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
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
  • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • 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
• • 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
  • C08C19/22—Incorporating nitrogen atoms into the molecule
• • 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
  • C08C19/25—Incorporating silicon atoms into the molecule
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
  • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

• the present invention relates to rubber compositions and tires.
• a modified conjugated diene system which is a reaction product of a compound [M] having a total of two or more groups selected from [M], which is an atom or a hydrocarbyl group, and A 1 is a monovalent group having an alkoxysilyl group.
• a rubber composition containing a polymer is disclosed, and the rubber composition is shown to have excellent low heat build-up (low tan ⁇ and excellent low loss property).
• a rubber composition characterized by is disclosed, and by applying the rubber composition to a tire, it is possible to improve steering stability and wet performance while reducing the rolling resistance of the tire.
• an object of the present invention is to solve the above-described problems of the prior art and to provide a rubber composition capable of improving tire loss reduction properties and steering stability.
• Another object of the present invention is to provide a tire that is excellent in low-loss properties and steering stability.
• the gist and configuration of the present invention for solving the above problems is as follows.
• the rubber composition of the present invention is a rubber composition containing a rubber component, a hydrogenated resin, and a filler
• a compound [M] having a total of two or more groups selected from ,
• the hydrogenated resin has a softening point higher than 110° C. and a polystyrene equivalent weight average molecular weight of 200 to 1200 g/mol, wherein the filler comprises silica; It is characterized by
• the tire of the present invention is characterized by including the rubber composition described above.
• the rubber composition which can improve the low loss property and steering stability of a tire can be provided. Moreover, according to the present invention, it is possible to provide a tire excellent in low-loss property and steering stability.
• the modified conjugated diene-based polymer improves the dispersibility of the silica-containing filler, thereby reducing the hysteresis loss and improving the low-loss property.
• the hydrogenated resin is easily compatible with the rubber component and improves the hardness (elastic modulus) of the rubber composition. can improve sexuality.
• the combination of the modified conjugated diene-based polymer and the hydrogenated resin provides a synergistic effect in reducing loss and improving steering stability. Therefore, by applying the rubber composition of the present invention to a tire, it is possible to significantly improve the low-loss property and steering stability of the tire.
• the modified conjugated diene-based polymer in the rubber component the dispersibility of the silica-containing filler is improved, and the loss reduction property of the rubber composition is improved.
• the modified conjugated diene-based polymer can greatly improve the low-loss property and the steering stability of the tire to which the rubber composition is applied by being combined with a hydrogenated resin described later.
• the conjugated diene-based polymer having the active terminal is obtained by polymerizing a monomer containing a conjugated diene compound.
• Conjugated diene compounds used for polymerization include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene and the like.
• 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene are preferred, and 1,3-butadiene is particularly preferred.
• the conjugated diene-based polymer may be a homopolymer of a conjugated diene compound, or a copolymer of a conjugated diene compound and another monomer. Moreover, from the viewpoint of increasing the hardness (elastic modulus) of the rubber composition, the conjugated diene-based polymer is preferably a copolymer of a conjugated diene compound and an aromatic vinyl compound.
• examples of aromatic vinyl compounds used for polymerization include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropyl Styrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethyl aminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-buty
• the conjugated diene-based polymer when it is a copolymer of a conjugated diene compound and an aromatic vinyl compound, it has a high living property in anionic polymerization. It is preferably a copolymer contained in. Furthermore, the copolymer preferably has a random copolymerized portion in which the conjugated diene compound and the aromatic vinyl compound are irregularly distributed, and further has a block portion composed of the conjugated diene compound or the aromatic vinyl compound.
• the proportion of aromatic vinyl units in the conjugated diene-based polymer is preferably less than 10% by mass. If the proportion of the aromatic vinyl units is less than 10% by mass, the low-loss property of the tire can be further improved when applied to the tire.
• compounds other than conjugated diene compounds and aromatic vinyl compounds may be used as monomers.
• Other monomers include, for example, acrylonitrile, methyl (meth)acrylate, and ethyl (meth)acrylate.
• the proportion of other monomers used is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total amount of monomers used for polymerization.
• a polymerization method for obtaining the conjugated diene-based polymer for example, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, or the like can be used, but a solution polymerization method is particularly preferable.
• a polymerization system either a batch system or a continuous system may be used.
• a monomer containing a conjugated diene compound is polymerized in the presence of a polymerization initiator and, optionally, a randomizer. method.
• At least one of an alkali metal compound and an alkaline earth metal compound is preferably used as the polymerization initiator used in the polymerization.
• the polymerization initiator include alkyllithium such as methyllithium, ethyllithium, n-propyllithium, n-butyllithium, sec-butyllithium and t-butyllithium, 1,4-dilithiobutane, and phenyllithium.
