) and the time to reach 5% of the maximum torque (t10) was measured. Example:! 5 to 5 and Comparative Examples 2 to 4 and the index of vulcanization rate (t90-t10) of Comparative Example 1 as 100. The index was set as an index with the vulcanization rate △ (t90-t10) of Comparative Example 5 being 100.

 (8) The exothermic index was determined using rheometrics: hMRDA-II, using 1% twist, 20 Hz, and 60 ° C ta η δ. 5 to 5 and Comparative Examples 2 to 4 and Comparative Example 1 were indicated by an index, and those of Examples 6 to 10 and Comparative Example 5 were indicated by an index of 100.

Reference Examples 1-3

A tank equipped with a stirrer was charged with 200 parts of water, 3 parts of ore diced stone, 0.15 parts of t-dodecyl mercaptan, and a monomer having the composition shown in Table 1. The reactor was kept at 5 ° C, and 0.1 parts of cumenehydride peroxide, 0.2 parts of sodium honolemaldehyde sulfoxylate, and 0.01 parts of ferric sulfate were added as radical polymerization initiators. Started. When the conversion reached 70%, the reaction was stopped by adding getylhydroxylamine. Next, the unreacted monomer was recovered, and 37.5 parts by weight of naphthenic oil (Diana Process Oil NS-24, manufactured by Idemitsu Kosan Co., Ltd., 5% by weight of aroma) was mixed per 100 parts by weight of the polymer. This was coagulated with sulfuric acid and salt to form crumb, and dried with a crumb drier to obtain conjugated diene rubbers 1-3. Table 1 shows the properties of the gen polymer. Conjugated gen rubber 2 is a conjugated gen rubber containing a polar group.

Reference example 4

 The autoclave with a stirrer having an internal volume of 3 liters was purged with nitrogen, and charged with 117 g of toluene, 158.7 g of triisobutylaluminum, and 296.4 g of getyl ether. The internal temperature was set at 30 ° C., and 23.5 g of orthophosphoric acid was gradually added with stirring. Further, 122.1 g of triethylamine was added, and the mixture was aged at 60 ° C. for 2 hours to obtain a catalyst solution.

 An autoclave with an internal volume of 5 liters equipped with a stirrer was purged with nitrogen, and 2100 g of n ^ xane and 63 g of a catalyst solution were charged. The temperature was set to 30 ° C, and 5% of a mixed solution consisting of 240 g of ethylene oxide, 60 g of propylene oxide, and 300 g of n-hexane was added with stirring. . After reacting for 1 hour, the internal temperature was set to 60 ° C, and the remaining 95% of the mixed solution was continuously added over 5 hours. After the addition was completed, a post-reaction was performed for 2 hours. The polymerization reaction rate was 99%. The polymer was separated and collected by a centrifugal separator, and vacuum dried at 60 ° C overnight. Table 2 shows the properties of the obtained ether polymer 1.

Reference example 5 A mixed solution consisting of 240 g of ethylene oxide, 6 g of propylene oxide, and 300 g of n-hexane was mixed with 261 g of ethylene oxide, 30 g of propylene oxide, 9 g of arydaricidyl ether, and 300 g of n-hexane. The same procedure as in Reference Example 4 was carried out except for using the mixed solvent consisting of g, to obtain an ether polymer 2. Table 2 shows the properties of polyether polymer 2. Table 2

Example 1-10, Comparative Examples 1 to 5

Based on the formulation shown in Table 3 (Examples! To 5), Table 4 (Comparative Examples: to 4) and Table 5 (Examples 6 to 10 and Comparative Example 5), a Brabender type with a capacity of 250m1 In a mixer, mix the entire amount of raw rubber, half of the sily force and half of the silane coupling agent at 170 ° C for 2 minutes, then add the remaining compounding ingredients except sulfur and the cross-linking accelerator and add the same temperature. For 2 minutes. The obtained mixture, sulfur and a crosslinking accelerator were added to an open roll at 50 ° C and kneaded, followed by press-crosslinking at 160 ° C for 30 minutes to prepare a test piece, and each physical property was measured. The results are shown in Tables 3, 4 and 5.

