CN103717662B - Pneumatic tyre - Google Patents
Pneumatic tyre Download PDFInfo
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- CN103717662B CN103717662B CN201280035523.9A CN201280035523A CN103717662B CN 103717662 B CN103717662 B CN 103717662B CN 201280035523 A CN201280035523 A CN 201280035523A CN 103717662 B CN103717662 B CN 103717662B
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- rubber
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Classifications
-
- 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
-
- 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
-
- 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
- B60C1/0041—Compositions of the carcass layers
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C2009/0269—Physical properties or dimensions of the carcass coating rubber
-
- 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
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C2009/0269—Physical properties or dimensions of the carcass coating rubber
- B60C2009/0276—Modulus; Hardness; Loss modulus or "tangens delta"
-
- 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
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
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- 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)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides the pneumatic tyre of excellent in te pins of durability.Namely, the present invention relates to a kind of pneumatic tyre, it is the pneumatic tyre with sidewall and carcass, sidewall is made up of rubber composition for side wall, the content of the divinyl rubber in described rubber composition for side wall in 100 quality % rubber constituents is 30 ~ 70 quality %, relative to 100 mass parts rubber constituents, the content of sulphur is more than 1.29 mass parts, less than 2.30 mass parts, the steel wire cord of carcass is coated by steel wire cord rubber composition for coating, and the sulphur content of rubber composition for side wall and steel wire cord rubber composition for coating meets following relational expression.2.70 < (content relative to the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(content relative to the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 4.20.
Description
Technical field
The present invention relates to pneumatic tyre.
Background technology
Pneumatic tyre is also made up of the various component such as sidewall, carcass except the tyre surface be connected with road surface.In the past, in the Mixed Design of the rubber combination for each component, often kind of rubber combination all carry out laboratory experiment of each component, each component designs best rubber combination (such as, patent documentation 1 ~ 3).And based on the evaluation result of this laboratory test, each component that is made up of each best rubber combination of arranging in pairs or groups is to make pneumatic tyre.But, from the result of the independent laboratory sulfuration laboratory test of rubber combination, there is made airtyred weather resistance lower than the more problem of the situation of the weather resistance expected.
Prior art
[patent documentation]
[patent documentation 1] Japanese Patent No. 4308289 publication
[patent documentation 2] Japanese Patent Laid-Open 2008-24913 publication
[patent documentation 3] Japanese Patent No. 4246245 publication
Summary of the invention
The object of the present invention is to provide the pneumatic tyre that can solve described problem, excellent in te pins of durability.
The present inventor concentrates on studies to above-mentioned problem, result expects following hypothesis: in sulfuration or in use tire, sulphur moves between components, due to the movement of this sulphur, the change of physical property is there is, the weather resistance that the airtyred weather resistance that result makes is expected lower than the result from laboratory test in each component.
And, find: the movement being conceived to the sulphur of the steel wire cord rubber composition for coating for carcass, specific relational expression is met by the content of the sulphur making the rubber composition for side wall used in steel wire cord rubber composition for coating and the sidewall as the adjoining members of carcass, the airtyred weather resistance made is very excellent, determine sulfur content according to the distinctive estimated performance in sidewall further, complete the present invention.
Namely, the present invention relates to a kind of pneumatic tyre, it is the pneumatic tyre with sidewall and carcass, sidewall is made up of rubber composition for side wall, in described rubber composition for side wall, the content of the divinyl rubber in 100 quality % rubber constituents is 30 ~ 70 quality %, relative to 100 mass parts rubber constituents, the content of sulphur is more than 1.29 mass parts, less than 2.30 mass parts, the steel wire cord of carcass is coated by steel wire cord rubber composition for coating, and the sulphur content of rubber composition for side wall and steel wire cord rubber composition for coating meets following relational expression.
2.70 < (content relative to the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(content relative to the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 4.20
The content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating preferably meets following relational expression.
2.80 < (content relative to the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(content relative to the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 3.70
The steam filling temp of metal sulphide mould temperature or vulcanizer preferably 130 ~ 158 DEG C.
Total content preferably 30 ~ 70 quality % of natural rubber, polyisoprene rubber, aqueous polyisoprene rubber and styrene-butadiene rubber(SBR) in the rubber constituent 100 quality % of rubber composition for side wall.
Rubber composition for side wall preferably comprises the divinyl rubber containing advising polyhutadiene crystal between 1,2-.
The content of the vulcanization accelerator of rubber composition for side wall, preferably relative to 100 mass parts rubber constituents, is 0.3 ~ 0.8 mass parts.
Above-mentioned pneumatic tyre is heavy tire for heavy load use preferably.
