WO2008004676A1 - Composition de caoutchouc et bandage pneumatique fabriqué à partir de celle-ci - Google Patents
Composition de caoutchouc et bandage pneumatique fabriqué à partir de celle-ci Download PDFInfo
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- WO2008004676A1 WO2008004676A1 PCT/JP2007/063608 JP2007063608W WO2008004676A1 WO 2008004676 A1 WO2008004676 A1 WO 2008004676A1 JP 2007063608 W JP2007063608 W JP 2007063608W WO 2008004676 A1 WO2008004676 A1 WO 2008004676A1
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- rubber composition
- rubber
- compound
- carbon atoms
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Classifications
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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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/14—Anti-skid inserts, e.g. vulcanised into the tread band
- B60C2011/147—Foamed rubber or sponge rubber on the tread band
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- 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
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
Definitions
- the present invention relates to a rubber composition and a pneumatic tire using the rubber composition. More specifically, the present invention enhances the reinforcing property with a filler and improves the braking / driving performance (DRY performance) of the tire on a dry road surface.
- the present invention relates to a rubber composition having excellent braking and driving performance (on-ice performance) of a tire on an icy and snowy road surface, and a pneumatic tire using the rubber composition in a tread.
- Patent Document 1 it has been proposed to further increase the coefficient of friction on the icy and snowy road surface by adding fine particles to the above-mentioned organic fiber and taking into account the pulling effect (for example, Patent Document 1 and (See Patent Document 2).
- a rubber component used in the tread natural rubber having a glass transition temperature of 60 ° C or lower, high cis polybutadiene, and the like are used.
- high cis polybutadiene has a glass transition.
- Increasing the proportion of high cis polybutadiene in the rubber component with low transition temperature improves the performance on ice, but with it, the DRY performance decreases. If the performance on ice is improved, there is a problem that the block rigidity of the tread decreases and the DRY performance tends to decrease.
- silica is used as a filler capable of improving the WET performance.
- silica and high cis polybutadiene are mixed, it is difficult to improve the mechanical performance of the composition like carbon black, which has poor workability.
- the present applicant can improve the above-mentioned problems by reacting the hydrocarbyloxysilane compound with the polymer having the active terminal, followed by a secondary reaction with a specific compound. (For example, see Patent Document 4).
- Patent Document 1 Japanese Patent Application Laid-Open No. 2003-201371
- Patent Document 2 JP 2001-233993 A
- Patent document 3 WO02Z02356 non-fret
- Patent Document 4 WO03Z46020 non-fret
- the present invention uses a rubber composition having improved reinforceability with a filler and maintaining DRY performance and having excellent on-ice performance, and the rubber composition used for a tread.
- the purpose is to provide a pneumatic tire.
- the present inventor As a result of intensive studies to achieve the above-mentioned object, the present inventor, as a result of containing closed cells, natural rubber as a rubber component, a specific terminal-modified conjugated gen-based polymer, a specific fine particle-containing organic It has been found that the object can be achieved by reducing the temperature dependence of the hardness of rubber by using a composition containing fibers and fillers.
- the present invention has been completed based on strong knowledge.
- a rubber assembly having closed cells comprising (A) a rubber component containing natural rubber and a terminal-modified conjugated gen-based polymer, (B) fine particle-containing organic fibers, and (C) a filler.
- the terminal-modified conjugation-based polymer is obtained by polymerizing a conjugated gen-based monomer mainly composed of 1,3 butadiene, and has a cis 1,4 bond content in the conjugation moiety of the main chain. 75 mol% or more of the active terminus of the conjugation copolymer having an active terminus, and hydrocarbyloxysilane compound I and ⁇ or a partial condensate thereof represented by the following general formula (I):
- the rubber composition according to the above (1) which is produced by a method including a step of reacting,
- a 1 is epoxy, thioepoxy, isocyanate, thioisocyanate, ketone, thioketone, aldehyde, thioaldehyde, imine, amide, isocyanuric acid trihydrocarbyl ester, carboxylic acid ester, thiocarboxylic acid ester, carboxylic acid anhydride.
- R 1 is a single bond or a divalent inert hydrocarbon group
- R 2 and R 3 are Each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms
- n is an integer of 0 to 2
- the plurality of OR 3 may be the same or different, and the molecule does not contain active protons and form salts.
- a hydrocarbyloxysilane compound is further added to promote condensation.
- a rubber composition according to the above (2) characterized in that it is produced by a method comprising the step (b) of performing secondary modification in the presence of an agent.
- the terminal-modified conjugation-based polymer is a hydrocarbyloxysilane compound represented by the general formula (I) as a hydrocarbyloxysilane compound used in the second modification step (b).
- the rubber composition according to the above (4) which is produced using at least one selected from hydrocarbyloxysilane compounds III and Z represented by
- a 2 represents cyclic tertiary amine, acyclic tertiary amine, pyridine, sulfide, multisulfide and -tolyl, cyclic tertiary amine amine salt, acyclic tertiary amine amine salt.
- R 4 is a single bond or a divalent non-activated carbon hydrocarbyl group
- R 5 and R 6 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms
- m is an integer of 0 to 2
- OR 6 there are plural, a plurality of OR 6 may be the same or different.
- a 3 represents alcohol, thiol, primary amine and its salt, cyclic secondary amine and its salt, acyclic secondary amine and its salt
- R 7 Is a single bond or a divalent inert hydrocarbon group
- R 8 and R 9 are each independently a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic carbon group having 6 to 18 carbon atoms.
- q is an integer from 0 to 2
- the OR 9 there are a plurality the plurality of OR 9 may be the same or different.
- the terminal-modified conjugation-based polymer uses at least one selected from the group force selected from the group (1) metal compound force represented by the following (1) Ka et al. (3) and water as the condensation accelerator.
- (1) to (5) V a rubber composition of any of the above,
- R 1Q is an organic group having 2 to 19 carbon atoms, and when there are a plurality of them, they may be the same or different.
- R 1Q is an organic group having 2 to 19 carbon atoms, and when there are a plurality of them, they may be the same or different.
- R 11 is an aliphatic hydrocarbon group having 1 to 30 carbon atoms
- B 1 is a hydroxyl group or halogen.
- a 4 includes (a) a carboxyl group having 2 to 30 carbon atoms, (b) an a, y-diol group having 5 to 30 carbon atoms, (c) a hydrocarbyloxy group having 3 to 30 carbon atoms, and (d) a siloxy group which is trisubstituted (which may be the same or different) in total with a hydrocarbyl group having 1 to 20 carbon atoms and Z or a hydrocarbyloxy group having 1 to 20 carbon atoms is also a group to be selected; A plurality of A 4 may be the same or different. ]
- Titanium compound with oxidation number 4 that satisfies the following general formula
- a 5 is a siloxy group (e) a hydrocarbyloxy group having 3 to 30 carbon atoms, (f) a siloxy group that is tri-substituted in total with an alkyl group having 1 to 30 carbon atoms and Z or a hydrocarbyloxy group having 1 to 20 carbon atoms. There may be different dates in the same if A 5 there is a plurality.
- B 2 is an a, y-diol group having 5 to 30 carbon atoms.
- conjugate conjugated polymer having an active terminal is a combination of at least one compound selected from each of the following elements (i), (ii), and (iii):
- (1) to (6) V which is produced by polymerizing a conjugated diene monomer mainly composed of 1,3-butadiene,
- Component alumoxane and / or A1R 12 R 14 R 14 (wherein R 12 and R 13 are the same or different, a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, R 14 is a carbon number of 1 to An organoaluminum compound corresponding to 10 hydrocarbon groups, wherein R 14 may be the same as or different from R 12 or R 13 above.
- the content of the cis 1,4 bond in the conjugation moiety of the main chain is 75 mol% or more, and the monomer constituting the conjugation polymer consists essentially of 1,3 butadiene (1) to (7) above V slip or rubber composition,
- the ratio of ( ⁇ ) fine particle-containing organic fiber to (D) fine particle-free organic fiber [( ⁇ ) fine particle-containing organic fiber Z (D) non-containing organic fiber] is 98 ⁇ 2 to 2 ⁇ 98 by mass ratio (11) or (12) rubber composition
- the (v) fine particle-containing organic fiber has a Mohs hardness of 2 or more as fine particles, 80% by mass or more of the frequency number of the particle size distribution is 10 to 50 ⁇ m, and the average particle size is 10 to 30 including those that are ⁇ m (1) to (14) 1 /, any rubber thread and composition,
- the fiber used in the (B) fine particle-containing organic fiber and the (D) fine particle-free organic fiber has a diameter of 0.01 to 0.1 mm and a length of 0.5 to 20 mm (10) ⁇ (15) any rubber composition,
- the above-mentioned (B) the fine particle-containing organic fiber and (D) the fine particle-free organic fiber are crystalline polymers made of polyethylene, Z, or polypropylene, and the melting point is 190 ° C or lower. (11) to (19) any pneumatic tire,
- M in the formula is at least one metal oxide or metal hydroxide selected from Al, Mg, Ti, and Ca, and X and y are both integers of 0 to 10. ]
- n is an integer of 0 to 4.