• the total amount of the polymerization initiator used is preferably 0.2 to 20 mmol with respect to 100 g of the monomer used for polymerization.
• the polymerization reaction may be carried out using, as a polymerization initiator, a mixture of at least one of an alkali metal compound and an alkaline earth metal compound and a compound having a functional group that interacts with silica.
• a polymerization initiator a mixture of at least one of an alkali metal compound and an alkaline earth metal compound and a compound having a functional group that interacts with silica.
• the polymerization initiation terminal of the conjugated diene-based polymer can be modified with a functional group that interacts with silica.
• the term "functional group that interacts with silica” means a group having an element that interacts with silica, such as nitrogen, sulfur, phosphorus, and oxygen.
• Interaction means forming a covalent bond between molecules or an intermolecular force weaker than a covalent bond (e.g., ion-dipole interaction, dipole-dipole interaction, hydrogen bonding, van der Waals It means to form an electromagnetic force acting between molecules such as force.
• a nitrogen-containing compound such as a secondary amine compound is preferable as the compound having a functional group that interacts with silica, which is used for modifying the polymerization initiation terminal.
• Specific examples of the nitrogen-containing compound include dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethyleneimine, N,N'-dimethyl-N'-trimethylsilyl-1,6-diaminohexane, piperidine and pyrrolidine.
• hexamethyleneimine hexamethyleneimine
• heptamethyleneimine dicyclohexylamine
• N-methylbenzylamine di-(2-ethylhexyl)amine
• diallylamine morpholine
• N-(trimethylsilyl)piperazine N-(tert-butyldimethylsilyl)piperazine, 1 ,3-ditrimethylsilyl-1,3,5-triazinane and the like.
• At least one of an alkali metal compound and an alkaline earth metal compound and a compound having a functional group that interacts with silica are mixed in advance, and the mixture is polymerized.
• Polymerization may be carried out by adding to the system.
• at least one of an alkali metal compound and an alkaline earth metal compound and a compound having a functional group that interacts with silica are added to the polymerization system, and the two are mixed in the polymerization system to carry out polymerization. good too. Any of these cases is included in the aspect of "polymerizing a monomer containing a conjugated diene compound in the presence of an initiator containing at least one of an alkali metal compound and an alkaline earth metal compound".
• the randomizer can be used for the purpose of adjusting the vinyl bond content, which indicates the content of vinyl bonds in the polymer.
• randomizers include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di(tetrahydrofuryl)propane, 2-(2-ethoxyethoxy)-2-methylpropane, triethylamine, pyridine. , N-methylmorpholine, tetramethylethylenediamine, and the like. These can be used individually by 1 type or in combination of 2 or more types.
• the organic solvent used for the polymerization may be any organic solvent that is inert to the reaction, such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.
• hydrocarbons having 3 to 8 carbon atoms are preferable, and specific examples include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2-butene, cis-2-butene, 1-pentyne, 2-pentyne, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1-pentene, 2-pentene, cyclohexene and the like.
• an organic solvent such as an
• the monomer concentration in the reaction solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, from the viewpoint of maintaining a balance between productivity and ease of polymerization control. more preferred.
• the temperature of the polymerization reaction is preferably -20°C to 150°C, more preferably 0°C to 120°C.
• the polymerization reaction is preferably conducted under sufficient pressure to keep the monomers substantially in the liquid phase. Such a pressure can be obtained by a method such as pressurizing the interior of the reactor with a gas inert to the polymerization reaction.
• the conjugated diene-based polymer preferably has a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 5.0 ⁇ 10 4 to 2.0 ⁇ 10 6 .
• Mw polystyrene equivalent weight average molecular weight measured by gel permeation chromatography
• GPC gel permeation chromatography
• the vinyl bond content in the conjugated diene unit (eg, butadiene unit) of the conjugated diene-based polymer having an active terminal is preferably 10 to 70% by mass, more preferably 20 to 60% by mass.
• the vinyl bond content is 10% by mass or more, the grip properties tend to improve, and when it is 70% by mass or less, the wear resistance of the resulting vulcanized rubber tends to improve.
• the term "vinyl bond content” refers to the content of structural units having a 1,2-bond with respect to all structural units of a conjugated diene compound (e.g., butadiene) in a conjugated diene polymer. values, measured by 1 H-NMR.
• the modified conjugated diene system modified with a group that has a large number of branches in the polymer chain and interacts with a filler such as silica by the modification step A polymer can be obtained.
• the hydrocarbyl group of R 1 includes, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkenyl group having 6 to 20 carbon atoms, An aryl group and the like can be mentioned.