According to the present invention, owing to being a kind of pneumatic tyre with sidewall and carcass, sidewall is made up of the rubber composition for side wall of the divinyl rubber containing specified quantitative, sulphur, the steel wire cord of carcass is formed by steel wire cord rubber composition for coating is coated, the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating meets specific relational expression, therefore excellent in te pins of durability.Again, obtain good driving stability, low oil consumption, elongation at break simultaneously.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is the schematic diagram of display sidewall periphery.
Embodiment
Namely, pneumatic tyre of the present invention has sidewall and carcass, sidewall is made up of rubber composition for side wall, the content of the divinyl rubber in described rubber composition for side wall in 100 quality % rubber constituents is 30 ~ 70 quality %, relative to 100 mass parts rubber constituents, the content of sulphur is more than 1.29 mass parts, less than 2.30 mass parts, the steel wire cord of carcass is coated by steel wire cord rubber composition for coating, and the sulphur content of rubber composition for side wall and steel wire cord rubber composition for coating meets following relational expression.Moreover in this manual, the content of medicine contained in steel wire cord rubber composition for coating, rubber composition for side wall all means the content in the rubber combination before sulfuration.That is, the content of contained in steel wire cord rubber composition for coating, rubber composition for side wall medicine means the theoretical content of medicine contained in the coated unvulcanized rubber composition of steel wire cord, sidewall unvulcanized rubber composition.Here, the amount of the medicine knocked down when theoretical content refers to preparation unvulcanized rubber composition.
2.70 < (content relative to the sulphur of the rubber constituent of 100 mass parts steel wire cord rubber composition for coating)-(content relative to the sulphur of the rubber constituent of 100 mass parts rubber composition for side wall) < 4.20
Carcass is generally made up of the component of fiber cord rubber composition for coating covered fiber cord.But, in the heavy tire for heavy load use of truck, bus's tire for vehicles, industrial tyre etc., use by the component of steel wire cord rubber composition for coating Cladding Steel silk cord as carcass.And, because the coating of the coated rubber of steel wire cord and steel wire cord is rubber-coated with fiber cord in conjunction with necessary sulfur content more than 1.5 times of fiber cord in conjunction with necessary sulfur content, therefore as pneumatic tyre of the present invention, carcass is that the concentration difference of the sulphur between carcass and sidewall easily increases by the situation of the component of steel wire cord rubber composition for coating Cladding Steel silk cord.
If reduce this concentration difference and excessively increase sidewall sulfur content, then the elongation at break after thermal ageing can reduce, easily because fatigue cracks, weather resistance can reduce.On the other hand, if the sulfur content on sidewall is few, then become greatly with the concentration difference of the sulphur of carcass, the sulfur transfer of carcass is to sidewall.In Fig. 1, the situation that display sulphur in medelling ground moves to the few sidewall of sulfur content from the carcass that sulfur content is many and the distribution of sulphur predicted according to the migration of sulphur.As the prediction distribution figure of this sulphur, be speculated as: the concentration gradient producing sulphur in sidewall rubber, the part sulfur content had a common boundary with carcass is maximum, from the part of having a common boundary with carcass to the middle body of the width of the tire axial on sidewall, sulfur content reduces at leisure, sulfur content is minimum near this middle body, and due to bloom (bloom), sulfur content increases again at leisure at sidewall surface.Moreover compared with riding tire for vehicles, although curing temperature is low, the wheelspan of tire is thick, even if easily carry out the heavy tire for heavy load use of long-time sulfuration, the migration of sulphur also can become remarkable.On the other hand, expect, in the air retaining wall of good ventilation property, often to use halogenated butyl rubber.This halogenated butyl rubber is the form of tightening up due to polymer morphology, accepts the strong element sulphur of polarity unlike elastoprene, therefore infers situation sulphur occurring hardly and moves to air retaining wall direction from carcass.
When sulphur moves from carcass to sidewall, the cross-linking density of sidewall rubber can increase, and the freedom from cracking growth property of sidewall rubber, elongation at break significantly worsen, and further, easily produce separation on the impregnation surface covering carcass, weather resistance significantly worsens.Further, in sulfuration or use in tire, the sulfur content on sidewall rubber surface becomes the sulfur content more than sidewall rubber inside, and sidewall rubber forms hard formation on the surface, and freedom from cracking growth property reduces, and weather resistance reduces..
On the other hand, due to above-mentioned movement, in the carcass that sulphur reduces, the sulphur concentration of steel wire cord periphery reduces, and is combined the sulphur that works again not to the sulphur between the coated rubber of coating and steel wire cord of steel wire cord, and binding property and then weather resistance can decline.
On the contrary, when sulphur moves from sidewall to carcass, if amount of movement is many, then the hardness (Hs) on sidewall reduces, and driving stability reduces.And in carcass, sulfur content increases, and improves with the binding property of steel wire cord, but the flexibility of carcass reduces, and easily because fatigue cracks, weather resistance reduces.
