WO2024224673A1 - タイヤ用ゴム組成物、トレッドゴム及びタイヤ - Google Patents
タイヤ用ゴム組成物、トレッドゴム及びタイヤ Download PDFInfo
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- WO2024224673A1 WO2024224673A1 PCT/JP2023/043332 JP2023043332W WO2024224673A1 WO 2024224673 A1 WO2024224673 A1 WO 2024224673A1 JP 2023043332 W JP2023043332 W JP 2023043332W WO 2024224673 A1 WO2024224673 A1 WO 2024224673A1
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- rubber
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a rubber composition for tires, tread rubber, and tires.
- Patent Document 1 discloses that by applying a rubber composition obtained by compounding a rubber component containing 70% by mass or more of natural rubber with a thermoplastic resin and a filler containing silica to the tread rubber of a tire, the braking performance of the tire on both dry and wet road surfaces is improved. Furthermore, from the viewpoint of tire economics, in the development of rubber compositions for tires, it is required to improve wear resistance in addition to fuel efficiency and wet braking performance.
- an object of the present invention is to provide a rubber composition for tires that solves the above-mentioned problems of the conventional technology and can provide an excellent balance between fuel efficiency, wet braking performance, and abrasion resistance of the product to which it is applied, and a tread rubber using such a rubber composition for tires.
- Another object of the present invention is to provide a tire including such a tread rubber that has an excellent balance of fuel economy, wet braking performance, and wear resistance.
- a rubber composition for tires comprising a rubber component and a filler,
- the rubber component contains at least an isoprene skeleton rubber and a styrene-butadiene rubber
- the filler includes at least silica,
- A is the content (parts by mass) of the isoprene skeleton rubber in 100 parts by mass of the rubber component
- B is the bound styrene amount (% by mass) of the styrene-butadiene rubber.
- a rubber composition for tires that can provide an excellent balance between fuel economy, wet braking performance, and abrasion resistance of a product to which the composition is applied, and a tread rubber using the rubber composition for tires.
- a tire including such a tread rubber which has an excellent balance of fuel economy performance, wet braking performance, and wear resistance.
- the compounds described in this specification may be derived in whole or in part from fossil resources, from biological resources such as plant resources, or from recycled resources such as used tires. They may also be derived from a mixture of two or more of fossil resources, biological resources, and recycled resources.
- the rubber composition for tires of the present invention is a rubber composition containing a rubber component and a filler.
- the rubber component contains at least an isoprene-based rubber and a styrene-butadiene rubber, and the filler contains at least silica.
- the rubber composition for tires of the present invention has The following formula (X): 10 ⁇ A 0.5 +B 1.5 ⁇ 100...
- (X) (In the formula, A is the content (parts by mass) of the isoprene skeleton rubber in 100 parts by mass of the rubber component, and B is the bound styrene amount (% by mass) of the styrene-butadiene rubber.) and, The following formula (Y): 0.55 ⁇ C/D ⁇ 0.75... (Y) (In the formula, C is the content (parts by mass) of the silica per 100 parts by mass of the rubber component, and D is the content (parts by mass) of the filler per 100 parts by mass of the rubber component.) Meet the following.
- the rubber component contains an isoprene skeleton rubber, which can increase the breaking strength of the rubber composition, thereby improving the fuel economy of the product to which the rubber composition is applied. Also, in the rubber composition for tires of the present invention, the rubber component contains a styrene-butadiene rubber, which can improve the abrasion resistance of the product to which the rubber composition for tires is applied.
- the rubber composition for tires of the present invention satisfies the above formula (X), thereby making it possible for a product to which the rubber composition for tires is applied to have both low fuel consumption performance and wet braking performance.Furthermore, the rubber composition for tires of the present invention satisfies the above formula (Y), thereby making it possible to ensure wear resistance. Therefore, the rubber composition for tires of the present invention satisfies both of the above formula (X) and formula (Y), and thus a product to which the rubber composition for tires is applied can have an excellent balance of fuel economy performance, wet braking performance, and abrasion resistance.
- the rubber composition for tires of the present invention contains a rubber component.
- the rubber component contains at least an isoprene skeleton rubber and a styrene-butadiene rubber.
- the rubber composition for tires of the present invention may further contain other rubber components.
- the isoprene-based rubber is a rubber having an isoprene unit as a main skeleton.
- examples of the isoprene-based rubber include natural rubber (NR) and synthetic isoprene rubber (IR).
- the rubber component contains an isoprene skeleton rubber, which can increase the breaking strength of the rubber composition for tires, thereby reducing the rolling resistance of a product to which the rubber composition for tires is applied, improving fuel economy, and improving the wear resistance of the product.
- the content of the isoprene skeleton rubber is preferably more than 0 parts by mass and less than 70 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of the rubber component.
- the content of the isoprene skeleton rubber is within the above range, the wet braking performance and fuel economy of the product to which the rubber composition for tires is applied can be improved.
- SBR styrene-butadiene rubber
- the content of the styrene-butadiene rubber (SBR) is preferably 20 to 99 parts by mass, more preferably 30 to 99 parts by mass, more preferably 40 to 99 parts by mass, even more preferably 50 to 99 parts by mass, and even more preferably 60 to 99 parts by mass, per 100 parts by mass of the rubber component.
- SBR styrene-butadiene rubber
- the styrene-butadiene rubber contained in the rubber composition for tires of the present invention may be one type alone, or may be two or more different types of styrene-butadiene rubber.
- the two or more different types of styrene-butadiene rubber for example, two or more types of styrene-butadiene rubber with different amounts of bound styrene can be used.
- the styrene-butadiene rubber preferably has a bound styrene content of less than 15% by mass, more preferably 14% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less.
- the bound styrene content of the styrene-butadiene rubber is less than 15% by mass, the glass transition temperature is likely to be low.
- the bound styrene content of the styrene-butadiene rubber is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more.
- the wear resistance of a product to which the rubber composition for tires is applied can be improved.
- the bound styrene content of the styrene-butadiene rubber means the ratio of styrene units contained in the styrene-butadiene rubber.
- the bound styrene amount of the styrene-butadiene rubber can be adjusted by the amount of monomer used in polymerization of the styrene-butadiene rubber, the degree of polymerization, etc.
- the bound styrene amount (mass%) is measured based on the amount of ultraviolet light absorbed by the phenyl group of styrene using a spectrophotometer "UV-2450" manufactured by Shimadzu Corporation, based on the amount of bound styrene relative to 100 mass% of the sample.
- the styrene-butadiene rubber may be modified with a modifying agent.
- a modifying agent When two or more types of styrene-butadiene rubber are used, only one of the styrene-butadiene rubbers may be modified, or all of the styrene-butadiene rubbers may be modified.
- each of the styrene-butadiene rubbers may be modified with a different modifying agent.
- the styrene-butadiene rubber is preferably modified with a modifier containing nitrogen and silicon.
- the styrene-butadiene rubber is modified with a modifier containing nitrogen and silicon, the balance between fuel economy, wet braking performance, and wear resistance of a product to which the rubber composition for tires is applied can be further improved, and in particular, the fuel economy and wear resistance can be further improved.
- the modifier containing nitrogen and silicon is a general term for modifiers containing at least one nitrogen and at least one silicon.
- the styrene-butadiene rubber is more preferably modified with a hydrocarbyloxysilane compound containing nitrogen and silicon.
- a so-called both-end modified styrene-butadiene rubber is obtained, which can further enhance the dispersibility and reinforcing properties of fillers such as carbon black and silica.
- hydrocarbyloxysilane compound containing nitrogen and silicon used as the modifying agent examples include N,N-bis(trimethylsilyl)aminopropylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldiethoxysilane, and 1-trimethylsilyl-2,2-diethoxymethyl-1-aza-2-silacyclopentane, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N- ⁇ 3-(triethoxysilyl)propyl ⁇ -4,5-dihydroimidazole, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, and dimethylamino
- the styrene-butadiene rubber is preferably modified with a modifier having a nitrogen-containing functional group and an alkoxy group.
- a modifier having a nitrogen-containing functional group and an alkoxy group the balance between fuel economy, wet braking performance, and wear resistance of a product to which the rubber composition for tires is applied can be further improved, and in particular, the fuel economy and wear resistance can be further improved.
- the modifying agent having a nitrogen-containing functional group and an alkoxy group is a general term for a modifying agent having a functional group containing at least one nitrogen atom and at least one alkoxy group.
- the functional group containing a nitrogen atom is preferably selected from the following:
- the functional group is selected from the group consisting of a primary amino group, a primary amino group protected with a hydrolyzable protecting group, an onium salt residue of a primary amine, an isocyanate group, a thioisocyanate group, an imine group, an imine residue, an amide group, a secondary amino group protected with a hydrolyzable protecting group, a cyclic secondary amino group, an onium salt residue of a cyclic secondary amine, a non-cyclic secondary amino group, an onium salt residue of a non-cyclic secondary amine, an isocyanuric acid triester residue, a cyclic tertiary amino group, a non-cyclic tertiary amino group, a nitrile group, a pyridine residue, an onium salt residue of a cyclic tertiary amine, and an onium salt residue of a non-cyclic terti
- the styrene-butadiene rubber is preferably modified with an aminoalkoxysilane compound, and from the viewpoint of having a high affinity for the filler, it is more preferable that the terminal is modified with an aminoalkoxysilane compound.
- the terminal of the styrene-butadiene rubber is modified with an aminoalkoxysilane compound, the interaction between the modified styrene-butadiene rubber and the filler (particularly silica) becomes particularly large.
- the modified site of the styrene-butadiene rubber may be the molecular terminal as described above, but may also be the main chain.
- Styrene-butadiene rubber having modified molecular terminals can be produced by reacting various modifiers with the terminals of a styrene-butadiene copolymer having active terminals, for example, according to the methods described in WO 2003/046020 and JP 2007-217562 A.
- the styrene-butadiene rubber with modified molecular ends can be produced by reacting an aminoalkoxysilane compound with the ends of a styrene-butadiene copolymer having active ends with a cis-1,4 bond content of 75% or more, and then reacting the resulting mixture with a carboxylic acid partial ester of a polyhydric alcohol for stabilization, according to the methods described in WO 2003/046020 and JP 2007-217562 A.
- the carboxylic acid partial ester of a polyhydric alcohol means an ester of a polyhydric alcohol and a carboxylic acid, which has one or more hydroxyl groups. Specifically, an ester of a sugar or modified sugar having 4 or more carbon atoms and a fatty acid is preferably used.
- this ester include (1) a fatty acid partial ester of a polyhydric alcohol, in particular a partial ester (which may be a monoester, diester, or triester) of a saturated higher fatty acid or an unsaturated higher fatty acid having 10 to 20 carbon atoms and a polyhydric alcohol, and (2) an ester compound in which 1 to 3 partial esters of a polycarboxylic acid and a higher alcohol are bonded to a polyhydric alcohol.
- the polyhydric alcohol used as a raw material for the partial ester is preferably a saccharide having 5 or 6 carbon atoms and at least three hydroxyl groups (which may or may not be hydrogenated), glycol, polyhydroxy compound, etc.
- the raw material 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.
- fatty acid partial esters of polyhydric alcohols sorbitan fatty acid esters are preferred, and specific examples thereof include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate.
- the aminoalkoxysilane compound is not particularly limited, but is preferably an aminoalkoxysilane compound represented by the following general formula (i).
- R 11 and R 12 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, at least one of R 11 and R 12 is substituted with an amino group, a is an integer of 0 to 2, and when there are multiple OR 12 , each OR 12 may be the same or different, and no active proton is contained in the molecule.
- aminoalkoxysilane compound an aminoalkoxysilane compound represented by the following general formula (ii) is also preferred.
- a 1 is at least one functional group selected from a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, a (thio)isocyanate group, an isocyanuric acid trihydrocarbyl ester group, a nitrile group, a pyridine group, a (thio)ketone group, an amide group, and a primary or secondary amino group having a hydrolyzable group.
- n4 is 2 or more
- a 1 may be the same or different, and A 1 may be a divalent group that bonds with Si to form a cyclic structure.
- R 21 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when n1 is 2 or more, R 21 may be the same or different.
- R 22 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, either of which may contain a nitrogen atom and/or a silicon atom. When n2 is 2 or greater, R 22 may be the same or different from each other, or may be joined together to form a ring.
- R 23 represents a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a halogen atom, and when n3 is 2 or greater, may be the same or different.
- R 24 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when n4 is 2 or greater, R 24 may be the same or different.
- the hydrolyzable group in the hydrolyzable group-containing primary or secondary amino group a trimethylsilyl group or a tert-butyldimethylsilyl group is preferred, and a trimethylsilyl group is particularly preferred.
- the aminoalkoxysilane compound represented by the above general formula (ii) is preferably an aminoalkoxysilane compound represented by the following general formula (iii).
- A2 is NRa (Ra is a monovalent hydrocarbon group, a hydrolyzable group, or a nitrogen-containing organic group).
- R 25 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 26 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a nitrogen-containing organic group, any of which may contain a nitrogen atom and/or a silicon atom.
- R 26 may be the same or different from each other, or may be joined together to form a ring.
- R 27 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a halogen atom.
- R 28 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- a trimethylsilyl group or a tert-butyldimethylsilyl group is preferred, and a trimethylsilyl group is particularly preferred.
- the aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (iv) or (v).
- R 31 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 32 and R 33 each independently represent a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 34 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q1 is 2, may be the same or different.
- R 35 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or greater, R 35 may be the same or different.
- R 36 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 37 is a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, a methylsilyl(methyl)aminomethyl group, a methylsilyl(methyl)aminoethyl group, a methylsilyl(ethyl)aminomethyl group, a methylsilyl(ethyl)aminoethyl group, a dimethylsilylaminomethyl group, a dimethylsilylaminoethyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they may be the same or different.
- R 38 is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2, they may be the same or different.
- a specific example of the aminoalkoxysilane compound represented by the general formula (v) is N-(1,3-dimethylbutylidene)-3-triethoxysilyl-1-propaneamine.
- the aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (vi) or (vii).
- R 40 represents a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 41 is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 42 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- TMS represents a trimethylsilyl group (hereinafter the same).
- R 43 and R 44 each independently represent a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 45 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and each R 45 may be the same or different.
- the aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (viii) or the following general formula (ix).
- s1+s2 is 3 (wherein s1 is an integer of 0 to 2, and s2 is an integer of 1 to 3).
- R 46 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 47 and R 48 are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Multiple R 47s or R 48s may be the same or different.
- X is a halogen atom.
- R 49 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 50 and R 51 are each independently a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or R 50 and R 51 combine together to form a divalent organic group.
- R 52 and R 53 each independently represent a halogen atom, a hydrocarbyloxy group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- R 50 and R 51 are preferably a hydrolyzable group, and the hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, and particularly preferably a trimethylsilyl group.
- the aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (x), the following general formula (xi), the following general formula (xii), or the following general formula (xiii).
- R 54 to R 92 in general formulas (x) to (xiii) may be the same or different and are a monovalent or divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent or divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- ⁇ and ⁇ are integers of 0 to 5.
- N1,N1,N7,N7-tetramethyl-4-((trimethoxysilyl)methyl)heptane-1,7-diamine 2-((hexyl-dimethoxysilyl)methyl)-N1,N1,N3,N3-2-pentamethylpropane-1,3-diamine, N1-(3-(dimethylamino)propyl)-N3,N3-dimethyl-N1-(3-(trimethoxysilyl)propyl)propane-1,3-diamine, and 4-(3-(dimethylamino)propyl)-N1,N1,N7,N7-tetramethyl-4-((trimethoxysilyl)methyl)heptane-1,7-diamine are particularly preferred.
