Classifications

• • 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
• • 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
• • 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
  • B60C1/0025—Compositions of the sidewalls
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
• • 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
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/24—Derivatives of hydrazine
  • C08K5/25—Carboxylic acid hydrazides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
  • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

• the present invention relates to rubber compositions and tires.
• Patent Document 1 discloses a rubber composition
• a rubber component comprising at least one rubber selected from the group consisting of natural rubber and synthetic rubber, and at least one selected from the hydrazide compound group.
• Patent Document 2 discloses a pneumatic tire made of a rubber composition containing a rubber component consisting of at least one selected from natural rubber and diene-based synthetic rubber, carbon black, and a hydrazide-based compound.
• An object of the present invention is to provide a rubber composition having excellent low heat build-up.
• the present inventors have made intensive studies to achieve the above object, and as a result, have found that it is possible to provide a rubber composition exhibiting excellent low heat build-up by using predetermined compounds and fillers. .
• the present inventors also found that it is possible to provide a rubber composition exhibiting excellent processability.
• the present invention provides the following rubber composition.
• a rubber composition A rubber composition comprising a diene rubber component, at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and a filler.
• R 1 and R 2 are the same or different and are each a hydrogen atom or a hydrocarbon group, and the hydrocarbon group further has an optional substituent, Also good. R 1 and R 2 may be bonded to each other. R 3 are the same or different and are optional substituents, and n represents an integer of 0-4. ]
• R 4 is the same or different and is an arbitrary substituent, and m represents an integer of 0 to 4. ]
• Section 2. The composition according to item 1, wherein in formula (1), R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• Item 3. The composition according to item 1 or 2, wherein in formula (1), R 2 is an alkyl group having 1 to 18 carbon atoms.
• the filler contains at least silica, 6.
• the diene rubber component contains at least natural rubber, 7.
• Item 8 A tire tread or tire sidewall using the rubber composition according to any one of the above items 1 to 7.
• the rubber composition of the present invention exhibits excellent low heat build-up.
• the rubber composition of the present invention further exhibits excellent processability.
• Rubber composition comprises at least one compound selected from the group consisting of a diene rubber component, a compound represented by formula (1), and a compound represented by formula (2), and Including filler.
• the rubber material obtained using the rubber composition of the present invention exhibits excellent low heat build-up.
• the rubber material obtained using the rubber composition of the present invention further exhibits excellent processability.
• the rubber material obtained using the rubber composition of the present invention can preferably be used for tires and the like.
• R 1 and R 2 are the same or different and are each a hydrogen atom or a hydrocarbon group, and the hydrocarbon group further has an optional substituent, Also good. R 1 and R 2 may be bonded to each other. R 3 are the same or different and are optional substituents, and n represents an integer of 0-4. ]
• R 1 and R 2 are the same or different and each is a hydrogen atom or a hydrocarbon group.
• the hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or the like.
• the aliphatic hydrocarbon group is preferably a saturated hydrocarbon group, an unsaturated hydrocarbon group, or the like, such as a linear, branched, or cyclic aliphatic hydrocarbon group.
• R 1 and R 2 are each preferably a hydrogen atom or a linear, branched or cyclic alkyl group.
• R 1 When R 1 is an alkyl group, R 1 preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and still more preferably 1 carbon atom.
• R 2 When R 2 is an alkyl group, R 2 preferably has 1-18 carbon atoms, more preferably 1-11 carbon atoms.
• R 1 and R 2 may optionally combine with each other to form an alkylene group.
• the hydrocarbon groups of R 1 and R 2 may each optionally have one or more identical or different substituents.
• R 3 is any one or more identical or different substituents.
• n indicates an integer from 0 to 4.
• the substituent is not particularly limited.
• Substituents are preferably halogen atoms, amino groups, aminoalkyl groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, amide groups, carboxyl groups, carboxyalkyl groups, formyl groups, nitrile groups, nitro groups, alkyl groups, hydroxy Alkyl groups, hydroxyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, thiol groups, alkylthio groups, arylthio groups and the like.
• the substituent may preferably have 1 to 4, more preferably 1 to 3, at substitutable positions.
• the amino group is preferably an amino group represented by -NH2 .