- FIG. 1 is a schematic sectional view of a tire according to the present invention.
- FIG. 2 (a) and (b) are cross-sectional schematic views along the circumferential direction and the width direction of the tread portion of the tire according to the present invention.
- FIG. 3 is an explanatory view explaining the principle of orienting fine particle-containing organic fibers in a certain direction.
- the rubber composition of the present invention has closed cells, and (A) a rubber component containing natural rubber and a terminal-modified conjugated-gen polymer, (B) fine particle-containing organic fiber, and (C) a filler. Is included.
- the terminal-modified conjugation-based polymer is prepared by reacting a hydrocarbyloxysilane compound with the terminal of a conjugation-based polymer having an active terminal having a cis 1,4 bond content of 75% or more. Furthermore, the hydrocarbyloxysilane compound residue introduced at the terminal is reacted with a specific compound.
- the ability to use any of the solution polymerization method, gas phase polymerization method, and Balta polymerization method is not particularly limited as to the method for producing a polymer having an active terminal having a cis 1,4 bond content of 75 mol% or more.
- a solution polymerization method is preferred.
- the polymerization method can be either batch or continuous.
- conjugation compound as a polymerization monomer examples include 1,3 butadiene; isoprene; 1,3 pentagen; 2,3 dimethylbutadiene; 2 phenyl 1,3 butadiene; 1,3 hexagen, and the like. These may be used alone or in combination of two or more. Among these, 1,3 butadiene is particularly preferred. May also be a small amount coexistence was of minor amounts of other hydrocarbon monomers in these conjugated diene monomers, but conjugated diene monomer is not preferable is the total monomers in the 80 mole 0/0 above.
- the method for producing the intermediate of the conjugation polymer having a cis bond of 75 mol% is not particularly limited, and a known one can be used, but the polymerization catalysts are as follows (i), (ii) A combination of at least one compound selected from each component of (iii) is preferred. That is, (i) Component
- the component (i) of the catalyst system used for the polymerization of the terminally active polymer is a compound containing a rare earth element having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds and a Lewis base. is there.
- a rare earth element having atomic numbers of 57 to 71 neodymium, praseodymium, cerium, lanthanum, gadolinium and the like, or a mixture thereof are preferable, and neodymium is particularly preferable.
- the rare earth element-containing compound is preferably a salt soluble in a hydrocarbon solvent.
- the rare earth element carboxylate, alkoxide, ⁇ -diketone complex, phosphate salt and Examples thereof include phosphates, and among these, carboxylates and phosphates are preferable, and carboxylates are particularly preferable.
- examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane, and heptane, and saturated alicyclic carbonizations having 5 to 20 carbon atoms such as cyclopentane and cyclohexane.
- Hydrogen, monoolefins such as 1-butene and 2-butene
- aromatic hydrocarbons such as benzene, toluene, and xylene
- halogenated hydrocarbons such as bromobenzene and toluene.
- the rare earth element carboxylates satisfy the following general formula:
- R is a hydrocarbon group having 1 to 20 carbon atoms, and M is a rare earth element having an atomic number of 57 to 71 in the periodic table
- R 14 is The alkyl group and alkenyl group, which may be saturated or unsaturated, may be linear, branched or cyclic, and the carboxyl group may be a primary, secondary or tertiary carbon atom.
- carboxylate examples include octanoic acid, 2-ethylhexanoic acid, oleic acid, neodecanoic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [Shelley Chemical Co., Ltd.] And a salt such as carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom.
- 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, Versatic acid salts are preferred.
- the rare earth element alkoxide satisfies the following general formula: (R ls O) M
- R ′′ is a hydrocarbon group having 1 to 20 carbon atoms
- M is a rare earth element having an atomic number of 57 to 71 in the periodic table.
- R ls O examples of the alkoxy group include 2-ethyl-hexylalkoxy group, oleylalkoxy group, stearylalkoxy group, phenoxy group, benzylalkoxy group, etc. Among them, 2-ethylhexylalkoxy group, benzyl Alkoxy groups are preferred.
- Examples of the rare earth element j8-diketone complex include a acetylylacetone complex, a benzoylacetone complex, a propio-tolylacetone complex, a valerylacetone complex, and an ethylacetylacetone complex of the rare earth element. .
- acetylacetone complex and ethylacetylacetone complex are preferable.
- the rare earth element phosphate and phosphite the rare earth element, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, bis (p -Norfu Engineering), Bisphosphate (Polyethylene Glycol-p Nourphele), Phosphoric Acid (1-Methylheptyl) (2-Ethylhexyl), Phosphoric Acid (2-Ethylhexyl) (p-N- 1-ethylhexylphosphonate mono-2-ethylhexyl, 2-ethylhexyl phosphonate monophenyl, bis (2-ethylhexyl) phosphinic acid, bis (1 Methylheptyl) phosphinic acid, bis (p-norphenyl) phosphinic acid, (1 methylheptyl) (2-ethylhexyl) phosphinic acid, (2-
- Rare earth elements bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, 2-ethylhexyl phosphonate mono-2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphine Salts with acids are preferred.
- neodymium phosphate and neodymium carbonate are more preferred, especially neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium versatic.
- neodymium branched carboxylates such as acid salts.
- the component (i) may be a reaction product of the rare earth element-containing compound and a Lewis base! / ⁇ .
- the reactant is improved in the solubility of the rare earth element-containing compound in the solvent by the Lewis base. It can be stored stably for a long time.
- the Lewis base used for easily solubilizing the rare earth element-containing compound in a solvent and stably storing for a long period of time is 0 to 30 mol, preferably 1 to 10 mol, per mol of the rare earth element. It is used as a mixture of the two or as a product obtained by reacting both in advance.
- examples of the Lewis base include acetylethylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, and a monovalent or divalent alcohol.
- the rare earth element-containing compounds as the component (i) described above or the reaction product of these compounds and a Lewis base can be used singly or in combination of two or more.
- the component (ii) of the catalyst system used for the polymerization of the terminal active polymer is an organic aluminum oxych compound and Z or the following general formula
- R 16 and R 17 are the same or different and are a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms
- R 18 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 18 is the above R It may be the same as or different from 16 or R 17 .
- alumoxane examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, black aluminoxane, and the like.
- organoaluminum compound examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, Tripentyl aluminum, Trihexyl aluminum, Tricyclohexyl aluminum, Trioctyl aluminum, Jetyl aluminum hydride, Di-n-propyl aluminum hydride, Di-n-butyl aluminum hydride, Diisobutyl aluminum hydride, Hydrogen Dihexyl aluminum, diisohexyl aluminum hydride, dioctyl aluminum hydride, water Diisooctylaluminum iodide; ethylaluminum dihydride, n-propylaluminum dinoide ride, isobutylaluminum dinoide ride, etc.
- triethylaluminum, triisobutylaluminum, hydrogenated jetylaluminum, Diisobutylaluminum hydride is preferred.
- the organic aluminum compound as component (B) described above can be used alone or in combination of two or more.
- the component (m) of the catalyst system used for the polymerization of the terminally active polymer is a group power comprising a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen. At least one halogen compound selected.
- the Lewis acid has Lewis acidity and is soluble in hydrocarbons. Specifically, methylaluminum dibromide, methylaluminum dichloride, acetylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, odor Jetylaluminum chloride, dimethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, sesquimethyl iodide, methylaluminum sesquichloride, sesquibromide chilled aluminum, sesquiethylaluminum chloride, dibutyltin dichloride, aluminum tribromide Examples thereof include antimony trichloride, pentachloride-antimony, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, and t
- reaction product of alkylaluminum and halogen such as a reaction product of triethylaluminum and bromine can be used.
- the metal halide constituting the complex compound of the above-mentioned metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, chloride.
- magnesium chloride, calcium chloride, barium chloride, mangan chloride, zinc chloride, and copper chloride are preferred.
- Magnesium chloride, salty manganese, zinc chloride, and salty copper are particularly preferred. .
- the Lewis base constituting the complex compound of the metal halide and Lewis base is preferably a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol, or the like.