- SBR styrene-butadiene rubber
- R 1 , R 2 and R 3 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
- R 4 , R 5 , R 6 , R 7 and R 9 each independently represent an alkyl group having 1 to 20 carbon atoms.
- R 8 and R 11 each independently represent an alkylene group having 1 to 20 carbon atoms.
- R 10 represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms.
- m represents an integer of 1 to 3;
- p represents 1 or 2.
- i, j, and k each independently represent an integer of 0 to 6, provided that (i+j+k) is an integer of 3 to 10.
- A represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorus atom and having no active hydrogen.
- the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic and aromatic hydrocarbon groups.
- the organic group not having active hydrogen include organic groups not having a functional group having active hydrogen, such as a hydroxyl group (-OH), a secondary amino group (>NH), a primary amino group (-NH 2 ) or a sulfhydryl group (-SH).
- the styrene-butadiene rubber modified with the coupling agent represented by the above general formula (I) has a weight average molecular weight (Mw) of 20 ⁇ 10 4 to 300 ⁇ 10 4 , contains 0.25 to 30 mass% of modified styrene-butadiene rubber having a molecular weight of 200 ⁇ 10 4 to 500 ⁇ 10 4 based on the total amount of the modified styrene-butadiene rubber, and preferably has a shrinkage factor (g') of less than 0.64.
- Mw weight average molecular weight
- g' shrinkage factor
- a polymer having branches tends to have a smaller molecular size compared to a linear polymer having the same absolute molecular weight
- the contraction factor (g') is an index of the ratio of the molecular size to that of a linear polymer having the same absolute molecular weight. That is, the contraction factor (g') tends to be smaller as the branching degree of the polymer increases.
- the intrinsic viscosity is used as an index of the molecular size
- the contraction factor (g') at each absolute molecular weight of the modified styrene-butadiene rubber is calculated, and the average value of the contraction factor (g') at the absolute molecular weight of 100 x 10 4 to 200 x 10 4 is taken as the contraction factor (g') of the modified styrene-butadiene rubber.
- “branch” is formed by directly or indirectly bonding one polymer to another polymer.
- “branching degree” is the number of polymers that are directly or indirectly bonded to one branch. For example, when five styrene-butadiene copolymer chains described later are indirectly bonded to each other via coupling residues described later, the degree of branching is 5.
- the coupling residue is a structural unit of a modified styrene-butadiene rubber bonded to the styrene-butadiene copolymer chain, and is, for example, a structural unit derived from a coupling agent produced by reacting a styrene-butadiene copolymer described later with a coupling agent.
- the styrene-butadiene copolymer chain is a structural unit of a modified styrene-butadiene rubber, and is, for example, a structural unit derived from a styrene-butadiene copolymer produced by reacting a styrene-butadiene copolymer described later with a coupling agent.
- the shrinkage factor (g') is preferably less than 0.64, more preferably 0.63 or less, more preferably 0.60 or less, even more preferably 0.59 or less, and particularly preferably 0.57 or less.
- the lower limit of the shrinkage factor (g') is not particularly limited and may be equal to or less than the detection limit, but is preferably 0.30 or more, more preferably 0.33 or more, even more preferably 0.35 or more, and particularly preferably 0.45 or more.
- the shrinkage factor (g') tends to depend on the degree of branching, for example, the shrinkage factor (g') can be controlled using the degree of branching as an index.
- the shrinkage factor (g') tends to be 0.59 or more and 0.63 or less
- the shrinkage factor (g') tends to be 0.45 or more and 0.59 or less.
- the styrene-butadiene rubber modified by the coupling agent represented by the general formula (I) preferably has a branch and a degree of branching of 5 or more.
- the modified styrene-butadiene rubber has one or more coupling residues and a styrene-butadiene copolymer chain bonded to the coupling residue, and more preferably the branch includes a branch in which 5 or more styrene-butadiene copolymer chains are bonded to one coupling residue.
- the contraction factor (g') can be more reliably made less than 0.64.
- the number of styrene-butadiene copolymer chains bonded to one coupling residue can be confirmed from the value of the contraction factor (g').
- the modified styrene-butadiene rubber has branches, and more preferably has a degree of branching of 6 or more.
- the modified styrene-butadiene rubber has one or more coupling residues and a styrene-butadiene copolymer chain bonded to the coupling residue, and further preferably includes a branch in which six or more styrene-butadiene copolymer chains are bonded to one coupling residue.
- the shrinkage factor (g') can be set to 0.63 or less.
- the modified styrene-butadiene rubber has branches, and the degree of branching is more preferably 7 or more, and even more preferably 8 or more.
- the upper limit of the degree of branching is not particularly limited, but is preferably 18 or less.
- the modified styrene-butadiene rubber has one or more coupling residues and a styrene-butadiene copolymer chain bonded to the coupling residue, and further, it is more preferable that the branching includes a branch in which 7 or more styrene-butadiene copolymer chains are bonded to one coupling residue, and it is particularly preferable that the branching includes a branch in which 8 or more styrene-butadiene copolymer chains are bonded to one coupling residue.
- the shrinkage factor (g') can be made 0.59 or less.
- At least one end of the styrene-butadiene copolymer chain is bonded to a silicon atom of the coupling residue.
- the ends of a plurality of styrene-butadiene copolymer chains may be bonded to one silicon atom.
- an end of the styrene-butadiene copolymer chain and an alkoxy group or hydroxyl group having 1 to 20 carbon atoms may be bonded to one silicon atom, and as a result, that one silicon atom may constitute an alkoxysilyl group or silanol group having 1 to 20 carbon atoms.
- the modified styrene-butadiene rubber can be an oil-extended rubber to which an extender oil has been added.
- the modified styrene-butadiene rubber may be either non-oil-extended or oil-extended, but from the viewpoint of wear resistance, it is preferable that the Mooney viscosity measured at 100°C is 20 or more and 100 or less, and more preferably 30 or more and 80 or less.
- the weight average molecular weight (Mw) of the modified styrene-butadiene rubber is preferably 20 ⁇ 10 4 or more and 300 ⁇ 10 4 or less, more preferably 50 ⁇ 10 4 or more, even more preferably 64 ⁇ 10 4 or more, and particularly preferably 80 ⁇ 10 4 or more.
- the weight average molecular weight is preferably 250 ⁇ 10 4 or less, more preferably 180 ⁇ 10 4 or less, and even more preferably 150 ⁇ 10 4 or less.
- the weight average molecular weight is 20 ⁇ 10 4 or more, the low loss property and wear resistance of the product to which the rubber composition for tires is applied can be sufficiently improved.
- the weight average molecular weight is 300 ⁇ 10 4 or less, the processability of the rubber composition is improved.
- the modified styrene-butadiene rubber preferably contains 0.25% by mass or more and 30% by mass or less of a modified styrene-butadiene rubber having a molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less (hereinafter also referred to as a "specific high molecular weight component") relative to the total amount (100% by mass) of the modified styrene-butadiene rubber.
- a specific high molecular weight component a modified styrene-butadiene rubber having a molecular weight of 200 ⁇ 10 4 or more and 500 ⁇ 10 4 or less
- the modified styrene-butadiene rubber preferably contains 1.0% by mass or more of the specific high molecular weight component, more preferably contains 1.4% by mass or more, more preferably contains 1.75% by mass or more, even more preferably contains 2.0% by mass or more, particularly preferably contains 2.15% by mass or more, and extremely preferably contains 2.5% by mass or more.
- the modified styrene-butadiene rubber contains the specific high molecular weight component in an amount of preferably 28% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 18% by mass or less.
- the "molecular weight" of the rubber component is the standard polystyrene equivalent molecular weight obtained by GPC (gel permeation chromatography).
- GPC gel permeation chromatography
- the amount of an organic monolithium compound used as a polymerization initiator described later may be adjusted.
- a method having a residence time distribution is used, that is, the time distribution of the propagation reaction is expanded.
- the molecular weight distribution (Mw/Mn), which is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 1.6 or more and 3.0 or less.
- Mw/Mn the molecular weight distribution of the modified styrene-butadiene rubber is in this range, the rubber composition has good processability.
- the manufacturing method of the modified styrene-butadiene rubber is not particularly limited, but it preferably has a polymerization step in which butadiene and styrene are copolymerized using an organic monolithium compound as a polymerization initiator to obtain a styrene-butadiene copolymer, and a reaction step in which a pentafunctional or higher reactive compound (hereinafter also referred to as a "coupling agent”) is reacted with the active terminal of the styrene-butadiene copolymer.
- a pentafunctional or higher reactive compound hereinafter also referred to as a "coupling agent”
- the polymerization step is preferably a polymerization by a propagation reaction due to a living anionic polymerization reaction, which makes it possible to obtain a styrene-butadiene copolymer having an active terminal and a modified styrene-butadiene rubber with a high modification rate.
- the styrene-butadiene copolymer is obtained by copolymerizing 1,3-butadiene and styrene.
- the amount of the organic monolithium compound used as a polymerization initiator is preferably determined depending on the molecular weight of the target styrene-butadiene copolymer or modified styrene-butadiene rubber.
- the amount of monomers such as 1,3-butadiene and styrene used relative to the amount of polymerization initiator used is related to the degree of polymerization, that is, the number average molecular weight and/or the weight average molecular weight. Therefore, in order to increase the molecular weight, it is preferable to adjust the amount of polymerization initiator to a smaller amount, and in order to decrease the molecular weight, it is preferable to adjust the amount of polymerization initiator to a larger amount.
- the organic monolithium compound is preferably an alkyllithium compound from the viewpoint of industrial availability and ease of control of the polymerization reaction.
- a styrene-butadiene copolymer having an alkyl group at the polymerization initiation terminal is obtained.
- the alkyllithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, and stilbenelithium.
- n-butyllithium and sec-butyllithium are preferred from the viewpoint of industrial availability and ease of control of the polymerization reaction.
- These organic monolithium compounds may be used alone or in combination of two or more.
- examples of the polymerization reaction mode include a batch polymerization mode and a continuous polymerization mode.
- the continuous mode one or more connected reactors can be used.
- a tank type or a tube type reactor equipped with an agitator is used.
- the monomer, the inert solvent, and the polymerization initiator are continuously fed into the reactor, a polymer solution containing the polymer is obtained in the reactor, and the polymer solution is continuously discharged.
- a tank type reactor equipped with an agitator is used for example.
- the monomer, the inert solvent, and the polymerization initiator are fed, and if necessary, the monomer is continuously or intermittently added during the polymerization, a polymer solution containing the polymer is obtained in the reactor, and the polymer solution is discharged after the polymerization is completed.
- a continuous mode is preferred, which allows the polymer to be continuously discharged and used for the next reaction in a short time.
- the polymerization step is preferably carried out in an inert solvent.
- the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons.
- specific examples of the hydrocarbon solvent include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene, and hydrocarbons consisting of mixtures thereof.
- styrene-butadiene copolymer having a high concentration of active ends tends to be obtained, and a modified styrene-butadiene rubber with a high modification rate tends to be obtained, which is preferable.
- a polar compound may be added.
- styrene By adding a polar compound, styrene can be randomly copolymerized with 1,3-butadiene, and the polar compound tends to be usable as a vinylating agent for controlling the microstructure of the 1,3-butadiene portion.
- polar compound examples include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, and 2,2-bis(2-oxolanyl)propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, and quinuclidine; alkali metal alkoxide compounds such as potassium tert-amylate, potassium tert-butylate, sodium tert-butylate, and sodium tert-amylate; and phosphine compounds such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more.
- ethers such as tetrahydrofuran, diethyl ether,
- the polymerization temperature is preferably 0°C or higher, more preferably 120°C or lower, and particularly preferably 50°C or higher and 100°C or lower. By keeping the temperature in this range, it tends to be possible to ensure a sufficient amount of reaction of the coupling agent with the active terminals after the polymerization is completed.
- the amount of bound butadiene in the styrene-butadiene copolymer or modified styrene-butadiene rubber is not particularly limited, but is preferably from 40% by mass to 100% by mass, and more preferably from 55% by mass to 80% by mass.
- the amount of bound butadiene can be calculated by measuring the amount of bound styrene through ultraviolet absorption of the phenyl group.
- the amount of vinyl bonds in the butadiene bond units is not particularly limited, but is preferably 10 mol % to 75 mol %, and more preferably 20 mol % to 65 mol %.
- the amount of vinyl bonds is within the above range, the low loss property and wear resistance of the product to which the rubber composition for tires is applied can be further improved.
- the amount of vinyl bonds (1,2-bonds) in the butadiene bond units can be determined by the Hampton method [R. R. Hampton, Analytical Chemistry, 21, 923 (1949)].
- the alkoxysilyl group of the coupling agent represented by the above general formula (I) tends to react with, for example, the active terminal of the styrene-butadiene copolymer, dissociating the alkoxylithium and forming a bond between the terminal of the styrene-butadiene copolymer chain and the silicon of the coupling residue.
- the number of alkoxysilyl groups in the coupling residue is the total number of SiOR in one molecule of the coupling agent minus the number of SiORs subtracted by the reaction.
- the azasilacycle group in the coupling agent forms an >N-Li bond and a bond between the terminal of the styrene-butadiene copolymer and the silicon of the coupling residue.
- the >N-Li bond tends to easily become >NH and LiOH due to water, etc. during finishing.
- the alkoxysilyl group remaining unreacted in the coupling agent tends to easily become a silanol (Si-OH group) due to water, etc. during finishing.
- the reaction temperature in the reaction step is preferably the same as the polymerization temperature of the styrene-butadiene copolymer, and is preferably from 0° C. to 120° C., more preferably from 50° C. to 100° C.
- the temperature change from the end of the polymerization step to the addition of the coupling agent is preferably 10° C. or less, more preferably 5° C. or less.
- the reaction time in the reaction step is preferably 10 seconds or more, more preferably 30 seconds or more.
- the time from the end of the polymerization step to the start of the reaction step is preferably shorter from the viewpoint of the coupling rate, and is more preferably within 5 minutes.
- the mixing in the reaction step may be performed by mechanical stirring, stirring with a static mixer, or the like.
- the reaction step is also a continuous process.
- the reactor used in the reaction step may be, for example, a tank type or a tube type equipped with a stirrer.
- the coupling agent may be diluted with an inert solvent and continuously fed to the reactor.
- the coupling agent may be added to the polymerization reactor, or may be transferred to another reactor to carry out the reaction step.
- A is preferably represented by any one of the following general formulas (II) to (V).
- a represented by any one of the general formulas (II) to (V) a modified styrene-butadiene rubber with superior performance can be obtained.
- B 1 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. When a plurality of B 1s are present, each B 1 is independent.
- B2 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms
- B3 represents an alkyl group having 1 to 20 carbon atoms
- a represents an integer of 1 to 10.
- B4 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. When a plurality of B4s are present, each B4 is independent.
- B5 represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. When a plurality of B5s are present, each B5 is independent.
- examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkylene group having 1 to 20 carbon atoms.
- A is represented by the general formula (II) or (III), and k is 0. More preferably, in the general formula (I), A is represented by the general formula (II) or (III), k represents 0, and in the general formula (II) or (III), a represents an integer of 2 to 10. More preferably, in said general formula (I), A is represented by said general formula (II), k represents 0, and in said general formula (II), a represents an integer of 2 to 10.
- Examples of such coupling agents include bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, and tetrakis(3-trimethoxysilylpropyl).
- the amount of the compound represented by general formula (I) added as the coupling agent can be adjusted so that the moles of the styrene-butadiene copolymer to the moles of the coupling agent react in the desired stoichiometric ratio, which tends to achieve the desired degree of branching.
- the specific number of moles of the polymerization initiator is preferably 5.0 times or more, more preferably 6.0 times or more, relative to the number of moles of the coupling agent.
