WO1996023027A1 - Composition de caoutchouc et son procede de preparation - Google Patents
Composition de caoutchouc et son procede de preparation Download PDFInfo
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- WO1996023027A1 WO1996023027A1 PCT/JP1996/000114 JP9600114W WO9623027A1 WO 1996023027 A1 WO1996023027 A1 WO 1996023027A1 JP 9600114 W JP9600114 W JP 9600114W WO 9623027 A1 WO9623027 A1 WO 9623027A1
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- rubber
- gen
- monomer
- hydroxyl group
- rubber composition
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a rubber composition obtained by compounding silica as a reinforcing agent with a gen-based rubber. More specifically, the present invention relates to a silica-containing gen-based rubber composition having excellent rebound resilience and excellent tensile properties, wear properties, hardness properties and processability, and a method for producing the same.
- the silicone rubber compounded gen-based rubber composition has the carbon black compounded gen-based rubber composition.
- An object of the present invention is to provide a silica-containing gen-based rubber composition, which has excellent rebound resilience as an index of rolling resistance, and has a tensile strength and resistance equivalent to or higher than that of a gen-based rubber composition containing carbon black. It is an object of the present invention to provide a composition which exhibits abrasion and has good workability and hardness characteristics.
- the inventors of the present invention have conducted intensive studies to overcome the problems of the prior art, and as a result, as a gen-based rubber component reinforced with silica, less of a hydroxyl group-containing gen-based rubber having a weight average molecular weight of 500,000 or more.
- a gen-based rubber component reinforced with silica less of a hydroxyl group-containing gen-based rubber having a weight average molecular weight of 500,000 or more.
- the present invention has been completed based on these findings.
- the gen-based rubber component in a rubber composition containing a gen-based rubber component and a silicic acid as a reinforcing agent, has a hydroxyl group-containing gen-based compound having a weight average molecular weight of 500,000 or more.
- the gen-based rubber component in a method for producing a rubber composition by mixing a gen-based rubber component, silica as a reinforcing agent and other compounding agents, has a weight average molecular weight of 50, Use of a hydroxy group-containing gen-based rubber (A) of not less than 000 or a combination of the hydroxy group-containing gen-based rubber (A) and another gen-based rubber (B); Mixing at least a part of a required amount of silica with the gen-based rubber component, and then mixing the obtained mixture with a residual amount of silica and other compounding agents.
- A hydroxy group-containing gen-based rubber
- B another gen-based rubber
- a hydroxyl-containing gen-based rubber (A) having a weight average molecular weight of 50,000 or more is used, or the hydroxyl-containing gen-based rubber (A) and another gen-based rubber are used. Used together with (B).
- the hydroxyl group-containing gen-based rubber (A) can be used in combination of two or more kinds. Two or more other gen-based rubbers (B) may be used in combination.
- the weight-average molecular weight of the hydroxyl-containing gen-based rubber (A) is the weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). It has a weight average molecular weight (Mw) of 50,000 or more, preferably 100,000 to 1,000,000, more preferably 100,000 to 800,000. If the weight average molecular weight is too small, sufficient rebound resilience and abrasion resistance cannot be obtained.
- the hydroxyl group in the hydroxyl group-containing rubber (A) may be a primary, secondary or tertiary hydroxyl group.
- the effect of improving rebound resilience, abrasion resistance, tensile strength, etc. is at a higher level.
- primary or secondary hydroxyl groups are preferred, with primary hydroxyl groups being particularly preferred.
- Examples of the hydroxyl group-containing rubber (A) include a copolymer of a hydroxyl group-containing vinyl monomer and a conjugated gen monomer, or a copolymer of a hydroxyl group-containing vinyl monomer and a conjugated gen monomer and another copolymer.
- a copolymer with a polymerizable monomer can be used.
