WO2003064516A1 - Composition de caoutchouc et son procede de production - Google Patents

Composition de caoutchouc et son procede de production Download PDF

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Publication number
WO2003064516A1
WO2003064516A1 PCT/JP2003/001003 JP0301003W WO03064516A1 WO 2003064516 A1 WO2003064516 A1 WO 2003064516A1 JP 0301003 W JP0301003 W JP 0301003W WO 03064516 A1 WO03064516 A1 WO 03064516A1
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rubber
weight
conjugated
parts
rubber composition
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PCT/JP2003/001003
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English (en)
Japanese (ja)
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Takeshi Karato
Yoshihiro Chino
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Zeon Corporation
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Publication of WO2003064516A1 publication Critical patent/WO2003064516A1/fr

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    • 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

Definitions

  • the present invention relates to a rubber composition and a method for producing the same, and more particularly, to a sheet obtained by molding a composition containing silica as a reinforcing agent into a sheet with a roll, and having excellent tensile properties and low tensile strength.
  • the present invention relates to a rubber composition having excellent heat build-up and a method for producing the same. Background art
  • JP-A-64-22940 discloses a conjugated gen-based rubber obtained by copolymerizing a conjugated gen and an amino group-containing monomer by a solution polymerization method using an organic alkali metal or the like as a polymerization catalyst.
  • a silicide compounded rubber composition having improved breaking strength and abrasion resistance.
  • this publication also discloses a specific compounding example in which a styrene-butadiene copolymer rubber having a natural rubber gum viscosity of about 50 is blended with the conjugated gen-based rubber.
  • Such conjugated rubbers generally have a narrow molecular weight distribution and thus are inferior in processability, and the conjugated rubber blends described above have slightly improved processability.
  • the rubber composition with poor processability is formed into a sheet by a roll.
  • the resulting rubber composition is inferior in surface shape, making it difficult to form a green tire in the tire manufacturing process.
  • JP-A Japanese Patent Application Laid-Open (JP-A) No. 11-344 discloses that a tertiary amino group-containing monomer containing 1 to 20% by weight of an emulsion-copolymerized conjugated gen-based rubber has excellent tensile properties and low heat build-up.
  • An excellent silica-containing rubber composition is disclosed.
  • This publication also discloses a specific compounding example in which a styrene-butadiene copolymer rubber having a natural rubber gum viscosity of about 50 is blended with the conjugated gen-based rubber.
  • the rubber composition containing such a conjugated diene rubber is inferior in processability, and the above rubber blend has insufficient heat resistance and low heat generation. Poor balance between properties and tensile properties.
  • Japanese Patent Laid-Open No. 8- 1 thirty-four thousand two hundred seventy-two, and a 1 weight 0/0 less than tertiary amino group-containing Yutan weight conjugated diene-based and the body copolymerized rubber and silane coupling agent the particular condition Discloses a silica compounded rubber composition kneaded in the above.
  • a rubber composition is excellent in extrusion processability, and excellent in tensile properties, low heat generation, etc., but the surface shape of the rubber composition when formed into a sheet by rolls is not satisfactory. Did not. Disclosure of the invention
  • an object of the present invention is to improve the surface shape of a sheet when a composition containing silica as a reinforcing agent is formed into a sheet by a roll, and to obtain tensile properties and low heat generation.
  • An object of the present invention is to provide a rubber composition excellent in water resistance and a method for producing the same.
  • the present inventors have conducted intensive studies to achieve the above object, and have a conjugated diene rubber having a relatively high viscosity with no amino group and a Mooney viscosity having a lower Mooney viscosity than that having an amino group. It has been found that a blend with a conjugated rubber is compounded with silica and gives a rubber composition which is excellent in the surface shape of a sheet when formed into a sheet by a roll, and which is excellent in tensile properties and low heat generation properties. Based on this finding, the present invention has been completed.
  • a conjugated diene unit 0 to 60% by weight of an aromatic vinyl monomer unit and 0 to 20% of other copolymerizable monomer units according to the present invention.
  • A conjugated gen-based rubber
  • A having a viscosity in the range of 70 to 200, and 40 to 99.8% by weight of a conjugated diene unit
  • an aromatic vinyl monomer And 5 to 20% by weight of a monomer unit, 0.2 to 20% by weight of an amino group-containing monomer unit, and 0 to 20% by weight of another copolymerizable monomer unit.
  • One viscosity is in the range of 20 to 150, and the conjugated rubber (A) contains 80 to 20 parts by weight of a conjugated rubber (B) having a Muney viscosity which is 10 or more lower than the mu viscosity of the conjugated rubber (A). (The total amount of the conjugated rubber (A) and the conjugated rubber (B) is 100 parts by weight.)
  • a rubber composition is provided.
  • the present invention provides a method for producing the rubber composition containing a conjugated diene rubber (A) and a conjugated diene rubber (B).