- the number of functional groups of the coupling agent ((m-1) x i + p x j + k) is preferably an integer of 5 to 10, and more preferably an integer of 6 to 10.
- the molecular weight distribution (Mw/Mn) of the styrene-butadiene copolymer is preferably 1.5 to 2.5, more preferably 1.8 to 2.2.
- the obtained modified styrene-butadiene rubber is preferably one in which a single peak is detected in the molecular weight curve by GPC.
- the peak molecular weight by GPC of the modified styrene-butadiene rubber is Mp 1 and the peak molecular weight of the styrene-butadiene copolymer is Mp 2 , it is preferable that the following formula is satisfied.
- Mp 1 /Mp 2 (Mp 1 /Mp 2 ) ⁇ 1.8 ⁇ 10-12 ⁇ (Mp 2 -120 ⁇ 10 4 ) 2 +2 It is more preferable that Mp2 is 20 ⁇ 10 4 or more and 80 ⁇ 10 4 or less, and Mp1 is 30 ⁇ 10 4 or more and 150 ⁇ 10 4 or less.
- Mp 1 and Mp 2 are calculated by gel permeation chromatography (GPC).
- the modification rate of the modified styrene-butadiene rubber is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. A modification rate of 30% by mass or more can further improve the low loss and wear resistance of a product to which the rubber composition for tires is applied.
- a deactivator, neutralizing agent, etc. may be added to the copolymer solution as necessary.
- deactivators include, but are not limited to, water; alcohols such as methanol, ethanol, isopropanol, etc.
- neutralizing agents include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid (a highly branched carboxylic acid mixture having 9 to 11 carbon atoms, with the majority being 10 carbon atoms); aqueous solutions of inorganic acids, and carbon dioxide gas.
- antioxidant such as 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, or 2-methyl-4,6-bis[(octylthio)methyl]phenol to the modified styrene-butadiene rubber.
- BHT 2,6-di-tert-butyl-4-hydroxytoluene
- n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate or 2-methyl-4,6-bis[(octylthio)methyl]phenol
- the modified styrene-butadiene rubber can be obtained from the polymer solution by known methods. Examples of such methods include a method in which the solvent is separated by steam stripping or the like, the polymer is filtered, and then dehydrated and dried to obtain the polymer, a method in which the polymer is concentrated in a flashing tank and then devolatilized using a vent extruder or the like, and a method in which the polymer is directly devolatilized using a drum dryer or the like.
- the modified styrene-butadiene rubber obtained by reacting the coupling agent represented by the above general formula (I) with a styrene-butadiene copolymer is represented, for example, by the following general formula (VI).
- D represents a styrene-butadiene copolymer chain
- the weight average molecular weight of the styrene-butadiene copolymer chain is preferably 10 ⁇ 10 4 to 100 ⁇ 10 4.
- the styrene-butadiene copolymer chain is a structural unit of a modified styrene-butadiene rubber, and is, for example, a structural unit derived from a styrene-butadiene copolymer generated by reacting a styrene-butadiene copolymer with a coupling agent.
- R 12 , R 13 and R 14 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
- R 15 and R 18 each independently represent an alkyl group having 1 to 20 carbon atoms.
- R 16 , R 19 , and R 20 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- R 17 and R 21 each independently represent an alkylene group having 1 to 20 carbon atoms.
- R 22 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
- m and x are integers of 1 to 3, with x ⁇ m; p is 1 or 2; y is an integer of 1 to 3, with y ⁇ (p+1); and z is an integer of 1 or 2.
- R 12 to R 22 , m, p, x, y, and z are each independent and may be the same or different.
- i represents an integer from 0 to 6
- j represents an integer from 0 to 6
- k represents an integer from 0 to 6
- (i+j+k) is an integer from 3 to 10
- ((x ⁇ i)+(y ⁇ j)+(z ⁇ k)) is an integer from 5 to 30.
- A represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of oxygen, nitrogen, silicon, sulfur, and phosphorus atoms, and having no active hydrogen.
- the hydrocarbon group represented by A includes saturated, unsaturated, aliphatic, and aromatic hydrocarbon groups.
- Examples of the organic group having no active hydrogen include organic groups having no functional groups having active hydrogen, such as a hydroxyl group (-OH), a secondary amino group (>NH), a primary amino group (-NH 2 ), or a sulfhydryl group (-SH).
- A is preferably represented by any one of the above general formulas (II) to (V).
- a represented by any one of general formulas (II) to (V) it is possible to further improve the low loss properties and wear resistance of a product to which the rubber composition for tires is applied.
- modified styrene-butadiene rubber-- It is also preferable that at least one end of the styrene-butadiene rubber (SBR) is modified with a modifying agent containing a compound (alkoxysilane) represented by the following general formula (1).
- SBR styrene-butadiene rubber
- the rubber component a styrene-butadiene rubber modified with a modifier containing a compound represented by the above general formula (1) containing an oligosiloxane and a tertiary amino group, which are filler affinity functional groups, the dispersibility of fillers such as silica can be improved.
- the tire rubber composition of the present invention has improved filler dispersibility, and therefore has significantly improved low loss properties, and the rolling resistance of tires to which the tire rubber composition is applied can be reduced, thereby improving fuel efficiency.
- R 1 to R 8 are each independently an alkyl group having 1 to 20 carbon atoms; L 1 and L 2 are each independently an alkylene group having 1 to 20 carbon atoms; and n is an integer of 2 to 4.
- R 1 to R 4 may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
- R 1 to R 4 When R 1 to R 4 are substituted, they may each independently be substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 4 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkanoyloxy group having 2 to 12 carbon atoms (Ra-COO-, where Ra is an alkyl group having 1 to 9 carbon atoms), an aralkyloxy group having 7 to 13 carbon atoms, an arylalkyl group having 7 to 13 carbon atoms, and an alkylaryl group having 7 to 13 carbon atoms
- R 1 to R 4 may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and even more specifically, R 1 to R 4 may be each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
- R 5 to R 8 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, specifically, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more specifically, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and when substituted, may be substituted with the substituents described above for R 1 to R 4 .
- R 5 to R 8 are not alkyl groups but hydrolyzable substituents, the bonds N-R 5 R 6 and N-R 7 R 8 may be hydrolyzed to N-H in the presence of moisture, which may adversely affect the processability of the polymer.
- R 1 to R 4 can be a methyl group or an ethyl group
- R 5 to R 8 can be an alkyl group having 1 to 10 carbon atoms.
- the amino groups in the compound represented by formula (1) are preferably tertiary amino groups.
- the tertiary amino groups provide the compound represented by formula (1) with better processability when used as a modifying agent.
- a protecting group for protecting an amino group is bonded to R 5 to R 8 or when hydrogen is bonded to R 5 to R 8, it may be difficult to realize the effect of the compound represented by formula (1).
- the anion reacts with hydrogen during the modification process and loses reactivity, making the modification reaction itself impossible, and when a protecting group is bonded, the modification reaction takes place, but in the state bonded to the polymer end, it is deprotected by hydrolysis during post-processing to become a primary or secondary amino group, and the deprotected primary or secondary amino group may cause an increase in viscosity of the compound during subsequent blending, which may cause a decrease in processability.
- L 1 and L 2 in the compound represented by the formula (1) are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. More specifically, L 1 and L 2 can each independently be an alkylene group having 1 to 10 carbon atoms, and even more specifically, an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group.
- the L 1 and L 2 are each independently an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, or a propylene group, and more specifically, a propylene group.
- L 1 and L 2 may be substituted with the substituents described above for R 1 to R 4 .
- the compound represented by the formula (1) is preferably, for example, any one of the compounds represented by the following structural formulas (1-1) to (1-5), because this allows for more excellent low loss properties to be realized.
- the compound represented by formula (1) has an alkoxysilane structure that bonds with the active end of the styrene-butadiene copolymer, while the Si-O-Si structure and three or more amino groups bonded to the end show affinity for fillers such as silica, and can therefore promote the bonding between the filler and the modified styrene-butadiene rubber compared to conventional modifiers containing one amino group in the molecule.
- the degree of bonding of the active end of the styrene-butadiene copolymer is uniform, and when the change in molecular weight distribution is observed before and after coupling, the molecular weight distribution after coupling does not increase and remains constant compared to before.
- the compound represented by the formula (1) can be produced through a condensation reaction represented by the following reaction scheme.
- R 1 to R 8 , L 1 and L 2 , and n are the same as those defined in the above formula (1), and R′ and R′′ are any substituents that do not affect the condensation reaction.
- R′ and R′′ can each independently be the same as any one of R 1 to R 4 .
- the reaction in the above reaction scheme proceeds in the presence of an acid, and the acid can be any acid that is generally used in condensation reactions, without any restrictions.
- the acid can be any acid that is generally used in condensation reactions, without any restrictions.
- Those skilled in the art can select an optimal acid depending on various process variables such as the type of reactor in which the reaction is carried out, the starting materials, and the reaction temperature.
- the styrene-butadiene rubber modified with a modifier containing the compound represented by formula (1) can have a narrow molecular weight distribution (Mw/Mn, also called “polydispersity index (PDI)”) of 1.1 to 3.0. If the molecular weight distribution of the modified styrene-butadiene rubber exceeds 3.0 or is less than 1.1, there is a risk of the tensile properties and viscoelasticity decreasing when applied to a rubber composition.
- Mw/Mn also called “polydispersity index (PDI)
- the molecular weight distribution of the modified styrene-butadiene rubber is preferably in the range of 1.3 to 2.0.
- the modified styrene-butadiene rubber has a molecular weight distribution similar to that of the styrene-butadiene copolymer before modification.
- the molecular weight distribution of the modified styrene-butadiene rubber can be calculated from the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
- the number average molecular weight (Mn) is the common average of the molecular weights of individual polymers calculated by measuring the molecular weights of n polymer molecules, calculating the sum of the molecular weights, and dividing the sum by n
- the weight average molecular weight (Mw) represents the molecular weight distribution of a polymer composition.
- the average of the total molecular weight can be expressed in grams per mole (g/mol).
- the weight average molecular weight and number average molecular weight are each a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).
- the modified styrene-butadiene rubber satisfies the above-mentioned molecular weight distribution conditions, and at the same time, the weight average molecular weight (Mw) can be 100,000 g/mol to 4,000,000 g/mol, more specifically, 300,000 g/mol to 1,500,000 g/mol.
- the modified styrene-butadiene rubber can have a number average molecular weight (Mn) of 50,000 g/mol to 2,000,000 g/mol, more specifically, 200,000 g/mol to 800,000 g/mol.
- the weight average molecular weight (Mw) of the modified styrene-butadiene rubber is 100,000 g/mol or more and the number average molecular weight (Mn) is 50,000 g/mol or more, the deterioration of tensile properties when applied to a rubber composition can be suppressed.
- the weight average molecular weight (Mw) is 4,000,000 g/mol or less and the number average molecular weight (Mn) is 2,000,000 g/mol or less, the deterioration of processability of the modified styrene-butadiene rubber can be suppressed, the workability of the rubber composition is not deteriorated, and the physical properties of the rubber composition can be sufficiently improved.
- the modified styrene-butadiene rubber satisfies the conditions of weight average molecular weight (Mw) and number average molecular weight (Mn) together with the molecular weight distribution
- Mw weight average molecular weight
- Mn number average molecular weight
- the modified styrene-butadiene rubber preferably has a vinyl bond content in the butadiene portion of 5% or more, more preferably 10% or more, and preferably 60% or less.
- the glass transition temperature can be adjusted to an appropriate range.
- the modified styrene-butadiene rubber may have a Mooney viscosity (MV) at 100° C. of 40 to 140, specifically 60 to 100.
- MV Mooney viscosity
- the Mooney viscosity can be measured using a Mooney viscometer, for example, MV2000E manufactured by Monsanto, at 100° C., rotor speed 2 ⁇ 0.02 rpm, and a large rotor.
- the sample used here is left at room temperature (23 ⁇ 3° C.) for 30 minutes or more, and then 27 ⁇ 3 g of the sample is taken and filled into the die cavity, and the platen is operated to measure.
- the modified styrene-butadiene rubber is preferably modified at one end with a modifier containing a compound represented by the above general formula (1), and is preferably further modified at the other end with a modifier containing a compound represented by the following general formula (2).
- R 9 to R 11 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms.
- R 12 is a single bond; an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; a cycloalkylene group having 5 to 20 carbon atoms which is substituted or unsubstituted with a substituent; or an arylene group having 5 to 20 carbon atoms which is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 13 is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; a heterocyclic group having 3 to 30 carbon atoms; or a functional group represented by the following general formula (2a) or general formula (2b), where m is an integer of 1 to 5, and at least one of R 13 is a functional group represented by the following general formula (2a) or general formula (2b), and when m is an integer of 2 to 5, the multiple R 13 may be the same as or different from each other.
- R 14 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 15 and R 16 are each independently an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 17 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms; and X is an N, O, or S atom, with the proviso that when X is O or S, R 17 does not exist.
- R 18 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- R 19 and R 20 are each independently an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms.
- R 9 to R 11 are each independently hydrogen; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms;
- R 12 is a single bond; or an unsubstituted alkylene group having 1 to 10 carbon atoms;
- R 13 is an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an alkynyl group having 2 to 10 carbon atoms; or a functional group represented by the above general formula (2a) or general formula (2b); in the above general formula (2a), R 14 is an unsubstituted alkylene group having 1 to 10 carbon atoms; R 15 and R 16 are each independently an unsubstituted alkylene group having 1 to 10 carbon atoms; R In the above general formula (2b), R 18 is an unsubstituted alkylene group having 1 to 10 carbon atoms,
- the compound represented by the above general formula (2) can be a compound represented by the following structural formulas (2-1) to (2-3).
- the modifying agent containing the compound represented by formula (2) is used as a modification initiator.
- a butadiene monomer and a styrene monomer are polymerized in a hydrocarbon solvent in the presence of a modifying agent containing the compound represented by formula (2), whereby a modifying group derived from the compound represented by formula (2) can be imparted to the styrene-butadiene copolymer.
- the rubber component may further contain other rubbers in addition to the isoprene skeleton rubber and the styrene-butadiene rubber, specific examples of which include butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), halogenated butyl rubber, ethylene-propylene rubber (EPR, EPDM), fluororubber, silicone rubber, and urethane rubber.
- the other rubber may include butadiene rubber (BR), but from the viewpoint of preventing deterioration of wet braking performance, it is preferable not to include butadiene rubber (BR). By not including butadiene rubber in the rubber component, deterioration of wet braking performance can be suppressed.
- the rubber composition for tires of the present invention contains a filler.
- the filler By containing the filler, the reinforcing property of the rubber composition is improved.
- the filler include silica and carbon black.
- the content of the filler in the rubber composition for tires is preferably in the range of 40 to 125 parts by mass per 100 parts by mass of the rubber component.
- the tire to which the rubber composition for tires is applied is sufficiently reinforced, and the wear resistance performance can be further improved.
- the content of the filler is 125 parts by mass or less per 100 parts by mass of the rubber component, the wet braking performance can be further improved.
- the content of the filler in the rubber composition for tires is more preferably 45 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 55 parts by mass or more per 100 parts by mass of the rubber component. Also, from the viewpoint of improving the wet braking performance of the tire, the content of the filler in the rubber composition for tires is more preferably 120 parts by mass or less, more preferably 115 parts by mass or less, and even more preferably less than 100 parts by mass per 100 parts by mass of the rubber component.
- the filler contains silica.
- the silica include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among these, wet silica is preferred. These silicas may be used alone or in combination of two or more.
- silica derived from silicic acid plants is also preferred from the viewpoint of reducing the environmental load.
- the silicic acid plants are present, for example, in mosses, ferns, horsetails, Cucurbitaceae, Urticaceae, and Gramineae plants.