• the rest of the structure of A 1 is not particularly limited as long as it has an alkoxysilyl group, but it is preferably a group further having a methylene group or a polymethylene group, and has a methylene group or a polymethylene group and an alkoxysilyl group.
• the number of specific imino groups possessed by the compound [M] may be 2 or more, preferably 2 to 6.
• the plurality of R 1 and A 1 in compound [M] may be the same or different.
• R 2 and R 3 are each independently a hydrocarbyl group having 1 to 20 carbon atoms
• R 4 is an alkanediyl group having 1 to 20 carbon atoms
• R 5 is an m-valent hydrocarbyl group having 1 to 20 carbon atoms, or a 1 to 2 carbon atom having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom and having no active hydrogen; 20 m-valent radicals.
• n is an integer of 1-3 and m is an integer of 2-10.
• a plurality of R 2 , R 3 , R 4 , A 2 and n may be the same or different.
• examples of hydrocarbyl groups for R 2 and R 3 include alkyl groups having 1 to 20 carbon atoms, allyl groups, cycloalkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. etc.
• the alkanediyl group (alkylene group) having 1 to 20 carbon atoms for R 4 is preferably linear.
• n is preferably 2 or 3, and more preferably 3, in terms of improving silica dispersibility.
• the m-valent hydrocarbyl group for R 5 is a chain hydrocarbon having 1 to 20 carbon atoms, an alicyclic hydrocarbon having 3 to 20 carbon atoms, or an aromatic hydrocarbon having 6 to 20 carbon atoms and m hydrogen atoms. are removed, and the like.
• a group obtained by removing m hydrogen atoms from a ring portion of an aromatic hydrocarbon (aromatic ring group) is preferable because it has a high effect of improving the abrasion resistance of the resulting vulcanized rubber.
• aromatic hydrocarbon examples include, for example, a ring structure represented by the following general formula (2), and a polycyclic structure in which two or more of the ring structures are linked (e.g., biphenyl group, etc.). .
• r is an integer of 0 to 5.
• R 5 is a C 1-20 m-valent group having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom and having no active hydrogen
• examples include an m-valent heterocyclic group and an m-valent group having a tertiary amine structure.
• the heterocyclic group is preferably a conjugated system, for example, a monocyclic or condensed ring such as pyridine, pyrimidine, pyrazine, quinoline, naphthalidine, furan, thiophene, or a plurality of such monocyclic or condensed rings linked together. Examples thereof include groups obtained by removing m hydrogen atoms from the ring portion of the structure.
• active hydrogen means a hydrogen atom bonded to an atom other than a carbon atom, preferably having a lower bond energy than the carbon-hydrogen bond of polymethylene.
• compound [M] examples include compounds represented by the following formulas (M-1) to (M-23).
• compound [M] may be used individually by 1 type, and may be used in combination of 2 or more type.
• R 7 in formula (M-11) represents a hydrogen atom or an alkyl group.
• the compound [M] can be synthesized by appropriately combining standard methods of organic chemistry.
• a monofunctional amine compound having an alkoxysilyl group and R4 for example, 3-aminopropyltriethoxysilane, 3-aminopropyl methyldiethoxysilane, etc.
• a polyfunctional aldehyde compound having R 5 e.g., terephthalaldehyde, isophthalaldehyde, phthaldialdehyde, 2,4-pyridinedicarboxaldehyde, etc.
• a polyfunctional amine compound having 5 e.g., tris(2-aminoethyl)amine, N,N'-bis(2-aminoethyl)methylamine, etc.
• an alkoxysilyl group and a monofunctional hydroxyl group having R 4 and a method of dehydration condensation with a contained compound e.
• the reaction between the conjugated diene-based polymer having an active terminal and the compound [M] can be carried out, for example, as a solution reaction.
• the proportion of the compound [M] used (the total amount when two or more types are used) is 0 per 1 mol of the metal atom involved in the polymerization of the polymerization initiator. It is preferably 0.01 mol or more, more preferably 0.05 mol or more.
• the upper limit is preferably less than 2.0 mol, more preferably less than 1.5 mol, per 1 mol of the metal atom involved in polymerization of the polymerization initiator. is more preferred.
• the temperature of the modification reaction is usually the same as that of the polymerization reaction, preferably from -20°C to 150°C, more preferably from 0°C to 120°C.
• the reaction time is preferably 1 minute to 5 hours, more preferably 2 minutes to 1 hour.
• the conjugated diene-based polymer having an active terminal and the compound [M] other modifiers or coupling agents may be used together with the compound [M].
• the other modifier or coupling agent is not particularly limited as long as it is a compound capable of reacting with the active terminal of the conjugated diene polymer obtained by the above polymerization.