- tri- 2-ethylhexyl phosphate, tricresyl phosphate, acetylethylacetone, 2-ethylhexanoic acid, versatic Acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.
- the Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide.
- the metal remaining in the polymer can be reduced.
- organic compound containing the active halogen examples include benzyl chloride.
- the amount or composition ratio of each component of the catalyst system used for the polymerization of the conjugation polymer is appropriately selected according to its purpose or necessity.
- the component (i) is preferably used in an amount of 0.00001 to 1.0 ⁇ dimonore, more preferably 0.0001 to 0.5 mmol, relative to the conjugate gen-based compound lOOg.
- (I) Keep component usage within the above range As a result, excellent polymerization activity is obtained, and the necessity of a deashing step is eliminated.
- the ratio of the organoaluminum compound of (i) component and (ii) component is molar ratio, (i) component:
- the organic aluminum compound is 1: 1 to 1: 700, preferably 1: 3 to 1: 500. Furthermore, the proportion of halogen in component (i) and component (iii) is a molar ratio, 1: 0.1-1: 30, preferably 1: 0.2-2: 1: 15, more preferably 1: 2.0-1: 0.
- the ratio of the alumoxane, which is the component (ii), to the component (i) is a molar ratio
- the polymerization reaction may be carried out in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.
- a small amount of a conjugate conjugated compound such as 1, 3 butadiene if necessary, specifically, the component (i) You may use it in the ratio of 0-: L000 mol per 1 mol of compounds.
- Conjugated genies such as 1,3 butadiene as catalyst components are not essential, but using them together has the advantage of further improving the catalytic activity.
- the components (i) to (m) are dissolved in a solvent, and a conjugated diene compound such as 1,3 butadiene is reacted as necessary.
- the order of addition of the respective components is not particularly limited, and from the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period, it is preferable to mix these components in advance and react and ripen.
- the aging temperature is about 0-100 ° C, preferably 20-80 ° C. When the temperature is lower than 0 ° C, it is difficult to ripen sufficiently. When the temperature exceeds 100 ° C, the catalytic activity may be reduced or the molecular weight distribution may be broadened.
- the aging time can be aged by bringing it into contact with the line before adding to the polymerization reactor without any restriction, and usually 0.5 minutes or more is sufficient, and it is stable for several days.
- all raw materials involved in the polymerization such as catalysts, solvents, and monomers, substantially remove reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds. It is desirable to use
- the polymer to be used has at least 10% of polymer chains having a living property.
- the hydrocarbylsilane compound used for the reaction with the active terminal of the polymer is preferably represented by the general formula (I)
- a 1 is (thio) epoxy, (thio) incyanate, (thio) ketone, (thio) aldehyde, imine, amide, isocyanuric acid triester, (thio) carboxylic acid hydrocarbyl ester, (thio) carbono
- R 1 is a single bond or a divalent inert carbon;
- a hydrogen group, R 2 and R 3 each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and n is 0 to an integer 2, if the oR 3 there are a plurality, the plurality of oR 3 is and active proton during Yogumata molecule be the same or different from each other O - ⁇ beam salts include Lena
- the partial condensate is a product in which a part (not all! /) Of SiOR of the hydrocarbyloxysilane compound is SiOSi bonded by condensation.
- imine includes ketimine, aldimine, and amidine
- (thio) carboxylic acid ester is an unsaturated carboxylic acid ester such as acrylate or metatalylate. Is included.
- the metal of the metal salt of (thio) carboxylic acid include alkali metals, alkaline earth metals, Al, Sn, and Zn.
- an alkylene group having 1 to 20 carbon atoms can be preferably exemplified.
- This alkylene group can be linear, branched or cyclic. Although it may be present, a linear one is particularly suitable.
- Examples of this linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an otatamethylene group, a decamethylene group, and a dodecamethylene group.
- R 2 and R 3 include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and the like.
- the alkyl group and alkenyl group may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an nbutyl group, and an isobutyl group.
- the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
- the aralkyl group has a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, etc.
- n is 0-2.
- An integer force 0 force S is preferred, and it is necessary to have no active protons and onium salts in the molecule.
- hydrocarbyloxysilane compound represented by the general formula (I) examples include (thio) epoxy group-containing hydrocarbyloxysilane compound, such as 2-glycidchichetiltrimethoxysilane.
- hydrocarbyloxy compounds include the following. That is, imine (amidine) group-containing compounds include 1- [3- (triethoxysilyl) propyl] -1,4,5 dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -1,4,5 Forces that can be mentioned such as dihydroimidazole, 3- [10 (triethoxysilyl) decyl] -4-oxazoline, among them 3- (1 hexamethyleneimino) propyl (triethoxy) silane, (1 —Hexamethyleneimino) methyl (trimethoxy) silane, 1- [3- (triethoxysilyl) propyl] -4,5 dihydroimidazole and 1 [3 (trimethoxysilyl) propyl] -4,5-dihydro Preference is given to imidazole.
- imine (amidine) group-containing compounds include 1- [3- (triethoxysilyl) propyl]
- N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methylethoxysilylpropyl) -4,5-dihydroimidazole and the like, among which N- (3-triethoxysilylpropyl) 4,5-dihydroimidazole is preferable.
- Examples of the carboxylic acid ester group-containing compound include 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxip.
- Examples include oral pyrmethylmethyloxysilane and 3-methacryloyloxypropyltriisopropoxysilane, among which 3-methacryloyloxypropyltrimethoxysilane is preferred.
- the isocyanate group-containing compounds include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropinomethylmethoxysilane, 3-isocyanatopropyltriisopropoxysilane. Of these, 3-isocyanatopropyltriethoxysilane is preferred.
- the carboxylic acid anhydride-containing compound include 3-triethoxysilylpropyl succinic anhydride, 3 trimethoxysilylpropyl succinic anhydride, and 3-methyljetoxysilylpropyl succinic anhydride. Preference is given to 3-triethoxysilylpropylsuccinic anhydride.
- hydrocarbyloxysilane compounds may be used alone or in combination of two or more.
- a partial condensate of the hydrocarbyloxysilane compound can also be used.
- the polymer having an active terminal and the hydrocarbyloxysilane compound first react with each other, and the introduced residue is subsequently subjected to (1) a carboxylic acid of a polyhydric alcohol. React with a partial ester to stabilize, or (2) react with a remaining or newly prepared hydrocarbyloxysilane compound in the presence of a condensation accelerator Either method is required.
- a condensation accelerator react with a remaining or newly prepared hydrocarbyloxysilane compound in the presence of a condensation accelerator
- the carboxylic acid partial ester of a polyhydric alcohol is an ester of a polyhydric alcohol and a carboxylic acid and means a partial ester having one or more hydroxyl groups.
- an ester of a saccharide having 4 or more carbon atoms or a modified saccharide and a fatty acid is preferably used.
- This ester is more preferably (a) a fatty acid partial ester of a polyhydric alcohol, particularly a partial ester of a saturated higher fatty acid or unsaturated higher fatty acid having 10 to 20 carbon atoms and a polyhydric alcohol (monoester, diester, Any of triesters), and (b) ester compounds in which 1 to 3 partial esters of polyhydric carboxylic acid and higher alcohol are bonded to polyhydric alcohol.
- the polyhydric alcohol used as a raw material for the partial ester is preferably a saccharide having 5 or 6 carbon atoms having at least three hydroxyl groups (even if hydrogenated, it is not hydrogenated and calorieated). Or glycols or polyhydroxy compounds.
- the raw fatty acid is preferably a saturated or unsaturated fatty acid having 10 to 20 carbon atoms, such as stearic acid, lauric acid, or palmitic acid.
- sorbitan fatty acid esters are preferred. Specifically, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monoester.
- examples of the commercial products include SPAN60 (Sorbitan stearate ester), SPAN80 (Sorbitan monooleate), SPAN85 (Sorbitan triolein) as trademarks of ICI. Acid ester).
- the addition amount of the partial ester is preferably 0.2 to 10 mol, particularly 1 to 10 mol, per 1 mol of the hydrocarbyloxysilyl group imparted to the polymer.
- hydrocarbyloxysilane compound may include the following hydrocarbyloxysilane compounds I and Z represented by the general formula (I) or a partial condensate thereof.
- a 2 represents cyclic tertiary amine, acyclic tertiary amine, pyridine, sulfide, multisulfide and -tolyl, cyclic tertiary amine amine salt, and acyclic tertiary amine amine salt.
- R 4 is a single bond or a divalent non-activated hydrogenated hydrogen group
- R 5 and R 6 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms
- m is an integer of 0 to 2 , and the case where OR 6 there are plural, a plurality of OR 6 may be the same or different.