• Said amino group is preferably methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino , neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino group, or a straight-chain C1-6 branched monoalkylamino group (substituted amino group ).
• the amino group is preferably a dialkylamino group (substituted amino group) having two linear or branched alkyl groups having 1 to 6 carbon atoms, such as dimethylamino, ethylmethylamino and diethylamino groups.
• an amino group and a hydroxyl group are preferred, and a hydroxyl group is more preferred. Further, the substitution position is particularly preferably 3-position.
• the compound represented by formula (1) is preferably N'-(1-methylethylidene)picolinic hydrazide, N'-(1,3-dimethylbutylidene)picolinic hydrazide, N'-(1,3 -dimethylbutylidene) 3-hydroxypicolinic hydrazide, N'-(1-methyldodecylidene)picolinic acid hydrazide, N'-octylidenepicolinic acid hydrazide, N'-decylidenepicolinic acid hydrazide, N'-dodecyl Lidene picolinic hydrazide, N'-(1,3-dimethylbutylidene)-4-chloropicolinic hydrazide, N'-(1,3-dimethylbutylidene)-4-methoxypicolinic hydrazide, N'-(1 ,3-dimethylbutylidene)-3-methylpicolinic
• a more preferred compound is N'-(1,3-dimethylbutylidene)picolinic acid hydrazide.
• R 4 is the same or different and is an arbitrary substituent, and m represents an integer of 0 to 4. ]
• R 4 is any one or more identical or different substituents.
• n indicates an integer from 0 to 4.
• the substituent is not particularly limited.
• Substituents are preferably halogen atoms, amino groups, aminoalkyl groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, amide groups, carboxyl groups, carboxyalkyl groups, formyl groups, nitrile groups, nitro groups, alkyl groups, hydroxy Alkyl groups, hydroxyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, thiol groups, alkylthio groups, arylthio groups and the like.
• the substituent may preferably have 1 to 4, more preferably 1 to 3, at substitutable positions.
• the amino group is preferably an amino group represented by -NH2 .
• Said amino group is preferably methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, 1-ethylpropylamino, n-pentylamino , neopentylamino, n-hexylamino, isohexylamino, 3-methylpentylamino group, or a straight-chain C1-6 branched monoalkylamino group (substituted amino group ).
• the amino group is preferably a dialkylamino group (substituted amino group) having two linear or branched alkyl groups having 1 to 6 carbon atoms, such as dimethylamino, ethylmethylamino and diethylamino groups.
• an amino group and a hydroxyl group are preferred, and a hydroxyl group is more preferred. Further, the substitution position is particularly preferably 3-position.
• the compound represented by formula (2) is preferably picolinic hydrazide, 3-hydroxypicolinic hydrazide, 4-hydroxypicolinic hydrazide, 5-hydroxypicolinic hydrazide, 6-hydroxypicolinic hydrazide, 3-aminopicolinic acid acid hydrazide, 4-aminopicolinic hydrazide, 5-aminopicolinic hydrazide, 6-aminopicolinic hydrazide and the like.
• the rubber composition of the present invention contains a diene rubber component.
• the diene rubber component is preferably natural rubber (NR), synthetic diene rubber, a mixture of natural rubber and synthetic diene rubber, or the like.
• natural rubber is preferably used.
• natural rubber is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and particularly preferably Contains 70% to 100% by mass.
• the natural rubber is preferably natural rubber such as natural rubber latex, technical grade rubber (TSR), smoked sheet (RSS), gutta-percha, Eucommia-derived natural rubber, guayule-derived natural rubber, and Russian dandelion-derived natural rubber.
• Natural rubber is preferably modified natural rubber such as epoxidized natural rubber, methacrylic acid-modified natural rubber, styrene-modified natural rubber and the like.
• the synthetic diene rubber is preferably styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene Original copolymer rubber (EPDM), styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene-styrene triblock copolymer (SBS), etc., these modified synthetic diene rubbers, etc. .
• SBR styrene-butadiene copolymer rubber
• BR butadiene rubber
• IR isoprene rubber
• NBR nitrile rubber
• EPDM ethylene-propylene-diene Original copolymer rubber
• SIS styrene-isoprene-styrene triblock copolymer
• SBS s
• the modified synthetic diene rubber is preferably a diene rubber obtained by modification techniques such as main chain modification, single terminal modification, and both terminal modification.