• a known compound can be used.
• other modifiers or coupling agents their usage ratio is preferably 10 mol % or less, more preferably 5 mol % or less.
• the modified conjugated diene-based polymer contained in the reaction solution can be isolated by, for example, a known desolvation method such as steam stripping and a drying operation such as heat treatment.
• the weight average molecular weight of the modified conjugated diene-based polymer in terms of polystyrene by GPC is sufficiently high to obtain a modified conjugated diene-based polymer having sufficiently high Mooney viscosity and good shape stability, and a rubber composition excellent in processability. It is preferably 1.0 ⁇ 10 5 to 4.0 ⁇ 10 6 from the viewpoint of compatibility with obtaining a product. It is more preferably 1.8 ⁇ 10 5 to 3.0 ⁇ 10 6 , still more preferably 2.0 ⁇ 10 5 to 2.0 ⁇ 10 6 .
• the weight average molecular weight of the modified conjugated diene-based polymer is a value obtained from the maximum peak molecular weight of the GPC curve measured by GPC after the reaction between the conjugated diene-based polymer having an active terminal and the compound [M].
• the number of branches of the polymer chain per molecule of the modified conjugated diene-based polymer is preferably 3 or more from the viewpoint of sufficiently high Mooney viscosity of the obtained modified conjugated diene-based polymer and good cold flow. and more preferably in the range of 3-20.
• the modified conjugated diene-based polymer is preferably represented by the following general formula (3).
• R 2 is a hydrocarbyl group having 1 to 20 carbon atoms
• R 6 is a hydrocarbyloxy group having 1 to 20 carbon atoms, or a modified or unmodified conjugated diene polymer chain
• R 4 is an alkanediyl group having 1 to 20 carbon atoms
• Z is a group represented by the following general formula (4) or (5).
• R 5 is an m-valent hydrocarbyl group having 1 to 20 carbon atoms, or a 1 to 2 carbon atom having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom and having no active hydrogen; 20 m-valent radicals.
• n is an integer of 1-3 and m is an integer of 2-10.
• multiple R 2 , R 4 , R 6 , Z and n may be the same or different.
• R 1 is a hydrogen atom or a hydrocarbyl group
• Poly is a modified or unmodified conjugated diene polymer chain. "*" indicates a bond that binds to R5 .
• the modified conjugated diene-based polymer represented by the general formula (3) has a great effect of improving the dispersibility of the filler containing silica, and further improves the low-loss property of the rubber composition. Moreover, when the rubber composition is applied to a tire, the loss reduction property of the tire is further improved.
• R 1 , R 2 , R 4 and R 5 are the same as explained for general formula (1) above.
• the hydrocarbyloxy group for R6 is preferably an ethoxy group or a methoxy group.
• the conjugated diene-based polymer chain of R 6 and the conjugated diene-based polymer chain Poly in the general formulas (4) and (5) have structures corresponding to the conjugated diene-based polymer having an active terminal obtained in the above polymerization step. is. These conjugated diene-based polymer chains may have functional groups that interact with silica at the ends.
• the modified conjugated diene polymer has an aromatic vinyl unit and a conjugated diene unit, and the proportion of the aromatic vinyl unit in the modified conjugated diene polymer is 10% by mass or less. is preferably When the modified conjugated diene-based polymer has an aromatic vinyl unit and a conjugated diene unit, and the proportion of the aromatic vinyl unit is 10% by mass or less, when the rubber composition is applied to a tire, the loss of the tire is low. It is possible to further improve the properties.
• the modified conjugated diene polymer preferably has a vinyl bond content in conjugated diene units (eg, butadiene units) of 10 to 70% by mass, preferably 20 to 60% by mass. It is more preferable to have When the vinyl bond content is 10% by mass or more, the grip properties tend to improve, and when it is 70% by mass or less, the wear resistance of the resulting vulcanized rubber tends to improve.
• conjugated diene units eg, butadiene units
• the modified conjugated diene polymer preferably has a peak top molecular weight (Mp) of less than 1.0 ⁇ 10 6 .
• Mp peak top molecular weight
• the modified conjugated diene-based polymer preferably has a peak top molecular weight (Mp) of 50 ⁇ 10 3 or more.
• the peak top molecular weight (Mp) is a value obtained in terms of polystyrene from the retention time corresponding to the top of the maximum peak of the GPC curve obtained by gel permeation chromatography (GPC).
• the ratio of the modified conjugated diene-based polymer in the rubber component is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of low loss.
• the ratio of the modified conjugated diene polymer in the rubber component may be 100% by mass, preferably 60% by mass or less, and more preferably 50% by mass or less.