- a 3 is alcohol, thiol, primary amine or its salt, cyclic secondary amine or its salt, acyclic secondary amine or its salt
- R 7 Is a single bond or a divalent inert hydrocarbon group
- R 8 and R 9 are each independently a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic group having 6 to 18 carbon atoms.
- q is an integer of 0 to 2
- the OR 9 there are a plurality the plurality of OR 9 may be the same or different.
- hydrocarbyloxysilane compounds III and Z represented by the above or partial condensates thereof.
- the direct reaction with the active terminal does not substantially occur and remains in the reaction system as unreacted. Therefore, it is consumed for condensation with the hydrocarbyloxysilane compound residue introduced at the active end.
- the acyclic tertiary amine in A 2 contains N, N— (disubstituted) aromatic amine such as N, N— (disubstituted) aryline, and Cyclic tertiary amines are part of the ring (Thio) ether can be included.
- Divalent inactive hydrocarbon group among R 4, the R 5 ⁇ beauty R 6 each Formula in (I), is as described for R 2 and R 3. It is necessary that this molecule has no active protons or salt.
- hydrocarbyloxysilane compound represented by the general formula (II) examples include 3-dimethylaminopropyl (triethoxy) as an acyclic tertiary amine group-containing hydrocarbylsilane compound.
- cyclic tertiary amine group-containing hydrocarbyloxysilane compounds include 3- (1 hexamethyleneimino) propyl (triethoxy) silane, 3- (1-hexamethyleneimino) propyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (triethoxy) silane, 2- (1-hexamethyleneimino) ethyl (triethoxy) silane, 2 — (1-Hexamethyleneimino) ethyl (trimethoxy) silane, 3- (1-pyrrolidyl) propyl (triethoxy) silane, 3- (1-pyrrolidyl) propyl (trimethoxy) silane, 3— ( 1-heptamethyleneimino) propyl (triethoxy) silane, 3- (1-dedecamethyleneimino) propyl (triethoxy) silane,
- hydrocarbyloxysilane compounds include 2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine, 4-ethylpyridine and the like.
- hydrocarbyloxysilane compounds may be used alone or in combination of two or more. A combination of the above may be used. Moreover, partial condensates of these hydrocarbyloxysilane compounds can also be used.
- the hydrocarbyloxysilane compound II condensed with the residue of the hydrocarbyloxysilane compound I introduced into the active terminal of the polymer is as follows: The hydrocarbyloxysilane compound I represented by the general formula (I) and a partial condensate thereof, the hydrocarbyloxysilane compound II represented by the general formula ( ⁇ ) and the partial condensation thereof And at least one selected from the medium strength of the hydrocarbyloxysilane compound represented by the general formula (III) and its partial condensate III.
- primary amine of the A 3 encompasses aromatic Amin such ⁇ diphosphate
- non-cyclic secondary amine is N-(- substituted) ⁇ - Phosphorus
- N — (— substituted) aromatic amines such as
- acyclic tertiary amine amine salts include N, N— (disubstituted) aromatic amine salts such as N, N— (disubstituted) amines.
- (thio) ether can be contained as a part of the ring. Divalent inactive hydrocarbon group out of R 7, the R 8 and R 9, each of the formula in (I), is as described for R 2 and R 3.
- hydrocarbyloxysilane compound represented by the general formula (III) examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, hydroxymethyltrimethoxysilane, and hydroxymethyltriethoxy.
- Silane silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, aminophenoltrimethoxysilane, aminophenoltriethoxysilane, 3- (N-methylamino) propyltrimethoxysilane, 3- (N-methylamino) propyltri Ethoxysilane, Octadecyldimethyl (3-trimethylsilylpropyl) ammonium chloride, Octadecyldimethyl (3-triethylsilylpropyl) ammonium chloride, cyanomethyltrimethoxysilane, cyanomethyltriethoxysilane Sulfo - it can be exemplified methyl trimethoxy silane, sulfonyl methyltriethoxysilane, sulphinyl Rume trimethoxysilane, sulfide El methyltriethoxysilane and the like.
- This hydrocarbyloxysilane compound III may be used alone or in combination of two or more!
- the hydrocarbyloxysilane compound is an alkoxysilyl compound
- the condensation reaction between alkoxysilyl groups in the method (2) is (remaining or newly prepared).
- the reaction between the free alkoxysilane and the alkoxysilyl group at the end of the polymer, and in some cases, the reaction between the free alkoxysilanes, preferably between the alkoxysilyl groups at the end of the polymer, is unnecessary. . Therefore, when a new alkoxysilane compound is added, it is preferable to make the alkoxysilyl group hydrolyzable so that it does not exceed the hydrolyzability of the alkoxysilyl group at the end of the polymer.
- alkoxysilane I uses a highly hydrolyzable trimethoxysilyl group-containing compound, and newly added alkoxysilane II has a lower hydrolyzable alkoxysilyl group (for example, triethoxysilyl group).
- a combination using a compound containing is preferred.
- alkoxysilane I containing triethoxysilyl group and II containing trimethoxysilyl group are within the scope of the present invention, but are not preferable from the viewpoint of reaction efficiency.
- the modification reaction in the present invention is preferably a force solution reaction (which may be a solution containing an unreacted monomer used at the time of polymerization) that can use a difference between a solution reaction and a solid phase reaction.
- the type of the denaturation reaction is not particularly limited, and may be performed continuously using a multistage continuous reactor or an in-line mixer, which may be performed using a notch reactor.
- the polymerization temperature of the conjugate polymer can be used as it is. Specifically, a preferable range is 20 to 100 ° C. Temperature goes down And the viscosity of the polymer tends to increase, and when the temperature is high, the polymerization active terminal tends to be deactivated, which is not preferable.
- condensation accelerator a combination of a metal compound generally known as a curing catalyst for an alkoxy condensation curing room temperature crosslinking (RTV) silicone and water can be used.
- RTV alkoxy condensation curing room temperature crosslinking
- tin carboxylate and / or titanium alkoxide and water can be preferably mentioned.
- an organic solvent compatible with water such as alcohol
- water may be directly injected, dispersed, or dissolved in the hydrocarbon solution by using various chemical engineering techniques.
- Such a condensation accelerator is preferably composed of at least one selected from the group force consisting of metal compounds represented by the following (1) to (3) and water.
- R 1Q is an organic group having 2 to 19 carbon atoms, and when there are a plurality of them, they may be the same or different. ]
- R 11 is an aliphatic hydrocarbon group having 1 to 30 carbon atoms
- B 1 is a hydroxyl group or halogen.
- a 4 includes (a) a carboxyl group having 2 to 30 carbon atoms, (b) an ⁇ , ⁇ -diol group having 5 to 30 carbon atoms, (c) a hydrocarbyloxy group having 3 to 30 carbon atoms, and (d) A siloxy group having a total of three substitutions (which may be the same or different) with a hydrocarbyl group having 1 to 20 carbon atoms and Z or a hydrocarbyloxy group having 1 to 20 carbon atoms is also a group that can be selected. 4 may be the same or different when there are multiple. ]
- ⁇ is an integer of 2 or 4.
- ⁇ 5 is (a) an alkoxy group having 3 to 30 carbon atoms, (b) A siloxy group which is a total trisubstituted by alkoxy groups of the alkyl group and Z or 1 to 20 carbon atoms having 1 to 30 carbon atoms and may be the same or different if A 5 there is a plurality.
- B 2 is an a, y-diol group having 5 to 30 carbon atoms.
- the tin carboxylate include (1) a divalent tin dicarboxylate (particularly preferably a carboxylate having 8 to 20 carbon atoms) and (2) a tetravalent Dihydrocarbyltin dicarboxylates (including bis (hydrocarbyldicarboxylic acid) salts), bis ( ⁇ , ⁇ -diketonate), alkoxy halides, monocarboxylate hydroxides, alkoxy (trihydrocarbyl siloxides), alkoxy (di Hydrocarbylalkoxysiloxide), bis (trihydral carbylsiloxide), bis (dihydrocarbylalkoxysiloxide) and the like can be suitably used.
- a carbon number of 4 or more is desired, and a force of 4 carbon atoms is particularly preferable.
- titanium compound examples include tetraalkoxides of titanium having 4 acids and acids, dialkoxybis (sigma, ⁇ -diketonate), tetrakis (trihydrocarbyl oxysiloxide) and the like. Are preferably used.
