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WO2020021929A1 - Composition de caoutchouc - Google Patents

Composition de caoutchouc Download PDF

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Publication number
WO2020021929A1
WO2020021929A1 PCT/JP2019/024853 JP2019024853W WO2020021929A1 WO 2020021929 A1 WO2020021929 A1 WO 2020021929A1 JP 2019024853 W JP2019024853 W JP 2019024853W WO 2020021929 A1 WO2020021929 A1 WO 2020021929A1
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Prior art keywords
rubber
compound
weight
silica
modified
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English (en)
Japanese (ja)
Inventor
壽男 小野
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the present invention relates to a rubber composition for tires having excellent safety and low fuel consumption.
  • the rubber materials for tires have the trade-off between mechanical properties, abrasion resistance, low fuel consumption, wet grip performance, etc. Improvement is desired.
  • a method of using silica as a low heat-generating filler is known. For example, by blending silica or a silane coupling agent into the solution-polymerized SBR rubber, it is possible to improve the performance to some extent.
  • Solution-polymerized SBR rubber has a narrow molecular weight distribution, poor processability, and inferior durability when used as a tire.
  • Another problem is that the production cost is high because the solution polymerized rubber is modified with a special silane coupling agent or the like.
  • radically polymerized rubbers are widely manufactured industrially because they are easy to manufacture.
  • radically polymerized rubbers generally have a broad molecular weight distribution and can produce emulsion polymerized rubbers having good processability.
  • silica or a silane coupling agent is blended with the emulsion polymerized rubber, the effect of improving fuel economy and improving safety is smaller than that of the modified solution polymerized rubber.
  • Factors that hinder the fuel economy of tires are heat generation due to friction between reinforcing fillers, energy loss due to irreversible movement by low molecular compounds such as oil and soap, and irreversible movement of non-crosslinked terminal molecules. Is said to be due to energy loss.
  • Carbon black and silica are used as reinforcing fillers in rubber compositions such as tires.
  • the fuel efficiency of tires is greatly affected by reinforcing fillers, and the reinforcing fillers are agglomerated, meaning that when the tire is deformed, the reinforcing fillers generate friction and generate heat, consuming energy. Have been done.
  • Modified solution-polymerized SBR rubber with excellent fuel efficiency has a functional group that reacts with the reinforcing filler at the polymer end, and the reinforcing filler and rubber molecules are bonded to each other to improve the reinforcing properties during kneading.
  • the filler can be finely dispersed.
  • Non-Patent Document 1 the terminal of the radical polymerized rubber has no functional group that reacts with the reinforcing filler. Therefore, it does not react with the reinforcing filler, and the reinforcing filler cannot be finely dispersed.
  • the terminal of the radical polymerized rubber has a structure of hydrogen or an alkylthioether because mercaptan is used as a molecular weight regulator. Therefore, the rubber composition does not act on the reinforcing filler and does not finely disperse the reinforcing filler, so that the rubber composition has a large friction between the reinforcing fillers.
  • This method aims at the effect of the functional group and the reinforcing filler by polymerizing a polar functional group-containing thiol compound as a chain transfer agent.
  • washing and filtration were repeated several times with an aqueous solution of sodium carbonate in order to reduce the amount of acetone extracted. Therefore, the number of steps increases, and the cost increases as a manufacturing method. Further, if alkaline substances such as sodium carbonate remain, scorch may be caused during vulcanization, which is not preferable.
  • a compound other than a polar functional group-containing thiol compound is used in radical emulsion polymerization SBR.
  • a radical polymer of styrene butadiene using a xanthogen compound is disclosed in U.S. Pat. No. 2,401,346. It is described that by adding mercaptan and a xanthogen compound together during polymerization, the yield is increased, the benzene-soluble content is increased, and the strength of the crosslinked rubber is excellent.
  • U.S. Pat. No. 2,388,515 also discloses an example in which a benzothiazole compound is added during polymerization. These patents describe that the yield, the benzene-soluble content, and the strength of the crosslinked rubber are excellent. Both patents describe the compounding of rubber as a typical tire recipe.
  • Non-Patent Document 2 only carbon black is used as a filler of a rubber for a tire, and silica or a silane coupling agent is not used. Further, there is no mention of the fuel efficiency that is the object of the present invention.