• the modified functional group of the modified synthetic diene rubber is preferably a functional group containing a heteroatom such as an epoxy group, an amino group, an alkoxy group, or a hydroxyl group, and preferably contains one or more of these functional groups.
• the ratio of cis/trans/vinyl in the diene moiety is not particularly limited, and any ratio is preferable.
• the weight average molecular weight and molecular weight distribution of the diene rubber there are no particular restrictions on the weight average molecular weight and molecular weight distribution of the diene rubber, and the weight average molecular weight is preferably from 150,000 to 1,400,000.
• the method for producing the synthetic diene rubber is not particularly limited, and is preferably a synthesis method such as emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, or cationic polymerization.
• the synthetic diene rubber is preferably IR, SBR, BR, or a mixture of two or more selected from these, more preferably SBR, BR, or a mixture of two or more selected from these.
• the synthetic diene rubber is particularly preferably a diene rubber containing a structure obtained by polymerizing 1,3-butadiene.
• the glass transition point of the synthetic diene rubber (preferably a diene rubber containing a structure obtained by polymerizing 1,3-butadiene) is preferably from -110°C to -20°C from the viewpoint of achieving both wear resistance and braking characteristics. °C, more preferably -70°C to -20°C.
• the rubber composition of the present invention preferably contains 10% by mass to 60% by mass, more preferably 50% by mass to 60% by mass, preferably a glass transition point of -110°C to - It is a diene rubber in the range of 20°C (more preferably in the range of -70°C to -20°C).
• the compounding ratio of at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2) to the diene rubber component is 100 parts by mass of the diene rubber component. , preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, still more preferably 0.15 parts by mass to 5 parts by mass, particularly preferably 0.2 parts by mass part to 4 parts by mass.
• a preferred embodiment of the present invention is a rubber composition in which the diene rubber component contains at least natural rubber, and the natural rubber is contained in an amount of 40% by mass or more based on 100% by mass of the diene rubber component.
• the compounding ratio of at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2) to the diene rubber component is to be blended at the above ratio. Therefore, it exhibits excellent low heat build-up. In addition, by blending in the above ratio, further excellent workability is exhibited.
• the rubber composition of the present invention contains a filler (reinforcing material).
• filler a conventionally known filler used in the rubber industry is preferably used.
• the filler is preferably an inorganic filler such as silica or carbon black.
• Silica is more preferably used as the filler for the purpose of improving the low heat build-up effect.
• the inorganic filler is preferably a conventionally known inorganic compound used in the rubber industry.
• the inorganic compound is preferably alumina (Al 2 O 3 ) such as silica, ⁇ -alumina, ⁇ -alumina.
• the inorganic compound is preferably alumina monohydrate (Al 2 O 3 .H 2 O) such as boehmite, diaspore.
• the inorganic compound is preferably aluminum hydroxide [Al(OH) 3 ] such as gibbsite or bayerite.
• the inorganic compound is preferably aluminum carbonate [Al2 ( CO3 ) 3 ], magnesium hydroxide [Mg(OH) 2 ], magnesium oxide (MgO), magnesium carbonate ( MgCO3 ), talc ( 3MgO.4SiO2.
• Attapulgite 5MgO.8SiO2.9H2O
• titanium white TiO2
• titanium black TiO2n -1
• calcium oxide CaO
• Aluminum magnesium oxide MgO.Al2O3
• clay Al2O3.2SiO2
• kaolin Al2O3.2SiO2.2H2O
• pyrophyllite Al2O3.4SiO2 .
• the inorganic filler preferably has an organically treated surface in order to improve the affinity with the rubber component.
• the inorganic filler is preferably silica.
• the BET specific surface area of silica is not particularly limited, and preferably ranges from 40 m 2 /g to 350 m 2 /g. Silica having a BET specific surface area within this range has the advantage of being able to achieve both rubber reinforcing properties and dispersibility in the rubber component.
• the BET specific surface area is measured according to ISO 5794-1.
• the BET specific surface area of silica preferably ranges from 40 m 2 /g to 350 m 2 /g, more preferably from 100 m 2 /g to 270 m 2 /g, and particularly preferably from 110 m 2 /g to 270 m 2 /g.