  • the rubber composition of the present invention contains 40 to 100% by weight of a conjugated gen unit and 0 to 60% by weight of an aromatic vinyl monomer unit, and has a viscosity of 70 to 200. 20 to 80 parts by weight of a diene rubber (A), 40 to 99.8% by weight of a conjugated diene unit, 0 to 59.8% by weight of an aromatic vinyl monomer unit, and 0.2 to 2% of an amino group-containing monomer unit It comprises 20 weight 0, the range of beam one knee viscosity from 20 to 150, the conjugated diene-based rubber having a low ⁇ one knee viscosity 10 more than arm one knee viscosity of the conjugated diene rubber (a) (B) 80 ⁇ 20 parts by weight (the total amount of the conjugated rubber (A) and the conjugated rubber (B) is 100 parts by weight;).
  • the conjugated diene rubber (A) has a conjugated diene unit of 40 to 100% by weight, preferably 50 to 90% by weight, more preferably 55 to 80% by weight, and an aromatic vinyl monomer unit 0 to 60% by weight, preferably Contains 10 to 50% by weight 0 / o, more preferably 20 to 45% by weight, and has a Mooney viscosity (ML l + 4 , 100) of 70 to 200, preferably 90 to 160, more preferably 100 It is in the range of ⁇ 150.
  • ML l + 4 , 100 Mooney viscosity
  • the conjugated diene unit amount in the conjugated diene rubber (A) is small, low heat build-up is inferior. Both When the amount of the aromatic vinyl monomer unit in the role-based rubber (A) is large, low heat build-up is inferior.
  • the conjugated rubber (A) preferably contains an aromatic vinyl monomer unit from the viewpoint of more excellent tensile properties.
  • the conjugated gen-based rubber (A) contains other copolymerizable monomer units other than the conjugated gen unit and the aromatic vinyl monomer unit as long as the effects of the present invention are not essentially impaired. Is also good.
  • the amount of the copolymerizable monomer is usually 20% by weight or less, more preferably 10% by weight 0/0 or less in all monomer units. If this amount is too large, the physical property balance of the crosslinked rubber tends to deteriorate.
  • the conjugated rubber (A) does not contain an amino group-containing monomer unit.
  • it may contain amino group-containing monomer units in a range that does not substantially impair the effects of the present invention, usually less than 0.2% by weight, particularly less than 0.1% by weight. If this amount is too large, the viscosity of the composition becomes too high, making it difficult to apply, or the surface shape of the sheet becomes poor.
  • the conjugated diene rubber (A) has a low viscosity, low heat build-up and abrasion resistance are inferior. Conversely, if it is high, the surface shape of the sheet deteriorates and the viscosity of the compound becomes too high. It becomes difficult to add.
  • the conjugated diene rubber (B) has a conjugated diene unit content of 40 to 99.8% by weight, preferably 50 to 89.% by weight, more preferably 55 to 79.6% by weight, and an aromatic vinyl monomer unit 0- 59.8 weight 0 / o, preferably 1 0 to 49. off weight 0 / o, more preferably from 20 to 44.6 by weight%, and an amino group-containing monomer units 0.2 to 20 wt%, preferably Contains 0.3 to 10% by weight, more preferably 0.4 to 5% by weight.
  • the synergistic gen-based rubber (B) contains an aromatic vinyl monomer unit from the viewpoint of more excellent tensile properties.
  • the conjugated gen-based rubber (B) is a component other than a conjugated gen unit, an aromatic vinyl monomer unit and an amino group-containing monomer unit as long as the effect of the present invention is not substantially impaired. May contain other copolymerizable monomer units.
  • the amount of this copolymerizable monomer unit is usually at most 20% by weight, especially at most 10% by weight. If the amount is too large, the physical property balance of the crosslinked rubber tends to deteriorate.
  • the conjugated rubber (B) has a viscosity at ML ( +4 , 100 ° C.) of 20-150, preferably 40-"! 30, more preferably 50-100.
  • the viscosity is lower than the viscosity of the conjugated rubber (A) by 10 or more, preferably 20 or more, more preferably 25 or more.
  • the conjugated diene rubber (B) has low viscosity, low heat build-up and abrasion resistance are inferior. Conversely, if it is high, the surface shape of the sheet deteriorates and the compound viscosity becomes too high. It becomes difficult to add. If the difference between the viscosity of the conjugated rubber (B) and the viscosity of the conjugated rubber (A) is too small, the surface shape of the sheet may deteriorate or the viscosity of the compound may be reduced. It becomes too high and difficult to process.
  • the ratio of the conjugated rubber (A) to the conjugated rubber (B) is 20 to 80 parts by weight, preferably 30 to 7 parts by weight, based on a total of 100 parts by weight of both. It is 5 parts by weight, more preferably 40 to 70 parts by weight. If the amount of the conjugated diene rubber (A) is small, the surface shape of the sheet is deteriorated, or the viscosity of the compound is too high, making it difficult to apply. Conversely, if the amount is large, the tensile properties and low heat build-up are poor.
  • conjugated gen examples include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and the like. Is mentioned. Among these, 1,3-butadiene is preferred. These can be used alone or in combination of two or more.