  • the present invention considers the structure of the polymer formed by radical polymerization, improves the dispersion of the reinforcing filler by adding a functional group involved in crosslinking during the polymerization, and acts on the polymer and the polymer and the reinforcing filler. By reducing the energy loss of the polymer composition by doing, and by reducing the energy loss due to irreversible movement by cross-linking the terminal molecule, the heat generation of the rubber composition was reduced and the fuel economy was improved. .
  • the object of the present invention is to provide a rubber composition containing carbon black and silica, which are reinforcing fillers, has good processability, and can improve wet grip performance and fuel economy in a well-balanced manner.
  • Another object of the present invention is to provide a pneumatic fuel-efficient tire using the composition.
  • the present invention radically polymerizes a conjugated diene monomer and a radical polymerizable monomer in the presence of at least one compound selected from a xanthogen compound, a sulfenamide compound, a thiuram compound, a dithiocarbamic acid compound or a thiazole compound.
  • a composition containing carbon black, silica and a silane coupling agent a rubber composition having a good balance between wet grip performance and low fuel consumption can be obtained.
  • the present invention provides a polar functional group obtained by emulsion polymerization of a conjugated diene monomer and a radical polymerizable monomer in the presence of a xanthogen compound, a sulfenamide compound, a thiuram compound, a dithiocarbamic acid compound or a thiazole compound.
  • the present invention relates to a rubber composition for a tire using a modified rubber having the same.
  • a monomer is emulsified with a soap, and a molecular weight regulator is adjusted using a mercaptan compound. Therefore, the terminal of the molecule is a hydrogen or alkylthioether group.
  • the present inventors have conducted intensive studies, and obtained a polymer obtained by polymerizing a compound selected from a xanthogen compound, a sulfenamide compound, a thiuram compound, a dithiocarbamic acid compound or a thiazole compound in the presence of at least one kind.
  • Xanthogen compounds, sulfenamide compounds, thiuram compounds, dithiocarbamic acid compounds or thiazole compounds are known as rubber vulcanization accelerators.
  • the vulcanization accelerator has the effect of reacting with sulfur or zinc white to link rubber molecules with sulfur bonds. In the present invention, by introducing such a compound into rubber molecules, a bond between the molecules is generated, and the energy loss with respect to dynamic movement is reduced.
  • the production of the modified polymer having a polar functional group of the present invention can be achieved by coexisting a xanthogen compound, a sulfenamide compound, a thiuram compound, a dithiocarbamic acid compound or a thiazole compound during the emulsion polymerization of SBR.
  • the emulsion polymerization method may be hot polymerization performed at a polymerization temperature of about 30 ° C. to about 50 ° C. or cold polymerization performed at about 5 ° C.
  • a monomer is emulsified in water containing a surfactant, radicals are generated by a radical initiator to initiate polymerization, and the molecular weight of the produced polymer is adjusted by a molecular weight regulator.
  • the resulting emulsion polymer is coagulated by adding salt or acid to recover the polymer.
  • the conversion at the time of polymerization is preferably 60% or less. If the conversion exceeds 60%, the processability of the rubber is inferior.
  • persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, peroxides such as hydrogen peroxide and paramenthane hydroperoxide, and diazo compounds such as azoisobutyronitrile are used.
  • a chelating agent such as iron or copper may be added in order to accelerate the decomposition of these compounds.
  • sodium salts and potassium salts such as fatty acids, rosin acids, disproportionated rosin acids, naphthalenesulfonic acid formalin condensates, and alkylallylsulfonic acids can be used.
  • a xanthogen compound, a sulfenamide compound, a thiuram compound, a dithiocarbamic acid compound or a thiazole compound acts as a molecular weight regulator, but is generally a molecular weight regulator such as n-dodecylmercaptan, t-dodecylmercaptan, A mixture of n-dodecyl mercaptan and t-dodecyl mercaptan can be used in combination.
  • an electrolyte may be added to lower the viscosity of the polymerization system and prevent gelation.
  • electrolyte examples include potassium chloride, sodium phosphate, potassium phosphate and potassium sulfate.
  • a polymerization terminator hydroquinone, dimethyldithiocarbamate, sodium polysulfide, dimethyldithiocarbamate, polyethylene polyamine and the like can be used.
  • the present invention is achieved by adding a xanthogen compound, a sulfenamide compound, a thiuram compound, a dithiocarbamic acid compound or a thiazole compound to such an emulsion polymerization system.