- Gramineae plants are preferred.
- Examples of the Gramineae plants include rice, bamboo, and sugarcane, and among these, rice is preferred. Since rice is widely cultivated for food, it can be procured locally in a wide area, and since rice husks are generated in large quantities as industrial waste, it is easy to secure the amount.
- silica derived from rice husks (hereinafter also referred to as "rice husk silica”) is particularly preferred as silica.
- rice husk silica By using the rice husk silica, rice husks that become industrial waste can be effectively utilized, and since the raw material can be procured locally near the tire manufacturing plant, the energy and cost of transportation and storage can be reduced, which is environmentally preferable from various viewpoints.
- the rice husk silica may be a powder of rice husk charcoal obtained by carbonizing rice husks by heating, or may be precipitated silica produced by a wet method using an aqueous alkali silicate solution, which is prepared by extracting rice husk ash generated when rice husks are burned as fuel in a biomass boiler with an alkali and extracting the rice husk ash with an alkali silicate solution.
- the method for producing the rice husk charcoal is not particularly limited, and various known methods can be used.
- rice husks can be pyrolyzed by steaming them in a kiln to obtain rice husk charcoal.
- the rice husk charcoal thus obtained is pulverized using a known pulverizer (e.g., a ball mill), and then sorted and classified into a predetermined particle size range to obtain rice husk charcoal powder.
- a known pulverizer e.g., a ball mill
- the precipitated silica derived from rice husks can be produced by the method described in JP 2019-38728 A, etc.
- the silica preferably has a nitrogen adsorption specific surface area (BET method) of 80 m 2 /g or more and less than 330 m 2 /g.
- BET method nitrogen adsorption specific surface area
- the nitrogen adsorption specific surface area (BET method) of silica is 80 m 2 /g or more, the product to which the rubber composition for tires is applied can be sufficiently reinforced, and the rolling resistance of the product can be further reduced.
- the nitrogen adsorption specific surface area (BET method) of silica is less than 330 m 2 /g, the elastic modulus of the rubber composition for tires does not become too high, and the wet braking performance of the product to which the rubber composition for tires is applied is further improved.
- the nitrogen adsorption specific surface area (BET method) of silica is preferably 110 m 2 /g or more, more preferably 130 m 2 /g or more, even more preferably 150 m 2 /g or more, and particularly preferably 180 m 2 /g or more.
- the nitrogen adsorption specific surface area (BET method) of silica is preferably 300 m 2 /g or less, more preferably 280 m 2 /g or less, and even more preferably 270 m 2 /g or less.
- the content of silica in the rubber composition for tires is preferably 25 parts by mass or more, more preferably 28 parts by mass or more, and even more preferably 31 parts by mass or more, per 100 parts by mass of the rubber component, from the viewpoint of improving the mechanical strength of the product to which the rubber composition for tires is applied and further improving the abrasion resistance. Also, from the viewpoint of further improving the wet braking performance of the tire, the content of silica in the rubber composition for tires is preferably 93 parts by mass or less, more preferably 86 parts by mass or less, and even more preferably less than 75 parts by mass, per 100 parts by mass of the rubber component.
- the filler may contain carbon black, which can reinforce the rubber composition for tires and improve the abrasion resistance of a product to which the rubber composition for tires is applied.
- the carbon black is not particularly limited, and examples thereof include GPF, FEF, HAF, ISAF and SAF grade carbon black. These carbon blacks may be used alone or in combination of two or more.
- the carbon black is particularly preferably plant-derived carbon black or carbon black obtained by recycling.
- plant-derived carbon black include carbon black derived from castor oil and pine oil.
- carbon black obtained by recycling include carbon black obtained by pyrolysis of used tires and the like, and carbon black obtained from waste oil.
- the content of carbon black in the rubber composition for tires is preferably 12 parts by mass or more, more preferably 14 parts by mass or more, and even more preferably 16 parts by mass or more, per 100 parts by mass of the rubber component, from the viewpoint of improving the abrasion resistance of a product to which the rubber composition for tires is applied. Also, from the viewpoint of the wet braking performance of the rubber composition for tires, the content of carbon black in the rubber composition for tires is preferably 56 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of the rubber component.
- the filler may include inorganic fillers such as clay, talc, calcium carbonate, and aluminum hydroxide, in addition to silica and carbon black.
- the rubber composition for a tire of the present invention satisfies formula (X): 10 ⁇ A 0.5 +B 1.5 ⁇ 100 ...
- (X) (In the formula, A is the content (parts by mass) of the isoprene skeleton rubber in 100 parts by mass of the rubber component, and B is the bound styrene amount (% by mass) of the styrene-butadiene rubber.) and satisfying the formula (Z): 10 ⁇ A 0.5 +B 1.5 ⁇ 85 ...
- the rubber composition for tires of the present invention satisfies both the formula (X) and the formula (Y) described below, it is possible to provide a product to which the rubber composition for tires is applied with an excellent balance of low fuel consumption performance, wet braking performance, and wear resistance.
- the bound styrene amount of the styrene-butadiene rubber is an average value taking into account their mass ratios.
- n ⁇ (bound styrene amount of SBR n ⁇ content of SBR n ) / ⁇ (content of SBR n ) It can be calculated from:
- [ A0.5 + B1.5 ] in the formula (X) is preferably 15 or more, more preferably 25 or more, even more preferably 30 or more, and particularly preferably 35 or more. From the same viewpoint, it is preferably 85 or less, more preferably 80 or less, even more preferably 75 or less, and particularly preferably 70 or less.
- the value of [A 0.5 + B 1.5 ] in the formula (X) can be adjusted by changing the amounts of various rubbers contained in the rubber component, etc.
- the value of [A 0.5 + B 1.5 ] in the formula (X) can be increased by increasing the content of natural rubber in the rubber component, using a styrene-butadiene rubber with a higher bound styrene content , or, when two or more types of styrene-butadiene rubbers are used, increasing the amount of the styrene-butadiene rubber with a higher bound styrene content.
- the value of [A 0.5 +B 1.5 ] in formula (X) can be reduced by, for example, reducing the content of natural rubber in the rubber component, using a styrene-butadiene rubber with a lower bound styrene content, compounding a rubber other than styrene-butadiene rubber, such as butadiene rubber, and, when two or more types of styrene-butadiene rubber are used, increasing the amount of the styrene-butadiene rubber with the lower bound styrene content.
- the rubber composition for a tire of the present invention satisfies the formula (Y): 0.55 ⁇ C/D ⁇ 0.75 ... (Y) (In the formula, C is the content (parts by mass) of the silica per 100 parts by mass of the rubber component, and D is the content (parts by mass) of the filler per 100 parts by mass of the rubber component.) Meet the following. When the rubber composition for a tire satisfies the above formula (Y), abrasion resistance can be ensured.
- a product to which the rubber composition for a tire is applied can have an excellent balance of fuel economy, wet braking performance, and abrasion resistance.
- [C/D] in the formula (Y) is 0.55 or more, and preferably 0.57 or more. From the same viewpoint, it is 0.75 or less, and preferably 0.73 or less.
- the [C/D] in formula (Y) can be adjusted by adjusting the silica content in the filler, the total amount of filler, etc.
- the rubber composition for tires of the present invention may contain a resin component.
- the resin component is not particularly limited, and various resin components can be used.
- the rubber composition for tires of the present invention contains a resin component, the wet braking performance of a product to which the rubber composition for tires is applied can be improved.
- the resin component is at least partially hydrogenated and that the difference in SP value (solubility parameter) between the resin component and the isoprene skeleton rubber is 1.40 (cal/cm 3 ) 1/2 or less.
- SP value solubility parameter
- compatibility with the isoprene skeleton rubber is increased, the mobility of the rubber component is controlled, and the hysteresis loss (tan ⁇ ) in the low temperature region can be improved, so that the wet braking performance of the product to which the rubber composition for tires is applied is improved.
- the difference in SP value between the resin component and the isoprene skeleton rubber is preferably 1.35 (cal/cm 3 ) 1/2 or less, more preferably 0.50 (cal/cm 3 ) 1/2 or less, more preferably 0.45 (cal/cm 3 ) 1/2 or less, even more preferably 0.3 (cal/cm 3 ) 1/2 or less, and particularly preferably 0.25 (cal/cm 3 ) 1/2 or less.
- the difference in SP value between the resin component and the isoprene skeleton rubber is 0.50 (cal/cm 3 ) 1/2 or less, the compatibility between the resin component and the isoprene skeleton rubber is further improved, and the wet braking performance of a product to which the rubber composition is applied is further improved.
- the SP values (solubility parameters) of the isoprene skeleton rubber and the resin component are calculated according to the Fedors method.
- the mass ratio of the resin component to the isoprene skeleton rubber [mass ratio of resin component/isoprene skeleton rubber] is 0.5 or more.
- the mass ratio of the resin component to the isoprene skeleton rubber [mass ratio of resin component/isoprene skeleton rubber] is preferably 0.65 or more, more preferably 0.7 or more, and more preferably 0.8 or more, and is preferably 2.0 or less, more preferably 1.9 or less, and even more preferably 1.8 or less.
- the content of the resin component is preferably 1 part by mass or more and less than 50 parts by mass per 100 parts by mass of the rubber component.
- the content of the resin component in the rubber composition is 1 part by mass or more per 100 parts by mass of the rubber component, the effect of the resin component is fully expressed, and when it is less than 50 parts by mass, the resin component is less likely to precipitate from the tire, and the effect of the resin component can be fully expressed.
- the content of the resin component in the rubber composition is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, more preferably 9 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 17 parts by mass or more per 100 parts by mass of the rubber component.
- the content of the resin component in the rubber composition is more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less per 100 parts by mass of the rubber component.
- the resin component preferably has a softening point higher than 110° C. and a weight average molecular weight in terms of polystyrene of 200 to 1600 g/mol.
- the softening point of the resin component is measured in accordance with JIS-K2207-1996 (ring and ball method).
- the weight average molecular weight of the resin component is measured by gel permeation chromatography (GPC) and calculated as a polystyrene equivalent value.
- the softening point of the resin component is higher than 110°C, the product to which the rubber composition for tires is applied can be sufficiently reinforced, and the wear resistance can be further improved.
- the softening point of the resin component is preferably 116°C or higher, more preferably 120°C or higher, more preferably 123°C or higher, and even more preferably 127°C or higher.
- the softening point of the resin component is preferably 160°C or lower, more preferably 150°C or lower, more preferably 145°C or lower, more preferably 141°C or lower, and even more preferably 136°C or lower.
- the polystyrene-equivalent weight average molecular weight of the resin component is preferably 500 g/mol or more, more preferably 550 g/mol or more, even more preferably 600 g/mol or more, still more preferably 650 g/mol or more, and still more preferably 700 g/mol or more.
- the polystyrene-equivalent weight average molecular weight of the resin component is more preferably 1570 g/mol or less, more preferably 1530 g/mol or less, more preferably 1500 g/mol or less, more preferably 1470 g/mol or less, more preferably 1430 g/mol or less, more preferably 1400 g/mol or less, more preferably 1370 g/mol or less, more preferably 1330 g/mol or less, more preferably 1300 g/mol or less, more preferably 1200 g/mol or less, more preferably 1100 g/mol or less, more preferably 1000 g/mol or less, and even more preferably 950 g/mol or less.
- the ratio (Ts HR /Mw HR ) of the softening point (Ts HR ) (unit: ° C.) of the resin component to the polystyrene-equivalent weight average molecular weight (Mw HR ) (unit: g/mol) of the resin component is preferably 0.07 or more, more preferably 0.083 or more, more preferably 0.095 or more, more preferably 0.104 or more, more preferably 0.125 or more, more preferably 0.135 or more, more preferably 0.14 or more, and even more preferably 0.141 or more.
- the ratio (Ts HR /Mw HR ) is preferably 0.25 or less, preferably 0.24 or less, preferably 0.23 or less, preferably 0.19 or less, more preferably 0.18 or less, and even more preferably 0.17 or less.
- the polystyrene-equivalent weight average molecular weight is calculated by measuring the average molecular weight of the resin by gel permeation chromatography (GPC) under the following conditions. Column temperature: 40°C Injection volume: 50 ⁇ L Carrier and flow rate: Tetrahydrofuran 0.6 mL/min Sample preparation: Approximately 2.5 mg of resin component was dissolved in 10 mL of tetrahydrofuran.
- the hydrogenated resin component mentioned above means a resin obtained by reducing and hydrogenating a resin.
- resins that can be used as raw materials for the hydrogenated resin component include C5 resins, C5 - C9 resins, C9 resins, terpene resins, dicyclopentadiene resins, terpene-aromatic compound resins, etc. These resins may be used alone or in combination of two or more.
- the C5 resin may be an aliphatic petroleum resin obtained by (co)polymerizing a C5 fraction obtained by thermal cracking 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, and 3-methyl-1-butene, and diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene, etc.
- olefinic hydrocarbons such as 1-pentene, 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene
- diolefinic hydrocarbons such as 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, and 3-methyl-1,2-butadiene, etc.
- the C5 - C9 resin refers to a C5 - C9 synthetic petroleum resin.
- the C5-C9 resin include solid polymers obtained by polymerizing a petroleum-derived C5 - C11 fraction using a Friedel-Crafts catalyst such as AlCl3 or BF3 . More specifically, examples of the C5- C9 resin include copolymers mainly composed of styrene, vinyltoluene, ⁇ -methylstyrene, indene, etc.
- a resin having a small amount of C9 or more components is preferred from the viewpoint of compatibility with the rubber component.
- “having a small amount of C9 or more components” means that the amount of C9 or more components in the total amount of the resin is less than 50 mass%, preferably 40 mass% or less.
- Commercially available C5 - C9 resins can be used.
- the C9 resin refers to a C9 synthetic petroleum resin, for example, a solid polymer obtained by polymerizing a C9 fraction using a Friedel-Crafts type catalyst such as AlCl3 or BF3 .
- Examples of C9 resins include copolymers containing indene, ⁇ -methylstyrene, vinyltoluene, or the like as main components.
- the terpene resin is a solid resin obtained by blending turpentine, which is obtained at the same time as rosin is obtained from pine trees, or a polymerization component separated from this, and polymerizing it using a Friedel-Crafts catalyst, and examples of this include ⁇ -pinene resin and ⁇ -pinene resin.
- a representative example of a terpene-aromatic compound resin is terpene-phenol resin. This terpene-phenol resin can be obtained by reacting terpenes with various phenols using a Friedel-Crafts catalyst, or by further condensing them with formalin.
- terpenes used as raw materials there are no particular restrictions on the terpenes used as raw materials, and monoterpene hydrocarbons such as ⁇ -pinene and limonene are preferred, and those containing ⁇ -pinene are more preferred, with ⁇ -pinene being particularly preferred. Styrene, etc. may also be included in the skeleton.
- the dicyclopentadiene-based resin refers to a resin obtained by polymerizing dicyclopentadiene using a Friedel-Crafts type catalyst such as AlCl3 or BF3 .
- the resin that is the raw material for the hydrogenated resin component may contain, for example, a resin obtained by copolymerizing a C5 fraction with dicyclopentadiene (DCPD) ( C5 -DCPD resin).
- DCPD dicyclopentadiene
- the C5 - DCPD-based resin is considered to be included in the dicyclopentadiene-based resin.
- the C5 - DCPD-based resin is considered to be included in the C5 - based resin.
- the resin component is preferably at least one selected from the group consisting of hydrogenated C5 resins, hydrogenated C5 - C9 resins, hydrogenated dicyclopentadiene resins (hydrogenated DCPD resins), and hydrogenated terpene resins, more preferably at least one selected from the group consisting of hydrogenated C5 resins and hydrogenated C5 - C9 resins, and even more preferably hydrogenated C5 resins.