- the hydroxyl group-containing gen-based rubber (A) also includes a polymer of a conjugated gen-based monomer or a copolymer of a conjugated gen-based monomer and another copolymerizable monomer, and By reacting the (co) polymer having a bound active metal with at least one compound (modifier) selected from ketones, esters, aldehydes and epoxies, Co) A polymer having a hydroxyl group introduced into the polymer may be used.
- the method for producing the hydroxyl group-containing gen-based rubber (A) includes (1) primary, A method of copolymerizing a vinyl monomer having a secondary or tertiary hydroxyl group with a conjugated monomer or a conjugated monomer and another copolymerizable monomer (copolymerization method) , And (2) polymerizing a conjugated gen monomer or copolymerizing a conjugated gen monomer with another copolymerizable monomer to have an active metal bound in the molecule
- a gen-based polymer is prepared, and then the gen-based polymer is reacted with a modifying agent such as ketones, esters, aldehydes and epoxies to form a primary, secondary or A method (modification method) of introducing a tertiary hydroxyl group into the gen-based polymer is exemplified.
- the hydroxyl group-containing rubber (A) used in the present invention is a conjugated rubber having at least one hydroxyl group in the molecule.
- the hydroxyl group-containing gen-based rubber (A) is produced by the copolymerization method of the above (1), usually, 0.05 to 30% by weight of a hydroxyl group-containing vinyl monomer, a conjugated gen-based monomer Each monomer is mixed so as to have a content of 40 to 99.5 wt% and other copolymerizable monomers of 0 to 59.5 wt% (based on the amount of binding). Polymerize.
- the hydroxyl group-containing rubber (A) is produced by the modification method (2)
- an active metal-containing initiator is usually used, and the co-gen monomer is usually 40 to 100% by weight. % And other copolymerizable monomers.
- Each monomer is (co) polymerized so as to have a content of 0 to 60% by weight (based on the amount of binding), or a conjugated monomer.
- the polymer is reacted with an active metal-containing initiator to form an active metal. The metal is bound and then denatured with a denaturant.
- conjugated diene monomers examples include 1,3-butadiene and 2-methadiene. Chill-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 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.
- the conjugated gen-based monomers can be used alone or in combination of two or more.
- the other copolymerizable monomer is not particularly limited as long as it is a monomer copolymerizable with a conjugated diene monomer and does not impair the intended properties.
- Aromatic vinyl monomers are preferably used. Examples of aromatic vinyl monomers include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, , 4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene and the like are exemplified. Among them, styrene is preferred.
- the microstructure in the conjugated gen part of the hydroxyl group-containing gen-based rubber (A) is not particularly limited, and is appropriately selected depending on the purpose of use.
- the content of the vinyl group (1,2-vinyl group and 3,4-vinyl group) in the conjugated part is, for example, in the range of 10 to less than 30% when it is desired to improve the rebound resilience and abrasion resistance. In order to improve wet skid resistance, it is preferable to select a value within the range of 30 to 90%.
- the chain distribution of the aromatic vinyl unit is not particularly limited, but one aromatic vinyl unit is used. Is usually independent chain content It is at least 40% by weight, preferably at least 50% by weight, more preferably at least 55% by weight of the amount of the bound aromatic vinyl, and the content of the long chain having at least 8 aromatic vinyl units is usually
- the amount is preferably 5% by weight or less, more preferably 2.5% by weight or less, more preferably 1.5% by weight or less of the amount of the bound aromatic vinyl, such as rebound resilience, abrasion resistance, wet skid resistance, etc. It is desirable to achieve a high balance of such characteristics.
- hydroxyl group-containing rubber (A) by the copolymerization method (1), a vinyl monomer having a hydroxyl group [i] and a conjugated diene monomer [ii] or a conjugated diene rubber are used.
- a copolymer is produced from the monomer [ii] and the copolymerizable monomer [iii].