  • the amount of the xanthogen-based compound, sulfenamide-based compound, thiuram-based compound, dithiocarbamic acid-based compound or thiazole-based compound to be used is 0.01 to 5 parts by weight based on 100 parts by weight of the monomer. If the amount is less than 0.01 part by weight, the effect is small, and if it exceeds 5 parts by weight, unreacted substances may bleed, which increases the cost and is not economically preferable.
  • xanthogen compounds include dialkyl xanthogen disulfide, dialkyl xanthogen polysulfide, and metal salts of xanthogen acid.
  • dialkyl xanthogen disulfide examples include dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, diisobutyl xanthogen disulfide, and the like.
  • dialkyl xanthogen polysulfide examples include dimethyl xanthogen polysulfide, diethyl xanthogen polysulfide, diisopropyl xanthogen polysulfide, dibutyl xanthogen polysulfide, and the like.
  • metal xanthate examples include zinc isopropylxanthate, sodium isopropylxanthate, and zinc butylxanthate.
  • dimethyl xanthogen disulfide, dimethyl xanthogen polysulfide, diethyl xanthogen disulfide, diethyl xanthogen polysulfide, diisopropyl xanthogen disulfide, and diisopropyl xanthogen polysulfide are preferred.
  • sulfenamide compounds include N-cyclohexyl-2-benzothiazolylsulfenamide, Nt-butyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, diisopropyl -2-benzothiazolylsulfenamide, N-ethyl-N-t-butylbenzothiazole-2-sulfenamide, N-methyl-N-t-butylbenzothiazole-2-sulfenamide, N-propyl- Nt-butylbenzothiazole-2-sulfenamide, N-butyl-Nt-butylbenzothiazole-2-sulfenamide and the like can be mentioned.
  • thiuram-based compound tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, tetrabenzylthiuram disulfide, tetra (2-ethylhexyl) thiuram disulfide, bis (N- Methylpiperazino) thiuram disulfide and tetramethylthiuram monosulfide.
  • dithiocarbamic acid-based compound examples include dithiocarbamic acids such as dimethyldithiocarbamic acid, diethyldithiocarbamic acid, and dibutyldithiocarbamic acid, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, iron dimethyldithiocarbamate, and N-pentamethylenedithiocarbamate piperidine salt.
  • dithiocarbamic acids such as dimethyldithiocarbamic acid, diethyldithiocarbamic acid, and dibutyldithiocarbamic acid, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, iron dimethyldithiocarbamate, and N-pentamethylenedithiocarbamate piperidine salt.
  • Metal salts such as zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate and zinc dibenzyldithiocarbamate.
  • thiazole compound examples include 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazolecyclohexylamine salt, and 2- (4′-morpholinodithio). Benzothiazole and the like.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2,3-dimethylbutadiene, Examples thereof include 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, and 2-chloro-1,3-butadiene, butadiene and isoprene are preferred, and butadiene is most preferred.
  • radical polymerizable monomer examples include an aromatic vinyl monomer, an acrylate monomer, and a vinyl monomer. Styrene, divinylbenzene, methyl acrylate, and acrylonitrile are preferred, and styrene is most preferred.
  • the amounts of the preferred monomers styrene and butadiene are not particularly limited, but those having a styrene content of 5% to 50% by weight and a butadiene content of 95% to 50% by weight, which exhibit properties as a rubber, are preferred. preferable.
  • a monomer having an amino group, a hydroxyl group, an epoxy group and an alkoxysilane group may be copolymerized.
  • a monomer having an amino group, a hydroxyl group, an epoxy group and an alkoxysilane group may be copolymerized.
  • the affinity for carbon black or silica is improved, and the dispersion of the filler is improved.
  • the latex produced by emulsion polymerization may be partially cross-linked.
  • divinylbenzene as an aromatic polyvinyl compound or ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate as a polyfunctional acrylic monomer may be used.
  • the monomer having an amino group examples include a primary amino group-containing monomer, a secondary amino group-containing monomer, and a tertiary amino group-containing monomer.
  • the primary amino group-containing monomer examples include p-aminostyrene, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, and the like.
  • Examples of the secondary amino group-containing monomer include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide and the like. And the like.
  • Examples of the tertiary amino group-containing monomer include N, N-disubstituted aminoalkyl (meth) acrylate, N, N-disubstituted aminoalkyl (meth) acrylamide, N, N-disubstituted amino aromatic vinyl compound and Examples include a monomer having a pyridyl group.
  • N, N-disubstituted amino (meth) acrylate examples include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth).
  • N- dioctyl aminoethyl (meth) acrylate aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl ( Meth) acrylates are preferred.