But, in the present invention, while the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating meets above-mentioned relation formula, divinyl rubber, sulphur containing specified quantitative in rubber composition for side wall, therefore the movement of sulphur can be suppressed, regulate the amount of movement of sulphur to be appropriate amount, guarantee good driving stability, low oil consumption, elongation at break, obtain good weather resistance simultaneously.
Pneumatic tyre of the present invention has sidewall and carcass.
Carcass is the component be made up of steel wire cord and steel wire cord cladding rubber layer, is casing again.Particularly, the component as shown in Fig. 1 etc. of Japanese Patent Laid-Open 2010-043180 publication.
Sidewall is the component in the outside being configured at carcass, and Fig. 1 of such as Japanese Patent Laid-Open 2010-043180 publication waits the component of display particularly.
In the present invention, sidewall is made up of rubber composition for side wall, and the steel wire cord of carcass forms by steel wire cord rubber composition for coating is coated.
In the present invention, the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating meets following relational expression.Thus, can be suitable for improving airtyred weather resistance.Moreover when less than 2.70, the binding property between steel wire cord and the coated rubber of steel wire cord reduces, and weather resistance declines.Again, when more than 4.20, sidewall (particularly top layer, sidewall) cross-linking density increases, and freedom from cracking growth property reduces, and weather resistance declines.
2.70 < (content relative to the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(content relative to the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 4.20
Moreover in this manual, the amount of sulphur refers to the total content of the bright sulfur composition of the vulcanizing agent being mixed in rubber combination.Here, when bright sulfur composition refers to and such as uses the sulphur of oil-containing as vulcanizing agent oil-containing sulphur in contained sulphur composition, in addition, when containing compound (such as the alkylphenol sulfur subchloride condenses) of sulphur atom as vulcanizing agent use, the element sulphur composition contained in this compound.
The lower limit of above-mentioned relation formula preferably 2.80.
The upper limit of above-mentioned relation formula preferably 3.70, more preferably 3.55, further preferably 3.40.
Then, the rubber composition for side wall, the steel wire cord rubber composition for coating that use in the present invention are described.
(rubber composition for side wall)
As the vulcanizing agent that may be used for rubber composition for side wall without particular limitation of, can be suitable for using sulphur, alkylphenol sulfur subchloride condenses etc.The preferred sulphur of vulcanizing agent.
As sulphur, for example there are powder sulphur, precipitated sulfur, colloid sulphur, insoluble sulfur, polymolecularity sulphur etc.
In rubber composition for side wall, the content of sulphur relative to rubber constituent 100 mass parts, more than 1.29 mass parts, preferably greater than 1.40 mass parts, more preferably above 1.50 mass parts, further preferably greater than 1.60 mass parts.Time below 1.29 mass parts, the inflow quantitative change from the sulphur of carcass is many, and the freedom from cracking growth property of sidewall rubber, elongation at break, low oil consumption significantly worsen, and further, the impregnation surface contacted with carcass easily produces and is separated, and weather resistance significantly worsens.Again, sufficient driving stability can not be obtained.Further, the sulphur of carcass is inadequate, reduces with the binding property of steel wire cord, and weather resistance declines.Again, should quantity not sufficient 2.30 mass parts be contained, preferred less than 2.20 mass parts.Time more than 2.30 mass parts, elongation at break (elongation at break particularly after thermal ageing), freedom from cracking growth property worsen, and weather resistance worsens.
Divinyl rubber (BR) is used in rubber composition for side wall.Be not particularly limited as BR, such as can use Japanese ZEON(strain) VCR412, VCR617 etc. of making of the BR1220 that makes, space portion emerging product (strain) the contour BR along content of BR150B, the space portion emerging product (strain) that make containing advise between 1,2-the high-vinyl-content of the EuropreneBRHV80 of BR, PolimeriEuropa society of polyhutadiene crystal (SPB) etc. BR, use the BR(rare earth BR of rare earth element series catalysts synthesis) etc., general in tire industry material.Again, the tin modification divinyl rubber (tin modification BR) by tin compound modification can also be used.
Especially, from guaranteeing good driving stability, low oil consumption, elongation at break, and the reason obtaining good weather resistance is considered, preferred cis-content, at BR, the rare earth BR of the high cis-contents of more than 95 quality %, the BR containing SPB, more preferably contains the BR of SPB.
Rare earth element series catalysts for the synthesis of rare earth BR can use well-known, such as example there are group of the lanthanides row rare-earth element compound, organo-aluminium compound, aikyiaiurnirsoxan beta, halogen contained compound, as required containing the catalyzer of Lewis base.Especially, as group of the lanthanides row rare-earth element compound, particularly preferably employ the Nd series catalysts of the compound containing neodymium (Nd)..
As group of the lanthanides row rare-earth element compound, for example there are the halogenide of the rare earth metal of atom sequence number 57 ~ 71, carboxylate salt, alkoxide, thioalkoxide, acid amides etc.Especially, from the viewpoint of the BR obtaining high cis-contents, low vinyl content, preferably use Nd series catalysts as mentioned above..