  • aromatic vinyl monomer an aromatic vinyl compound having no amino group is used.
  • styrene a-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropyl
  • examples include styrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, and monofluorostyrene.
  • styrene is preferred. These can be used alone or in combination of two or more.
  • Amino group-containing monomers are selected from primary, secondary and tertiary amino groups in one molecule. Preferred are polymerizable monomers having at least one amino group, particularly those having a tertiary amino group.
  • Examples of the primary amino group-containing monomer include acrylamide, methacrylamide, p-aminostyrene, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate And the like.
  • secondary amino group-containing monomer examples include anilinostyrenes disclosed in JP-A-61-130355; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide N- (4-anilinophenyl) methacrylamide; N-monosubstituted (meth) acrylamides;
  • tertiary amino group-containing monomer examples include N, N-disubstituted aminoalkyl (meth) acrylate, N, N-disubstituted aminoalkyl (meth) acrylamide, N, N-disubstituted aminoaromatic
  • examples thereof include a vinyl compound and a polymerizable monomer having a pyridyl group.
  • N, N-disubstituted aminoalkyl (meth) acrylate examples include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate.
  • N, N-dimethylaminoethyl (meth) acrylate, N, N-getylaminoethyl (meth) acrylate, and N, N-dipropylaminoethyl (meth) acrylate are preferred.
  • N, N-disubstituted aminoalkyl (meth) acrylamide examples include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( (Meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-getylaminoethyl (meth) acrylamide, N, N- Getylaminopropyl (meth) acrylamide, N, N-getylaminobutyl (meth) acrylamide, N-methyl-1-N-ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) ) Acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminoprop
  • N, N-disubstituted aminoalkyl aromatic vinyl compound examples include N, N-dimethylaminoethylstyrene, N, N-getylaminoethylstyrene, N, N-dipropylaminoethylstyrene, N, N —Dioctylaminoethylstyrene and the like.
  • Examples of the polymerizable monomer having a pyridyl group include 2-vinylpyridine, 4-vinylpyridine, 5-methyl-1-vinylpyridine, 5-ethyl-2-vinylpyridine, and the like. Of these, 2-vinylpyridine and 4-vinylpyridine are preferred.
  • amino group-containing monomers can be used alone or in combination of two or more.
  • monomers other than the conjugated gen, the aromatic vinyl monomer and the amino group-containing monomer may be copolymerizable with the conjugated gen, the aromatic vinyl monomer and the amino group-containing monomer.
  • Specific examples thereof include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethyl (meth) acrylate.
  • Ethylenically unsaturated carboxylic acid ester monomers such as xyl, dibutyl maleate, getyl fumarate, and dibutyl itaconate; (meth) acrylic acid, maleic acid, fumaric acid, monoethyl maleate, monobutyl fumarate, etc.
  • Lenic unsaturated carboxylic acid monomers ethylenically unsaturated nitrile monomers such as (meth) acrylonitrile; vinyl chloride, vinyl acetate, etc. That.
  • the method for producing the conjugated rubbers (A) and (B) used in the present invention is not particularly limited, but an emulsion polymerization method or a solution polymerization method can be adopted.
  • Solution polymerization is a conjugate It can be preferably used when preparing a rubber having a vinyl bond content of 20 to 85% by weight in a conjugated gen unit in a rubber.
  • a conventional emulsion polymerization method may be used.
  • a method in which a predetermined amount of the above monomer is emulsified and dispersed in a dispersion medium in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator is employed.
  • Can be The amount of each monomer used is appropriately selected so that each monomer unit has a desired content.
  • a long-chain fatty acid salt having 10 or more carbon atoms and a phosphate or rhodium salt are used.
  • Specific examples thereof include potassium or sodium salts of fatty acids such as hydropric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.
  • Water is usually used as a dispersion medium used in the emulsion polymerization, and may contain a water-soluble organic solvent such as methanol or ethanol as long as the stability during polymerization is not impaired.
  • radical polymerization initiator examples 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; Redox initiators such as a combination of hydrogen oxide and ferric sulfate; and the like.
  • a chain transfer agent may be added.
  • the chain transfer agent include mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, r-terbinene, ⁇ -methylstyrene dimer and the like.
  • mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, r-terbinene, ⁇ -methylstyrene dimer and the like.
  • the temperature of the emulsion polymerization can be appropriately selected depending on the type of the radical polymerization initiator to be used, but is usually 0 to 100 ° C, preferably 0 to 60 ° C.
  • the polymerization mode may be any mode such as continuous polymerization or batch polymerization.
  • the polymerization conversion rate at the time of stopping the polymerization reaction is preferably 85 ⁇ 85 or less, more preferably 50-75 50.
  • Termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined polymerization conversion is reached.
  • the polymerization terminator include amine-based compounds such as isopropylhydroxylamine and getylhydroxylamine-hydroxylamine. Compounds; quinone-based compounds such as hydroquinone and benzoquinone; sodium nitrite, sodium dithiocarbamate and the like.