  • N, N-disubstituted amino aromatic vinyl compound examples include N, N-dimethylaminoethylstyrene, N, N-diethylaminoethylstyrene, N, N-dipropylaminoethylstyrene, N, N-dioctylaminoethyl Styrene and the like.
  • the monomer having a pyridyl group include 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, and 5-ethyl-2-vinylpyridine. Among them, 2-vinylpyridine, 4-vinylpyridine and a mixture thereof are preferable.
  • the hydroxyl group-containing monomer is a monomer having at least one primary, secondary or tertiary hydroxyl group in one molecule.
  • Specific examples of the hydroxyl group-containing monomer include, for example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, 2-chloro-3-hydroxypropyl (meth) acrylate, hydroxyhexyl (Meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylate
  • Glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, 2-hydroxypropyl (meth) acrylamide, and 3-hydroxypropyl (meth) acrylamide are preferred.
  • These monomers having a hydroxyl group can be used alone or in combination of two or more.
  • the epoxy group-containing monomer is a monomer having at least one epoxy group in one molecule.
  • the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and N-glycidyl (meth) ) Acrylamide, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-methyl-1-butene, 3,4-epoxy-1- Pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, styrene-p-glycidyl ether, N- [4- (2,
  • epoxy group-containing monomers can be used alone or in combination of two or more.
  • the alkoxysilyl group-containing monomer is a monomer having at least one alkoxysilyl group in one molecule.
  • alkoxysilyl group-containing monomer examples include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, ⁇ - (meth) acryloxyethyltrimethoxysilane, and ⁇ - (meth) acryloxyethyl Triethoxysilane, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxypropyltripropoxysilane, ⁇ - (meth) acryloxypropyltributoxy Silane, ⁇ - (meth) acryloxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropylethyldimethoxysilane, ⁇ - (meth) acryloxypropylhexyldimethoxysilane, ⁇ -acryloxyethyloxymethyl
  • ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryloxypropyltripropoxysilane, ⁇ - (meth) acryloxypropyltributoxysilane, ⁇ - ( ⁇ -acryloxyethyloxy) Propyltributoxysilane, ⁇ - ( ⁇ -methacryloxypropyloxy) propyltributoxysilane and vinylalkoxysilanes are preferred, and ⁇ - (meth) acryloxypropyltripropoxysilane and ⁇ - (meth) acryloxypropyltributoxysilane And vinyl tri-tert-butoxysilane are more preferred.
  • alkoxysilyl group-containing monomers can be used alone or in combination of two or more.
  • the modified polymer of the present invention can be used by blending with a commercially available solid rubber.
  • Rubbers that can be blended include natural rubber, isoprene rubber, butadiene rubber, emulsion polymerized SBR (styrene butadiene rubber), solution polymerized SBR (styrene butadiene rubber), styrene isoprene butadiene copolymer rubber, acrylonitrile butadiene copolymer rubber, chloroprene rubber, and the like. No.
  • blends of natural rubber, isoprene rubber, butadiene rubber, emulsion-polymerized SBR, and solution-polymerized SBR are preferable for improving the performance of the tire.
  • Compounding of the modified polymer of the present invention with carbon black, which is a reinforcing filler, and silica can be performed by mixing using a usual rubber kneader.
  • the composite can also be formed by mixing the emulsion of the modified polymer of the present invention, an aqueous dispersion of carbon black and silica, or a commercially available natural rubber or ordinary SBR latex, followed by co-coagulation.
  • the rubber composition of the present invention can be kneaded using a kneader such as a roll or an internal mixer. After molding, it is vulcanized, and can be used for tires such as tire treads, undertreads, carcass, sidewalls, and bead parts, as well as for applications such as vibration-proof rubber, belts, hoses, and other industrial products. Particularly, it is suitably used for rubber for tires.
  • a kneader such as a roll or an internal mixer.
  • carbon black that can be complexed with the modified polymer of the present invention for example, furnace black, acetylene black, thermal black, channel black, graphite, and the like can be used.
  • furnace black is particularly preferable, and specific examples thereof include grades such as SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF.
  • grades such as SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF.
  • the silica that can be complexed with the modified polymer of the present invention is not particularly limited.
  • various types of silica such as combustion-process silica of dry process silica, heating process silica, and wet process silica such as gel process silica and precipitation process silica, can be used.
  • the pneumatic tire of the present invention is manufactured by a usual method using the rubber composition of the present invention.