AlR can be used as organo-aluminium compound
ar
br
c(R in formula
a, R
b, R
cidentical or different, represent water element or the alkyl of carbonatoms 1 ~ 8) material that represents.As aikyiaiurnirsoxan beta, for example there are chain aikyiaiurnirsoxan beta, Cyclic aluminoxane.As halogen contained compound, for example there are AlX
kr
d 3-k(in formula, X represents halogen, R
drepresent the alkyl of carbonatoms 1 ~ 20, aryl or aralkyl, k represents 1,1.5,2 or 3) aluminum halide that represents; Me
3srCl, Me
2srCl
2, MeSrHCl
2, MeSrCl
3deng strontium halogenide; The metal halides such as silicon tetrachloride, tin tetrachloride, titanium tetrachloride.Lewis base is used for making the complexing of group of the lanthanides row rare-earth element compound, and what be suitable for use has methyl ethyl diketone, ketone, ethanol etc.
Above-mentioned rare earth element series catalysts can use in the state that be dissolved in organic solvent (normal hexane, hexanaphthene, normal heptane, toluene, dimethylbenzene, benzene etc.) when polymerized butadiene, and the suitable carrier that also can be mounted in silicon-dioxide, magnesium oxide, magnesium chloride etc. uses.As polymerizing condition, can be any one of solution polymerization or mass polymerization, preferred polymerization temperature be-30 ~ 150 DEG C, and polymerization pressure can be selected arbitrarily according to other conditions.
Above-mentioned rare earth BR, the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) preferably more than 1.2, more preferably more than 1.5.During less than 1.2, processibility has the tendency significantly becoming and worsen.This Mw/Mn preferably less than 5, more preferably less than 4.During more than 5, the tendency having wear resistance to improve effect to diminish.
The Mw of above-mentioned rare earth BR preferably more than 300,000, more preferably more than 500,000, again preferably less than 1,500,000, more preferably less than 1,200,000.Further, the Mn of above-mentioned uncommon great soil group system BR preferably more than 100,000, more preferably more than 150,000, again preferably less than 1,000,000, more preferably less than 800,000.Under Mw and Mn deficiency in limited time, the tendency that wear resistance reduces or low oil consumption worsens is had.Exceed in limited time, the deterioration of processibility is worrying.
In addition, in the present invention, Mw, Mn are the values converted according to polystyrene standard with gel permeation chromatography (GPC).
Cis-content preferably more than the 90 quality % of above-mentioned rare earth BR, more preferably more than 93 quality %, preferably 95 Quality measure more than % further.During less than 90 quality %, wear resistance, low oil consumption may decline.
Contents of ethylene preferably below the 1.8 quality % of above-mentioned rare earth BR, more preferably below 1.0 quality %, further preferably below 0.5 quality %, particularly preferably below 0.3 quality %.During more than 1.8 quality %, wear resistance may decline.
Moreover in the present invention, contents of ethylene (1,2-bonding divinyl unit vol) and the cis-content (cis-Isosorbide-5-Nitrae-bonding divinyl unit vol) of rare earth BR can be measured by infrared absorption spectroscopy.
BR containing SPB can be used in the general thing of tire industry, preferably advises the thing that polyhutadiene crystal and BR chemical bond merge dispersion between 1,2-.Arranging to the direction of extrusion by advising polyhutadiene crystal between contained 1,2-, obtaining the sufficient complex modulus of tire circumferential direction, can rigidity be improved, thus obtaining good driving stability.Again, the island structure of the BR containing SPB inhibits the growth in crack aptly, obtains outstanding freedom from cracking growth property, can be suitable for improving weather resistance.
The fusing point preferably more than 180 DEG C of polyhutadiene crystal is advised, more preferably more than 190 DEG C between 1,2-.If less than 180 DEG C, then advise polyhutadiene crystal during mixing of rubber between 1,2-and melt, rigidity may decline.Again, this fusing point preferably less than 220 DEG C, more preferably less than 210 DEG C.During more than 220 DEG C, the dispersiveness in rubber combination has the tendency of deterioration.
Containing in the BR of SPB, advise content preferably more than the 2.5 quality % of polyhutadiene crystal between 1,2-, more preferably more than 10 quality %.During less than 2.5 quality %, fully may not improve weather resistance.Again, this content is below 20 quality % preferably, more preferably below 18 quality %, further preferred below 15 quality %.During more than 20 quality %, the BR containing SPB is difficult to be dispersed in rubber combination, and weather resistance has the tendency of decline.