  • an antioxidant may be added to the obtained latex, if necessary.
  • salts such as sodium chloride, calcium chloride and potassium chloride are used as a coagulant, and nitric acid, sulfuric acid and the like are used as necessary.
  • the acid can be added to adjust the pH of the coagulation system to a predetermined value while coagulating the polymer as crumb, and then separating the dispersion medium to recover the polymer.
  • the crumb can be washed and dehydrated and then dried with a band dryer or the like to obtain the desired geno rubber.
  • a latex and an extender oil which has been previously made into an emulsified dispersion can be mixed and recovered as an oil-extended rubber.
  • the solution polymerization method may be a conventional solution polymerization method.
  • the above monomer is polymerized in a polymerization solvent using an organic alkali metal as an anion polymerization catalyst, if desired, in the presence of a polar compound. .
  • polymerization solvent examples include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic rings such as cyclopentane, cyclohexane, and methylcyclopentane.
  • hydrocarbons aromatic hydrocarbons such as benzene and toluene; and the like.
  • unsaturated hydrocarbons having low anion polymerizability such as 1-butene, cis-1-butene, and 2-hexene may be used in combination.
  • These polymerization solvents are used alone or in combination of two or more kinds, and are usually used in a ratio such that the monomer concentration becomes 1% by weight to 40% by weight 0/0.
  • organic alkali metal examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; dilithiomethane, 1,4 dilithiobutane, 1,4 Polyfunctional organic lithium compounds such as —dilithio—2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene and potassium naphthalene; Of these, organic lithium compounds are preferred, and organic monolithium compounds are particularly preferred. These organic alkali metals can be used alone or in combination of two or more.
  • the amount of organic alkali metal used depends on the required polymer although it is appropriately selected depending on the molecular weight, it is usually in the range of 0.1 to 30 mmol, preferably 0.2 to 15 mmol, more preferably 0.3 to 1 Ommol per 100 g of monomer. is there.
  • the organic alkali metal may be used as an organic alkali metal amide by previously reacting with a secondary amine such as dibutylamine, dihexylamine or dibenzylamine.
  • an organic alkali metal When used as a polymerization catalyst, it is preferable not to use such a monomer since there are monomers that affect the polymerization reaction. From this point of view, it is preferable to use a tertiary amino group-containing monomer as the amino group-containing monomer, and it is particularly preferable to use an N, N-disubstituted amino aromatic vinyl compound. Dimethylaminoethylstyrene is most preferred.
  • the polar compound is not particularly limited as long as it is a compound generally used in anion polymerization to adjust the microstructure of conjugated gen units and the distribution of aromatic vinyl in the copolymer chain.
  • Specific examples thereof include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol ethyl ether; tertiary amines such as trimethylethylenediamine and trimethylamine; potassium mono-t-amyloxide; Alkali metal alkoxides such as amyloxide; phosphine compounds such as triphenylphosphine; and the like.
  • tertiary amines are preferred, and tetramethylethylenediamine is particularly preferred, in that the amount of vinyl bonds in the conjugated gen unit and the amount of independent bond units of aromatic vinyl can be greatly increased.
  • the amount of the polar compound used is preferably in the range of 0.1 to 100 mol, more preferably 0.5 to 50 mol, and particularly preferably 1 to 30 mol, per 1 mol of the organic alkali metal used as the polymerization initiator. It is. Within this range, the amount of vinyl bonds in the conjugated gen unit can be adjusted appropriately.
  • the polymerization reaction is usually carried out at a temperature in the range of 170 to 150 ° C, preferably 0 to 100 ° C, and more preferably 30 to 90 ° C, in a batch or continuous polymerization mode.
  • the composition ratio of the aromatic vinyl monomer and the conjugated gen in the polymerization system is improved in order to improve the randomness of the bond between the aromatic vinyl monomer units. It is preferable to supply the conjugated gen or a mixture of the conjugated gen and the aromatic vinyl monomer continuously or intermittently to the reaction system so that the content of the aromatic vinyl monomer is in a specific concentration range. .
  • an alcohol such as methanol or isopropanol is added as a polymerization terminator to terminate the reaction to obtain a polymerization solution.
  • tin tetrachloride, tetrachlorosilane, tetramethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolylenediisocyanate which can react with the polymerization active terminal
  • a polymerization terminal modifier such as 4,4′-bis (getylamino) benzophenone, N-methylpyrrolidone, and N-vinylpyrrolidone.
  • the polymerization solvent is separated from the polymerization solution by direct drying or steam stripping, and the target rubber is recovered.
  • the extension oil and the polymerization solution may be mixed in advance and recovered as an oil-extended rubber.
  • the rubber composition of the present invention is prepared by kneading and blending a conjugated rubber (A) and a conjugated rubber (B) in the form of a solid rubber, respectively, or as a solid rubber.
  • the dispersion medium is separated and obtained as a solid rubber-like blend. Is also good.