  • the rubber composition of the present invention containing various chemicals as described above is extruded into a member for tread in an unvulcanized stage, and is pasted and molded by a normal method on a tire molding machine. Then, a green tire is formed. The green tire is heated and pressed in a vulcanizer to obtain a tire.
  • the pneumatic tire of the present invention thus obtained has excellent fuel economy, safety, excellent breaking characteristics and abrasion resistance, and also has good processability of the rubber composition and high productivity.
  • the modified polymer rubber of the present invention can contain an extender oil.
  • the extender oil those commonly used in the rubber industry can be used, and examples thereof include a paraffinic extender oil, an aromatic extender oil, and a naphthenic extender oil.
  • the pour point of the extender oil is preferably -20 to 50 ° C, more preferably -10 to 30 ° C. Within this range, a rubber composition that is easily extensible and has an excellent balance between tensile properties and low heat build-up can be obtained.
  • the preferred aroma carbon content (CA%, Kurz analysis) of the extender oil is preferably at least 20%, more preferably at least 25%, and the preferred paraffin carbon content (CP%) of the extender oil is , Preferably 55% or less, more preferably 45%. If the CA% is too small or the CP% is too large, the tensile properties will be insufficient.
  • the content of polycyclic aromatic compound in the extender oil is preferably less than 3%. This content is measured by the IP346 method (the test method of The Institute Petroleum, UK).
  • the content of the extender oil is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the rubber composition.
  • the viscosity of the rubber composition containing silica is moderate and the balance between the tensile properties and the low heat generation is excellent.
  • the modified polymer rubber of the present invention is used as a rubber composition for tires, natural rubber, isoprene rubber, butadiene rubber, emulsion-polymerized styrene-butadiene rubber and solution-polymerized styrene can be used as long as the effects of the present invention are not substantially impaired.
  • a reinforcing material to be filled when the modified polymer rubber of the present invention is used for a tire particularly for a tire tread, a filler having a hydroxyl group on the surface such as silica and carbon black are most suitable. It is preferable to use silica and carbon black in combination.
  • the filling amount of the filler is preferably 2 to 120 parts by weight, more preferably 10 to 120 parts by weight, based on 100 parts by weight of the total rubber component.
  • the silica include dry silica, wet silica, colloidal silica, and precipitated silica. Among them, wet silica mainly containing hydrous silicic acid is particularly preferable. These silicas can be used alone or in combination of two or more.
  • the particle size of the silica primary particles is not particularly limited, but is 1 to 200 nm, more preferably 3 to 100 nm, and particularly preferably 5 to 60 nm. When the particle size of the primary silica particles is in this range, the balance between the tensile properties and the low heat buildup is excellent.
  • the particle size of the primary particles can be measured with an electron microscope, a specific surface area, or the like.
  • the amount of silica is 1 to 120 parts by weight, preferably 2 to 80 parts by weight, particularly preferably 3 to 50 parts by weight, based on 100 parts by weight of the rubber component.
  • Examples of carbon black include grades such as N110, N220, N330, N440, and N550. These carbon blacks can be used alone or in combination of two or more.
  • the specific surface area of the carbon black is not particularly limited, but is preferably 5 to 200 m2 / g, more preferably 50 to 150 m2 / g, and particularly preferably 80 to 130 m2 / g in terms of a nitrogen adsorption specific surface area (N2SA). .
  • the DBP adsorption amount of carbon black is also not particularly limited, but is preferably 5 to 300 ml / 100 g, more preferably 50 to 200 ml / 100 g, and particularly preferably 80 to 160 ml / 100 g. When the DBP adsorption amount is within this range, a rubber composition having more excellent tensile properties can be obtained.
  • the adsorption (CTAB) specific surface area of cetyltrimethylammonium bromide disclosed in JP-A-5-230290 is 110 to 170 m2 / g, and compression is repeated four times at a pressure of 24,000 psi.
  • the abrasion resistance can be improved by using a high-structure carbon black having a DBP (24M4DBP) oil absorption of 110 to 130 ml / 100 g after completion.
  • the compounding amount of carbon black is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, particularly preferably 2 to 30 parts by weight based on 100 parts by weight of the rubber component.
  • a silane coupling agent for the purpose of further improving the tensile properties and low heat build-up, it is preferable to incorporate a silane coupling agent into the rubber composition of the present invention.