- Water is preferably used in the form of a simple substance, a solution of alcohol or the like, or a dispersed micelle in a hydrocarbon solvent, or a reaction system such as water adsorbed on a solid surface or hydrated water of a hydrate if necessary. Water that is potentially contained in compounds that can release water can also be used effectively
- the amount of the condensation accelerator used is preferably 0.1 or more in terms of the molar ratio of the metal of the metal compound and the number of moles of water effective in the reaction to the total amount of hydrocarbyloxysilyl groups present in the reaction system.
- the upper limit varies depending on the purpose and reaction conditions, it is preferable that there is effective water having a molar ratio of about 0.5 to 3 with respect to the total amount of hydrocarbyloxysilyl groups bonded to the end of the polymer before the condensation treatment.
- the molar ratio of the metal of the metal compound and the water effective for the reaction is preferably about a force I / O.5-1Z20 which varies depending on the required reaction conditions.
- a condensation accelerator is added and reacted, and then the polyhydric alcohol is further reacted. It can also be made to react with the carboxylic acid ester compound.
- a known anti-aging agent or short stop agent is optionally added in the step after introducing the hydrocarbyloxysilane compound residue into the active terminal of the polymer.
- a conventionally known post-treatment such as desolvation can be performed to obtain the desired modified polymer.
- Analysis of the polymer chain end-modifying group of this modified polymer is carried out using high-performance liquid chromatography (HPLC), thin-layer chromatography and other liquid chromatography carrier chromatography and nuclear magnetic resonance spectroscopy (NMR). be able to.
- HPLC high-performance liquid chromatography
- NMR nuclear magnetic resonance spectroscopy
- the molecular weight distribution (Mw / Mn) force of the polymer isolated before modification of the terminal-modified conjugation polymer is more preferably 5 to 3.5, 1.5 to 2, 6 force ⁇ .
- the Mooney viscosity (ML, 100 ° C) at 100 ° C is 10 to 150, more preferably 15 to 70.
- the content of cis 1,4 bonds in the conjugation moiety of the main chain is 75 mol% or more, more preferably 90 mol% or more, and the content of vinyl bonds is desirably low. It is preferably less than 1.0 mol%, more preferably less than 1.0 mol%, and the monomer constituting the conjugated gen-based polymer is preferably a substance that is substantially only 1,3 butadiene.
- the modified polymer modified with the above modifier and condensation accelerator by setting the various properties of the unmodified unmodified polymer based on the above range has excellent workability and a filler.
- the rubber composition having excellent on-ice performance from extremely low temperature to around 0 ° C can be obtained.
- the rubber composition of the present invention has closed cells as an essential requirement or component, and (A) contains a natural rubber in addition to the modified conjugate conjugated polymer as a rubber component, and (B) contains fine particles. It is necessary to include organic fiber and (C) filler.
- the rubber composition having closed cells is preferably used as a tread rubber having a foamed layer substantially in contact with the road surface.
- the foamed rubber layer has a foaming ratio in the range of 3 to 50%, more preferably 15 to 40%.
- the rubber component used in combination with the modified polymer includes gen-based synthetic rubber.
- the gen-based synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR ), Polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, and mixtures thereof. Further, some of them may have a branched structure by using a multifunctional type, for example, a denaturing agent such as tin tetrachloride or tetrasalt silicon.
- component (B) it is necessary to contain fine particle-containing organic fibers as component (B), and it is preferable to use a combination of component (B) and organic particles not containing fine particles (D).
- component (B) When the component (B) is used in the foamed layer of the rubber, it is effective for removing water and increasing friction on the tire surface, and improves the performance on ice.
- the surface of the vulcanized rubber and the molded product is affected at the time of extrusion due to the relationship with the diameter of the organic fiber to be contained. In addition, it causes a decrease in workability in the factory along with such causes. Therefore, it is preferable that the rubber layer contain (D) organic particles not containing fine particles together with the component (B) in a predetermined ratio.
- the ratio of the component (D) component Z (B) is preferably in the range of 98Z2 to 2Z98, particularly in the range of 95Z5 to 5Z95 by mass ratio.
- the amount of component (B) is preferably 0.02 to 20 parts by mass with respect to 100 parts by mass of (A) rubber component. More preferably, it is 0.1 to 15 parts by mass.
- the total amount of the component (D) and the component (B) is increased in the rubber layer.
- the rubber component is desirably 1 to 20 parts by mass, particularly preferably 1.5 to 15 parts by mass with respect to 100 parts by mass.
- the organic fibers used in the component (B) and the component (D) are not necessarily used at the same time and have different materials, shapes, diameters, lengths, and the like. Machine fibers may be used, but it is desirable to use organic fibers in the range having the following properties.
- the material of the organic fiber used for the component (B) and the component (D) can be appropriately selected according to the purpose without particular limitation.
- the viscosity characteristics that are lower than the viscosity of the rubber matrix of the rubber component (A) from the relationship with the rubber component to the maximum vulcanization temperature during vulcanization.
- the resin constituting the organic fiber has such thermal characteristics, it functions as a micro drainage groove in the vulcanized rubber obtained by vulcanizing the rubber composition.
- the above-mentioned long bubbles can be easily formed.
- the maximum vulcanization temperature means the maximum temperature reached by the rubber composition during vulcanization of the rubber composition.
- the maximum vulcanization temperature can be measured, for example, by embedding a thermocouple in the rubber composition.
- the viscosity of the rubber matrix means fluid viscosity, and is measured using, for example, a corn rheometer or a chiral rheometer.
- the viscosity of the resin constituting the organic fiber means melt viscosity, and is measured using, for example, a corn rheometer, a capillary rheometer, or the like.
- preferred examples of the preferred resin selected in the present invention include crystalline polymer resin whose melting point is lower than the maximum vulcanization temperature.
- the time when it becomes lower than the viscosity of the tassel is earlier.
- the gas present in the rubber composition such as the gas generated from the foaming agent blended in the rubber composition, collects inside the polymer having a lower viscosity than the rubber matrix. .
- the closed cells having a resin layer containing fine particles between the rubber matrix that is, the capsule-like long cells covered with the resin are not crushed. It is formed efficiently.
- the capsule-like long bubbles appear on the surface of the tread, and the groove formed by the surface wear functions as the above-mentioned micro drainage groove.
- the edge effect and spike effect are also fully demonstrated.
- the melting point of the resin constituting the organic fiber when the melting point of the resin constituting the organic fiber is close to the maximum vulcanization temperature of the rubber composition, it does not melt quickly at the initial stage of vulcanization but melts at the end stage of vulcanization. At the end of vulcanization, part of the gas present in the rubber composition is taken into the vulcanized rubber matrix and does not collect inside the molten resin. As a result, the long bubbles that function effectively as the micro drainage grooves are not efficiently formed, and when the melting point of the organic fibers is too low, the organic fibers are blended in the rubber composition. When kneading, fusion of organic fibers occurs, resulting in poor dispersion of organic fibers.
- the melting point of the organic fiber resin should be selected in such a range that the viscosity of the rubber matrix and the resin is reversed during the vulcanization process without melting and softening at the temperature before each process. Is preferred.
- the upper limit of the melting point of the resin constituting the organic fiber is not particularly limited, but is preferably selected in consideration of the above points. It is lower than the maximum vulcanization temperature of the rubber matrix. It is more preferable that the temperature is lower than ° C. It is particularly preferable that the temperature is lower than 20 ° C.
- the industrial vulcanization temperature of rubber compositions is generally a maximum of about 190 ° C. For example, the maximum vulcanization temperature When the temperature is set to exceed 190 ° C, the melting point of the resin is selected in the range of 190 ° C or less, and 180 ° C or less is preferable, and 170 ° C or less is more preferable.
- the melting point of the resin can be measured using a known melting point measuring device or the like.
- the melting peak temperature measured using a DSC measuring device can be used as the melting point.
- the resin constituting the organic fiber may be formed of a crystalline polymer and Z or an amorphous polymer cartridge.
- the phase transition force because of the phase transition force, the change in viscosity occurs rapidly at a certain temperature, and the organic material force containing a large amount of crystalline high molecules is formed in terms of easy viscosity control. More preferably, it is formed only from the preferred crystalline polymer.
- crystalline polymer examples include, for example, polyethylene (PE), polypropylene (PP), polybutylene, polybutylene succinate, polyethylene succinate, syndiotactic 1,2-polybutadiene (SPB), Single-composition polymers such as polybulal alcohol (PVA) and polysalt-vinyl (PVC), and those whose melting point is controlled to an appropriate range by copolymerization or blending can be used. It can also be used with added agents. These may be used alone or in combination of two or more.
- polyolefins and polyolefin copolymers are preferred, and polyethylene (PE) and polypropylene (PP) are more preferred because they are generally available and easy to handle.
- polyethylene (PE) is particularly preferred.