- each monomer unit in the copolymer is appropriately selected according to the required properties, but the ratio of the unit [i], the unit [ii] and the unit [iii] is Usually, [0.05 to 30% by weight]: [40 to 99.95% by weight]: [0 to 59.95% by weight], preferably [0.1 to 20% by weight: [50 to 90% by weight]: [9.9 to 49.9% by weight], more preferably [0.3 to: 15% by weight]: [60 to 85% by weight]: [14.7 to 39.7% by weight] . If the content of the hydroxyl group-containing vinyl monomer [i] is too small, it is difficult to obtain a sufficient improvement effect, and if it is too large, the balance between processability and rebound resilience is reduced. However, neither is preferred.
- the conjugated monomer [ii] and other copolymerizable monomers [iiii] used in this method are as described above.
- hydroxyl group-containing vinyl monomer a polymerizable monomer having at least one primary, secondary or tertiary hydroxyl group in one molecule is used.
- hydroxyl group-containing vinyl monomers include, for example, Unsaturated carboxylic acid monomers containing a vinyl group, vinyl ether monomers, aromatic vinyl monomers, and vinyl ketone simple monomers. Dimers are preferred.
- the hydroxyl-containing unsaturated carboxylic acid-based monomer include, for example, acrylic acid,
- esters of unsaturated carboxylic acids such as lylic acid, itaconic acid, fumaric acid, and maleic acid, and derivatives such as amides and acid anhydrides, and preferably acrylate esters and methacrylic acid. Acid esters and the like.
- hydroxymethyl (meth) acrylate 2- Hydroxyshetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 31-phenoxy1-2-hydroxypropyl (meth) acrylate, glycer Roll mono (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl
- Examples thereof include (meth) acrylamide and 3-hydroxypropyl (meth) acrylamide.
- particularly preferred are hydroxymethyl (meth) acrylate, 2-hydroxyshethyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate.
- These hydroxyl group-containing vinyl monomers can be used alone or in combination of two or more.
- the polymerization method is not particularly limited, but usually an emulsion polymerization method is employed.
- the emulsion polymerization method may be a conventional emulsion polymerization method.For example, a method in which a predetermined amount of each of the above monomers is emulsified and dispersed in an aqueous medium in the presence of an emulsifier, and emulsion polymerization is performed using a radical polymerization initiator. No.
- a long-chain fatty acid salt having 10 or more carbon atoms and / or a rosinate are used.
- Specific examples include potassium salts such as cabric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid, and sodium salts.
- radical polymerization initiator examples include a persulfate such as ammonium persulfate and persulfate permeate; a combination of ammonium persulfate and ferric sulfate.
- Redox initiators such as combinations of organic peroxides with ferric sulfate, and combinations of hydrogen peroxide with ferric sulfate; and the like.
- a chain transfer agent can be added to adjust the molecular weight of the copolymer.
- chain transfer agent for example, mercaptans such as t-dodecylmercaptan, n-dodecylmerbutane, carbon tetrachloride, thioglycolic acid, diterpenes, terpinolene, water terpinenes and the like can be used.
- the temperature of the emulsion polymerization can be appropriately selected depending on the kind of the radical polymerization initiator used, but is usually from 0 to 10 ° C, preferably from 0 ° C to
- the polymerization mode may be either continuous polymerization or batch polymerization.
- the polymerization conversion is preferably suppressed to 80% or less, and it is particularly preferable to suppress the polymerization within the range of 40 to ⁇ 0 to 70%.
- the termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached.
- a polymerization terminator for example, an amine compound such as getyl hydroxysylamine ⁇ hydroxylamine, a quinone compound such as hydroquinone or benzoquinone, sodium nitrite,
- the hydroxy group-containing rubber (A) is produced by the modification method of the above (2).
- a gen-based rubber containing an active metal bonded to a molecule is first produced, and then the gen-based rubber is modified by reacting with a modifier to introduce a hydroxyl group.
- the amount of the conjugated diene monomer in the diene rubber is usually
- L 00% by weight preferably 50 to 90% by weight, more preferably 60 to 85% by weight, and the amount of other copolymerizable monomers is usually to 0 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 50% by weight
- the active metal those generally known in the technical field of gen-based rubber may be used.