  • silane coupling agent examples include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -glycidoxypropylmethoxysilane, ⁇ -methacryloxypropylmethoxysilane, ⁇ -aminopropylmethoxysilane, N - ⁇ (aminoethyl) ⁇ -aminopropylmethoxysilane, ⁇ -mercaptopropylmethoxysilane, triethoxysilylpropylisocyanate, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyl Methyldimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ - (polyethyleneamino) -propyltrimethoxysi
  • the silane coupling agent is preferably one containing four or less sulfur in one molecule. More preferably, those having two or less sulfur are preferable. These silane coupling agents can be used alone or in combination of two or more.
  • the compounding amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 2 to 10 parts by weight based on 100 parts by weight of silica.
  • a vulcanizing agent can be used in an amount of preferably 0.5 to 10 phr, more preferably 1 to 6 phr, based on 100 phr of all rubber components.
  • Typical examples of the vulcanizing agent include sulfur, and other examples include a sulfur-containing compound and a peroxide.
  • a vulcanization accelerator such as a xanthogen-based compound, a sulfenamide-based compound, a thiuram-based compound, a dithiocarbamic acid-based compound, a thiazole-based compound, or a guanidine-based vulcanizing agent may be used in an amount as needed in combination with a vulcanizing agent. Good.
  • zinc white, a vulcanization aid, an antioxidant, a processing aid and the like may be used in necessary amounts.
  • various compounding agents of the rubber composition obtained by using the modified polymer rubber of the present invention are not particularly limited, but they may improve workability at the time of kneading, or balance wet skid characteristics, rebound resilience and abrasion resistance.
  • compatibilizers for example, an organic compound selected from an epoxy group-containing compound, a carboxylic acid compound, a carboxylic acid ester compound, a ketone compound, an ether compound, an aldehyde compound, a hydroxyl group-containing compound, and an amino group-containing compound.
  • the present invention when kneading a silicone compound selected from an alkoxysilane compound, a siloxane compound and an aminosilane compound, It can also be pressurized.
  • a silicone compound selected from an alkoxysilane compound, a siloxane compound and an aminosilane compound it can also be pressurized.
  • the physical properties of the polymer, the kneading properties, and the physical properties of the vulcanized rubber were measured by the following methods.
  • the Mooney viscosity of the polymer was measured at 100 ° C. using a Mooney viscometer.
  • the amount of styrene units in the copolymer was measured according to JIS-K6383 (refractive index method).
  • the kneading of the rubber composition for preparing a vulcanized product was conducted in accordance with JIS K6299: 2001 “Rubber—Method for preparing test sample”.
  • the kneading of the rubber composition to prepare a vulcanizate was carried out by first kneading the rubber composition containing no vulcanizing agent (A kneading) using a Mix-Labo500 kneader manufactured by Moriyama Seisakusho Co., Ltd. Approximately 65% (volume ratio), the rotation speed of the rotor was 50 rpm, and the kneading start temperature was 90 ° C.
  • the kneading conditions (B kneading) for mixing the vulcanizing agent into the rubber composition after kneading A were a Mix-Labo500 kneader manufactured by Moriyama Seisakusho Co., Ltd., the filling ratio was about 60% (volume ratio), and the rotor rotation speed. was carried out at 50 rpm and the kneading start temperature was 60 ° C.
  • the kneaded rubber composition was formed into a sheet by a roll and vulcanized at 160 ° C. The vulcanized sheet was punched out with a predetermined cutter and subjected to a tensile test and a viscoelasticity test.
  • the tensile properties were measured according to JIS K6251 such as strength at break (TB), modulus, elongation at break, and the like.
  • JIS K6251 strength at break (TB), modulus, elongation at break, and the like.
  • TB strength at break
  • modulus modulus
  • elongation at break elongation at break
  • the measurement was performed on a sample having a test piece shape of “5 mm in width ⁇ 40 mm in length ⁇ 2 mm in thickness”. The smaller the tan ⁇ (60 ° C.), the lower the heat generation, and the better the fuel economy as a tire.
  • Examples and Comparative Examples a modified polymer rubber or an unmodified polymer rubber was produced, and a filler and a rubber chemical were kneaded. After the rubber composition was formed into a sheet by a roll, it was heated and vulcanized and molded with a press, and the physical properties were measured.