- non-crystalline polymer resin examples include polymethylmethacrylate (PMMA), acrylonitrile butadiene styrene copolymer (ABS), polystyrene (PS), polyacrylonitrile, and copolymers thereof.
- PMMA polymethylmethacrylate
- ABS acrylonitrile butadiene styrene copolymer
- PS polystyrene
- copolymers thereof examples include polymethylmethacrylate (PMMA), acrylonitrile butadiene styrene copolymer (ABS), polystyrene (PS), polyacrylonitrile, and copolymers thereof.
- ABS acrylonitrile butadiene styrene copolymer
- PS polystyrene
- polyacrylonitrile and copolymers thereof.
- the blended material etc. are mentioned. These may be used alone or in combination of two or more.
- the fiber length is in the range of 0.5 to 20 mm, particularly in the range of 1 to 10 mm. It is preferable that
- organic fibers are present in such a length in the vulcanized rubber when forming the foamed rubber layer, the edge effect and the spike effect will work effectively, and the foaming agent and the like described later can be added. When included, it is possible to sufficiently form long bubbles that can function efficiently as micro drainage channels.
- the fiber diameter is preferably in the range of 0.01 to 0.1 mm, particularly preferably in the range of 0.015 to 0.09 mm.
- the diameter of the organic fiber is 0.01 mm or more, the organic fiber is less likely to be cut, and the edge effect or spike effect can be sufficiently exhibited. Further, when the diameter is 0.1 mm or less, the workability can be improved.
- the fine particles contained in the organic fiber include inorganic fine particles and organic fine particles.
- the inorganic fine particles include glass fine particles, hydroxyaluminum hydroxide fine particles, alumina fine particles, and iron fine particles.
- the organic fine particles include (meth) acrylic resin fine particles, epoxy resin fine particles, and the like. These may be used alone or in combination of two or more. Among these, inorganic fine particles are preferable from the viewpoint of excellent pulling effect on ice.
- the fine particles used in the present invention preferably have a Mohs hardness of more than 2, particularly higher than 5. If the Mohs hardness of the fine particles is not less than the hardness of ice (1 to 2), that is, 2 or more, a single pulling effect can be exhibited as a tread on the surface portion of the foamed rubber layer. For this reason, the obtained tire has excellent on-ice performance (the surface braking / driving performance of the tire on an icy and snowy road surface) with a large coefficient of friction with the icy and snowy road surface.
- Examples of such fine particles having high hardness include gypsum, calcite, fluorite, orthofeldspar, quartz, and gangue.
- silica glass having a Mohs hardness of 5 or more hardness 6.5
- quartz Hardness 7.0
- fused alumina hardness 9.0
- silica glass, alumina (acid aluminum) and the like can be easily used at low cost.
- the fine particles have a particle size distribution frequency number of 80% by mass or more, preferably 90% by mass or more in the range of 10 to 50 ⁇ m. Preferably in the range of 30 ⁇ m.
- the particle size at the above frequency number is 10 m or more
- the particles tend to aggregate and the dispersibility tends to be improved.
- the used tire can exert a sufficient pulling effect, an edge effect, or a spike effect.
- the particle size is 50 m or less, problems such as fiber breakage during the production of component (B) are prevented, and the desired component (B) can be obtained efficiently.
- the fine particles preferably have a frequency number at the peak value of the particle size distribution of 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. If the frequency number at the peak value of the fine particles is 20% by mass or more, the particle size distribution curve of the fine particles becomes sharp and the particle size becomes uniform. For this reason, good fibers are obtained that are less likely to be broken when the component (B) is spun, and the performance on ice is stabilized when strong fibers are used in the tire. Also, with the size of the particle size within the above range, the on-ice performance of the tire improves as the particle size increases.
- the frequency number refers to the mass ratio of the existing particles in the particle size distribution when the particle size in the particle size distribution (particle size distribution curve) with respect to the total particle mass is divided by a step size of 2 ⁇ m.
- the frequency number at the peak value means the frequency number in the segment width that includes the maximum peak value in the above step size in the particle size distribution curve.
- the fine particles preferably have an aspect ratio of 1.1 or more and preferably have corners.
- the aspect ratio is more preferably 1.2 or more, and still more preferably 1.3 or more.
- the presence of a corner means that the entire surface is not a spherical surface or a smooth curved surface!
- the fine particles of the present invention can also be used with fine particles having corners at first, but even if the fine particles are spherical, they can be used with the corners existing on the surface of the fine particles by grinding, More corners can be present.
- the shape of the fine particles can be confirmed by observing the fine particle group with an electron microscope, and is confirmed to be not spherical. Further, if the aspect ratio representing the ratio of the major axis to the minor axis of the particle is 1.1 or more, the existence of corners formed on the particle surface can be sufficiently angulated. For this reason, in a tire using fine particle-containing organic fibers containing such fine particles, the pulling effect, the edge effect, and the spike effect can be sufficiently enhanced.
- the fine particles are preferably contained in an amount of 5 to 50 parts by mass, particularly 7 to 50 parts by mass with respect to 100 parts by mass of the resin constituting the component (B).
- foaming agent examples include dinitrosopentamethylenetetramine (DPT), azodi-functional rubonamide (ADCA), dinitrosopentastyrenetetramine, benzenesulfonhydrazide derivatives, and oxybisbenzenesulfurhydrazide (OBSH).
- DPT dinitrosopentamethylenetetramine
- ADCA azodi-functional rubonamide
- OBSH oxybisbenzenesulfurhydrazide
- foaming agents in consideration of processability, dinitrosopentamethylenetetramine (DPT) and azodicarbonamide (ADCA) are preferred, and azodicarbonamide (ADCA) is particularly preferred. These may be used alone or in combination of two or more.
- DPT dinitrosopentamethylenetetramine
- ADCA azodicarbonamide
- these may be used alone or in combination of two or more.
- a foaming aid as the other component and to use it together with the foaming agent.
- the foaming aid include, for example, urea, zinc stearate, zinc benzenesulfinate, zinc white and the like, which are usually used for producing foamed products. Of these, urea, zinc stearate, zinc benzenesulfinate and the like are preferable. These may be used alone or in combination of two or more.
- the content of the foaming agent may be appropriately determined according to the purpose, but is generally preferably about 1 to L0 parts by mass with respect to 100 parts by mass of the rubber component.
- the above foaming agent may be blended in rubber matrix or in each organic fiber.
- the foamed rubber layer must further contain (C) a reinforcing filler.
- C a reinforcing filler.
- the reinforcing filler carbon black, silica and the like are usually mentioned. As long as the carbon black enhances the mechanical performance of the rubber layer and improves the workability, etc., the range of I adsorption amount, CTAB specific surface area, N adsorption amount, DBP adsorption amount, etc. was appropriately selected.
- Any known carbon black can be used.
- the type of carbon black for example, known ones such as SAF, ISAF-LS, HAF, and HAF-HS can be appropriately selected and used. In consideration of wear resistance, SAF having a fine particle size is preferable.
- the content of carbon black is 5 to 95 parts by mass, preferably 10 to 60 parts by mass with respect to 100 parts by mass of the (A) rubber component.
- silica means a caustic filler that does not show only silicon dioxide in a narrow sense.
- caustic acid in addition to anhydrous caustic acid, hydrous caustic acid, caustic acid includes silicates such as calcium and aluminum silicates.
- the content of silica is 5 to 95 parts by mass, preferably 15 to 80 parts by mass with respect to 100 parts by mass of the (A) rubber component.
- the total amount of carbon black and silica combined is 40 to 80 parts by mass with respect to 100 parts by mass of component (A), and the mixing ratio of carbon black and silica [carbon black] Z [silica] is mass.
- the ratio is preferably 0.04 to 6.0.
- the rubber composition of the present invention preferably further comprises (E) an inorganic compound powder having an average particle size of not more than 50 ⁇ m represented by the following general formula (IV).
- M in the formula is a metal oxide or metal hydroxide selected from Al, Mg, Ti, and Ca, and x and y are integers of 0 to 10, which may be different from each other.
- the inorganic compound powder (E) represented by the general formula (I) has at least one metal oxide selected from Al, Mg, Ti, and Ca when both X and y are 0. Or it becomes a metal hydroxide salt.
- inorganic compound powder represented by the general formula (IV) include alumina (Al 2 O 3),
- magnesium calcium silicate (CaMgSiO)
- the general formula (IV) is preferably (E) an inorganic compound powder or aluminum hydroxide represented by the following general formula (V).
- M in the formula ( ⁇ ) is an integer of 1 to 4, and ⁇ is an integer of 0 to 4.