- Alkali earth metals such as beryllium, magnesium, calcium, strontium, barium, etc .; Lanthanide series rare earth metals such as lanthanum, neodymium, etc. .
- alkali metals such as beryllium, magnesium, calcium, strontium, barium, etc .
- Lanthanide series rare earth metals such as lanthanum, neodymium, etc.
- alkaline earth metals are preferred, and alkali metals are particularly preferred.
- Gen-based rubber to which an active metal is bound is prepared by using an active metal-based catalyst as an initiator to form a solution of a conjugated gen monomer or a conjugated gen monomer and another copolymerizable monomer. It can be produced by polymerizing according to a polymerization method (JP-A-58-166604). Also other As a method, a gen-based polymer is produced by various polymerization methods (emulsion polymerization method, solution polymerization method, etc.), and then an active metal is added to the gen-based polymer chain by a post-reaction (Japanese Patent Laid-Open No. 58-189,203). However, it is not limited to these methods.
- an organic alkali metal catalyst an organic alkaline earth metal catalyst, an organic lanthanide series rare earth metal catalyst and the like are used.
- organic alkali metal catalyst examples include, for example, organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium: dilithiummethane, 1,4-dilithiobutane, Polyfunctional organic lithium compounds such as 1,4-diethyl-1-ethyl ethyl hexane and 1,3,5-trilithobenzene; sodium naphthalene, potassium naphthalene, and the like.
- organic lithium compound is preferable, and an organic monolithium compound is particularly preferable.
- Organic alkaline earth metal catalysts include, for example, n-butylmagnesium, n-hexylmagnesium, ethoxycalcium, stearylate, t-butoxystrontium, ethkinbarium, isopropoxybarium, ethyl mercaptobarium , T-butoxybarium, phenoxybarium, getylaminobarium, barium stearate, ethylvalium and the like.
- organic lanthanide series rare earth metal catalyst examples include, for example, neodymium triethylaluminum versatate / ethylaluminum sesquioxide as described in JP-B-63-644444. Consists of Composite catalysts and the like are included.
- active metal-containing initiators can be used alone or in combination of two or more.
- the amount of the active metal-containing initiator used depends on the type of the initiator or the required amount.
- It is appropriately selected depending on the molecular weight of the resulting polymer, and is usually in the range of 1 to 20 millimoles, preferably 2 to 15 millimoles, more preferably 3 to 10 millimoles per kg of the generated rubber. .
- the anion polymerization using the above-mentioned initiator is performed in a hydrocarbon-based solvent which does not break the initiator.
- Suitable hydrocarbon solvents include ordinary anion
- aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, iso-octane and the like
- Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and the like: aromatic hydrocarbons such as benzene and toluene; and the like, preferably to n- Xane, cyclohexane, benzene and the like.
- unsaturated hydrocarbons having low polymerizability such as 1-butene, cis-1-butene, 2-hexene and the like may be used. These hydrocarbon solvents are used singly or in combination of two or more, and are usually used in a ratio such that the monomer content becomes 1 to 30 weight.
- the anion polymerization reaction is usually carried out in a batch or continuous polymerization mode at a temperature in the range of 178 to 150 ° C.
- the conjugated gen is adjusted so that the ratio of the aromatic vinyl monomer and the conjugated gen-based monomer in the polymerization system falls within a specific range. It is desirable to continuously or intermittently supply a system monomer or a mixture of a conjugated diene monomer and an aromatic vinyl monomer to the reaction system.
- polystyrene-butadiene copolymer examples include polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-isoprene copolymer, and the like.
- an active polymer a conjugated gen-based polymer having an active metal bonded to the terminal of the polymer chain
- an active metal in a post-reaction for example, an equimolar amount of methanol or isopropanoate to the active polymer is used.
- the polymerization reaction is stopped by adding an alcohol such as alcohol
- the active metal is added by newly adding an active metal-containing initiator and, if necessary, the polar compound.