The content of the BR in rubber constituent 100 quality % is at more than 30 quality %.During less than 30 quality %, can not get elongation at break, the weather resistance after sufficient driving stability, low oil consumption, thermal ageing.The content of this BR at below 70 quality %, preferably below 50 quality %.If more than 70 quality %, then can not obtain elongation at break, the weather resistance after sufficient elongation at break, thermal ageing.When the content of BR is in above-mentioned scope, good driving stability, low oil consumption, elongation at break were both guaranteed, good weather resistance of getting back.
As the rubber constituent that may be used for rubber composition for side wall except BR, be not particularly limited, such as, for example there are the diene series rubber of natural rubber (NR), polyisoprene rubber (IR), liquid polyisoprene rubber (L-IR), styrene-butadiene rubber(SBR) (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), paracril (NBR) etc.Rubber constituent can be used alone, and also can be used together more than 2.Especially, from both guaranteeing good driving stability, low oil consumption, elongation at break, freedom from cracking growth property, the reason of good weather resistance of getting back, preferred NR, IR, L-IR and SBR, more preferably NR, IR, NR is preferred further.
Be not particularly limited as NR, such as, SIR20, RSS#3, TSR20 etc. can be used at the general material of tire industry.Be not particularly limited as IR, such as, can use the IR that IR2200 etc. is general in tire industry.
Total content (the total content of preferred NR and IR, the more preferably content of NR) preferably more than 30 quality %, more preferably more than the 50 quality % of NR, IR, L-IR and SBR in rubber constituent 100 quality %.During less than 30 quality %, there is the tendency of the elongation at break after can not get sufficient elongation at break, thermal ageing, weather resistance.This content is below 70 quality % preferably.During more than 70 quality %, there is the tendency of the elongation at break after can not get sufficient driving stability, low oil consumption, thermal ageing, weather resistance.When above-mentioned content is in above-mentioned scope, good driving stability, low oil consumption, elongation at break were both guaranteed, good weather resistance of getting back.
In the present invention, C5 through-stone oleo-resinous, C9 through-stone oleo-resinous, process oil, vegetables oil, coumarone-indene resin etc. can be used as tenderizer.Especially, from binding property, elongation at break, resistance to ozone ageing excellence, cheap reason, preferred C5 through-stone oleo-resinous.
C5 through-stone oleo-resinous is by by C5(carbonatoms 5) through-stone petroleum hydrocarbon polymerization and obtaining.Here, C5 through-stone petroleum hydrocarbon refers to the C 5 fraction (cut of carbonatoms 5) obtained by the thermolysis of petroleum naphtha.For example there are the alkadiene of isoprene, 1,3-pentadiene, dicyclo pentane diene, m-pentadiene etc. or the monoene class of 2-methyl-1-butene alkene, 2-methyl-2-butene, cyclopentenes etc. particularly.
From the reason of the binding property of appropriateness, elongation at break excellence, C5 through-stone oleo-resinous content preferably 1 ~ 5 mass parts, more preferably 1 ~ 3 mass parts.
Process oil can relax the compactness of polymkeric substance, makes the movement of sulphur become easy.The mobile facilitation effect of the sulphur brought by process oil is larger than other tenderizers such as C5 through-stone oleo-resinouss.And the original cross-linking density of rubber composition for side wall is lower, and therefore the movability of medicine, sulphur is large.Thus, the few person of amount of process oil, can suppress the inflow of the sulphur from carcass.Therefore, process oil content relative to rubber constituent 100 mass parts, preferably below 10 mass parts, more preferably below 5 mass parts, further preferably below 0.5 mass parts.During more than 10 mass parts, the influx from the sulphur of carcass can increase, and weather resistance may decline.
Also can mixed carbon black in rubber composition for side wall.By mixed carbon black, can improve reinforcing, freedom from cracking growth property, weather resistance, driving stability, UV resistant deterioration can be improved.As the example of operable carbon black, for example there are GPF, FEF, HAF, ISAF, SAF etc., but be not particularly limited.
When using carbon black, the N2 adsorption specific surface area (N of carbon black
2sA) 20m is preferably
2/ more than g, more preferably 60m
2/ more than g.If N
2sA is less than 20m
2/ g, then freedom from cracking growth property, weather resistance, driving stability may decline.In addition, the N of carbon black
2the preferred 120m of SA
2/ below g, more preferably 100m
2/ below g.N
2sA is more than 120m
2during/g, sufficient low oil consumption, processibility may be can not get.
Moreover in this specification sheets, the N2 adsorption specific surface area of carbon black is tried to achieve according to JISK6217-2:2001..
The content of carbon black relative to rubber constituent 100 mass parts, preferably more than 10 mass parts, preferably more than 20 mass parts.During less than 10 mass parts, can not obtain reinforcing fully, have the tendency that freedom from cracking growth property, weather resistance, driving stability worsen.Again, the content of carbon black relative to rubber constituent 100 mass parts, preferably below 100 mass parts, more preferably below 70 mass parts, further preferably below 50 mass parts.During more than 100 mass parts, low oil consumption may worsen.