  • the latter method is preferable because the dispersibility of the conjugated rubber (A) and the conjugated rubber (B) is excellent, and it is particularly preferable to mix the latexes or the solutions.
  • the dispersion medium is mainly composed of water in the case of latex, and is mainly composed of the polymerization solvent in the case of solution.
  • the rubber composition of the present invention preferably contains an extension oil so that the viscosity of the compound when silica is compounded does not become too high.
  • an extender oil those commonly used in the rubber industry can be used, and examples thereof include a paraffin extender oil, an aromatic extender oil, and a naphthenic extender oil.
  • the pour point of the extender oil is preferably between 20 and 50 ° C, more preferably between 10 and 30 ° C. Within this range, the extensibility and the balance between tensile properties and low heat build-up are excellent.
  • the aroma carbon content (CA%) of the extended oil by Kurz analysis is preferably 15% or more, more preferably 25% or more, and the paraffin carbon content (CP%) is preferably 65% or less, more preferably Preferably it is 45%. If CAo / o is too small or CP% is too large, the tensile properties will be insufficient.
  • the polycyclic aromatic content of the extender oil is preferred. Or less than 3%. This content is measured by the method of IP346 (test method of THE INSTITUTE PETROLEUM in the UK).
  • the content of the extender oil is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, based on 100 parts by weight of the total of the conjugated rubber (A) and the conjugated rubber (B). Preferably it is 20 to 60 parts by weight.
  • the content of the extender oil is in this range, the viscosity of the compound containing silicide is appropriate, and the tensile properties and the low heat generation balance are excellent.
  • the rubber composition of the present invention preferably contains at least one selected from silicic acid and carbon black as a reinforcing agent, and more preferably contains silica as an essential component.
  • a reinforcing agent a carbon-silica dual 'phase' filler having silica supported on the carbon black surface may be used.
  • silica examples include dry-process white carbon, wet-process white carbon, colloidal silica, and precipitated silica disclosed in JP-A-62-62838.
  • wet-process white carbon containing hydrous gay acid as a main component is particularly preferable.
  • 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) is preferably from 5O ⁇ 400m 2 Zg, more preferably 100 ⁇ 220m 2 Zg, particularly preferably 12 0 ⁇ 190m 2 Zg .
  • BET method a nitrogen adsorption specific surface area
  • the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTMD3037-81.
  • furnace black for example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used.
  • furnace black is particularly preferred, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF. Grade grades. These carbon blacks can be used alone or in combination of two or more.
  • the specific surface area of carbon black is not particularly limited, a nitrogen absorption specific surface area (N 2 SA), preferably 5 ⁇ 200m 2 Zg, more preferably 50m ⁇ 150m 2 Zg, particularly preferably 80 ⁇ 130m 2 Zg is there.
  • N 2 SA nitrogen absorption specific surface area
  • the nitrogen adsorption specific surface area is in this range, the tensile characteristics are more excellent.
  • the adsorption amount of dibutylphthalate (KDBP) of the power pump rack is not particularly limited, and the power is preferably 5 to 300 ml 1 OOg, more preferably 50 to 200 ml / 1 OOg, and particularly preferably 80 to "! 60 ml / 100 g When the DBP adsorption amount is within this range, the tensile properties are more excellent.
  • KDBP dibutylphthalate
  • the adsorption (CTAB) specific surface area of cetyltrimethylammonium bromide disclosed in JP-A-5-230290 is 110 to 170 m 2 Zg, and at a pressure of 24, OOOpsi.
  • Abrasion resistance can be improved by using high-structure one-strength black, which has a DBP (24M4D BP) oil absorption of 110-130mlZ100g after repeated compression.
  • the compounding amount of the reinforcing agent is preferably 10 to 200 parts by weight, more preferably 20 to "! 50 parts by weight, particularly preferably 30 to"! 20 parts by weight.
  • the mixing ratio is preferably 10:90 to 99: 1, more preferably 30:70 to 95: 5, by weight ratio of silica: force—bon black, It is preferably 50:50 to 90:10 for temples.
  • the rubber composition of the present invention contains silica as a reinforcing agent, it is preferable to add a silane coupling agent for the purpose of further improving tensile properties and low heat build-up.
  • silane coupling agent examples include vinyltriethoxysilane,-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (monoaminoethyl) -r- aminopropyl trimethoxysilane, (3- (triethoxysilyl) propyl) tetrasulfide, bis (3- (triethoxysilyl) propyl) disulphide and the like, and r-trimethoxysilylpropyl dimethylthiothiol described in JP-A-6-248116 Lubamil tetrasulfide, 7-trimethoxysilylpropylbenzothiazyltetrasulfide And the like. Since scorch at the time of kneading can be avoided, the silane coupling agent is preferably one containing four or less sulfur in one molecule. These silane coupling agents can be used alone or in combination of two or more.
  • the amount of the silane coupling agent to be added is preferably 0.1 to 30 parts by weight, more preferably "! To 20 parts by weight, particularly preferably 2 to 10 parts by weight, based on 100 parts by weight of silica. .