• Rubber components other than the modified conjugated diene polymer include natural rubber (NR), polyisoprene rubber (IR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), halogenated Butyl rubber, ethylene-propylene rubber (EPR, EPDM) and the like.
• the ratio of the other rubber component in the rubber component is preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 40% by mass or more, further preferably 50% by mass or more.
• the rubber composition of the present embodiment contains a hydrogenated resin, and the hydrogenated resin has a softening point higher than 110° C. and a polystyrene equivalent weight average molecular weight of 200 to 1200 g/mol.
• the softening point of the hydrogenated resin is preferably 115° C. or higher, more preferably 118° C. or higher, and more preferably 121° C. or higher, from the viewpoint of further improving tire loss property and steering stability. It is more preferably 123°C or higher, even more preferably 125°C or higher, even more preferably 127°C or higher, even more preferably 128°C or higher, and 129°C or higher. is even more preferable.
• the softening point of the hydrogenated resin is preferably 145° C. or lower, preferably 143° C. or lower, and 140° C. or lower from the viewpoint of further improving tire loss property and steering stability. is more preferred.
• the polystyrene-equivalent weight average molecular weight of the hydrogenated resin is less than 200 g/mol, the hydrogenated resin precipitates from the tire, and the effect of the hydrogenated resin cannot be fully exhibited. If it exceeds mol, the hydrogenated resin cannot be compatible with the rubber component.
• the polystyrene-equivalent weight average molecular weight of the hydrogenated resin is preferably 300 g/mol or more, and is 500 g/mol or more. preferably 700 g/mol or more, and even more preferably 750 g/mol or more.
• the polystyrene-equivalent weight average molecular weight of the hydrogenated resin is preferably 1150 g/mol or less, such as 1100 g/mol. It is more preferably 1050 g/mol or less, more preferably 1050 g/mol or less.
• the hydrogenated resin means a resin obtained by reducing and hydrogenating a resin.
• resins used as raw materials for hydrogenated resins include C5-based resins, C5- C9 - based resins, C9 - based resins, terpene-based resins, dicyclopentadiene-based resins, terpene-aromatic compound-based resins, and the like. These resins may be used singly or in combination of two or more.
• Examples of the C5 - based resin include aliphatic petroleum resins obtained by ( co)polymerizing a C5 fraction obtained by pyrolysis of naphtha in the petrochemical industry.
• the C5 fraction usually contains olefinic hydrocarbons such as 1 - pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 2-methyl- Diolefinic hydrocarbons such as 1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene and 3-methyl-1,2-butadiene are included.
• a commercially available product can be used as the C5 - based resin.
• the C 5 -C 9 resin refers to a C 5 -C 9 synthetic petroleum resin, and examples of the C 5 -C 9 resin include petroleum-derived C 5 -C 11 fractions, AlCl 3 , Examples include solid polymers obtained by polymerization using a Friedel-Crafts catalyst such as BF3 , and more specifically, copolymers containing styrene, vinyl toluene, ⁇ -methylstyrene, indene, etc. as main components. is mentioned. As the C 5 -C 9 resin, a resin containing less C 9 or higher components is preferable from the viewpoint of compatibility with the rubber component.
• the phrase "lower amount of C9 or higher components” means that the C9 or higher components in the total amount of the resin are less than 50% by mass, preferably 40% by mass or less.
• a commercially available product can be used as the C 5 -C 9 based resin.
• the C9 resin refers to a C9 synthetic petroleum resin, and refers to a solid polymer obtained by polymerizing a C9 fraction using a Friedel - Crafts type catalyst such as AlCl3 or BF3 .
• Examples of C9 -based resins include copolymers mainly composed of indene, ⁇ -methylstyrene, vinyltoluene, and the like.
• the terpene-based resin is a solid resin obtained by blending turpentine oil obtained at the same time as rosin is obtained from a pine tree, or a polymer component separated from it, and polymerizing using a Friedel-Crafts-type catalyst. , ⁇ -pinene resin, ⁇ -pinene resin, and the like.
• a typical example of the terpene-aromatic compound resin is a terpene-phenol resin.
• This terpene-phenol resin can be obtained by reacting terpenes with various phenols using a Friedel-Crafts type catalyst, or by further condensing them with formalin.
• Terpenes used as raw materials are not particularly limited, and monoterpene hydrocarbons such as ⁇ -pinene and limonene are preferred, those containing ⁇ -pinene are more preferred, and ⁇ -pinene is particularly preferred.
• the dicyclopentadiene-based resin refers to a resin obtained by polymerizing dicyclopentadiene using a Friedel-Crafts-type catalyst such as AlCl 3 or BF 3 .