In above-mentioned rubber combination except described composition, can containing the mixture used in rubber industry in the past, the fillers such as such as silicon-dioxide, wax, antioxidant, anti-aging agent, vulcanization accelerator additive (stearic acid, zinc oxide etc.), mixed cross-linker (HTS, PK900 etc. of Flexsys society), vulcanization accelerator etc..
As vulcanization accelerator, for example there are guanidine system, aldehyde-amine system, aldehyde-ammonia system, thiazole, sulfinyl amine system, thiocarbamide system, thiuram system, dithiocar-bamate (or ester) are, the compound etc. of xanthonate system.These vulcanization accelerators can be used alone, and also can arranging in pairs or groups, two or more uses.Especially, consider from the stability of the dispersiveness rubber, sulfuration physical property, preferred sulfinyl amine system vulcanization accelerator (the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (TBBS), N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine (CBS), N, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine (DCBS), N, N-di-isopropyl-2-[4-morpholinodithio sulfinyl amine etc.), the N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine (TBSI), two-2-[4-morpholinodithio based bisulfide (DM), more preferably TBBS, CBS, TBSI, DM, further preferred TBBS.
The content of vulcanization accelerator relative to 100 mass parts rubber constituents, preferably more than 0.3 mass parts, more preferably more than 0.5 mass parts.In addition, this combined amount is preferably below 0.8 mass parts, more preferably below 0.7 mass parts.Vulcanization accelerator combined amount in the above range time, obtain suitable cross-linking density, the freedom from cracking growth property as sidewall rubber, the amount of movement of sulphur can be adjusted to the amount of appropriateness, obtain effect of the present invention preferably.
The manufacture method of rubber composition for side wall can use known method, such as, can manufacture by adopting the compounding rubber device such as mill, Ben Baili Banbury mixer to carry out mixing method etc. above-mentioned each composition.
(steel wire cord rubber composition for coating)
The rubber that may be used for steel wire cord rubber composition for coating without particular limitation of, the diene series rubber same with rubber composition for side wall can be used.Rubber constituent may be used alone, two or more kinds can also be used.Especially, from both guaranteeing good driving stability, low oil consumption, elongation at break, the reason of good weather resistance of getting back is considered, preferred NR.
Be not particularly limited as NR, the NR identical with rubber composition for side wall can be used.
Content preferably more than the 50 quality % of the NR in rubber constituent 100 quality %, more preferably more than 80 quality %, further preferred 100 quality %.When the content of NR is above-mentioned amount, good driving stability, low oil consumption, elongation at break were both guaranteed, good weather resistance of getting back.
Be not particularly limited as the vulcanizing agent that can use, the vulcanizing agent identical with rubber composition for side wall can be used.
In steel wire cord rubber composition for coating, the content of sulphur relative to rubber constituent 100 mass parts, preferably greater than 3.0 mass parts, more preferably above 4.50 mass parts, further preferably greater than 4.80 mass parts.If below 3.0 mass parts, then low with the binding property of steel wire cord, weather resistance may decline.Again, sufficient low oil consumption, elongation at break may not be obtained.Again, this content is preferred less than 6.00 mass parts, more preferably less than 5.80 mass parts, further preferably less than 5.30 mass parts.If more than 6.00 mass parts, then elongation at break, freedom from cracking growth property reduce, and weather resistance declines.Again, sufficient low oil consumption may not be obtained.The content of sulphur in the above range time, both guaranteed good driving stability, low oil consumption, good elongation at break of getting back, freedom from cracking growth property, binding property with steel wire cord, result obtains good weather resistance.
Be not particularly limited as the tenderizer that can use, can be suitable for using the tenderizer identical with rubber composition for side wall.
From the reason of the binding property of appropriateness, elongation at break excellence, C5 through-stone oleo-resinous content preferably 1 ~ 5 mass parts, more preferably 1 ~ 3 mass parts.
The content of process oil relative to rubber constituent 100 mass parts, preferably below 10 mass parts, more preferably below 5 mass parts, further preferably below 0.5 mass parts.During more than 10 mass parts, the discharge from the sulphur of carcass increases, and weather resistance may decline.
Also can mixed carbon black in steel wire cord rubber composition for coating.By mixed carbon black, can improve reinforcing, weather resistance, driving stability can be improved.
When using carbon black, the N2 adsorption specific surface area (N of carbon black
2sA) 40m is preferably
2/ more than g, more preferably 60m
2/ more than g.If N
2sA is less than 40m
2/ g, then weather resistance, driving stability may decline.In addition, the N of carbon black
2the preferred 150m of SA
2/ below g, more preferably 100m
2/ below g.N
2sA is more than 150m
2during/g, bad dispersibility, may can not get sufficient low oil consumption.