  • the rubber composition of the present invention may contain other rubbers other than the conjugated rubber (A) and the conjugated rubber (B) as long as the effects of the present invention are not substantially impaired.
  • other rubbers include natural rubber, high cis-polyisoprene rubber, high cis-polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, butyl rubber, and ethylene-propylene-one-gen copolymer rubber.
  • the rubber composition of the present invention contains, in addition to the above components, compounding agents such as a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an antioxidant, an activator, a plasticizer, a lubricant, and a filler according to a conventional method. Each of them can be contained in a required amount.
  • cross-linking agent examples include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl valoxide, tert-butyl butyl oxide.
  • Quinonedioximes such as P-quinondioxime, p, p'-dibenzoylquinonedioxime; triethylenepentramine, hexamethylenediamine powerbamate, 4,4'-methylenebis-o-chloroa
  • Organic polyamine compounds such as diphosphorus; alkylpheno having a methylol group
  • crosslinking agents may be used alone or in combination of two or more.
  • the compounding amount of the crosslinking agent is preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.
  • crosslinking accelerator examples include N-cyclohexyl-1-benzothiazolesulfenamide, Nt-butyl-2-benzothiazolsulfenamide, N-oxyethylene-12-benzothiazolsulfenamide, and N-oxyethylene 2-benzothiazolsulfenamide, N, N'-diisopropyl-1-benzothiazolesulfenamide, etc.
  • Sulfenamide-based crosslinking accelerators guanidine-based crosslinking accelerators such as diphenylguanidine, dioritoltriguanidine, and o-tolylbiguanidine; thioperia-based crosslinking accelerators such as getylthioperia; 2-mercaptobenzothiazole Thiazole-based cross-linking accelerators such as dimethyl, dibenzothiazyl disulfide and 2-mercaptobenzothiazol zinc salt; thiuram-based cross-linking accelerators such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Cross-linking accelerators such as sodium rubamate and dithiol-rubic acid-based cross-linking accelerators such as getyldithi-rich zinc rubamate; sodium xanthate-based cross-linking accelerators such as sodium isopropylxanthate, zinc isopropylxanthate and zinc butylxant
  • sulfenamide-based crosslinking accelerators are preferred. These cross-linking accelerators are used alone or in combination of two or more.
  • the compounding amount of the crosslinking accelerator is preferably from 0.3 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.
  • crosslinking activator for example, higher fatty acids such as stearic acid, zinc oxide, and the like can be used. It is preferable to use zinc oxide having a surface activity of 5 m or less as the zinc oxide, and it is preferable to use active zinc white having a particle size of 0.05 to 0.2 jum or zinc white having a particle size of 0.3 to 1 ⁇ m. Can be mentioned. Zinc oxide may be surface-treated with an amine-based dispersant or wetting agent. 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.
  • the blending amount of the higher fatty acid is preferably from 0.3 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component.
  • the amount of zinc oxide is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the rubber component.
  • examples of the compounding agent include an activator such as diethylene glycol, polyethylene glycol, and silicone oil; a filler such as calcium carbonate, talc, clay, and aluminum hydroxide; and a wax.
  • the rubber composition containing a reinforcing agent can be obtained by kneading each component according to a conventional method.
  • a kneading product may be kneaded with a crosslinking agent and a crosslinking accelerator to obtain a rubber composition.
  • the kneading temperature of the compounding agent, the reinforcing agent, and the rubber component excluding the crosslinking agent and the crosslinking accelerator is preferably 80 to 200 ° C, more preferably 100 to 190 ° C, and particularly preferably 140 to 180 ° C.
  • the obtained kneaded product is preferably 100 ° C. or less, more preferably 80 ° C. or less, it is kneaded with a crosslinking agent and a crosslinking accelerator.
  • the rubber composition containing the reinforcing agent is obtained as a wet master batch rubber by mixing a reinforcing agent at a predetermined ratio in advance into each polymer latex or polymer solution before obtaining as a solid rubber. You can also.
  • the rubber composition of the present invention is usually used after crosslinking.
  • the crosslinking method is not particularly limited, and may be selected according to the shape, size, and the like of the crosslinked product.
  • the crosslinking temperature and the crosslinking time are also not particularly limited, and may be selected according to the shape and size of the crosslinked product.
  • the crosslinking temperature is preferably from 120 to 200 ° C, more preferably from 140 to 180 ° C.
  • the properties of the copolymer and the rubber composition were measured according to the following methods.
  • Styrene unit amount in copolymer Measured according to JIS K6383 (refractive index method).
  • Mooney viscosity of copolymer rubber (ML, +4 , 100 ° C): Measured according to JIS K6300.
  • Tensile properties of crosslinked rubber The stress at 300% elongation (MPa) was measured according to JIS K6301. This property was expressed as an index (tensile property index) with the reference sample as 100. The larger the value, the better.