Table 3

 Example

 1 2 3 4 5 Composition of the composition

Conjugate Nocom 1 1 100 100 100-1 Conjugate 2--100 100 ·> ,,-! ■, ·

Conjugate Nenocom 3--1-1 1 5 5 5 5-1-5----------------------------------------- Nore <ji 1] 2 5 ― ― one-two,. ", ~ F | |, ^ Female M

Nfuno force Nnorinoku agent I 4 4 4 4 Nofuno 7J Nnorinoku劑2 4 - scan Ding J Reno ^ ¹ J 2 2 2 2 2 oxide, 1.5 1.5 1.5 1.5 1.5

Λ Λ レ 15 15 15 15 15 化 吐 化: agent fell 2 2 2 2 2 old 1.5 1.5 1.5 1.5 1.5 vulcanization accelerator 2.5 2.5 2.5 2.5 2.5 workability

Mu-one-scorch time

 t 5 (index) 115 110 121 121 114 Vulcanization rate

Δ (t 10-t 90) (index) 75 82 78 73 76 Fever (index) 91 93 94 93 90

Table 4

H

 G

 Table 5

 Lyrics Example Example

 6 7 8 9 10 ο 組成 Composition of the composition (parts by weight)

Conjugated gen rubber 1 60 60 60

Conjugated gen rubber 2 1-1 1 60 60 60 Conjugated gen rubber 3 1 1 ― ― ―

 5 5 1 10 5 5 Ether polymer 2 1 1 1 1 1 1

Butadiene rubber 40--1 40 40 40 40 2-tolyl rubber ― 40 ― ― ―

Silica 70 70 70 70 35 70 Carbon black ― ― ― I 35

Silylating agent 1 5 5 5 5 5

Silylating agent 2 ― ― ― ― ―

Silane coupling agent 1 4 4 4 4 4 Silane coupling agent 2 ― 4 1 ―

Stearin 2 2 2 2 2 2 Zinc oxide 1.5 1.5 1.5 1.5 1.5 1.5 Oil 15 15 15 15 15 lb Antioxidant 2 2 2 2 2 2 Sulfur 1.5 1.5 1.5 1.5 1.5 Vulcanization accelerator 2.5 2.5 2.5 2.5 2.5 2.5 Workability

Mu-one-scorch time

 t 5 (index) 113 128 121 108 106 100 Vulcanization rate

△ (t 1 0—t 90) (index) 88 92 89 81 78 100 Heat generation (index) 86 86 88 86 93 100 Siri force is Zeozi 1 1 165MP (Rhone Poulin, nitrogen adsorption specific surface area 175m ² / g), Sirinorei 1 is phenyltriethoxysilane, Sirenoletting agent 2 is diphenylethoxysilane, silane coupling agent 1 is Si 69 (Degussa, silane coupling agent 2 is mercaptopropyltrimethoxysilane) , Zinc oxide is zinc white # 1 (this chemical cane, particle size 4 μπι), oil is Sansen 410 (Nippon Oil Co., Ltd.), antioxidant is Nocrack 6C (Ouchi Shinko Byeon: fc), and crosslinking is promoted. Noxeller CZ (Ouchi Shiningune) was used as the preparation. Gen rubber used Nipo 1 BR122 (made by Nippon Zeon) and natural rubber used RSS # 3. Industrial applicability

 The rubber composition of the present invention is excellent in strength properties because silica is sufficiently dispersed, and excellent in fuel efficiency and high in crosslinking speed because silica is used as a scavenger, and scorch Is unlikely to occur. It can significantly improve the tensile strength, low heat build-up, and abrasion resistance, which were disadvantages without impairing the rolling resistance, which is a characteristic of silica-containing materials, and have excellent properties in terms of workability. Have.

 The rubber composition of the present invention can be used for tire parts such as treads, carcass, sidewalls, and bead parts, or for rubbers such as hoses, window frames, belts, shoe soles, vibration-isolating rubber, and automobile parts. It can be used for products, and also as resin-resistant rubber such as impact-resistant polystyrene and ABS resin. In particular, the rubber composition of the present invention makes use of the above-mentioned properties, and is particularly excellent in tire trails of fuel-efficient tires, but in addition to tires, sidewalls, and tires such as all-season tires, high-performance tires and studless tires. Can be used for under treads, carcass, beats, etc.