- the reaction temperature is usually in the range of 78 to 150 ° C, preferably 20 to 100 ° C
- the reaction time is usually 0.1 to 24 hours, preferably 0.5 to 100 ° C. 4 hours range.
- an active polymer having an active metal bonded to the polymer main chain is obtained.
- an active metal can be introduced into a molecular chain by reacting with an active metal-containing initiator using a conjugated gen-based polymer obtained by another method such as emulsion polymerization.
- the modifier is not particularly limited as long as it can react with the active metal to form a hydroxyl group.
- ketones, esters, aldehydes, epoxies and the like are used. Can be. Among these, epoxies having an epoxy ring structure at the molecular terminal are particularly preferable because they can generate a primary hydroxyl group.
- These denaturing agents can be used alone or in combination of two or more.
- Ketones include, for example, acetone, benzophenone, aminoacetone, aminobenzophenone, acetylacetone and the like.
- the esters include methyl acetate, methyl adipate, ethyl ethyl adipate, methyl methacrylate, and ethyl methacrylate.
- aldehydes examples include benzaldehyde, pyridine aldehyde, and the like.
- Epoxy compounds include, for example, general formula (1)
- R 2 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and and and R 2 may combine to form a cyclic structure.
- Epoxies in which at least one of R and R 2 in formula (1) is a hydrogen atom are preferred.
- the number of carbon atoms of the hydrocarbon group which may have a substituent is usually 20 or less, preferably 1 to 10, more preferably 1 to 6 lower hydrocarbon groups.
- Specific examples of the hydrocarbon group which may have a substituent include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxyalkyl group, a dialkylaminoalkyl group, and a dialkyl group.
- Examples include a reelaminoalkyl group, a trialkoxysilylalkyl group, and a trialkylsilylalkyl group.
- Examples of the ring structure formed by combining R and R 2 include a cycloalkyl group.
- an alkyl group, an alkenyl group, an aryl group, an alkoxyalkyl group, a dialkylaminoalkyl group, a diarylaminoalkyl group, a trialkoxysilylalkyl group, and a trialkylsilylalkyl group are preferable, and an alkyl group is particularly preferable. preferable.
- epoxies include, for example, ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, 1,2-epoxyhexane , 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetrade Can, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-1-pentylpropane, 3,4-epoxy-1-butene, 1,2 —Epoxy-5-hexene, 1,2-epoxy-9-decene, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane, 1,2-epoxy Butylbenzene, 1,2-epoxy-1-methoxy-1-methylpropyl mouthpan, gly
- Epoxies also include ephalohydrins, ie, compounds in which at least one hydrogen atom of the above-mentioned epoxies has been replaced with a halogen atom.
- ephalohydrins and examples of hydrocarbon groups Is the same as the above epoxies.
- epichlorohydrin, moebulin in the mouth of eviv epiodohydrin, 2,3-epoxy—1,1,1,1-trifluorob bread, 1,2-epoxy-1H, 1H, 2 H, 3H, 3H-heptadecafluoroundecane and the like, preferably, epichlorohydrin and epibromohydrin.
- the amount of the modifier used is appropriately selected depending on the type of the modifier and the required properties, but is usually 0.1 to 10 mol, preferably 0.5 to 5 mol, more preferably 1 to 1.5 mol per mol of active metal. Range.
- the modification reaction is carried out by contacting the active polymer having an active metal bonded in the molecule with a modifier.
- a modification reaction is usually performed by adding a predetermined amount of a modifier to the active polymer solution before the termination of the polymerization.
- both terminal modification and main chain modification may be performed.
- an active metal may be introduced into the main chain of the syngeneic polymer end-modified with a modifying agent, and further reacted with the modifying agent.
- the reaction temperature and reaction time in the denaturation reaction can be selected from a wide range, but are generally from room temperature to 120 and from several seconds to several hours.
- the hydroxyl group-containing gen-based rubber (A) used in the present invention may be one produced by a method other than the above (1) and (2).