  • Production Example 1 was repeated except that the monomer was changed to the charge composition shown in Table 1, and the amount of t-dodecyl mercaptan used was changed appropriately so that the Mooney viscosity of the obtained solid rubber became the value shown in Table 1. Polymerization was carried out in the same manner to obtain polymer latexes containing polymers HA1, L1 and LA1 to A3, respectively.
  • a solid rubber was prepared in the same manner as in Production Example 1.
  • Table 1 shows the composition and muci-viscosity of each solid rubber.
  • N, N-Dimethylaminoethylstyrene unit 1.16 viscosity 1 22 1 20 70 67 54 7 6
  • the obtained kneaded product was combined with 1.4 parts of sulfur and a crosslinking accelerator (a mixture of 1.8 parts of N-cyclohexyl-2-benzothiazylsulfenamide and 1.7 parts of diphenylguanidine). After kneading with an open roll at 50 ° C., the mixture was taken out in a sheet form.
  • a crosslinking accelerator a mixture of 1.8 parts of N-cyclohexyl-2-benzothiazylsulfenamide and 1.7 parts of diphenylguanidine.
  • An oil-extended rubber was prepared in the same manner as in Example 1, except that the mixing ratio was changed to the polymer shown in Table 2.
  • Table 2 shows the Mooney viscosity of each oil-extended rubber.
  • Example 4 A rubber composition was prepared and processed in the same manner as in Example 1 except that the obtained oil-extended rubber was used, and the physical properties of the crosslinked rubber were evaluated. The results are shown in Table 2. (Example 4)
  • Enerthenel 849A manufactured by Pretty Petroleum Co., Ltd.
  • extender oil 100 parts of the polymer!.
  • the polymer latex containing the extended oil was coagulated with sodium chloride while adjusting the pH to 3 to 5 with sulfuric acid to obtain a crumb-like solid.
  • the crumb was dried with a hot air dryer at 80 ° C to obtain an oil-extended rubber.
  • a rubber composition was prepared in the same manner as in Example 1 except that the oil-extended rubber containing the polymer H1 and the oil-extended rubber containing the polymer LA1 were used so that the ratios shown in Table 2 were obtained. The processability was evaluated, and further the physical properties of the crosslinked rubber were evaluated. Table 2 shows the results.
  • Enerthenel 849A manufactured by Pretty Petroleum Co.
  • the polymer latex containing the extended oil was coagulated with sodium chloride while adjusting the pH to 3 to 5 with sulfuric acid to obtain a crumb-like solid.
  • the crumb was dried with a hot air dryer at 80 ° C to obtain an oil-extended rubber.
  • a rubber composition was prepared and its processability was evaluated in the same manner as in Comparative Example 1 except that the polymer H1 was changed to the polymer LA1, and further, the physical properties of the crosslinked rubber were evaluated.
  • Table 2 shows the results.
  • a rubber composition was prepared and the processability thereof was evaluated in the same manner as in Example 1 except that the polymer and the compounding ratio were changed as shown in Table 2, and further, the physical properties of the crosslinked rubber were evaluated. Table 2 shows the results. Comparative Example ''
  • the rubber composition of Comparative Example 1 containing only the polymer H1 having no amino group has good processability, but is inferior in the properties of the crosslinked rubber.
  • the rubber composition of Comparative Example 2 containing only the polymer LA1 having an amino group is superior to Comparative Example 1 in the properties of the crosslinked rubber, but is inferior in processability.
  • the rubber composition of Comparative Example 3 blended with a polymer H1 having no amino group and a polymer HA1 having an amino group but having a difference in viscosity of less than the range specified in the present invention is: The properties of the crosslinked rubber are good, but the processability is poor.
  • the rubber compositions containing silica of Examples 1 to 4 of the present invention have good processability and excellent properties of crosslinked rubber.
  • Table 3 shows the composition and Mooney viscosity of each polymer.
  • the polymer solution containing the polymer SH1 and the polymer solution containing the polymer SLA1 were mixed so that each polymer had the compounding ratio shown in Table 4, and then, based on 100 parts of the whole polymer, w extended oil was added. Enerthenel 849 A (British Petroleum) as 37/5 Added.
  • the polymerization solvent was separated and removed from the polymer solution containing the extended oil by a steam stripping method, dewatered by a roll, and further dried by a hot air dryer at 80 ° C to obtain an oil-extended rubber.
  • Table 4 shows the Mooney viscosity of the oil-extended rubber.
  • the obtained kneaded material was combined with 1.4 parts of sulfur and a crosslinking accelerator (a mixture of 1.8 parts of N-cyclohexyl-2-benzothiazylsulfenamide and 1.9 parts of diphenylguanidine). After kneading with an open roll at 50 ° C., the mixture was taken out in a sheet form.
  • a crosslinking accelerator a mixture of 1.8 parts of N-cyclohexyl-2-benzothiazylsulfenamide and 1.9 parts of diphenylguanidine.
  • a rubber composition was prepared and its processability was evaluated in the same manner as in Example 5, except that the polymers and the compounding ratio shown in Table 4 were used, and the physical properties of the crosslinked rubber were evaluated. Table 2 shows the results.