Claims

The scope of the claims

1. (a) Extreme'-containing rubber component mainly containing gen rubber, (b) silica-containing reinforcing material, (c) ether polymer, (d) silane coupling agent and

(e) A conjugated rubber composition containing a silylating agent.

 2. The composition according to claim 1, wherein the conjugated diene rubber containing the polar '14' is a copolymer of a conjugated diene monomer and a polar group-containing monomer copolymerizable with the diene monomer. object.

 3. The rubber composition according to claim 2, wherein the polar group-containing monomer is a polar group-containing vinyl monomer.

 4. The pole tt¾ is a polar group having an atom selected from Groups 5B and 6B of the Periodic Tables 2-4. 4. The gen-rubber composition according to any one of (1) to (3).

 5. The extreme ten-containing monomer is a hydroxyl-containing vinylinole monomer, an amino-containing vinyl monomer or an oxy-group-containing vinyl monomer. The conjugated gen rubber composition according to the above.

 6. The conjugated diene rubber composition according to any one of claims 2 to 5, wherein the polar '(4¾-containing monomer is a tertiary amino group-containing biel monomer).

 7. The S: according to claim 6, wherein the tertiary amino group-containing vinyl monomer is N, N-disubstituted aminoanolequinoleacrylate or N, N-disubstituted aminoalkylacrylamide. Gen rubber composition.

8. polar group-containing conjugated Jengomu is, conjugated diene monomer units from 40 to 99.99 by weight _^0/0, the pole ttS-containing vinyl monomer units 0. 01-20 wt _^0/0 and of these the copolymerizable containing Shinano Les poles' 14¾, conjugated Jengomu composition according to any one of claims 3-7 claims Ru der those containing monomeric units from 0 to 59.99 weight ^_0/0.

 9. The conjugated diene rubber composition according to any one of claims 1 to 8, wherein the pole-containing conjugated diene rubber has a Mooney viscosity (ML i + 4, 100 ° C) of 20 to 200.

10. The conjugated rubber composition according to any one of claims 1 to 9, wherein (a) the rubber component contains at least 50% by weight of a conjugated rubber having a polar group.

1 1. The conjugated rubber composition according to any one of claims 1 to 10, wherein the reinforcing material contains silica having a specific surface area of 50 to 400 m.

12. (b) Reinforcing material: Silica 10 ~: 100 weight ⁰ /. The conjugated gen-rubber composition according to any one of claims 1 to 11, wherein the composition comprises:

 13. (c) The ether polymer according to any one of claims 1 to 12, wherein the ether polymer is a copolymer of two or more alkylene oxides or a copolymer of an alkylene oxide and an unsaturated epoxide. Conjugated gen rubber composition.

14. (c) The ethylene polymer has an ethylene oxide unit of 50 to 98.9 weight ⁰ /. , Propylene O sulfoxide 1-35 wt%, and unsaturated Epokishido 0.1 to 1 5 weight ⁰ /. 14. The conjugated rubber composition according to claim 13, which is:

 15. The composition according to claim 14, wherein the unsaturated epoxide is alkeninoleglycidyl ether.

 16. (e) The silylating agent has the general formula 1:

A

 /

 RO—S i—B

 \

 C

(In the formula, R is an alkyl group, A is a phenyl group or an alkylphenyl group, B is a phenyl group, an alkylphenyl group or an alkoxy group, C is a phenyl group, an alkylphenyl group or an alkoxy group. The conjugated rubber composition according to any one of claims 1 to 15, wherein the composition is represented by:

 17. (a) 100 to 100 parts by weight of a rubber component containing a polar group-containing gen rubber as a main component, (b) 10 to 200 parts by weight of a reinforcing material containing silica, (c) 0.1 to 50 parts by weight of an athenole polymer, (e) 0.1 to 20 parts by weight of a silylating agent, and 100 to 100 parts by weight of silica. (d) 0.1 to 20 parts by weight of a silane coupling agent. The conjugated gen rubber composition according to the above.

 18. (a) Cross-linking agent per 100 parts by weight of rubber component. 18. The conjugated diene rubber composition according to any one of items 17 to 17.