- the resin is a resin having a hydrogenated DCPD structure or a hydrogenated cyclic structure in at least a monomer.
- the rubber composition for tires of the present invention may further contain a styrene-based thermoplastic elastomer (TPS).
- the styrene-based thermoplastic elastomer (TPS) has a styrene-based polymer block (hard segment) and a conjugated diene-based polymer block (soft segment), and the styrene-based polymer portion forms a physical crosslink to become a crosslinking point, while the conjugated diene-based polymer block imparts rubber elasticity.
- the double bonds of the conjugated diene-based polymer block (soft segment) may be partially or completely hydrogenated.
- the styrene-based thermoplastic elastomer is thermoplastic, whereas the rubber component (preferably, the diene-based rubber) is not thermoplastic, and therefore, in this specification, the styrene-based thermoplastic elastomer (TPS) is not included in the rubber component.
- the content of the styrene-based thermoplastic elastomer (TPS) is preferably in the range of 1 to 30 parts by mass per 100 parts by mass of the rubber component.
- the styrene-based thermoplastic elastomer may be at least one of styrene/butadiene/styrene (SBS) copolymer, styrene/isoprene/styrene (SIS) block copolymer, styrene/butadiene/isoprene/styrene (SBIS) block copolymer, styrene/isoprene (SI) block copolymer, styrene/butadiene/isoprene (SBI) block copolymer, styrene/ethylene/butylene/styrene (SEBS) block copolymer, styrene/ethylene/propylene/styrene (SEPS) block copolymer, styrene/ethylene/ethylene/propylene/styrene (SEEPS) block copolymer, styrene/ethylene/ethylene
- the rubber composition for tires of the present invention may contain, in addition to the above-mentioned rubber component, filler, resin component, and styrene-based thermoplastic elastomer, various components usually used in the rubber industry, such as silane coupling agents, antioxidants, waxes, softeners, processing aids, stearic acid, zinc oxide (zinc oxide), vulcanization accelerators, vulcanizing agents, etc., as necessary, appropriately selected within ranges that do not impair the objects of the present invention. Commercially available products can be suitably used as these compounding agents.
- the rubber composition for tires of the present invention contains silica, it is preferable to contain a silane coupling agent in order to improve the effect of the silica.
- the silane coupling agent include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trime
- the content of the silane coupling agent is preferably in the range of 2 to 20 parts by mass, and more preferably in the range of 5 to 15 parts by mass, per 100 parts by mass of the silica.
- antioxidant examples include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6C), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (TMDQ), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (AW), and N,N'-diphenyl-p-phenylenediamine (DPPD).
- the content of the antioxidant is not particularly limited, and is preferably 0.1 part by mass or more and 5 parts by mass or less, and more preferably 1 part by mass or more and 4 parts by mass or less, per 100 parts by mass of the rubber component.
- the wax examples include paraffin wax, microcrystalline wax, etc.
- the content of the wax is not particularly limited, and is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 1 part by mass or more and 4 parts by mass or less, per 100 parts by mass of the rubber component.
- Zinc oxide (zinc white) The content of the zinc oxide (zinc white) is not particularly limited, and is preferably 0.1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less, per 100 parts by mass of the rubber component.
- Vulcanization accelerator examples include sulfenamide-based vulcanization accelerators, guanidine-based vulcanization accelerators, thiazole-based vulcanization accelerators, thiuram-based vulcanization accelerators, and dithiocarbamate-based vulcanization accelerators. These vulcanization accelerators may be used alone or in combination of two or more.
- the content of the vulcanization accelerator is not particularly limited, and is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.2 parts by mass or more and 4 parts by mass or less, relative to 100 parts by mass of the rubber component.
- the vulcanizing agent examples include sulfur.
- the content of the vulcanizing agent is preferably 2.5 parts by mass or less, and more preferably 1.4 parts by mass or more and 2.5 parts by mass or less, based on 100 parts by mass of the rubber component, in terms of sulfur content.
- the content of the vulcanizing agent is more preferably 1.6 parts by mass or more and 2.3 parts by mass or less, and even more preferably 1.7 parts by mass or more and 2.2 parts by mass or less, based on 100 parts by mass of the rubber component.
- the method for producing the rubber composition for tires is not particularly limited, but for example, the rubber composition can be produced by blending various components appropriately selected as necessary with the above-mentioned rubber component and filler, and kneading, heating, extruding, etc.
- the obtained rubber composition can be vulcanized to produce a vulcanized rubber.
- a rubber composition for tires that satisfies formula (X) can be produced.
- a rubber composition for tires that satisfies formula (Y) can be produced.
- kneading there are no particular limitations on the conditions for the kneading, and the input volume of the kneading device, the rotation speed of the rotor, the ram pressure, etc., as well as the conditions for the kneading temperature, kneading time, type of kneading device, etc., can be appropriately selected according to the purpose.
- kneading devices include Banbury mixers, intermixes, kneaders, rolls, etc., which are typically used for kneading rubber compositions.
- heat-in process temperature heat-in process time
- heat-in process equipment heat-in process equipment
- other conditions can be appropriately selected according to the purpose.
- the heat-in process equipment include a heat-in process roll machine typically used for heat-in process of rubber compositions.
- extrusion conditions there are no particular limitations on the extrusion conditions, and various conditions such as extrusion time, extrusion speed, extrusion equipment, and extrusion temperature can be appropriately selected depending on the purpose.
- extrusion equipment include extruders that are typically used for extruding rubber compositions.
- the extrusion temperature can be appropriately determined.
- Typical vulcanization equipment includes a mold vulcanizer that uses a mold to vulcanize rubber compositions.
- the vulcanization temperature is, for example, about 100 to 190°C.
- the tread rubber of the present invention is characterized in that it uses the above-mentioned rubber composition for tires. Since the tread rubber of the present invention uses the above-mentioned rubber composition for tires, by applying the tread rubber of the present invention to tires, the tire can have an excellent balance of fuel efficiency performance, wet braking performance, and wear resistance.
- the tread rubber of the present invention may be applied to new tires or retread tires.
- the tire of the present invention is characterized by including the above-mentioned tread rubber. Since the tire of the present invention includes the above-mentioned tread rubber, it has an excellent balance of fuel efficiency performance, wet braking performance, and wear resistance.
- the tire of the present invention may be obtained by molding an unvulcanized rubber composition and then vulcanizing it, depending on the type of tire to which it is applied, or may be obtained by molding a semi-vulcanized rubber that has been subjected to a pre-vulcanization step or the like, and then further vulcanizing it.
- the tire of the present invention is preferably a pneumatic tire, and the gas to be filled in the pneumatic tire may be normal air or air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium.
- Bound styrene content The synthesized styrene-butadiene rubber was used as a sample, and 100 mg of the sample was diluted with chloroform to 100 mL and dissolved to prepare a measurement sample. The bound styrene content (mass%) relative to 100 mass% of the sample was measured based on the amount of absorption of ultraviolet light by the phenyl group of styrene at a wavelength (near 254 nm).
- the measurement device used was a spectrophotometer "UV-2450" manufactured by Shimadzu Corporation.
- SP value (solubility parameter)
- SP values (solubility parameters) of natural rubber (isoprene skeleton rubber) and styrene-butadiene rubber were calculated according to the Fedors method.
- SP value (solubility parameter) The SP value (solubility parameter) of the resin component was calculated according to the Fedors method.