  • the rubber composition of Comparative Example 5 containing only the polymer SH1 having no amino group had good processability but was inferior in the properties of the crosslinked rubber.
  • the rubber composition of Comparative Example 6, which contains only the polymer SLA1 having an amino group, is superior to Comparative Example 5 in the properties of the crosslinked rubber, but is inferior in processability.
  • the rubber composition of Comparative Example 8 in which a polymer SL 1 having no amino group and a polymer S HA 1 having an amino group having a higher viscosity than that of the polymer SL 1 were blended has poor processability, and Poor properties of crosslinked rubber.
  • the rubber composition containing the silica of Example 5 within the range specified by the present invention has good processability and excellent properties of the crosslinked rubber. Industrial applicability
  • the rubber composition of the present invention is excellent in the surface shape of a sheet when a compound containing silica as a reinforcing agent is formed into a sheet by a roll, and is excellent in tensile properties and low heat generation.
  • the rubber composition of the present invention can be used in various applications that make use of its properties, for example, tire members such as treads, under treads, force scums, sidewalls, bead portions; hoses, window frames, belts, shoes. It can be used for rubber materials such as bases, anti-vibration rubber, seismic isolation rubber, and automotive parts; resin-reinforced rubber materials such as impact-resistant polystyrene and ABS resin. Among them, it is suitable as a tire member and particularly suitable as a tire tread of a fuel-efficient tire.

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Abstract

La présente invention concerne une composition de caoutchouc comprenant : 20 à 30 parties en poids d'un caoutchouc diénique conjugué (A) comportant 40 à 100 % en poids d'unités diéniques conjugués et 0 à 60 % en poids d'unités de monomères vinyliques aromatiques et présentant une consistance Mooney de 70 à 200 ; et 80 à 20 parties en poids d'un caoutchouc diénique conjugué (B) comportant 40 à 99,8 % d'unités diéniques, 0 à 59,8 % d'unités de monomères vinyliques aromatiques, et 0,2 à 20 % en poids d'unités monomères aminés et présentant une consistance Mooney qui est de 20 à 150 et inférieure d'au moins 10 à celle du caoutchouc diénique conjugué (A) (la somme totale de caoutchouc diénique conjugué (A) et de caoutchouc diénique conjugué (B) est de 100 parties en poids). Un composé obtenu par le compoundage de ladite composition de caoutchouc avec une charge renforçante de silice permet d'obtenir, grâce au moulage avec des cylindres, une feuille présentant une forme de surface et des propriétés excellentes avec une réduction d'accumulation thermique.
PCT/JP2003/001003 2002-01-31 2003-01-31 Composition de caoutchouc et son procede de production WO2003064516A1 (fr)

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JP4624753B2 (ja) * 2003-10-31 2011-02-02 三ツ星ベルト株式会社 Ｖリブドベルト
JP4624747B2 (ja) * 2003-10-31 2011-02-02 三ツ星ベルト株式会社 動力伝動ベルト
JP4624748B2 (ja) * 2003-10-31 2011-02-02 三ツ星ベルト株式会社 歯付ベルト
BRPI0604797A (pt) * 2005-11-30 2007-10-09 Goodyear Tire & Rubber polìmeros de borracha funcionalizados
JP2011140613A (ja) 2009-12-09 2011-07-21 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物及び空気入りタイヤ
JP2011184521A (ja) * 2010-03-05 2011-09-22 Sumitomo Rubber Ind Ltd クリンチ用ゴム組成物及び空気入りタイヤ
JP5702070B2 (ja) * 2010-03-08 2015-04-15 住友ゴム工業株式会社 サイドウォール用ゴム組成物及び空気入りタイヤ
WO2023145771A1 (fr) * 2022-01-26 2023-08-03 株式会社Ｅｎｅｏｓマテリアル Procédé de production de composition polymère, composition polymère, corps réticulé et pneumatique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01101344A (ja) * 1987-10-14 1989-04-19 Bridgestone Corp タイヤ
JPH0255747A (ja) * 1988-08-22 1990-02-26 Bridgestone Corp ゴム組成物
WO1996030444A1 (fr) * 1995-03-29 1996-10-03 Nippon Zeon Co., Ltd. Composition de caoutchouc dienique
WO1997009378A1 (fr) * 1995-09-05 1997-03-13 Nippon Zeon Co., Ltd. Composition de caoutchouc dienique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01101344A (ja) * 1987-10-14 1989-04-19 Bridgestone Corp タイヤ
JPH0255747A (ja) * 1988-08-22 1990-02-26 Bridgestone Corp ゴム組成物
WO1996030444A1 (fr) * 1995-03-29 1996-10-03 Nippon Zeon Co., Ltd. Composition de caoutchouc dienique
WO1997009378A1 (fr) * 1995-09-05 1997-03-13 Nippon Zeon Co., Ltd. Composition de caoutchouc dienique

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