- ( ⁇ ) inorganic compound powder represented by the general formula (V) are clay (Al ⁇ ⁇
- Minum also includes alumina hydrate.
- the (E) inorganic compound powder has an average particle size of 50 ⁇ m or less, preferably 0.05 to 5 m, and more preferably 0.1 to 3 / ⁇ ⁇ . .
- the average particle size of the inorganic compound powder is the above range, it is possible to maintain the wear resistance, which is the fracture resistance of rubber for tire treads.
- Particularly preferred for use in the present invention are (ii) inorganic compound powders such as clay (Al 2 ⁇ 2SiO), aluminum hydroxide [A1 (OH)], and alumina (Al 2 O 3).
- the (E) inorganic compound powder having the above characteristics used in the present invention can be used alone or in admixture of two or more.
- (E) Inorganic compound powders, such as sulfates selected from Al, Mg, Ti, Ca, and other structures such as sulfates and carbonates have improved wet skid performance. Is effective!
- the content of the (E) inorganic compound powder having the above characteristics used in the present invention is determined according to the rubber composition.
- the amount is 5 to 50 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass.
- vulcanizing agents such as sulfur
- vulcanizing accelerators such as dibenzothiazyl disulfide, Vulcanization accelerator, N-cyclohexyl 2-benzothiodilusulfenamide, N-oxydiethylene monobenzothiadisulfenamide, antisulfurization agent, ozone deterioration inhibitor, colorant
- antistatic agents dispersants, lubricants, antioxidants, softeners, inorganic fillers such as carbon black and silica, etc.
- various compounding agents usually used in the rubber industry are appropriately selected and used according to the purpose. can do. These may be used alone or in combination of two or more.
- FIG. 1 is a schematic sectional view of a tire according to the present invention.
- 2 (a) and 2 (b) are schematic cross-sectional views along the circumferential direction and the width direction of the tread portion of the tire according to the present invention.
- FIG. 3 is an explanatory diagram for explaining the principle of orienting the fine particle-containing organic fibers in a certain direction.
- the tire according to the present invention is a tire in which a foamed rubber layer is provided on a surface substantially in contact with the road surface. Specifically, as shown in FIGS. 1 to 3, the tire tread has at least a surface substantially in contact with the road surface. Also, a pneumatic tire force provided with a foamed rubber layer containing closed cells is obtained.
- a pair of bead portions 1, a carcass 2 connected to the pair of bead portions 1 in a toroidal shape, a belt 3 for tightening a crown portion of the carcass 2, and a cap It has a radial structure in which a portion 6 and a tread 5 having a two-layer force of the base portion 7 are sequentially arranged. Since the internal structure other than the tread 5 is the same as that of a general radial tire, the explanation is omitted.
- the surface portion of the tread 5 is a foamed rubber layer formed by vulcanizing the rubber composition according to the present invention.
- the manufacturing method of the tire 4 is not particularly limited.
- the tire 4 is vulcanized and molded with a predetermined mold at a predetermined temperature and a predetermined pressure.
- a tire having a cap portion 6 formed of a foamed rubber layer according to the present invention obtained by vulcanizing an unvulcanized tread. 4 is obtained.
- FIG. 2 (a) and 2 (b) are schematic cross-sectional views along the circumferential direction and the width direction of the tread portion of the tire according to the present invention.
- the vulcanized rubber 6A has spherical bubbles 18 and a tread portion as shown in Fig. 2 (a). There are long bubbles 12 extending in the circumferential direction (arrow A direction). Due to wear on the tread surface due to running, a force is formed on the surface of the cap portion 6 to form a concave portion 13 due to the long bubbles 12 and a concave portion 19 due to the spherical bubbles 18.
- the entire vulcanized rubber 6A is long Since the bubbles are scattered, even if the surface force S disappears due to further wear, the newly formed recess 13 and recess 19 can continue to maintain high performance on ice.
- the protective layer 14 and the fine particle 20 of the fine particle-containing organic fiber sufficiently exhibit the edge effect and the spike effect which are not only wear resistance in the surface layer, but the performance on ice is further improved.
- the force tread structure described as an example of a tread having a two-layer structure is not particularly limited, and may be a single-layer structure composed of the rubber composition of the present invention. Furthermore, at least a part of the surface layer of the tread, which may be a multilayer structure divided in the tire radial direction, or a structure divided in the tire circumferential direction or tread width direction, is constituted by the rubber composition of the present invention! / I prefer to do that!
- the rubber composition described in detail above is kneaded, heated, extruded, and the like under the following conditions and methods.
- the kneading can be appropriately selected according to the purpose for which there are no particular restrictions on the various conditions of the kneading apparatus such as the input volume to the kneading apparatus, the rotational speed of the rotor, the kneading temperature, and the kneading time.
- the kneading apparatus a commercially available product can be suitably used.
- Heating or extruding can be appropriately selected according to the purpose for which there are no particular restrictions on conditions such as heating or extruding time, heating or extruding equipment and the like.
- a commercially available product can be suitably used as the heating or extrusion device.
- the heating or extrusion temperature is appropriately selected within a range that does not cause foaming when a foaming agent is present.
- the extrusion temperature is preferably about 90-110 ° C
- the organic fiber is preferably oriented in the extrusion direction by extrusion or the like.
- the fluidity of the rubber composition is controlled within a limited temperature range.
- aroma oil, naphthenic oil, Processability modifiers such as plasticizers such as paraffin oil and ester oil, and liquid polymers such as liquid polyisoprene rubber and liquid polybutadiene rubber are added as appropriate to change the viscosity of the rubber composition and to improve its fluidity. Increase.
- an organic fiber in order to produce a foam rubber layer of a tread, (B) the fine particle-containing organic fiber and (D) the fine particle-free organic fiber are arranged in a direction parallel to the ground contact surface in the tread. Orientation, that is, orientation in the circumferential direction of the tire is good. The drainage in the running direction of the tire can be improved, and the performance on ice can be effectively improved.
- a method of aligning and aligning the organic fibers in the foamed rubber layer for example, as shown in FIG. 3, a rubber composition 16 containing fine particle-containing organic fibers 15 is used, and the cross-sectional area of the flow path is at the outlet.
- the fine-particle-containing organic fibers 15 and the like may be oriented in a certain direction by extruding from the die 17 of the extruder that decreases with the direction of force.
- the fine particle-containing organic fibers 15 etc. in the rubber composition 16 before being extruded are gradually aligned along the extrusion direction (arrow P direction) in the process of being extruded to the die 17.
- the longitudinal direction can be oriented almost completely in the extrusion direction (arrow A direction in FIG. 2).
- the degree of orientation of the fine particle-containing organic fibers 15 and the like in the rubber composition 16 is changed depending on the degree of reduction in the cross-sectional area of the flow path, the extrusion speed, the viscosity of the rubber composition 16 before vulcanization, and the like.
- the conditions for vulcanization and the like can be appropriately selected according to the type of rubber component and the like, which are not particularly limited, but in the case of producing a foam rubber layer as a tread as in the present invention. Mold vulcanization is good.
- the vulcanization temperature is preferably selected so that the maximum vulcanization temperature of the rubber composition during vulcanization is equal to or higher than the melting point of the resin constituting the organic fiber. If the maximum vulcanization temperature is lower than the melting point of the resin, the fibers do not melt as described above, and the gas generated by foaming cannot be taken into the resin. Long bubbles cannot be efficiently formed in the foamed rubber layer.
- the vulcanizing apparatus there is no particular limitation, and a commercially available product can be preferably used.
- the recess has the above-described protective layer, particularly a protective layer in which fine particles are present, the recess has an anti-peeling property, a water channel shape retaining property, a water channel edge portion abrasion property, a water channel retaining property when a load is input, and the like. Excellent. Further, in the tire of the present invention, since the elongated bubbles are present in the entire foamed rubber layer, the functions of the recess are exhibited until the end of the initial use force, and the above-mentioned performance on ice is excellent.
- the average diameter of the elongated bubbles formed in the foamed rubber layer (the average of the inner diameters of the elongated bubbles 12 shown in Fig. 2 (b)) is 10 to 500 m. It is preferable that it is about. When the average diameter is 10 m or more, it is possible to prevent deterioration of the water drainage performance of the micro drainage grooves formed on the rubber surface. When the average diameter is 500 m or less, the cut resistance of rubber and block chipping can be prevented, and the wear resistance on dry road surfaces can be prevented.
- the tire according to the present invention can be suitably applied not only to so-called passenger cars but also to various vehicles such as trucks and buses. It can be suitably used for structures that need to suppress slipping on icy and snowy road surfaces, and tire treads can be used, for example, treads for replacement of retreaded tires, as long as it is necessary to suppress slipping on the ice. Can be used for solid tires, etc.