- Rubber compositions of Examples and Comparative Examples were prepared by blending and kneading each component according to the formulations shown in Tables 1 and 2.
- the amount of each component is the amount (parts by mass) relative to 100 parts by mass of the rubber component.
- vulcanized rubber test pieces were evaluated for fuel economy, wet braking performance, and abrasion resistance by the following methods.
- the tire rubber composition of the present invention can be used primarily in the tire manufacturing industry.
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Abstract
Description
例えば、特許文献1には、天然ゴムを70質量%以上含むゴム成分に対して、熱可塑性樹脂と、シリカを含む充填剤とを配合してなるゴム組成物を、タイヤのトレッドゴムに適用することで、乾燥路面及び湿潤路面の双方に対するタイヤの制動性能が向上することが開示されている。
さらに、タイヤの経済性の観点から、タイヤ用ゴム組成物の開発にあたっては、低燃費性能及びウェット制動性能に加えて、耐摩耗性能を向上させることも求められている。
また、本発明は、低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスが優れた、かかるトレッドゴムを具えるタイヤを提供することをさらなる課題とする。
前記ゴム成分が、少なくともイソプレン骨格ゴムと、スチレン-ブタジエンゴムと、を含み、
前記充填剤が、少なくともシリカを含み、
下記の式(X):
10≦A0.5+B1.5≦100 ・・・ (X)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
と、
下記の式(Y):
0.55≦C/D≦0.75 ・・・ (Y)
(式中、Cは、前記ゴム成分100質量部に対する前記シリカの含有量(質量部)であり、Dは、前記ゴム成分100質量部に対する前記充填剤の含有量(質量部)である。)
を満たす、タイヤ用ゴム組成物。
10≦A0.5+B1.5≦85 ・・・ (Z)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
を満たす、[1]~[5]のいずれか一つに記載のタイヤ用ゴム組成物。
また、本発明によれば、低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスが優れた、かかるトレッドゴムを具えるタイヤを提供することができる。
本発明のタイヤ用ゴム組成物は、ゴム成分と、充填剤と、を含むゴム組成物である。前記ゴム成分は、少なくともイソプレン骨格ゴムと、スチレン-ブタジエンゴムとを含み、前記充填剤は、少なくともシリカを含む。
さらに、本発明のタイヤ用ゴム組成物は、
下記の式(X):
10≦A0.5+B1.5≦100 ・・・ (X)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
と、
下記の式(Y):
0.55≦C/D≦0.75 ・・・ (Y)
(式中、Cは、前記ゴム成分100質量部に対する前記シリカの含有量(質量部)であり、Dは、前記ゴム成分100質量部に対する前記充填剤の含有量(質量部)である。)
を満たす。
本発明のタイヤ用ゴム組成物においては、ゴム成分がイソプレン骨格ゴムを含有することで、ゴム組成物の破壊強度を高めることができ、その結果、該ゴム組成物を適用した製品の低燃費性能を向上させることができる。また、本発明のタイヤ用ゴム組成物においては、ゴム成分がスチレン-ブタジエンゴムを含むことで、該タイヤ用ゴム組成物を適用した製品の耐摩耗性能を向上させることができる。
更に、本発明のタイヤ用ゴム組成物は、上記式(X)を満たすことで、該タイヤ用ゴム組成物を適用した製品の低燃費性能と、ウェット制動性能とを両立させることができる。また更に、本発明のタイヤ用ゴム組成物は、上記の式(Y)を満たすことにより、耐摩耗性能を確保することができる。
従って、本発明のタイヤ用ゴム組成物は、上記の式(X)及び式(Y)の両方を満たすことで、該タイヤ用ゴム組成物を適用した製品の低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスを優れたものとすることができる。
本発明のタイヤ用ゴム組成物は、ゴム成分を含む。該ゴム成分は、少なくともイソプレン骨格ゴムと、スチレン-ブタジエンゴムとを含む。また、本発明のタイヤ用ゴム組成物は、さらに他のゴム成分を含んでもよい。
前記イソプレン骨格ゴムとは、イソプレン単位を主たる骨格とするゴムである。イソプレン骨格ゴムとしては、例えば天然ゴム(NR)及び合成イソプレンゴム(IR)等が挙げられる。
ゴム成分が、イソプレン骨格ゴムを含有することで、タイヤ用ゴム組成物の破壊強度を高めることができる。その結果、前記タイヤ用ゴム組成物を適用した製品の転がり抵抗を小さくして、低燃費性能を向上させることができ、また、製品の耐摩耗性能を向上させることもできる。
前記ゴム成分は、スチレン-ブタジエンゴム(SBR)を含む。
前記スチレン-ブタジエンゴムの結合スチレン量は、スチレン-ブタジエンゴムの重合に用いる単量体の量及び重合度等により調整することができる。なお、結合スチレン量は、島津製作所社製の分光光度計「UV-2450」を用いて、スチレンのフェニル基による紫外線吸収波長(254nm付近)の吸収量により、試料100質量%に対しての結合スチレン量(質量%)を測定する。
前記スチレン-ブタジエンゴムは、窒素とケイ素とを含む変性剤で変性されていることが好ましい。スチレン-ブタジエンゴムが窒素とケイ素とを含む変性剤で変性されている場合、前記タイヤ用ゴム組成物を適用した製品の低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスを更に向上させ、特には、低燃費性能と耐摩耗性能を更に向上させることができる。
ここで、窒素とケイ素とを含む変性剤とは、少なくとも1つの窒素、及び少なくとも1つのケイ素とを含む変性剤の総称である。
これらの変性剤は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
ここで、前記窒素を含む官能基とアルコキシ基とを有する変性剤とは、少なくとも1つの窒素原子を含む官能基と、少なくとも1つのアルコキシ基とを有する変性剤の総称である。
第一アミノ基、加水分解可能な保護基で保護された第一アミノ基、第一アミンのオニウム塩残基、イソシアネート基、チオイソシアネート基、イミン基、イミン残基、アミド基、加水分解可能な保護基で保護された第二アミノ基、環状第二アミノ基、環状第二アミンのオニウム塩残基、非環状第二アミノ基、非環状第二アミンのオニウム塩残基、イソシアヌル酸トリエステル残基、環状第三アミノ基、非環状第三アミノ基、ニトリル基、ピリジン残基、環状第三アミンのオニウム塩残基及び非環状第三アミンのオニウム塩残基からなる群から選択される官能基を有し、直鎖、分枝、脂環若しくは芳香族環を含む炭素数1~30の1価の炭化水素基、又は酸素原子、硫黄原子及びリン原子から選ばれる少なくとも1種のヘテロ原子を含んでいても良い、直鎖、分枝、脂環又は芳香族環を含む炭素数1~30の1価の炭化水素基である。
前記スチレン-ブタジエンゴム(SBR)は、アミノアルコキシシラン化合物で変性されていることが好ましく、充填剤に対して高い親和性を有する観点から、末端がアミノアルコキシシラン化合物で変性されていることが更に好ましい。スチレン-ブタジエンゴムの末端がアミノアルコキシシラン化合物で変性されている場合、変性スチレン-ブタジエンゴムと充填剤(特には、シリカ)との相互作用が特に大きくなる。
分子末端が変性されたスチレン-ブタジエンゴムは、例えば、国際公開第2003/046020号、特開2007-217562号公報に記載の方法に従って、活性末端を有するスチレン-ブタジエン共重合体の末端に、種々の変性剤を反応させることで製造できる。
部分エステルの原料に用いられる多価アルコールとしては、好ましくは少なくとも3つの水酸基を有する炭素数5又は6の糖類(水素添加されていても、水素添加されていなくてもよい)、グリコールやポリヒドロキシ化合物等が用いられる。また、原料脂肪酸としては、好ましくは炭素数10~20の飽和又は不飽和脂肪酸であり、例えば、ステアリン酸、ラウリン酸、パルミチン酸が用いられる。
多価アルコールの脂肪酸部分エステルの中では、ソルビタン脂肪酸エステルが好ましく、具体的には、ソルビタンモノラウリン酸エステル、ソルビタンモノパルミチン酸エステル、ソルビタンモノステアリン酸エステル、ソルビタントリステアリン酸エステル、ソルビタンモノオレイン酸エステル、ソルビタントリオレイン酸エステル等が挙げられる。
R11 a-Si-(OR12)4-a ・・・ (i)
一般式(i)中、R11及びR12は、それぞれ独立に炭素数1~20の一価の脂肪族炭化水素基又は炭素数6~18の一価の芳香族炭化水素基を示し、R11及びR12の少なくとも1つはアミノ基で置換されており、aは0~2の整数であり、OR12が複数ある場合、各OR12は互いに同一でも異なっていてもよく、また、分子中には活性プロトンは含まれない。
A1は、飽和環状3級アミン化合物残基、不飽和環状3級アミン化合物残基、ケチミン残基、ニトリル基、(チオ)イソシアナート基、イソシアヌル酸トリヒドロカルビルエステル基、ニトリル基、ピリジン基、(チオ)ケトン基、アミド基、並びに加水分解性基を有する第一若しくは第二アミノ基の中から選択される少なくとも1種の官能基である。n4が2以上の場合には、A1は、同一でも異なっていてもよく、A1は、Siと結合して環状構造を形成する二価の基であってもよい。
R21は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、n1が2以上の場合には同一でも異なっていてもよい。
R22は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、いずれも窒素原子及び/又はケイ素原子を含有していてもよい。n2が2以上の場合には、R22は、互いに同一若しくは異なっていてもよいし、或いは、一緒になって環を形成してもよい。
R23は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基、炭素数6~18の一価の芳香族炭化水素基又はハロゲン原子であり、n3が2以上の場合には同一でも異なっていてもよい。
R24は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基であり、n4が2以上の場合には同一でも異なっていてもよい。
加水分解性基を有する第一若しくは第二アミノ基における加水分解性基としては、トリメチルシリル基又はtert-ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。
A2は、NRa(Raは、一価の炭化水素基、加水分解性基又は含窒素有機基である)である。
R25は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基である。
R26は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基、炭素数6~18の一価の芳香族炭化水素基又は含窒素有機基であり、いずれも窒素原子及び/又はケイ素原子を含有していてもよい。p2が2の場合には、R26は、互いに同一でも異なっていてもよいし、或いは、一緒になって環を形成していてもよい。
R27は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基、炭素数6~18の一価の芳香族炭化水素基又はハロゲン原子である。
R28は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
加水分解性基としては、トリメチルシリル基又はtert-ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。
R31は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
R32及びR33は、それぞれ独立して、加水分解性基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基である。
R34は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、q1が2の場合には同一でも異なっていてもよい。
R35は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、q2が2以上の場合には同一でも異なっていてもよい。
R36は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
R37は、ジメチルアミノメチル基、ジメチルアミノエチル基、ジエチルアミノメチル基、ジエチルアミノエチル基、メチルシリル(メチル)アミノメチル基、メチルシリル(メチル)アミノエチル基、メチルシリル(エチル)アミノメチル基、メチルシリル(エチル)アミノエチル基、ジメチルシリルアミノメチル基、ジメチルシリルアミノエチル基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、r1が2以上の場合には同一でも異なっていてもよい。
R38は、炭素数1~20のヒドロカルビルオキシ基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、r2が2の場合には同一でも異なっていてもよい。
一般式(v)で表されるアミノアルコキシシラン化合物の具体例としては、N-(1,3-ジメチルブチリデン)-3-トリエトキシシリル-1-プロパンアミンが挙げられる。
R41は、炭素数1~20のヒドロカルビルオキシ基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基である。
R42は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
ここで、TMSは、トリメチルシリル基を示す(以下、同じ。)。
R45は、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であり、各R45は、同一でも異なっていてもよい。
R46は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
R47及びR48は、それぞれ独立して炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基である。複数のR47又はR48は、同一でも異なっていてもよい。
R49は、炭素数1~20の二価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の二価の芳香族炭化水素基である。
R50及びR51は、それぞれ独立して加水分解性基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基であるか、或いは、R50及びR51は結合して二価の有機基を形成している。
R52及びR53は、それぞれ独立してハロゲン原子、ヒドロカルビルオキシ基、炭素数1~20の一価の脂肪族若しくは脂環式炭化水素基又は炭素数6~18の一価の芳香族炭化水素基である。
R50及びR51としては、加水分解性基が好ましく、加水分解性基として、トリメチルシリル基、tert-ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。
一般式(x)~(xiii)中のR54~92は、同一でも異なっていてもよく、炭素数1~20の一価若しくは二価の脂肪族又は脂環式炭化水素基、或いは炭素数6~18の一価若しくは二価の芳香族炭化水素基である。
一般式(xiii)中のα及びβは、0~5の整数である。
また、一般式(xiii)を満たす化合物の中でも、特に、N,N-ジメチル-2-(3-(ジメトキシメチルシリル)プロポキシ)エタンアミン、N,N-ビス(トリメチルシリル)-2-(3-(トリメトキシシリル)プロポキシ)エタンアミン、N,N-ジメチル-2-(3-(トリメトキシシリル)プロポキシ)エタンアミン、N,N-ジメチル-3-(3-(トリメトキシシリル)プロポキシ)プロパン-1-アミンが好ましい。
前記スチレン-ブタジエンゴム(SBR)は、下記一般式(I)で表されるカップリング剤によって変性されていることも好ましい。この場合、前記タイヤ用ゴム組成物を適用した製品の低燃費性能と耐摩耗性能を更に向上させることができる。
R4、R5、R6、R7及びR9は、それぞれ独立して炭素数1~20のアルキル基を示す。
R8及びR11は、それぞれ独立して炭素数1~20のアルキレン基を示す。
R10は、炭素数1~20の、アルキル基又はトリアルキルシリル基を示す。
mは、1~3の整数を示し、pは、1又は2を示す。
R1~R11、m及びpは、複数存在する場合、それぞれ独立している。
i、j及びkは、それぞれ独立して0~6の整数を示す。但し、(i+j+k)は、3~10の整数である。
Aは、炭素数1~20の、炭化水素基、又は、酸素原子、窒素原子、ケイ素原子、硫黄原子及びリン原子からなる群から選択される少なくとも一種の原子を有し、活性水素を有しない有機基を示す。
ここで、一般式(I)中、Aが示す炭化水素基は、飽和、不飽和、脂肪族、及び芳香族の炭化水素基を包含する。活性水素を有しない有機基としては、例えば、水酸基(-OH)、第2級アミノ基(>NH)、第1級アミノ基(-NH2)、スルフヒドリル基(-SH)等の活性水素を有する官能基、を有しない有機基が挙げられる。
前記収縮因子(g’)は、好ましくは0.64未満であり、より好ましくは0.63以下であり、より好ましくは0.60以下であり、より一層好ましくは0.59以下であり、特に好ましくは0.57以下である。また、収縮因子(g’)の下限は、特に限定されず、検出限界値以下であってもよいが、好ましくは0.30以上であり、より好ましくは0.33以上であり、より一層好ましくは0.35以上であり、特に好ましくは0.45以上である。収縮因子(g’)がこの範囲である変性スチレン-ブタジエンゴムを使用することで、ゴム組成物の加工性が向上する。
収縮因子(g’)は分岐度に依存する傾向にあるため、例えば、分岐度を指標として収縮因子(g’)を制御することができる。具体的には、分岐度が6である変性スチレン-ブタジエンゴムとした場合には、その収縮因子(g’)は0.59以上0.63以下となる傾向にあり、分岐度が8である変性スチレン-ブタジエンゴムとした場合には、その収縮因子(g’)は0.45以上0.59以下となる傾向にある。
また、前記変性スチレン-ブタジエンゴムは、分岐を有し、分岐度が6以上であることがより好ましい。また、変性スチレン-ブタジエンゴムは、1以上のカップリング残基と、該カップリング残基に対して結合するスチレン-ブタジエン共重合体鎖とを有し、更に、上記分岐が、1の当該カップリング残基に対して6以上の当該スチレン-ブタジエン共重合体鎖が結合している分岐を含むことが、更に好ましい。分岐度が6以上であること、及び、分岐が、1のカップリング残基に対して6以上のスチレン-ブタジエン共重合体鎖が結合している分岐を含むよう、変性スチレン-ブタジエンゴムの構造を特定することにより、収縮因子(g’)を0.63以下にすることができる。