• the resin that is the raw material of the hydrogenated resin may contain, for example, a resin (C 5 -DCPD-based resin) obtained by copolymerizing a C 5 fraction and dicyclopentadiene (DCPD).
• a resin C 5 -DCPD-based resin obtained by copolymerizing a C 5 fraction and dicyclopentadiene (DCPD).
• DCPD dicyclopentadiene
• the C 5 -DCPD-based resin is included in the dicyclopentadiene-based resin.
• the C 5 -DCPD resin is included in the C 5 resin.
• the hydrogenated resin is selected from hydrogenated C5 resins and hydrogenated C5 - C9 resins. and hydrogenated dicyclopentadiene-based resin (hydrogenated DCPD-based resin), preferably at least one selected from the group consisting of hydrogenated C5-based resin and hydrogenated C5 - C9 - based resin. It is more preferably at least one selected from the group consisting of, more preferably a hydrogenated C5 resin.
• the hydrogenated resin is at least one selected from the group consisting of hydrogenated C5-based resins, hydrogenated C5 - C9 - based resins, and hydrogenated dicyclopentadiene-based resins
• the rubber composition is When applied to a tire, it is possible to further improve the low-loss property and steering stability of the tire.
• the content of the hydrogenated resin is preferably in the range of 5 to 50 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the hydrogenated resin is 5 parts by mass or more with respect to 100 parts by mass of the rubber component, the effect of the hydrogenated resin is sufficiently exhibited. Precipitation can be suppressed, and the effect of the hydrogenated resin can be fully expressed.
• the content of the hydrogenated resin in the rubber composition is more preferably 6 parts by mass or more, more preferably 7 parts by mass or more, with respect to 100 parts by mass of the rubber component, from the viewpoint of further enhancing the effect of the hydrogenated resin. is more preferable, and 8 parts by mass or more is even more preferable.
• the content of hydrogenated resin in the rubber composition is 47 parts by mass or less with respect to 100 parts by mass of the rubber component. , more preferably 43 parts by mass or less, and even more preferably 40 parts by mass or less.
• the rubber composition of this embodiment contains a filler.
• the filler has a function of reinforcing the rubber composition.
• the content of the filler in the rubber composition is preferably in the range of 40 to 125 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the filler in the rubber composition is 40 parts by mass or more with respect to 100 parts by mass of the rubber component, the rubber composition is sufficiently reinforced, and if it is 125 parts by mass or less, the rubber composition The elastic modulus of the material does not become too high, and the steering stability of the tire is improved.
• the content of the filler in the rubber composition is preferably 45 parts by mass or more, more preferably 50 parts by mass or more, relative to 100 parts by mass of the rubber component. More preferably, it is 55 parts by mass or more.
• the content of the filler in the rubber composition is preferably 110 parts by mass or less, and 100 parts by mass or less, relative to 100 parts by mass of the rubber component. , and more preferably 90 parts by mass or less.
• the filler includes silica.
• silica By including silica in the rubber composition, it is possible to improve low-loss properties and improve steering stability when applied to tires.
• the silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among these, wet silica is preferable. These silicas may be used singly or in combination of two or more.
• the silica preferably has a nitrogen adsorption specific surface area (BET method) of 130 m 2 /g or more and less than 330 m 2 /g.
• BET method nitrogen adsorption specific surface area
• the reinforcement of the rubber composition is sufficient.
• the nitrogen adsorption specific surface area (BET method) of silica is less than 330 m 2 /g, the elastic modulus of the rubber composition does not become too high, and the steering stability of the tire is improved.
• the nitrogen adsorption specific surface area (BET method) of silica is more preferably 180 m 2 /g or more, and more preferably 190 m 2 /g or more. Further, from the viewpoint of further improving the low loss property of the tire, the nitrogen adsorption specific surface area (BET method) of silica is more preferably 300 m 2 /g or less, more preferably 280 m 2 /g or less, It is more preferably 270 m 2 /g or less.
• the silica preferably has a cetyltrimethylammonium bromide adsorption specific surface area (CTAB) of 100 m 2 /g or more, more preferably 150 m 2 /g or more, and further preferably 180 m 2 /g or more. preferable.
• CTAB cetyltrimethylammonium bromide adsorption specific surface area
• the silica preferably has a cetyltrimethylammonium bromide adsorption specific surface area (CTAB) of 300 m 2 /g or less, more preferably 270 m 2 /g or less, and further preferably 250 m 2 /g or less. preferable.
• the content of silica in the filler is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more. is more preferred.
• the content of silica in the rubber composition is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, with respect to 100 parts by mass of the rubber component. is more preferable, and 40 parts by mass or more is even more preferable.
• the content of silica in the rubber composition is preferably 90 parts by mass or less, and 85 parts by mass or less with respect to 100 parts by mass of the rubber component. is more preferable, and 80 parts by mass or less is even more preferable.