  • test rubber Modified polymer rubber production 1 (MSBR-1)) 170 g of water, 5 g of fatty acid soap, 28 g of styrene, 72 g of butadiene and 0.3 g of diisopropylxanthogen disulfide were charged into a pressure-resistant reactor equipped with a stirrer, and 10 g of water in which 0.3 g of potassium persulfate was dissolved was poured. At 45 ° C. to initiate polymerization. A part of the aqueous solution was taken out at regular intervals, the solid content was measured, and the polymerization conversion was determined.
  • MSBR-1 test rubber Modified polymer rubber production 1
  • Termination of the polymerization and post-treatment were carried out in the same manner as in Modified Polymer Rubber Production 1.
  • a modified emulsion-polymerized SBR rubber (MSBR-2) having a Mooney viscosity of 55 and a styrene content of 23.4% was obtained. The results are shown in Table 1.
  • Modified polymer rubber production 3 (MSBR-3)) The modified polymer rubber preparation 1 was polymerized by changing diisopropylxanthogen disulfide to diethylxanthogen disulfide. Termination of the polymerization and post-treatment were carried out in the same manner as in Modified Rubber Production 1.
  • MSBR-3 A modified emulsion-polymerized SBR rubber (MSBR-3) having a Mooney viscosity of 52 and a styrene content of 23.5% was obtained.
  • the results are shown in Table 1.
  • Modified polymer rubber production 4 (MSBR-4) 27.7 g of styrene and 71.3 g of butadiene, which are monomers of the modified polymer rubber production 1, were used, and 1 g of dimethylaminoethyl methacrylate was added for polymerization. Termination of the polymerization and post-treatment were carried out in the same manner as in Modified Polymer Rubber Production 1.
  • a modified emulsion-polymerized SBR rubber (MSBR-4) having a Mooney viscosity of 62 and a styrene content of 23.0% was obtained.
  • the results are shown in Table 1.
  • Unmodified polymer rubber production 1 (SBR-1) Polymerization was carried out by adding 0.2 g of t-dodecyl mercaptan as a molecular weight control without adding the diisopropylxanthogen disulfide of Modified Polymer Rubber Production 2. Termination of the polymerization and post-treatment were carried out in the same manner as in Modified Polymer Rubber Production 1.
  • a wet rubber composition of carbon black and a modified polymer rubber was obtained. After the obtained crumb mixed with carbon black was washed with water to remove the acid, a wet-modified carbon black rubber composition (WMBR-1) was obtained. The wet-modified carbon black rubber composition (WMBR-1) was dried with a hot air dryer at 105 ° C. to obtain a sample for evaluation.
  • the modified polymer rubber (MSBR-1) of Example 1 was kneaded and vulcanized in the same manner as in Example 1 of the wet modified carbon black rubber composition (WMBR-1). Comparative Example 1 Kneading and vulcanization were carried out in the same manner as in Example 1 except that the modified polymer rubber (MSBR-1) of Example 1 was changed to the unmodified polymer rubber (SBR-1). Comparative Example 2 The modified polymer rubber (MSBR-1) of Example 1 was changed to an unmodified commercially available emulsion-polymerized SBR rubber (SBR1502) to eliminate the silica of Example 1, the amount of carbon black was 59 parts, the silane coupling agent and polyethylene were used.
  • SBR1502 commercially available emulsion-polymerized SBR rubber
  • Vulcanized Rubber Properties Table 3 shows the tensile properties of Examples 1-4 and Comparative Examples 1 and 2, and the measurement results of tan ⁇ at 0 ° C and 60 ° C.
  • the values of tan ⁇ at 0 ° C. and 60 ° C. are represented by indexing the value of Comparative Example 1 to 100.
  • the higher the index value of tan ⁇ at 0 ° C. the higher the wet skid resistance and the better the tire safety.
  • the lower the tan ⁇ index value at 60 ° C. the lower the heat generation of the rubber and the better the fuel economy of the tire.
  • the index value of tan ⁇ at 0 ° C. of the rubber vulcanizate using the modified polymer rubber of the example is higher than that of the unmodified rubber and excellent in wet skid resistance, and the index value of tan ⁇ at 60 ° C. is lower than that of the unmodified rubber and lower. It can be seen that the fuel economy is excellent. In addition, it can be seen that the wet skid resistance and the fuel economy are excellent even when compared with a carbon compounded rubber of SBR1502 using a commercially available t-dodecyl mercaptan as a molecular weight regulator.
  • the wet-modified carbon black rubber composition using the modified polymer rubber of the present invention has a higher tensile strength and a lower value of tan ⁇ at 60 ° C. than the carbon black compound of Comparative Example 2, resulting in low fuel consumption. It turns out that it is excellent.