• Carbon black is not particularly limited, and examples include commercially available carbon black, Carbon-Silica Dual phase filler, and the like.
• the carbon black is preferably high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade carbon black etc. .
• Carbon black is preferably SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, FEF grade carbon black.
• the DBP absorption range of carbon black is not particularly limited, preferably from 60 cm 3 /100 g to 200 cm 3 /100 g, more preferably from 70 cm 3 /100 g to 180 cm 3 /100 g, particularly preferably 80 cm 3 /100 g to 160 cm 3 /100 g.
• the nitrogen adsorption specific surface area of carbon black is preferably in the range of 30 m 2 /g to 200 m 2 /g, more preferably 40 m 2 / g to 180 m 2 /g, particularly preferably 50 m 2 /g to 160 m 2 /g.
• the amount of the filler compounded is preferably 30 to 120 parts by mass, more preferably 30 to 100 parts by mass, still more preferably 40 parts by mass, per 100 parts by mass of the diene rubber component. It is 90 parts by mass to 90 parts by mass.
• the amount of silica compounded is preferably 5 to 120 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the diene rubber component. is more preferably 10 to 90 parts by mass, particularly preferably 10 to 50 parts by mass, and most preferably 10 to 30 parts by mass.
• a preferred embodiment of the present invention is a rubber composition in which the filler contains at least silica, and the silica is contained in an amount of 5 parts by mass or more with respect to 100 parts by mass of the diene rubber component.
• the rubber composition of the present invention preferably contains compounding agents commonly used in the rubber industry in addition to the above-mentioned compound, rubber component and filler.
• Ingredients preferably include antioxidants, antiozonants, softeners, processing aids, waxes, resins, blowing agents, oils, stearic acid, zinc white (ZnO), vulcanization accelerators, vulcanization retarders, A vulcanizing agent (sulfur) or the like is appropriately selected and blended.
• silica When silica is used as a filler, a silane coupling agent is preferably blended for the purpose of increasing the reinforcing properties of the rubber composition with silica, and for the purpose of increasing the low heat build-up and abrasion resistance of the rubber composition.
• Silane coupling agents that can be used in combination with silica are not particularly limited, and commercial products are preferably used.
• the silane coupling agent is preferably a sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, or alkyl-based silane coupling agent.
• Sulfide-based silane coupling agents are preferably bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(3-methyldimethoxysilylpropyl) tetrasulfide, bis( 2-triethoxysilylethyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(3-methyldimethoxysilylpropyl) disulfide, bis(2-triethoxysilyl) ethyl) disulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-trimethoxysilylpropyl) trisulfide, bis(3-methyldimethoxysilylpropyl) trisul
• the sulfide-based silane coupling agent is more preferably bis(3-triethoxysilylpropyl)tetrasulfide.
• Thioester-based silane coupling agents are preferably 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane.
• Thiol-based silane coupling agents are preferably 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-[ethoxybis(3,6,9,12,15 -pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol and the like.
• the olefinic silane coupling agent is preferably dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, allyltrimethoxysilane, Ethoxysilane, p-styryltrimethoxysilane, 3-(dimethoxymethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, 3-[tris(trimethylsiloxy)s
• Epoxy-based silane coupling agents are preferably 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, triethoxy(3-glycidyloxypropyl)silane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.
• the epoxy-based silane coupling agent is more preferably 3-glycidyloxypropyltrimethoxysilane.
• Amino-based silane coupling agents are preferably N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)- 2-aminoethyl-3-aminopropyltrimethoxysilane and the like.
• the amino-based silane coupling agent is more preferably 3-aminopropyltriethoxysilane.
• the alkyl-based silane coupling agent is preferably methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane.
• the alkyl-based silane coupling agent is more preferably methyltriethoxysilane.
• the silane coupling agent is more preferably bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, 3-[ethoxybis(3,6,9,12,15-pentaoxa octacosan-1-yloxy)silyl]-1-propanethiol and the like.
• the silane coupling agent may be used singly or in combination of two or more.
• the amount of the silane coupling agent compounded is preferably 2 to 20 parts by mass, more preferably 3 to 15 parts by mass, relative to 100 parts by mass of silica.