• the filler preferably contains carbon black.
• carbon black is preferably contained within a range in which the content of silica in the filler is 80% by mass or more.
• Carbon black reinforces the vulcanized rubber and improves the wear resistance of the vulcanized rubber.
• Examples of carbon black include, but are not limited to, GPF, FEF, HAF, ISAF, and SAF grade carbon blacks. These carbon blacks may be used singly or in combination of two or more.
• the content of carbon black in the rubber composition is preferably 0.5 parts by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the rubber component. More preferably, it is 2 parts by mass or more.
• the content of carbon black in the rubber composition is preferably 15 parts by mass or less, and 12 parts by mass or less with respect to 100 parts by mass of the rubber component. is more preferably 9 parts by mass or less.
• the ratio of the content of the carbon black to the content of the silica is preferably 0.05 to 1.2, more preferably 0.07 to 1.0, and 0.08 to 0.7 is particularly preferred.
• the content ratio of the carbon black is preferably 0.05 to 1.2, more preferably 0.07 to 1.0, and 0.08 to 0.7.
• the filler may contain inorganic fillers such as clay, talc, calcium carbonate, aluminum hydroxide, etc., in addition to silica and carbon black.
• other ingredients are appropriately selected and blended into the rubber composition according to the purpose or need within a range that does not impair the effects of the present invention. be able to.
• Other components include, for example, antioxidants, cross-linking accelerators, cross-linking agents, cross-linking accelerator aids, silane coupling agents, softeners, antiozonants, surfactants, etc., which are commonly used in the rubber industry. Additives can be appropriately blended.
• a known anti-aging agent can be used, and is not particularly limited.
• phenol-based anti-aging agents, imidazole-based anti-aging agents, amine-based anti-aging agents and the like can be mentioned.
• These antioxidants can be used singly or in combination of two or more.
• the content of the antioxidant is not particularly limited, and is preferably in the range of 0.1 to 5 parts by mass, more preferably 1 to 4 parts by mass, relative to 100 parts by mass of the rubber component.
• cross-linking accelerator a known one can be used, and it is not particularly limited.
• thiazole vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; N-cyclohexyl-2-benzothiazylsulfenamide and Nt-butyl-2-benzothiazylsulfenamide Sulfenamide-based vulcanization accelerators; guanidine-based vulcanization accelerators such as diphenylguanidine; Thiuram-based vulcanization accelerators such as pentamethylenethiuram tetrasulfide; dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate; and zinc dialkyldithiophosphate.
• the content of the cross-linking accelerator is not particularly limited, and is preferably in the range of 0.1 to 8 parts by mass, more preferably in the range of 0.2 to 5 parts by mass, based on 100 parts
• cross-linking agent examples include sulfur.
• the content of the cross-linking agent is not particularly limited, and is preferably in the range of 0.1 to 8 parts by mass, more preferably in the range of 1 to 4 parts by mass in terms of sulfur content, per 100 parts by mass of the rubber component.
• the cross-linking accelerator aid examples include zinc oxide (ZnO) and fatty acids.
• the fatty acid may be saturated or unsaturated, linear or branched, and the number of carbon atoms in the fatty acid is not particularly limited. More specifically, cyclohexanoic acid (cyclohexanecarboxylic acid), naphthenic acids such as alkylcyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acids such as neodecanoic acid), dodecanoic acid, tetradecane saturated fatty acids such as acid, hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid; and resin acids such as rosin, tall oil acid and abietic acid.
• ZnO
• the content of the cross-linking accelerator is not particularly limited, and is preferably in the range of 0.5 to 8 parts by mass, more preferably in the range of 1 to 5 parts by mass, based on 100 parts by mass of the rubber component.
• silane coupling agent examples include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-tri ethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,
• silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more types.
• the content of the silane coupling agent is not particularly limited, but from the viewpoint of improving the dispersibility of silica, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more with respect to 100 parts by mass of the silica. , is preferably 20 parts by mass or less, more preferably 15 parts by mass or less.
• the softening agent examples include naphthenic oils, paraffinic oils, and aromatic oils.
• the softener can also be used as an extender oil for the rubber component.
• the content of the softening agent is not particularly limited, and it is preferable to blend 2 to 50 parts by mass with respect to 100 parts by mass of the rubber component.
• the content of the softening agent is 2 parts by mass or more with respect to 100 parts by mass of the rubber component, the processability of the rubber composition is improved.
• the content of the softening agent is 50 parts by mass or less per 100 parts by mass of the rubber component, the softening agent hardly seeps out onto the surface of the rubber product, and sufficient wear resistance can be ensured.