  • Effect of the Invention Emulsion polymerization SBR rubber is modified with a compound comprising a xanthogen-based compound, a sulfenamide-based compound, a thiuram-based compound, a dithiocarbamic acid-based compound, and a thiazole-based compound to provide excellent wet skid resistance, low heat generation, and low fuel consumption.
  • An SBR rubber having excellent safety can be obtained, and a tire using the SBR rubber can provide a fuel-efficient tire having excellent safety.
  • a rubber composition containing silica is excellent in fuel efficiency.
  • the rubber composition comprising the modified emulsion-polymerized SBR of the present invention is suitable as a material for tires, particularly as a material for tire treads, because of its excellent wet skid resistance and low fuel consumption.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Tires In General (AREA)

Abstract

Les pneus économisant du carburant se sont répandus et les pneus comprenant de la silice en tant que charge deviennent de plus en plus courants. Les SBR polymérisés en solution, modifiés, pour la silice sont largement utilisés dans le but d'utiliser de la silice comme charge. Entre-temps, les SBR polymérisés en émulsion n'agissent pas sur la silice et il existe un souhait de SBR polymérisé en émulsion, modifié, utilisable dans les compositions de caoutchouc contenant de la silice pour réduire la consommation de carburant. Selon l'invention, un monomère polymérisable par voie radicalaire, par exemple un diène conjugué, est polymérisé par voie radicalaire en présence d'au moins un composé choisi parmi les composés de xanthogène, les composés de sulfénamide, les composés de thiurame, les composés d'acide dithiocarbamique et les composés de thiazole pour ainsi obtenir un polymère modifié présentant des groupes fonctionnels. Une composition de caoutchouc contenant un SBR polymérisé en émulsion, modifié, ainsi obtenu est hautement efficace pour réduire la consommation de carburant.
PCT/JP2019/024853 2018-07-23 2019-06-17 Composition de caoutchouc Ceased WO2020021929A1 (fr)

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Citations (7)

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JPH01247403A (ja) * 1988-03-29 1989-10-03 Nippon Shokubai Kagaku Kogyo Co Ltd Ｓｈ末端テレケリツク重合体の製造方法
JPH05202136A (ja) * 1991-09-19 1993-08-10 Bayer Ag 官能基を含む、新規硫黄−修飾ブタジエンコポリマー及び他のゴムとのその混合物
JPH09501459A (ja) * 1993-08-04 1997-02-10 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー ポリクロロプレン・コポリマー組成物
JP2005537349A (ja) * 2002-08-30 2005-12-08 株式会社ブリヂストン 官能性ポリマー、及びそれにより改良された加硫物
JP2009024045A (ja) * 2007-07-17 2009-02-05 Bridgestone Corp 防振ゴム組成物及びそれを用いてなる防振ゴム
JP2012172105A (ja) * 2011-02-23 2012-09-10 Tosoh Corp 硫黄変性クロロプレン重合体の製造方法
WO2018110369A1 (fr) * 2016-12-14 2018-06-21 デンカ株式会社 Caoutchouc de chloroprène modifié par un xanthogène ainsi que composition de caoutchouc associée, et corps moulé par vulcanisation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01247403A (ja) * 1988-03-29 1989-10-03 Nippon Shokubai Kagaku Kogyo Co Ltd Ｓｈ末端テレケリツク重合体の製造方法
JPH05202136A (ja) * 1991-09-19 1993-08-10 Bayer Ag 官能基を含む、新規硫黄−修飾ブタジエンコポリマー及び他のゴムとのその混合物
JPH09501459A (ja) * 1993-08-04 1997-02-10 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー ポリクロロプレン・コポリマー組成物
JP2005537349A (ja) * 2002-08-30 2005-12-08 株式会社ブリヂストン 官能性ポリマー、及びそれにより改良された加硫物
JP2009024045A (ja) * 2007-07-17 2009-02-05 Bridgestone Corp 防振ゴム組成物及びそれを用いてなる防振ゴム
JP2012172105A (ja) * 2011-02-23 2012-09-10 Tosoh Corp 硫黄変性クロロプレン重合体の製造方法
WO2018110369A1 (fr) * 2016-12-14 2018-06-21 デンカ株式会社 Caoutchouc de chloroprène modifié par un xanthogène ainsi que composition de caoutchouc associée, et corps moulé par vulcanisation

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