The content of carbon black relative to rubber constituent 100 mass parts, preferably more than 10 mass parts, more preferably more than 20 mass parts.During less than 10 mass parts, can not obtain reinforcing fully, weather resistance, driving stability have the tendency of deterioration.Again, the content of carbon black relative to rubber constituent 100 mass parts, preferably below 100 mass parts, more preferably below 80 mass parts.During more than 100 mass parts, low oil consumption may worsen.
For improving the fusible object with steel wire cord, the preferred mixed organic acid cobalt of steel wire cord rubber composition for coating.Organic acid cobalt plays a part rubber and steel wire cord are cross-linked, and therefore by containing organic acid cobalt, can improve the binding property between steel wire cord and rubber.
As organic acid cobalt, for example there are cobalt stearate, cobalt naphthenate, new cobalt decanoate, boron 3 new cobalt decanoate, sylvic acid cobalt etc.Especially, excellent from processibility (viscosity), easily carry out vulcanization reaction consideration, preferred cobalt stearate.
The content of organic acid cobalt, relative to rubber constituent 100 mass parts, is scaled cobalt, is preferably more than 0.05 mass parts, more preferably more than 0.07 mass parts.If less than 0.05 mass parts, then the binding property between steel wire cord and rubber may be insufficient.Again, this content is scaled cobalt, preferably below 0.15 mass parts, more preferably below 0.12 mass parts.If more than 0.15 mass parts, then resistance to oxidation deterioration, freedom from cracking growth property, weather resistance have the tendency of deterioration.
In above-mentioned rubber combination except described composition, can containing the mixture used in rubber industry in the past, the filler, wax, antioxidant, anti-aging agent, vulcanization accelerator additive (stearic acid, zinc oxide etc.), vulcanization accelerator etc. of such as silicon-dioxide etc.
The content of zinc oxide is relative to rubber constituent 100 mass parts, preferably 3 ~ 20 mass parts, more preferably 6 ~ 12 mass parts.If the content of zinc oxide is in the above range, then both guaranteed good driving stability, low oil consumption, good elongation at break of getting back, freedom from cracking growth property, with the binding property of steel wire cord, result obtains good weather resistance.
Vulcanization accelerator can use the thing identical with rubber composition for side wall, from the reason of the binding property excellence between cord, and more preferably DCBS, TBSI.
The combined amount of vulcanization accelerator relative to rubber constituent 100 mass parts, preferably more than 0.3 mass parts, more preferably more than 0.8 mass parts.Again, this combined amount is preferably below 2.0 mass parts, more preferably below 1.2 mass parts.The combined amount of vulcanization accelerator in the above range time, obtain, as the suitable cross-linking density of the coated rubber of steel wire cord, the amount of movement of sulphur to be adjusted to the amount of appropriateness, to obtain effect of the present invention preferably.
As the manufacture method of steel wire cord rubber composition for coating, the method identical with rubber composition for side wall can be used.
Pneumatic tyre of the present invention uses above-mentioned rubber combination according to usual method manufacture.That is, will be mixed with the rubber combination of various additive as required, in the unvulcanized stage, according to the shape of each component, (situation on sidewall, by the shape of rubber composition for side wall according to sidewall; The situation of carcass, in the unvulcanized stage by the shape of the steel wire cord rubber composition for coating of sheet according to the carcass of the extrusion cladding up and down from steel wire cord) extrusion processing, tyre building machine is shaped with usual method, be bonded together with other structural tire part, after forming unvulcanized tire, in vulcanizer (preferred dome type vulcanizer), heating and pressurizing carries out sulfuration, manufactures tire.
Metal sulphide mould temperature when carrying out the sulfuration of tire or the steam filling temp preferably 130 ~ 158 DEG C of vulcanizer, more preferably 130 ~ 155 DEG C, preferably 130 ~ 152 DEG C further, particularly preferably 130 ~ 145 DEG C, most preferably 130 ~ 140 DEG C.Curing temperature is higher, and the thin sidewall of gauge is by overvulcanize, and easily reversion occurs, sulphur moves to sidewall from carcass and easily promoted, weather resistance declines.Herein, it is sulfur-crosslinked cut-off that reversion refers to temporarily to be formed, sulphur at side polymer chain with the sagging phenomenon of vertical pendant shape, or the phenomenon of the molecular chain scission of polymkeric substance self.
Be not particularly limited as steel wire cord, the layer sth. made by twisting steel wire cord etc. of steel wire cord, k+m structure twisted with the fingers by the list that such as can exemplify 1 × n structure.Here, steel wire cord twisted with the fingers by the list of 1 × n structure is the twisted steel wire cord of 1 layer making the monofilament twisted of n stock and obtain.Again, the layer of k+m structure is twisted with the fingers steel wire cord and is referred to have different sth. made by twisting to, 2 Rotating fields of the lay pitch, internal layer have k stock monofilament, skin has m stock monofilament steel wire cord.N is the integer of 1 ~ 27, and k is the integer of 1 ~ 10, and m is the integer of 1 ~ 3.The plating such as brass (brass), Zn, owing to improve the initial bond relative to rubber combination, are therefore preferably used in the surface of steel wire cord.