• the method for producing the rubber composition is not particularly limited. , heating, extrusion, or the like. Further, vulcanized rubber can be obtained by vulcanizing the obtained rubber composition.
• the kneading conditions are not particularly limited, and various conditions such as the input volume of the kneading device, the rotation speed of the rotor, the ram pressure, the kneading temperature, the kneading time, the type of the kneading device, etc. It can be selected as appropriate.
• the kneading device include Banbury mixers, intermixes, kneaders, rolls, etc., which are usually used for kneading rubber compositions.
• heating conditions there are no particular restrictions on the heating conditions, and various conditions such as the heating temperature, heating time, and heating device can be appropriately selected according to the purpose.
• the heating device include a heating roll machine or the like which is usually used for heating the rubber composition.
• the extrusion conditions are also not particularly limited, and various conditions such as extrusion time, extrusion speed, extrusion equipment, and extrusion temperature can be appropriately selected according to the purpose.
• the extrusion device include an extruder or the like that is usually used for extrusion of a rubber composition.
• the extrusion temperature can be determined appropriately.
• a molding vulcanizer with a mold used for vulcanization of a rubber composition is generally used.
• the temperature is, for example, about 100 to 190.degree.
• the rubber composition of this embodiment can be used for various rubber products including tires.
• the rubber composition of the present invention is preferable as a rubber composition for tires.
• a tire of the present embodiment is characterized by including the rubber composition described above.
• the tire of this embodiment is excellent in low-loss property and steering stability.
• the tire of this embodiment is preferably a pneumatic tire.
• the tire of the present embodiment preferably has the rubber composition in the tread portion, that is, preferably includes a tread rubber obtained by vulcanizing the rubber composition.
• the tire may be obtained by vulcanizing after molding using an unvulcanized rubber composition, depending on the type and member of the tire to be applied. After obtaining a semi-vulcanized rubber from the composition, it may be molded and then vulcanized.
• the gas to be filled into the pneumatic tire may be normal air or air with adjusted oxygen partial pressure, or inert gas such as nitrogen, argon, or helium.
• the vinyl bond content, bound styrene content, and peak top molecular weight (Mp) of the modified conjugated diene polymer are measured by the following methods.
• the softening point and weight average molecular weight of the hydrogenated resin are measured by the following methods.
• the softening point of the hydrogenated resin is measured according to JIS-K2207-1996 (ring and ball method).
• ⁇ Comparative Example 1> According to the formulation shown in Table 1, each component was blended and kneaded using a Banbury mixer to prepare a rubber composition sample. The compounding amounts in Table 1 are shown in parts by mass with respect to 100 parts by mass of the rubber component. The resulting rubber composition sample was subjected to a production vulcanization step (vulcanization temperature: 150° C.) to obtain a vulcanized rubber composition sample.
• the modified conjugated diene-based polymer A contained in the rubber composition sample was prepared according to the following method.
• the resulting modified conjugated diene polymer A has a bound styrene content of 10% by mass, a vinyl bond content of the butadiene portion of 40% by mass, and a peak top molecular weight (Mp) of 215 ⁇ 10 3 .
• Example 1 According to the formulation shown in Table 1, each component is blended and kneaded using a Banbury mixer to prepare a rubber composition sample. The compounding amounts in Table 1 are shown in parts by mass with respect to 100 parts by mass of the rubber component. Each sample of the obtained rubber composition is subjected to a production vulcanization step (temperature during vulcanization: 150° C.) to obtain a vulcanized rubber composition sample.
• the modified conjugated diene-based polymer B contained in the rubber composition sample is prepared according to the following method.
• a modifier compound (M-1) is obtained under the following conditions.
• a 100 mL eggplant flask was charged with 80 mL of toluene solvent, 4.55 g (33.92 mmol) of terephthalaldehyde, and 15.02 g (67.84 mmol) of 3-aminopropyltriethoxysilane, and refluxed at 120° C. using a Dean-Stark apparatus. I do. After the water has run out, the mixture is refluxed for 2 hours, filtered, and the toluene solvent is distilled off under reduced pressure.
• the resulting modified conjugated diene polymer B has a bound styrene content of 5% by mass, a vinyl bond content of the butadiene portion of 40% by mass, and a peak top molecular weight (Mp) of 120 ⁇ 10 3 .
• SBR Styrene-butadiene rubber, trade name “HP755” manufactured by JSR Corporation, oil-extended rubber blended with 37.5 parts by mass of extender oil per 100 parts by mass of rubber component *2
• the rubber composition of the present invention can be used for various rubber products including tires.

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• 2021
  • 2021-12-06 EP EP21931720.3A patent/EP4309916A4/en active Pending
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