• the compounding amount of the silane coupling agent By setting the compounding amount of the silane coupling agent to 2 parts by mass or more with respect to 100 parts by mass of silica, the low heat build-up effect of the rubber composition can be more suitably exhibited.
• the compounding amount of the silane coupling agent By setting the compounding amount of the silane coupling agent to 20 parts by mass or less with respect to 100 parts by mass of silica, it is possible to reduce the cost of the rubber composition and improve economic efficiency.
• the tire of the present invention can be produced by a conventional method, except that the rubber composition of the present invention is used.
• Tires are preferably tires for trucks, buses, heavy loads, winter, and the like.
• the rubber composition is preferably used for at least one member selected from the tread portion, sidewall portion, bead area portion, belt portion, carcass portion and shoulder portion.
• members such as the tread portion and sidewall portion are more preferably formed from the rubber composition of the present invention.
• the tread portion has a tread pattern and is in direct contact with the road surface, and is the outer skin of the tire that protects the carcass and prevents abrasion and damage.
• the tread portion refers to a cap tread that constitutes the ground contact portion of the tire and/or a base tread that is provided inside the cap tread.
• the rubber composition is particularly preferably used in the tread portion.
• the sidewall part is the part from the lower side of the shoulder part to the bead part in the pneumatic radial tire.
• the sidewall portion protects the carcass and is the portion that bends the most during running.
• the rubber composition is particularly preferably used in the sidewall portion.
• the bead area is the part that fixes both ends of the carcass cord and at the same time fixes the tire to the rim.
• a bead is a bundled structure of high carbon steel.
• the belt part is a reinforcing band stretched in the circumferential direction between the radial structure tread and the carcass.
• the carcass is strongly tightened like a hoop on a bucket, increasing the rigidity of the tread.
• the carcass part is the cord layer part that forms the frame of the tire, and plays a role in withstanding the load, impact, and filling air pressure that the tire receives.
• the shoulder part is the shoulder part of the tire and serves to protect the carcass.
• the tire of the present invention is preferably manufactured according to a method known in the field of tires.
• inert gas such as normal air or oxygen partial pressure adjusted air, nitrogen, argon, or helium.
• a preferred embodiment of the present invention is a tire tread or tire sidewall using the rubber composition.
• the method for producing the rubber composition of the present invention is not particularly limited, but preferably it can be based on mixing the above compound, rubber component, filler, and, if necessary, other components. . Moreover, the said compound is manufactured by a well-known method.
• the mixing method is not particularly limited, and a known method is preferably used.
• the compound and, if necessary, other ingredients are kneaded using a kneader or the like.
• the present invention is not limited to these.
• Production Example 1 Production of Picolinic Acid Hydrazide (Compound a) To 25.3 g of methyl picolinate and 20 mL of methanol, 9.71 g of hydrazine monohydrate was added and heated under reflux for 18 hours. After cooling to room temperature, the reaction solution was filtered, and the resulting solid was crushed and washed with 20 mL of isopropyl alcohol and dried under reduced pressure to obtain 22.9 g of the desired product (yield 90%).
• Production Example 2 Production of N'-(1,3-dimethylbutylidene)picolinic acid hydrazide (compound b) To 10 g of picolinic acid hydrazide and 20 mL of methanol was added 14.6 g of methyl isobutyl ketone, followed by heating under reflux for 18 hours. The solvent was distilled off under reduced pressure, 20 mL of isopropyl alcohol was added to the resulting residue, and the mixture was stirred under ice-cooling to precipitate crystals. The crystals were filtered, washed with isopropyl alcohol, and the obtained solid was dried under reduced pressure to obtain 15.6 g of the desired product (yield 98%).
• Production Example 3 Production of 3-hydroxypicolinic acid hydrazide (compound c) 2.8 g of concentrated sulfuric acid was added to 75 mL of methanol containing 5.00 g of 3-hydroxypicolinic acid, and the mixture was heated under reflux for 36 hours. The solvent was distilled off under reduced pressure, and an aqueous potassium carbonate solution was added to the resulting residue under ice-cooling to adjust the pH to 8. The product was extracted with dichloromethane, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 4.36 g of methyl ester (yield 74%).