- a method of introducing a hydroxyl group by reacting an epoxidized gen-based rubber with an alcohol Japanese Patent Publication No. 60-53511
- heating epoxidized polybutadiene in the presence of an amine and a carboxylic acid Japanese Patent Publication No. 60-53512, Japanese Patent Application Laid-Open No. 60-55004, and Japanese Patent Application Laid-Open No.
- the hydroxyl group-containing rubber (A) can be used alone as a rubber component of the rubber composition of the present invention, but may be used in combination with other rubber (B).
- gen-based rubbers include, for example, natural rubber (NR), polyisoprene rubber (IR), emulsion-polymerized styrene-butadiene copolymer rubber (SBR), solution-polymerized random SBR (bonded styrene amount 5 to 50% by weight, 1,2-bonding amount of butadiene unit 10-80%), trans SBR (70-95% of trans in butadiene part), low cis polybutadiene rubber (BR), high cis BR, high trans BR ( (Butadiene transance 70-95%), styrene-isoprene copolymer rubber (SIR), butadiene-isoprene copolymer rubber, solution-polymerized random styrene Tajene soprene copolymer rubber (SIBR), emulsion polymerization SIBR, emulsion polymerization styrene-acrylonitrile-butadiene copolymer rubber,
- 5 click copolymer rubber and the like can be appropriately selected according to the required characteristics.
- These gen-based rubbers can be used alone or in combination of two or more.
- NR, BR, IR, SBR, SIBR and the like are preferable, and from the viewpoint of workability, NR and IR are particularly preferable.
- the sili force used in the present invention is one generally used for compounding general-purpose rubber. Specific examples include dry-process white carbon, wet-process white carbon, colloidal silica, and precipitated silica disclosed in JP-B-62-62838, which are generally used as a reinforcing agent. It is a wet-process white carbon mainly composed of hydrous gay acid.
- Silica is preferably in the acidic region in order to improve dispersibility. Silica treated with a cutting agent or the like can also be used.
- the specific surface area of silica is not particularly limited, usually, 50 to 400 111 2 8, preferably more preferably from 100 to 250,111 2 8 :, range of 120 to 190 m 2 Zg. If the specific surface area is excessively small, the reinforcing property is inferior. Conversely, if the specific surface area is excessively large, the workability is inferior, and the abrasion resistance and rebound resilience are not sufficiently improved.
- the use ratio of silica is not particularly limited, but is usually 20 to 150 parts by weight, preferably 40 to 120 parts by weight, based on 100 parts of the gen-based rubber component. If the use ratio of the sili force is excessively small, the reinforcement is inferior. On the other hand, if the ratio is excessively large, the viscosity of the unvulcanized rubber composition increases, resulting in poor processability.
- a silane coupling agent can be preferably used.
- Various known silane coupling agents can be used. Typical examples thereof include 7-mercaptopropyltrimethoxysilane (A 189; manufactured by Union Carbide Co., Ltd.) and 7-aminobutamate. Examples include built-in ethoxysilane (A1100: manufactured by Union Carbide) and bis [31- (triethoxysilyl) propyl] tetrasulfide (Si-69; manufactured by Degussa).
- the use ratio of the silane coupling agent is usually 0.01 to 30 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the rubber component.
- the rubber composition of the present invention can be obtained by kneading each component according to a conventional method.
- the rubber composition of the present invention comprises, in addition to the gen-based rubber component and silica, other compounding agents such as a vulcanizing agent, a vulcanization accelerator, an antioxidant, a plasticizer, a lubricant, a filler, and the like according to a conventional method.
- a vulcanizing agent such as a vulcanizing agent, a vulcanization accelerator, an antioxidant, a plasticizer, a lubricant, a filler, and the like according to a conventional method.
- vulcanizing agents such as sulfur and peroxyside: vulcanization accelerators such as thiazole, thiuram, sulfonamide, and guanidine.