更に、前記変性スチレン-ブタジエンゴムは、分岐を有し、分岐度が7以上であることが更に好ましく、分岐度が8以上であることがより一層好ましい。分岐度の上限は、特に限定されないが、18以下であることが好ましい。また、変性スチレン-ブタジエンゴムは、1以上のカップリング残基と、該カップリング残基に対して結合するスチレン-ブタジエン共重合体鎖とを有し、更に、上記分岐が、1の当該カップリング残基に対して7以上の当該スチレン-ブタジエン共重合体鎖が結合している分岐を含むことが、より一層好ましく、1の当該カップリング残基に対して8以上の当該スチレン-ブタジエン共重合体鎖が結合している分岐を含むことが特に好ましい。分岐度が8以上であること、及び、分岐が、1のカップリング残基に対して8以上のスチレン-ブタジエン共重合体鎖が結合している分岐を含むよう、変性スチレン-ブタジエンゴムの構造を特定することにより、収縮因子(g’)を0.59以下にすることができる。
なお、本明細書において、ゴム成分の「分子量」とは、GPC(ゲルパーミエーションクロマトグラフィー)によって得られる、標準ポリスチレン換算分子量である。特定の高分子量成分の含有量がこのような範囲にある変性スチレン-ブタジエンゴムを得るためには、後述する重合工程と反応工程とにおける反応条件を制御することが好ましい。例えば、重合工程においては、後述する有機モノリチウム化合物の重合開始剤としての使用量を調整すればよい。また、重合工程において、連続式、及び回分式のいずれの重合様式においても、滞留時間分布を有する方法を用いる、即ち、成長反応の時間分布を広げるとよい。
前記スチレン-ブタジエン共重合体は、1,3-ブタジエンとスチレンを共重合して得られる。
前記有機モノリチウム化合物は、工業的入手の容易さ及び重合反応のコントロールの容易さの観点から、好ましくは、アルキルリチウム化合物である。この場合、重合開始末端にアルキル基を有する、スチレン-ブタジエン共重合体が得られる。アルキルリチウム化合物としては、例えば、n-ブチルリチウム、sec-ブチルリチウム、tert-ブチルリチウム、n-ヘキシルリチウム、ベンジルリチウム、フェニルリチウム、及びスチルベンリチウムが挙げられる。アルキルリチウム化合物としては、工業的入手の容易さ及び重合反応のコントロールの容易さの観点から、n-ブチルリチウム、及びsec-ブチルリチウムが好ましい。これらの有機モノリチウム化合物は、1種単独で用いてもよいし、2種以上を併用してもよい。
前記極性化合物としては、例えば、テトラヒドロフラン、ジエチルエーテル、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル、ジメトキシベンゼン、2,2-ビス(2-オキソラニル)プロパン等のエーテル類;テトラメチルエチレンジアミン、ジピペリジノエタン、トリメチルアミン、トリエチルアミン、ピリジン、キヌクリジン等の第3級アミン化合物;カリウム-tert-アミラート、カリウム-tert-ブチラート、ナトリウム-tert-ブチラート、ナトリウムアミラート等のアルカリ金属アルコキシド化合物;トリフェニルホスフィン等のホスフィン化合物等を用いることができる。これらの極性化合物は、1種単独で用いてもよいし、2種以上を併用してもよい。
なお、結合ブタジエン量は、結合スチレン量をフェニル基の紫外吸光によって測定でき、ここから結合ブタジエン量を求めることができる。
なお、変性スチレン-ブタジエンゴムについては、ハンプトンの方法[R.R.Hampton,Analytical Chemistry,21,923(1949)]により、ブタジエン結合単位中のビニル結合量(1,2-結合量)を求めることができる。
前記反応工程における反応時間は、好ましくは10秒以上であり、より好ましくは30秒以上である。重合工程の終了時から反応工程の開始時までの時間は、カップリング率の観点から、より短い方が好ましいが、より好ましくは5分以内である。
反応工程における混合は、機械的な攪拌、スタティックミキサーによる攪拌等のいずれでもよい。重合工程が連続式である場合は、反応工程も連続式であることが好ましい。反応工程における反応器は、例えば、撹拌機付きの槽型、管型のものが用いられる。カップリング剤は、不活性溶媒により希釈して反応器に連続的に供給してもよい。重合工程が回分式の場合は、重合反応器にカップリング剤を投入する方法でも、別の反応器に移送して反応工程を行ってもよい。
より好ましくは、前記一般式(I)において、Aは、前記一般式(II)又は(III)で表され、kは、0を示し、前記一般式(II)又は(III)において、aは、2~10の整数を示す。
より一層好ましくは、前記一般式(I)において、Aは、前記一般式(II)で表され、kは、0を示し、前記一般式(II)において、aは、2~10の整数を示す。
かかるカップリング剤としては、例えば、ビス(3-トリメトキシシリルプロピル)-[3-(2,2-ジメトキシ-1-アザ-2-シラシクロペンタン)プロピル]アミン、トリス(3-トリメトキシシリルプロピル)アミン、トリス(3-トリエトキシシリルプロピル)アミン、トリス(3-トリメトキシシリルプロピル)-[3-(2,2-ジメトキシ-1-アザ-2-シラシクロペンタン)プロピル]-1,3-プロパンジアミン、テトラキス[3-(2,2-ジメトキシ-1-アザ-2-シラシクロペンタン)プロピル]-1,3-プロパンジアミン、テトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミン、テトラキス(3-トリメトキシシリルプロピル)-1,3-ビスアミノメチルシクロヘキサン、トリス(3-トリメトキシシリルプロピル)-メチル-1,3-プロパンジアミン、ビス[3-(2,2-ジメトキシ-1-アザ-2-シラシクロペンタン)プロピル]-(3-トリスメトキシシリルプロピル)-メチル-1,3-プロパンジアミン等が挙げられ、これらの中でも、テトラキス(3-トリメトキシシリルプロピル)-1,3-プロパンジアミン、テトラキス(3-トリメトキシシリルプロピル)-1,3-ビスアミノメチルシクロヘキサンが特に好ましい。
前記変性スチレン-ブタジエンゴムのGPCによるピーク分子量をMp1、スチレン-ブタジエン共重合体のピーク分子量をMp2とした場合、以下の式が成り立つことが好ましい。
(Mp1/Mp2)<1.8×10-12×(Mp2-120×104)2+2
Mp2は、20×104以上80×104以下、Mp1は30×104以上150×104以下がより好ましい。
なお、Mp1及びMp2は、ゲル透過クロマトグラフィー(GPC)により算出する。
また、前記変性スチレン-ブタジエンゴムは、重合後のゲル生成を防止する観点、及び加工時の安定性を向上させる観点から、例えば、2,6-ジ-tert-ブチル-4-ヒドロキシトルエン(BHT)、n-オクタデシル-3-(4’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェノール)プロピネート、2-メチル-4,6-ビス[(オクチルチオ)メチル]フェノール等の酸化防止剤を添加することが好ましい。
R12、R13及びR14は、各々独立に、単結合又は炭素数1~20のアルキレン基を示す。
R15及びR18は、各々独立に、炭素数1~20のアルキル基を示す。
R16、R19、及びR20は、各々独立に、水素原子又は炭素数1~20のアルキル基を示す。
R17及びR21は、各々独立に、炭素数1~20のアルキレン基を示す。
R22は、水素原子又は炭素数1~20のアルキル基を示す。
m及びxは、1~3の整数を示し、x≦mであり、pは、1又は2を示し、yは1~3の整数を示し、y≦(p+1)であり、zは、1又は2の整数を示す。
それぞれ複数存在する場合のD、R12~R22、m、p、x、y、及びzは、各々独立しており、同じであっても異なっていてもよい。
また、iは、0~6の整数を示し、jは0~6の整数を示し、kは0~6の整数を示し、(i+j+k)は3~10の整数であり、((x×i)+(y×j)+(z×k))は、5~30の整数である。
Aは、炭素数1~20の炭化水素基、又は、酸素原子、窒素原子、ケイ素原子、硫黄原子、及びリン原子からなる群より選ばれる少なくとも1種の原子を有し、かつ、活性水素を有しない有機基を示す。Aが示す炭化水素基は、飽和、不飽和、脂肪族、及び芳香族の炭化水素基を包含する。上記活性水素を有しない有機基としては、例えば、水酸基(-OH)、第2級アミノ基(>NH)、第1級アミノ基(-NH2)、スルフヒドリル基(-SH)等の活性水素を有する官能基、を有しない有機基が挙げられる。
前記スチレン-ブタジエンゴム(SBR)は、少なくとも一方の末端が以下の一般式(1)で表される化合物(アルコキシシラン)を含む変性剤で変性されていることも好ましい。
より具体的には、前記R1~R4は、置換又は非置換の炭素数1~10のアルキル基であってもよく、さらに具体的には、前記R1~R4は、それぞれ独立して置換又は非置換の、炭素数1~6のアルキル基であってもよい。
なお、前記R5~R8がアルキル基ではなく、加水分解可能な置換基の場合、N-R5R6及びN-R7R8の結合が水分存在下でN-Hに加水分解され、重合体の加工性に悪影響を及ぼし得る。
なお、前記R5~R8にアミノ基を保護するための保護基が結合するか、又は、水素が結合する場合には、前記式(1)で表される化合物による効果の具現が難しい可能性がある。水素が結合する場合、変性過程で陰イオンが水素と反応して反応性を失うようになって変性反応自体が不可能となり、保護基が結合する場合、変性反応が行われるが、重合体末端に結合した状態で後加工時に加水分解によって脱保護されて1級又は2級アミノ基になり、脱保護された1級又は2級アミノ基は、その後の配合時に配合物の高粘度化を引き起こし、加工性低下の原因になるおそれがある。
より具体的には、L1及びL2は、それぞれ独立して炭素数1~10のアルキレン基、更に具体的には、メチレン基、エチレン基又はプロピレン基のような炭素数1~6のアルキレン基とすることができる。
また、前記重量平均分子量及び数平均分子量は、それぞれゲル透過クロマトグラフィ(GPC)で分析されるポリスチレン換算分子量である。
前記変性スチレン-ブタジエンゴムの重量平均分子量(Mw)が100,000g/mol以上、及び数平均分子量(Mn)が50,000g/mol以上の場合、ゴム組成物に適用する際の引張特性の低下を抑えることができる。また、重量平均分子量(Mw)が4,000,000g/mol以下、及び数平均分子量(Mn)が2,000,000g/mol以下の場合には、変性スチレン-ブタジエンゴムの加工性の低下を抑えることができ、ゴム組成物の作業性が悪化せず、また、ゴム組成物の物性を十分に向上させることができる。
より具体的には、前記変性スチレン-ブタジエンゴムは、前記分子量分布とともに、重量平均分子量(Mw)及び数平均分子量(Mn)の条件を同時に満たしている場合には、ゴム組成物に適用した場合、ゴム組成物の粘弾性と加工性をバランスよく改善させることができる。
前記ムーニー粘度は、ムーニー粘度計、例えば、Monsanto社のMV2000Eで、100℃、ローター速度2±0.02rpmで、大ローターを使って測定することができる。このとき用いられた試料は、室温(23±3℃)で30分以上放置した後、27±3gを採取して、ダイキャビティの内部に満たしておき、プラテンを作動させて測定することができる。
また、式(2)において、R12は、単結合;置換基で置換又は非置換の炭素数1~20のアルキレン基;置換基で置換又は非置換の炭素数5~20のシクロアルキレン基;又は置換基で置換又は非置換の炭素数5~20のアリーレン基であり、ここで、上記置換基は、炭素数1~10のアルキル基、炭素数5~10のシクロアルキル基、又は炭素数6~20のアリール基である。
また、式(2)において、R13は、炭素数1~30のアルキル基;炭素数2~30のアルケニル基;炭素数2~30のアルキニル基;炭素数1~30のヘテロアルキル基;炭素数2~30のヘテロアルケニル基;炭素数2~30のヘテロアルキニル基;炭素数5~30のシクロアルキル基;炭素数6~30のアリール基;炭素数3~30の複素環基;又は下記一般式(2a)若しくは一般式(2b)で表される作用基であり、mは1~5の整数であり、R13のうち少なくとも1つは、下記一般式(2a)若しくは一般式(2b)で表される作用基であり、mが2~5の整数の場合、複数のR13は、互いに同一であっても、異なってもよい。
また、式(2a)において、R15及びR16は、互いに独立に、炭素数1~10のアルキル基、炭素数5~10のシクロアルキル基、又は炭素数6~20のアリール基で置換又は非置換の炭素数1~20のアルキレン基である。
また、式(2a)において、R17は、水素;炭素数1~30のアルキル基;炭素数2~30のアルケニル基;炭素数2~30のアルキニル基;炭素数1~30のヘテロアルキル基;炭素数2~30のヘテロアルケニル基;炭素数2~30のヘテロアルキニル基;炭素数5~30のシクロアルキル基;炭素数6~30のアリール基;炭素数3~30の複素環基であり、Xは、N、O又はS原子であり、但し、XがO又はSである場合、R17は存在しない。
また、式(2b)において、R19及びR20は、互いに独立に、炭素数1~30のアルキル基;炭素数2~30のアルケニル基;炭素数2~30のアルキニル基;炭素数1~30のヘテロアルキル基;炭素数2~30のヘテロアルケニル基;炭素数2~30のヘテロアルキニル基;炭素数5~30のシクロアルキル基;炭素数6~30のアリール基;炭素数3~30の複素環基である。
具体的には、例えば、炭化水素溶媒中で、式(2)で表される化合物を含む変性剤の存在下にて、ブタジエン単量体及びスチレン単量体を重合させることで、式(2)で表される化合物由来の変性基を、前記スチレン-ブタジエン共重体に付与することができる。
前記ゴム成分は、前記イソプレン骨格ゴム及び前記スチレン-ブタジエンゴムに加えて、更に他のゴムを含んでもよい。該他のゴムの具体例としては、ブタジエンゴム(BR)、クロロプレンゴム(CR)、ブチルゴム(IIR)、ハロゲン化ブチルゴム、エチレン-プロピレンゴム(EPR、EPDM)、フッ素ゴム、シリコーンゴム、ウレタンゴム等が挙げられる。
なお、上述のとおり、他のゴムとしてブタジエンゴム(BR)を含むこともできるが、ウェット制動性能の低下を防ぐ観点から、ブタジエンゴム(BR)を含まないことが好ましい。ゴム成分がブタジエンゴムを含まないことで、ウェット制動性能の低下を抑えることができる。
本発明のタイヤ用ゴム組成物は、充填剤を含む。充填剤を含むことで、ゴム組成物の補強性が向上する。該充填剤としては、例えばシリカ、カーボンブラック等が挙げられる。
前記タイヤ用ゴム組成物中の充填剤の含有量は、前記ゴム成分100質量部に対して、40~125質量部の範囲が好ましい。充填剤の含有量が、前記ゴム成分100質量部に対して、40質量部以上であると、前記タイヤ用ゴム組成物を適用したタイヤの補強が十分であり、耐摩耗性能を更に向上させることができる。また、充填剤の含有量が、前記ゴム成分100質量部に対して、125質量部以下であると、ウェット制動性能を更に向上させることができる。タイヤの転がり抵抗をより低くする観点(低燃費性能を向上させる観点)から、タイヤ用ゴム組成物中の充填剤の含有量は、ゴム成分100質量部に対し、45質量部以上であることがより好ましく、50質量部以上であることがより好ましく、55質量部以上であることが更に好ましい。また、タイヤのウェット制動性能を向上させる観点から、タイヤ用ゴム組成物中の充填剤の含有量は、ゴム成分100質量部に対し、120質量部以下であることがより好ましく、115質量部以下であることがより好ましく、100質量部未満であることが更に好ましい。
前記充填剤は、シリカを含有する。該シリカとしては、例えば湿式シリカ(含水ケイ酸)、乾式シリカ(無水ケイ酸)、ケイ酸カルシウム、ケイ酸アルミニウム等が挙げられる。これらの中でも、湿式シリカが好ましい。また、これらのシリカは、一種単独で用いてもよいし、二種以上を併用してもよい。
前記充填剤は、カーボンブラックを含んでいてもよい。該カーボンブラックは、タイヤ用ゴム組成物を補強して、該タイヤ用ゴム組成物を適用した製品の耐摩耗性能を向上させることができる。
カーボンブラックとしては、特に限定されるものではなく、例えばGPF、FEF、HAF、ISAF及びSAFグレードのカーボンブラックが挙げられる。これらのカーボンブラックは、1種単独で用いてもよいし、2種以上を併用してもよい。
前記充填剤は、シリカ及びカーボンブラック以外に、クレー、タルク、炭酸カルシウム、及び水酸化アルミニウム等の無機充填剤を含んでいてもよい。
本発明のタイヤ用ゴム組成物は、式(X):10≦A0.5+B1.5≦100 ・・・ (X)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
を満たし、式(Z):10≦A0.5+B1.5≦85 ・・・ (Z)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
を満たすことが好ましい。
本発明のタイヤ用ゴム組成物が前記式(X)を満たすことにより、低燃費性能と、ウェット制動性能とを両立させることができ、更には、前記式(Z)を満たすことにより、低燃費性能を向上させることができる。また、本発明のタイヤ用ゴム組成物が式(X)及び下記で説明する式(Y)をいずれも満たすことで、該タイヤ用ゴム組成物を適用した製品の低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスを優れたものとすることができる。
2種のスチレン-ブタジエンゴムを、それぞれスチレン-ブタジエンゴム1、及びスチレン-ブタジエンゴム2とすると、
B=x×a/(a+b)+y×b/(a+b)
(x:スチレン-ブタジエンゴム1の結合スチレン量(質量%)
y:スチレン-ブタジエンゴム2の結合スチレン量(質量%)
a:スチレン-ブタジエンゴム1の含有量(質量部)
b:スチレン-ブタジエンゴム2の含有量(質量部))
となる。
同様に、n種のスチレン-ブタジエンゴムを使用するときには、n種類目のスチレン-ブタジエンゴムを「SBRn」とすると、以下の式:
B=Σ(SBRnの結合スチレン量×SBRnの含有量)/Σ(SBRnの含有量)
から算出することができる。
本発明のタイヤ用ゴム組成物は、式(Y):0.55≦C/D≦0.75 ・・・ (Y)
(式中、Cは、前記ゴム成分100質量部に対する前記シリカの含有量(質量部)であり、Dは、前記ゴム成分100質量部に対する前記充填剤の含有量(質量部)である。)
を満たす。
タイヤ用ゴム組成物が上記式(Y)を満たすことにより、耐摩耗性能を確保することができる。また、タイヤ用ゴム組成物が上記で説明した式(X)及び式(Y)をいずれも満たすことで、該タイヤ用ゴム組成物を適用した製品の低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスを優れたものとすることができる。
本発明のタイヤ用ゴム組成物は、樹脂成分を含んでもよい。該樹脂成分としては、特に限定されるものではなく、種々の樹脂成分を使用することができる。本発明のタイヤ用ゴム組成物が樹脂成分を含むことで、該タイヤ用ゴム組成物を適用した製品のウェット制動性能を向上させることができる。
なお、前記イソプレン骨格ゴム及び樹脂成分のSP値(溶解度パラメータ)は、Fedors法に従って、算出する。
ここで、樹脂成分の軟化点は、JIS-K2207-1996(環球法)に準拠して測定する。
また、樹脂成分の重量平均分子量は、ゲル透過クロマトグラフィー(GPC)により測定し、ポリスチレン換算の値を算出する。
前記樹脂成分のポリスチレン換算の重量平均分子量は、タイヤからの樹脂成分の析出を抑制し、タイヤ外観の低下を抑制する観点から、500g/mol以上であることが好ましく、550g/mol以上であることがより好ましく、600g/mol以上であることがより好ましく、650g/mol以上であることがより好ましく、700g/mol以上であることがより一層好ましい。また、ゴム成分への樹脂成分の相溶性を高め、樹脂成分による効果をより高める観点から、樹脂成分のポリスチレン換算の重量平均分子量は、1570g/mol以下であることがより好ましく、1530g/mol以下であることがより好ましく、1500g/mol以下であることがより好ましく、1470g/mol以下であることがより好ましく、1430g/mol以下であることがより好ましく、1400g/mol以下であることがより好ましく、1370g/mol以下であることがより好ましく、1330g/mol以下であることがより好ましく、1300g/mol以下であることがより好ましく、1200g/mol以下であることがより好ましく、1100g/mol以下であることがより好ましく、1000g/mol以下であることがより好ましく、950g/mol以下であることがより一層好ましい。