- an inert gas such as nitrogen can be used in addition to air as the gas filled inside.
- a tread having a two-layer structure has been described as an example.
- the structure of the tread is not particularly limited, and may be a one-layer structure.
- at least a part of the surface layer of the tread which may be a multi-layer structure divided in the tire radial direction, or a structure divided in the tire circumferential direction or tread width direction, is constituted by the rubber composition of the present invention. preferable.
- a glass bottle with a rubber stopper with a volume of about 900 milliliters is dried and purged with nitrogen, and then a dry purified butadiene cyclohexane solution and dry cyclohexane are added to each, and 12.5 wt% cyclohexane solution power 00g was put into the state.
- 2.28 ml (0.025 mmol in terms of neodymium) of the prepared catalyst solution was added, and polymerization was carried out in a 50 ° C. hot water bath for 1.0 hour.
- GMOS 3 glycidoxypropyltrimethoxysilane
- N- (3-triethoxysilylpropyl) -4,5 dihydroimidazole (TEOSIP DI) (secondary modifier) as a hexane solution (1.0 M) was charged with 23.5 mmol.
- the vulcanization temperature at the time of vulcanization of each rubber composition was measured while a thermocouple was embedded in the rubber composition. By reaching the maximum vulcanization temperature, the melting point of each organic fiber resin was exceeded, and when the rubber composition was vulcanized, the viscosity of the resin was lower than the viscosity of the rubber matrix.
- the viscosity at the maximum vulcanization temperature (melt viscosity) of each organic fiber resin is measured using a cone rheometer (end when the rubber torque reaches Max, torque is changed to rubber viscosity, torque change and foaming) The change in pressure was measured.
- the viscosity at the maximum vulcanization temperature (flow viscosity) of the rubber composition is a corn rheometer model 1-C manufactured by Monsantone, giving a constant amplitude input of 100 cycles Z while changing the temperature. The torque was measured over time, and the minimum torque at that time was taken as the viscosity (dome pressure 0.59 MPa, holding pressure 0.778 MPa, closing pressure 0.778 MPa, swing angle ⁇ 5). .
- Each of the obtained rubber compositions was used for a tread (foamed rubber layer) to produce a test passenger radial tire and tire size 185 / 70R15 by a conventional method.
- Vs (p / p 1) X 100 (%)
- p represents the density (gZcm 3 ) of the vulcanized rubber (foam rubber).
- Comparative Example 1 was displayed as an index as 100 (equivalent to 8000 kmZmm). The larger the index, the better the wear resistance. The evaluation results are shown in Table 1.
- Anti-aging agent (N-Isopropyl-N, -Fu-Lu p-Phenol-diamine) * 7.
- Vulcanization accelerator (MBTS: Dibenzothiazyl disulfide)
- Organic fiber containing fine particles Fatty acid constituting the fiber (polyethylene melting point 132 ° C, fine particle content 15 parts by mass, fine particle average particle size 20 m, fiber average diameter 32 m, fiber average length 2 mm
- Fine particle-free organic fiber The properties of the fiber that makes up the fiber are the same as the fine particle-containing organic fiber.
- Inorganic compound powder Hydroxide-aluminum (Hijilite H-43: Showa Denko) Table 1 The following is understood.
- Example 4 in which a large amount of carbon black was added to silica, the DRY performance was maintained as compared with Comparative Example 1, and both the wear resistance and the performance on ice were greatly improved.
- Example 4 in which the use ratio of the modified polybutadiene rubber in the rubber component is high can be improved with a good balance between wear resistance and performance on ice.
- Example 3 is on ice so that (A) rubber component and (C) filler are divided in comparison with Example 3 and Comparative Example 5. Both performance and wear resistance are improved.
- the present invention can provide a rubber composition having improved reinforceability with a filler, maintaining DRY performance and having excellent on-ice performance, and a pneumatic tire using the rubber composition in a tread. .
- it can be suitably used for passenger car tires.
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US12/305,987 US20090306269A1 (en) | 2006-07-06 | 2007-07-06 | Rubber composition and pneumatic tire using the same |
JP2008523765A JPWO2008004676A1 (ja) | 2006-07-06 | 2007-07-06 | ゴム組成物及びそれを用いた空気入りタイヤ |
EP07768333A EP2048191A4 (en) | 2006-07-06 | 2007-07-06 | RUBBER COMPOSITION AND AIR TIRES THEREWITH |
Applications Claiming Priority (2)
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JP2006-186775 | 2006-07-06 | ||
JP2006186775 | 2006-07-06 |
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WO2008004676A1 true WO2008004676A1 (fr) | 2008-01-10 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/JP2007/063608 WO2008004676A1 (fr) | 2006-07-06 | 2007-07-06 | Composition de caoutchouc et bandage pneumatique fabriqué à partir de celle-ci |
Country Status (4)
Country | Link |
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US (1) | US20090306269A1 (ja) |
EP (1) | EP2048191A4 (ja) |
JP (1) | JPWO2008004676A1 (ja) |
WO (1) | WO2008004676A1 (ja) |
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JP2009173838A (ja) * | 2008-01-28 | 2009-08-06 | Bridgestone Corp | ゴム組成物及びそれを用いた空気入りタイヤ |
JP2009173840A (ja) * | 2008-01-28 | 2009-08-06 | Bridgestone Corp | タイヤ |
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JP2010202867A (ja) * | 2009-02-06 | 2010-09-16 | Bridgestone Corp | ゴム組成物およびそれを用いた空気入りタイヤ |
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JP2010254852A (ja) * | 2009-04-27 | 2010-11-11 | Bridgestone Corp | ゴム組成物及びそれを用いたタイヤ |
US8022159B2 (en) | 2008-11-24 | 2011-09-20 | The Goodyear Tire & Rubber Company | Terminating compounds, polymers, and their uses in rubber compositions and tires |
JP2012131893A (ja) * | 2010-12-21 | 2012-07-12 | Sumitomo Rubber Ind Ltd | ゴム組成物及びスタッドレスタイヤ |
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RU2471637C2 (ru) * | 2007-08-10 | 2013-01-10 | Бриджстоун Корпорейшн | Пневматическая шина |
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JP6240731B1 (ja) * | 2016-09-30 | 2017-11-29 | 住友ゴム工業株式会社 | スタッドレスタイヤ用キャップトレッドゴム組成物 |
WO2018079803A1 (en) * | 2016-10-31 | 2018-05-03 | Compagnie Generale Des Etablissements Michelin | A tire comprising a tread |
JP7099919B2 (ja) * | 2018-09-14 | 2022-07-12 | 株式会社Eneosマテリアル | ゴム組成物、架橋体及びタイヤ |
WO2020096027A1 (en) * | 2018-11-08 | 2020-05-14 | Compagnie Generale Des Etablissements Michelin | An article, in particular a tire |
WO2021045537A1 (ko) * | 2019-09-03 | 2021-03-11 | 주식회사 엘지화학 | 고무 조성물 및 이로부터 제조된 성형품 |
FR3108910B1 (fr) * | 2020-04-07 | 2023-06-02 | Michelin & Cie | Composition de caoutchouc comprenant du polyethylene a basse temperature de fusion |
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JP2010006185A (ja) * | 2008-06-25 | 2010-01-14 | Bridgestone Corp | 空気入りタイヤ |
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US8022159B2 (en) | 2008-11-24 | 2011-09-20 | The Goodyear Tire & Rubber Company | Terminating compounds, polymers, and their uses in rubber compositions and tires |
JP2010202867A (ja) * | 2009-02-06 | 2010-09-16 | Bridgestone Corp | ゴム組成物およびそれを用いた空気入りタイヤ |
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JP2018111780A (ja) * | 2017-01-12 | 2018-07-19 | 横浜ゴム株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
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US10889659B2 (en) | 2018-02-07 | 2021-01-12 | Chi Mei Corporation | Modified polymethylhydrosiloxane, modified high-cis conjugated diene polymer, and manufacturing method for the same, and rubber composition and tire using the same |
JP7420474B2 (ja) | 2018-02-07 | 2024-01-23 | 奇美實業股▲ふん▼有限公司 | 変性ポリメチルヒドロシロキサン、変性高シス共役ジエンポリマー、およびそれの製造方法、ならびにそれを使用するゴム組成物およびタイヤ |
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Also Published As
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EP2048191A1 (en) | 2009-04-15 |
JPWO2008004676A1 (ja) | 2009-12-10 |
US20090306269A1 (en) | 2009-12-10 |
EP2048191A4 (en) | 2009-11-25 |
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