- Vulcanization aids such as stearic acid, zinc white, etc .; power-supplying agents such as silane-based power-supplying agents; activators such as diethylene glycol, polyethylene glycol and organic silica compounds; FEF, HAF Reinforcing agents such as grades of carbon black, calcium carbonate, etc., grades of carbon black, ISAF, SAF, etc .; Plasticizers; Fillers, such as thermal black, acetylene black, graphite, clay, talc, etc .; Oils and the like. From these various compounding agents, the necessary compounding agent can be appropriately selected according to the purpose and application.
- a gen-based rubber component and silica are mixed using a mixer such as a roll, Banbury, and the like, and then, if other compounding agents are added and mixed, dispersibility is improved.
- a rubber composition having better properties can be obtained.
- the silica may be added all at once, but if the predetermined amount is added preferably in two or more portions, the dispersion becomes easier and the mixing of the silica and the gen-based rubber component becomes easier. For example, 10 to 90% by weight of the total amount of silica can be added in the first time, and the remainder can be added in the second and subsequent times.
- the silane coupling agent and the activator may be added as needed at the time of the initial mixing of the gen-based rubber component and the silicic acid. However, it is preferable to add it in the subsequent steps.
- silane-based Addition of a compounding agent other than the activating agent or the activator increases the mixing time and may reduce the reinforcing properties of silica.
- the temperature for mixing the diene rubber component and silica is usually 80 to 2
- the mixing time is usually 30 seconds or more, preferably 1 to 30 minutes.
- the tensile strength and abrasion resistance which have been disadvantages hitherto, can be significantly improved without impairing the rebound resilience characteristic of the silica-containing rubber composition, and the hardness is high.
- a rubber composition having excellent properties and processability is provided.
- the rubber composition of the present invention can be used in various applications, for example, as a raw material for producing automobile tires, automobile parts, hoses, window frames, belts, shoe soles, anti-vibration rubbers, etc. , High impact polystyrene,
- the rubber composition of the present invention is particularly excellent as a rubber material for tread in fuel-efficient tires, and is also suitable for all season tires, high-performance tires or studless tires. It can also be suitably used as a rubber material for a metal, a carcass, a beat portion and the like.
- the amount of hydroxyl group-containing monomer in the polymer is determined by 13 C-NMR spectrum after treating the polymer with phenyl isocyanate according to the method described in JP-A-3-174408. It was calculated by quantifying the phenyl group of the diisocyanate.
- the styrene chain distribution was determined by ozonolysis of the polymer according to the method described in the Proceedings of the Society of Polymer Science, Vol. 29, No. 9, page 2055, followed by GPC measurement. The amount of chains and the amount of long chains in which eight or more styrene units were linked were calculated.
- Abrasion resistance was measured using a pico abrasion tester according to ASTM D-2228. This property is expressed as an index (pico wear index).
- ethylene oxide (EO) was added in an equimolar amount to the polymerization active terminal (L i), and the mixture was reacted for 20 minutes.
- Gen-based rubber No. 9 was obtained.
- gen-based rubber Nos. 12 to 16 were obtained under the polymerization conditions described in Table 2, and the properties of these polymers are shown in Table 2.
- aminostyrene (AST) was used as a modifier for generating an amino group.
- the polymerization was stopped by adding an equimolar amount of methanol to the active terminal (L i). To this solution, 60 millimoles of sec-butyllithium and 60 millimoles of TMEDA were added, and the mixture was reacted at 70 for 1 hour. Then, 60 millimoles of ethylene oxide (EO) was added, and the mixture was further stirred for 20 minutes. Add 120 mmol of methanol After stopping the reaction, the polymer was recovered in the same manner as in Production Example 2 to obtain gen-based rubber No. 10. Table 2 shows the properties of the polymer.
- EO ethylene oxide
- the rubber composition (Example 16) using a hydroxyl group-containing gen-based rubber as the gen-based rubber component can be rolled without increasing the hardness and the compound viscosity. It can be seen that the workability is excellent and the tensile strength, rebound resilience, and wear resistance are sufficiently improved. In addition, the strength characteristics, rebound resilience, and elasticity of the case where the primary rubber having a hydroxyl group (Example 26) were used were higher than those of the secondary rubber having a hydroxyl group (Example 1). It can be seen that the effect of improving the wear characteristics is great.