なお、ポリスチレン換算の重量平均分子量は、以下の条件で、ゲル透過クロマトグラフィー(GPC)により、樹脂の平均分子量を測定し、ポリスチレン換算の重量平均分子量を算出する。
・カラム温度:40℃
・注入量:50μL
・キャリアー及び流速:テトラヒドロフラン 0.6mL/min
・サンプル調製:樹脂成分約2.5mgをテトラヒドロフラン10mLに溶解
水素添加されている樹脂成分の原料となる樹脂としては、C5系樹脂、C5-C9系樹脂、C9系樹脂、テルペン系樹脂、ジシクロペンタジエン系樹脂、テルペン-芳香族化合物系樹脂等が挙げられる。これら樹脂は1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
C5留分には、通常1-ペンテン、2-ペンテン、2-メチル-1-ブテン、2-メチル-2-ブテン、3-メチル-1-ブテン等のオレフィン系炭化水素、2-メチル-1,3-ブタジエン、1,2-ペンタジエン、1,3-ペンタジエン、3-メチル-1,2-ブタジエン等のジオレフィン系炭化水素等が含まれる。なお、C5系樹脂は、市販品を利用することができる。
C5-C9系樹脂としては、C9以上の成分の少ない樹脂が、ゴム成分との相溶性の観点から好ましい。ここで、「C9以上の成分が少ない」とは、樹脂全量中のC9以上の成分が50質量%未満、好ましくは40質量%以下であることを言うものとする。C5-C9系樹脂は、市販品を利用することができる。
C9系樹脂としては、例えば、インデン、α-メチルスチレン、ビニルトルエン等を主成分とする共重合体等が挙げられる。
ここで、樹脂全量中のジシクロペンタジエン由来成分が50質量%以上の場合、C5-DCPD系樹脂はジシクロペンタジエン系樹脂に含まれるものとする。樹脂全量中のジシクロペンタジエン由来成分が50質量%未満の場合、C5-DCPD系樹脂はC5系樹脂に含まれるものとする。更に第三成分等が少量含まれる場合でも同様である。
本発明のタイヤ用ゴム組成物は、さらにスチレン系熱可塑性エラストマー(TPS)を含んでもよい。該スチレン系熱可塑性エラストマー(TPS)は、スチレン系重合体ブロック(ハードセグメント)と、共役ジエン系重合体ブロック(ソフトセグメント)とを有し、スチレン系重合体部分が物理架橋を形成して橋かけ点となり、一方、共役ジエン系重合体ブロックがゴム弾性を付与する。共役ジエン系重合体ブロック(ソフトセグメント)の二重結合は、一部又は全部が水素化されていてもよい。
なお、スチレン系熱可塑性エラストマー(TPS)は、熱可塑性である一方、前記ゴム成分(好ましくは、ジエン系ゴム)は、熱可塑性ではない。そのため、本明細書においては、スチレン系熱可塑性エラストマー(TPS)は、前記ゴム成分に含めないものとする。
本発明のタイヤ用ゴム組成物は、既述のゴム成分、充填剤、樹脂成分、スチレン系熱可塑性エラストマーに加え、必要に応じて、ゴム工業界で通常使用される各種成分、例えばシランカップリング剤、老化防止剤、ワックス、軟化剤、加工助剤、ステアリン酸、酸化亜鉛(亜鉛華)、加硫促進剤、加硫剤等を、本発明の目的を害しない範囲内で適宜選択して含有していてもよい。これらの配合剤としては、市販品を好適に使用することができる。
本発明のタイヤ用ゴム組成物はシリカを含むため、該シリカの効果を向上させるために、シランカップリング剤を含むことが好ましい。該シランカップリング剤としては、ビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(3-トリエトキシシリルプロピル)トリスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィド、ビス(2-トリエトキシシリルエチル)テトラスルフィド、ビス(3-トリメトキシシリルプロピル)テトラスルフィド、ビス(2-トリメトキシシリルエチル)テトラスルフィド、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリエトキシシラン、2-メルカプトエチルトリメトキシシラン、2-メルカプトエチルトリエトキシシラン、3-トリメトキシシリルプロピル-N,N-ジメチルチオカルバモイルテトラスルフィド、3-トリエトキシシリルプロピル-N,N-ジメチルチオカルバモイルテトラスルフィド、2-トリエトキシシリルエチル-N,N-ジメチルチオカルバモイルテトラスルフィド、3-トリメトキシシリルプロピルベンゾチアゾリルテトラスルフィド、3-トリエトキシシリルプロピルベンゾチアゾリルテトラスルフィド、3-トリエトキシシリルプロピルメタクリレートモノスルフィド、3-トリメトキシシリルプロピルメタクリレートモノスルフィド、ビス(3-ジエトキシメチルシリルプロピル)テトラスルフィド、3-メルカプトプロピルジメトキシメチルシラン、ジメトキシメチルシリルプロピル-N,N-ジメチルチオカルバモイルテトラスルフィド、ジメトキシメチルシリルプロピルベンゾチアゾリルテトラスルフィド等が挙げられる。
前記老化防止剤としては、N-(1,3-ジメチルブチル)-N’-フェニル-p-フェニレンジアミン(6C)、2,2,4-トリメチル-1,2-ジヒドロキノリン重合体(TMDQ)、6-エトキシ-2,2,4-トリメチル-1,2-ジヒドロキノリン(AW)、N,N’-ジフェニル-p-フェニレンジアミン(DPPD)等が挙げられる。
該老化防止剤の含有量は、特に制限はなく、前記ゴム成分100質量部に対して、0.1質量部以上5質量部以下であることが好ましく、1質量部以上4質量部以下であることがより好ましい。
前記ワックスとしては、例えば、パラフィンワックス、マイクロクリスタリンワックス等が挙げられる。該ワックスの含有量は、特に制限はなく、前記ゴム成分100質量部に対して、0.1質量部以上5質量部以下であることが好ましく、1質量部以上4質量部以下であることがより好ましい。
前記酸化亜鉛(亜鉛華)の含有量は、特に制限はなく、前記ゴム成分100質量部に対して、0.1質量部以上10質量部以下であることが好ましく、1質量部以上8質量部以下であることがより好ましい。
前記加硫促進剤としては、スルフェンアミド系加硫促進剤、グアニジン系加硫促進剤、チアゾール系加硫促進剤、チウラム系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤等が挙げられる。これら加硫促進剤は、1種単独で使用してもよく、2種以上を併用してもよい。該加硫促進剤の含有量は、特に制限はなく、前記ゴム成分100質量部に対して、0.1質量部以上5質量部以下であることが好ましく、0.2質量部以上4質量部以下であることがより好ましい。
前記加硫剤としては、硫黄等が挙げられる。該加硫剤の含有量は、前記ゴム成分100質量部に対して、硫黄分として2.5質量部以下であることが好ましく、1.4質量部以上2.5質量部以下であることが更に好ましい。加硫剤の含有量が前記範囲であると、ウェット制動性能の低下を抑制することができる。また、加硫剤の含有量は、前記ゴム成分100質量部に対して、1.6質量部以上2.3質量部以下であることがより好ましく、1.7質量部以上2.2質量部以下であることがより一層好ましい。
前記タイヤ用ゴム組成物の製造方法は、特に限定されるものではないが、例えば、既述のゴム成分及び充填剤に、必要に応じて適宜選択した各種成分を配合して、混練り、熱入れ、押出等することにより製造することができる。また、得られたゴム組成物を加硫することで、加硫ゴムとすることができる。
本発明のトレッドゴムは、上記のタイヤ用ゴム組成物を用いることを特徴とする。かかる本発明のトレッドゴムは、上記のタイヤ用ゴム組成物を用いるため、タイヤに適用することで、該タイヤの低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスを優れたものとすることができる。
なお、本発明のトレッドゴムは、新品タイヤに適用してもよいし、更生タイヤに適用してもよい。
本発明のタイヤは、上記のトレッドゴムを具えることを特徴とする。かかる本発明のタイヤは、上記のトレッドゴムを具えるため、低燃費性能と、ウェット制動性能と、耐摩耗性能とのバランスが優れている。
本発明のタイヤは、適用するタイヤの種類に応じ、未加硫のゴム組成物を用いて成形後に加硫して得てもよく、又は予備加硫工程等を経た半加硫ゴムを用いて成形後、さらに本加硫して得てもよい。なお、本発明のタイヤは、好ましくは空気入りタイヤであり、空気入りタイヤに充填する気体としては、通常の或いは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。
ゴム成分について、以下の方法により分析を行った。
合成したスチレン-ブタジエンゴムを試料として、試料100mgを、クロロホルムで100mLにメスアップし、溶解して測定サンプルとした。スチレンのフェニル基による紫外線吸収波長(254nm付近)の吸収量により、試料100質量%に対しての結合スチレン量(質量%)を測定した。なお、測定装置として、島津製作所社製の分光光度計「UV-2450」を用いた。
合成したスチレン-ブタジエンゴムを試料として、TAインスツルメンツ社製DSC250を用い、ヘリウム50mL/分の流通下、-100℃から20℃/分で昇温しながらDSC曲線を記録し、DSC微分曲線のピークトップ(Inflection point)をガラス転移温度とした。
天然ゴム(イソプレン骨格ゴム)及びスチレン-ブタジエンゴムのSP値(溶解度パラメータ)は、Fedors法に従って算出した。
樹脂成分について、以下の方法により分析を行った。
樹脂成分の軟化点は、JIS-K2207-1996(環球法)に準拠して測定した。
以下の条件で、ゲル透過クロマトグラフィー(GPC)により、樹脂成分の平均分子量を測定し、ポリスチレン換算の重量平均分子量を算出した。
・カラム温度:40℃
・注入量:50μL
・キャリアー及び流速:テトラヒドロフラン 0.6mL/min
・サンプル調製:樹脂成分約2.5mgをテトラヒドロフラン10mLに溶解
樹脂成分のSP値(溶解度パラメータ)は、Fedors法に従って算出した。
下記表1及び表2に示す配合処方に従って、各成分を配合して混練し、実施例及び比較例のゴム組成物を調製した。なお、表1及び表2において、各成分の量は、ゴム成分100質量部に対する量(質量部)である。
*2 SBR1: 下記の方法で合成したヒドロカルビルオキシシラン化合物変性スチレン-ブタジエンゴム、Tg=-65℃、SP値=8.65(cal/cm3)1/2、結合スチレン量=10質量%
*3 SBR2: ブチルリチウムを開始剤として得られるスチレン-ブタジエンゴムの末端をN-(1,3-ジメチルブチリデン)-3-トリエトキシシリル-1-プロパンアミンで変性した、変性スチレン-ブタジエンゴム、Tg=-38℃、SP値=8.95(cal/cm3)1/2、結合スチレン量=35質量%
*4 BR: UBEエラストマー株式会社製、商品名「BR150」
*5 カーボンブラック: 旭カーボン株式会社製、商品名「旭#70」
*6 シリカ: 東ソーシリカ株式会社製、商品名「ニップシールAQ」
*7 シランカップリング剤: Evonik社製、商品名「Si75」
*8 樹脂成分: 水添C5系樹脂、Eastman社製、商品名「登録商標Impera P1780」、軟化点=130℃、重量平均分子量(Mw)=909g/mol、SP値=8.35(cal/cm3)1/2
*9 老化防止剤: 大内新興化学工業株式会社製、商品名「ノクラック6C」
*10 ワックス: 日本精蝋株式会社製、商品名「オゾエース0701」
*11 加硫促進剤A: 大内新興化学工業株式会社製、商品名「ノクセラーDM-P」
*12 加硫促進剤B: 三新化学工業株式会社製、商品名「サンセラーNS-G」
乾燥し、窒素置換した800mLの耐圧ガラス容器に、1,3-ブタジエンのシクロヘキサン溶液及びスチレンのシクロヘキサン溶液を、1,3-ブタジエン67.5g及びスチレン7.5gになるように加え、2,2-ジテトラヒドロフリルプロパン0.6mmolを加え、0.8mmolのn-ブチルリチウムを加えた後、50℃で1.5時間重合を行った。この際の重合転化率がほぼ100%となった重合反応系に対し、変性剤としてN,N-ビス(トリメチルシリル)-3-[ジエトキシ(メチル)シリル]プロピルアミンを0.72mmol添加し、50℃で30分間変性反応を行った。その後、2,6-ジ-t-ブチル-p-クレゾール(BHT)のイソプロパノール5質量%溶液2mLを加えて反応を停止させ、常法に従い乾燥して変性SBRを得た。
得られた変性SBRのミクロ構造を測定した結果、結合スチレン量が10質量%であり、また、ガラス転移温度(Tg)は、-65℃であった。
得られた実施例及び比較例のゴム組成物を加硫し、加硫ゴム試験片を得た。得られた加硫ゴム試験片に対して、以下の方法で、低燃費性能、ウェット制動性能、耐摩耗性能を評価した。
試験片の損失正接(tanδ)を、粘弾性測定装置(レオメトリックス社製)において、温度50℃、歪1%、周波数52Hzの条件で測定した。試験結果は、比較例1のtanδの逆数を100として指数表示した。指数値が大きいほどtanδが小さく、低燃費性能に優れることを示す。
ポータブル・フリクション・テスターを用いて、湿潤アスファルト路面に対する試験片の摩擦係数を測定した。試験結果は、比較例1の摩擦係数を100として指数表示した。指数値が大きいほど摩擦係数が大きく、ウェット制動性能に優れることを示す。
JIS K 6264-2:2005に準拠し、上島製作所製ランボーン摩耗試験機を使用して、研磨輪にサンドペーパーを張り付け、スリップ率15%で、室温で摩耗量を測定した。試験結果は、比較例1の摩耗量の逆数を100として指数表示した。指数値が大きいほど摩耗量が少なく、耐摩耗性能に優れることを示す。
一方で、比較例1及び2のタイヤ用ゴム組成物は、式(X)(及び式(Z))は満たすが、式(Y)は満たさないため、低燃費性能又はウェット制動性能に劣ることが分かる。また、比較例3~6のタイヤ用ゴム組成物は、式(Y)は満たすが、式(X)(及び式(Z))は満たさないため、低燃費性能、ウェット制動性、又は耐摩耗性のいずれかが劣っていることが分かる。
Claims (11)
- ゴム成分と、充填剤と、を含むタイヤ用ゴム組成物であって、
前記ゴム成分が、少なくともイソプレン骨格ゴムと、スチレン-ブタジエンゴムと、を含み、
前記充填剤が、少なくともシリカを含み、
下記の式(X):
10≦A0.5+B1.5≦100 ・・・ (X)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
と、
下記の式(Y):
0.55≦C/D≦0.75 ・・・ (Y)
(式中、Cは、前記ゴム成分100質量部に対する前記シリカの含有量(質量部)であり、Dは、前記ゴム成分100質量部に対する前記充填剤の含有量(質量部)である。)
を満たす、タイヤ用ゴム組成物。 - さらに樹脂成分を含む、請求項1に記載のタイヤ用ゴム組成物。
- 前記スチレン-ブタジエンゴムが、窒素とケイ素とを含む変性剤で変性されている、請求項1に記載のタイヤ用ゴム組成物。
- 前記スチレン-ブタジエンゴムが、窒素を含む官能基とアルコキシ基とを有する変性剤で変性されている、請求項1に記載のタイヤ用ゴム組成物。
- 前記イソプレン骨格ゴムの含有量が、前記ゴム成分100質量部中、0質量部を超え、70質量部未満である、請求項1に記載のタイヤ用ゴム組成物。
- 下記の式(Z):
10≦A0.5+B1.5≦85 ・・・ (Z)
(式中、Aは、前記ゴム成分100質量部中の前記イソプレン骨格ゴムの含有量(質量部)であり、Bは、前記スチレン-ブタジエンゴムの結合スチレン量(質量%)である。)
を満たす、請求項1に記載のタイヤ用ゴム組成物。 - 前記ゴム成分が、ブタジエンゴムを含まない、請求項1に記載のタイヤ用ゴム組成物。
- 前記ゴム組成物中の硫黄量が、前記ゴム成分100質量部に対して、2.5質量部以下である、請求項1に記載のタイヤ用ゴム組成物。
- 前記スチレン-ブタジエンゴムは、結合スチレン量が15質量%未満である、請求項1に記載のタイヤ用ゴム組成物。
- 請求項1に記載のゴム組成物を用いた、トレッドゴム。
- 請求項10に記載のトレッドゴムを具える、タイヤ。
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| JPH03252433A (ja) * | 1990-03-02 | 1991-11-11 | Bridgestone Corp | 空気入りタイヤ |
| JPH0790122A (ja) * | 1993-09-20 | 1995-04-04 | Yokohama Rubber Co Ltd:The | タイヤトレッド用ゴム組成物 |
| WO2003046020A1 (fr) | 2001-11-27 | 2003-06-05 | Bridgestone Corporation | Polymere dienique conjugue, procede de fabrication et compositions elastomeres contenant ce polymere |
| WO2006098103A1 (ja) * | 2005-03-14 | 2006-09-21 | Bridgestone Corporation | ゴム組成物及びそれを用いた空気入りタイヤ |
| JP2007217562A (ja) | 2006-02-16 | 2007-08-30 | Bridgestone Corp | ゴム組成物及びこれを用いたタイヤ |
| WO2015079703A1 (ja) | 2013-11-27 | 2015-06-04 | 株式会社ブリヂストン | ゴム組成物及びタイヤ |
| WO2018190430A1 (ja) * | 2017-04-14 | 2018-10-18 | 住友ゴム工業株式会社 | 空気入りタイヤ |
| JP2019038728A (ja) | 2017-08-28 | 2019-03-14 | 味の素株式会社 | 沈降シリカの製造法 |
| JP2019131646A (ja) * | 2018-01-29 | 2019-08-08 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物およびタイヤ |
| WO2020100628A1 (ja) * | 2018-11-16 | 2020-05-22 | 株式会社ブリヂストン | ゴム組成物、加硫ゴム及びタイヤ |
| JP2020186322A (ja) * | 2019-05-15 | 2020-11-19 | 住友ゴム工業株式会社 | タイヤ用ゴム組成物及び空気入りタイヤ |
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-
2023
- 2023-12-04 WO PCT/JP2023/043332 patent/WO2024224673A1/ja not_active Ceased
- 2023-12-04 JP JP2025516505A patent/JPWO2024224673A1/ja active Pending
- 2023-12-04 EP EP23935444.2A patent/EP4703425A1/en active Pending
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| WO2003046020A1 (fr) | 2001-11-27 | 2003-06-05 | Bridgestone Corporation | Polymere dienique conjugue, procede de fabrication et compositions elastomeres contenant ce polymere |
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| See also references of EP4703425A1 |
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