• Production Example 4 Production of N'-(1,3-dimethylbutylidene) 3-hydroxypicolinic acid hydrazide (compound d) To 3.10 g of 3-hydroxypicolinic acid hydrazide in 40 mL of methanol was added 8.00 g of methyl isobutyl ketone for 18 hours. Heated to reflux. The solvent was distilled off under reduced pressure, and 20 mL of hexane was added to the resulting residue and stirred to precipitate crystals. The crystals were filtered, washed with hexane, and the obtained solid was dried under reduced pressure to obtain 5.80 g of the desired product (yield 92%).
• Production Example 6 Production of N'-(1,3-dimethylbutylidene)nicotinic acid hydrazide (compound f) To 10 g of nicotinic acid hydrazide and 100 mL of methanol was added 14.6 g of methyl isobutyl ketone, and the mixture was heated under reflux for 18 hours. The solvent was distilled off under reduced pressure, 50 mL of hexane was added to the resulting residue, and the mixture was stirred. After removing the supernatant hexane layer, 50 mL of hexane was further added and stirred to precipitate crystals. The crystals were filtered, washed with hexane, and dried under reduced pressure to obtain 15.3 g of the desired product (yield 96%).
• Production Example 7 Production of N'-(1,3-dimethylbutylidene)isonicotinic acid hydrazide (compound h) To 10 g of isonicotinic acid hydrazide and 100 mL of methanol, 14.6 g of methyl isobutyl ketone was added and the mixture was heated under reflux for 18 hours. The solvent was distilled off under reduced pressure, and 100 mL of hexane was added to the resulting residue and stirred to precipitate crystals. The crystals were filtered, washed with hexane, and the obtained solid was dried under reduced pressure to obtain 15.8 g of the desired product (yield 97%).
• Examples 1 to 8 and Comparative Examples 1 to 12 Production of rubber composition Each component described in Step (I) of Table 1 was mixed in its ratio (parts by weight) and kneaded in a Banbury mixer.
• each component listed in Step (II) in Table 1 is added in each proportion (parts by weight), and the maximum temperature of the mixture is adjusted to 110°C or less. While kneading, an unvulcanized rubber composition was produced.
• Each rubber composition was obtained by heating the obtained unvulcanized rubber composition at 150°C for 25 minutes using a vulcanization press.
• Low heat build-up index (Tan ⁇ value of rubber compositions of Examples 1 to 4 and Comparative Examples 2 to 6) ⁇ 100/(Tan ⁇ value of Comparative Example 1)
• Low heat build-up index (Tan ⁇ value of rubber compositions of Examples 5 and 6 and Comparative Examples 8 and 9) ⁇ 100/(Tan ⁇ value of Comparative Example 7)
• Low heat build-up index (Tan ⁇ value of rubber compositions of Examples 7 and 8 and Comparative Examples 11 and 12) ⁇ 100/(Tan ⁇ value of Comparative Example 10)
• Mooney viscosity measurement Measured according to JIS K6300-1 (Method for determining viscosity and scorch time using a Mooney viscometer; ML1+4, 100°C).
• a rubber composition (Comparative Example 1) was prepared using the same compounding content and the same manufacturing method as in each example except that no compound was added. Based on this, the workability index was calculated.
• a smaller value of the workability index indicates better workability.
• Processability index (Mooney viscosity value of rubber compositions of Examples 1 and 2 and Comparative Example 6) x 100/(Mooney viscosity value of Comparative Example 1)
• the rubber composition of the present invention contains at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2), and a filler in the rubber component. Additives of at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2) Despite containing, it exhibits excellent low heat build-up.
• the rubber composition of the present invention further exhibits excellent processability.
• the rubber composition of the present invention can be suitably used as a material for tires, particularly tire treads or tire sidewalls.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=84690251

Family Applications (1)

Country Status (5)

Citations (4)

Family Cites Families (9)

• 2022
  • 2022-06-29 JP JP2023532012A patent/JP7808109B2/ja active Active
  • 2022-06-29 US US18/574,520 patent/US20240317978A1/en active Pending
  • 2022-06-29 CN CN202280045266.0A patent/CN117561303A/zh active Pending
  • 2022-06-29 WO PCT/JP2022/025932 patent/WO2023277057A1/ja not_active Ceased
  • 2022-06-29 EP EP22833203.7A patent/EP4365229A4/en active Pending

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events