- V N Ultrasil VN 3 G (made by Degussa)
- the gen-based rubber and at least a part of the sily force are kneaded, rather than the method of kneading the gen-based rubber together with all the compounding agents other than sulfur and the vulcanization accelerator (formulation 2).
- the method of mixing and kneading with the addition of compounding agents other than sulfur and the vulcanization accelerator (Formulation 1) shows that the effect of improving all the properties is higher than that of Example 4 and Example 8. You can see from the comparison.
- VN Ultrasilil VN 3 G (made by Degussa)
- Nibusil AQ Nibusil AQ (manufactured by Nippon Silica Co., Ltd.) From the results in Table 6, it can be seen that the difference in effect due to differences in the kneading method, the type of silica, and the polar group (hydroxyl group and tertiary amino group) of the gen-based rubber, It can be seen that this is the same as when the hydroxyl group-containing gen-based rubber produced by the polymerization method was used (see Table 5).
- the primary hydroxyl group-containing gen-based rubber modified with ethylene oxide (EO) is better than the tertiary hydroxyl-containing gen-based rubber modified with benzophenone (BPH) (Example 13). Rubber (Example 12) has a higher improvement effect under the same conditions.
- Karuru Nibusil AQ (manufactured by Nippon Silica Co., Ltd.) From the results in Table 6, it can be seen that the difference in effect due to differences in the kn
- Example Comparative example The same experiment as in Example 1 was performed using a blend of the gen-based rubber prepared in Production Examples 2 to 4 and natural rubber and / or polybutadiene (BR1220; manufactured by Zeon Corporation) as the raw material rubber.
- Table 7 shows the composition of the raw rubber and the results.
- the conventional polybutadiene (BR1220) is inferior in processability and does not have sufficient physical properties when blended with natural rubber and silica (Comparative Example 8), but water modified by ethylene oxide
- BR 1220 an acid-containing polybutadiene rubber instead of BR 1220
- the processability is improved, and the tensile strength, rebound resilience, and abrasion resistance are improved.
- the effect of improvement can be sufficiently exhibited also when a three-component rubber including a hydroxyl group-containing rubber, natural rubber, and polybutadiene rubber is used (Example 20).
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- Medicinal Chemistry (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/875,293 US6057397A (en) | 1995-01-23 | 1996-01-23 | Rubber composition and process for preparing the same |
EP96900736A EP0806452A4 (en) | 1995-01-23 | 1996-01-23 | RUBBER COMPOSITION AND PROCESS FOR THE PREPARATION THEREOF |
JP52277296A JP3488926B2 (ja) | 1995-01-23 | 1996-01-23 | ゴム組成物及びその製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7/27543 | 1995-01-23 | ||
JP2754395 | 1995-01-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996023027A1 true WO1996023027A1 (fr) | 1996-08-01 |
Family
ID=12224009
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1996/000114 WO1996023027A1 (fr) | 1995-01-23 | 1996-01-23 | Composition de caoutchouc et son procede de preparation |
Country Status (4)
Country | Link |
---|---|
US (1) | US6057397A (ja) |
EP (1) | EP0806452A4 (ja) |
JP (1) | JP3488926B2 (ja) |
WO (1) | WO1996023027A1 (ja) |
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- 1996-01-23 JP JP52277296A patent/JP3488926B2/ja not_active Expired - Fee Related
- 1996-01-23 EP EP96900736A patent/EP0806452A4/en not_active Withdrawn
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Also Published As
Publication number | Publication date |
---|---|
JP3488926B2 (ja) | 2004-01-19 |
US6057397A (en) | 2000-05-02 |
EP0806452A4 (en) | 1998-05-13 |
EP0806452A1 (en) | 1997-11-12 |
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