Pneumatic tyre of the present invention, as uses such as riding tire for vehicles, heavy tire for heavy load use, is suitable for reusing tire used as heavy duty especially.Moreover the heavy tire for heavy load use in this specification sheets is the tire that weather resistance is excellent especially, the industrial tyre etc. that the industrial vehicle that for example there are truck bus tire for vehicles, heavy equipment etc. uses.Heavy tire for heavy load use uses the cord used in carcass, buffer layer (breaker) to be all wire tyre of steel wire cord usually.
[embodiment]
According to embodiment, the present invention is specifically described, but the present invention is not limited to this.
Then, the various medicines used in embodiment and comparative example are summarized.
NR：TSR20
IR:JSR(strain) IR2200 that makes
BR1: the BR150B(cis-content that space portion emerging product (strain) makes: 97 quality %)
The CB24(of BR2: ラ Application Network セ ス (strain) uses BR, Tg:-116 DEG C, cis-content of the synthesis of Nd series catalysts: 96 quality %, contents of ethylene: 0.7 quality %, ML
1+4(100 DEG C): 45, Mw/Mn:2.69, Mw:50 ten thousand, Mn:18.6 ten thousand)
The content of polyhutadiene crystal is advised: 3.8 quality %) between BR3: the VCR450(that space portion emerging product (strain) the makes BR, 1,2-containing SPB
The content of polyhutadiene crystal is advised: 12 quality %) between BR4: the VCR412(that space portion emerging product (strain) the makes BR, 1,2-containing SPB
Carbon black 1: DIABLACKH(N330, N that Mitsubishi Chemical's (strain) makes
2sA:78m
2/ g)
C5 resin: ball is apt to the マ Le カ レ ッ Star T-100AS(C5 through-stone oleo-resinous that petrochemical industry (strain) is made)
Zinc oxide: No. 1, the zinc oxide that Mitsui Metal Co., Ltd.'s mining industry (strain) is made
Stearic acid: the stearic acid " camellia " made day oil (strain)
Anti-aging agent: Sumitomo Chemical (strain) ア Application processed チ ゲ Application 6C(N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine)
Insoluble sulfur containing 10% oil: Japanese destructive distillation industry (strain) セ イ processed ミ OT
TBBS: the NoccelerNS(N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine that the emerging chemical industry of imperial palace (strain) is made)
Carbon black 2: DIABLACKLH(N326, N that Mitsubishi Chemical's (strain) makes
2sA:84m
2/ g)
Cobalt stearate: the cost-F(cobalt contents that large Japanese ink chemical industry (strain) is made: 9.5 quality %)
Insoluble sulfur containing 20% oil: the ミ ュ ー Network ロ OT-20 that four countries change into (strain) makes
DCBS: the emerging chemical industry of imperial palace (strain) NoccelerDZ(N, N-dicyclohexyl processed-2-[4-morpholinodithio base sulfinyl amine)
Embodiment and comparative example
About rubber composition for side wall, mixed content according to table 1,2, about steel wire cord rubber composition for coating, according to table 1,2 and following shown in mixed content, use Ben Baili Banbury mixer, by mixing for the material outside sulphur removal agent and vulcanization accelerator 5 minutes under the condition of 160 DEG C, obtain mixing thing.Then, in the mixing thing obtained, add sulphur and vulcanization accelerator, use mill, under the condition of 105 DEG C mixing 3 minutes, make unvulcanized rubber composition.
Then, if make steel wire cord rubber composition for coating, the thickness then unvulcanized rubber composition obtained being configured as the thin slice after rubberizing is 0.8mm, then this thin slice is coated on steel wire cord (3+9+15/0.175), be configured as the shape of carcass, if making rubber composition for side wall, be then configured as sidewall shape (sidewall rubber of the tire axial maximum width of tire is thick is 5mm).And, according to the combination shown in table 1,2, fitting with other structural tire parts, by carrying out compression molding 12 minutes of dome type vulcanizer at the temperature of table 1,2 displays, having made test pneumatic tyre (whole steel wire radial tyre) (295/80R22.5).
In steel wire cord coated Xiang Jiao Group compound, relative to NR100 mass parts, be mixed with insoluble sulfur (amount shown in table 1,2 represents bright sulfur composition), the 1 mass parts DCBS containing 20% oil of 60 mass parts of carbon black 2,1 mass parts cobalt stearates, 10 mass parts zinc oxide, 2 mass parts C5, the amount shown in table 1,2.
Fill in baking box at the air of 80 DEG C and the test pneumatic tyre obtained is left standstill 3 weeks, as the test pneumatic tyre after thermal ageing.
From obtained test by airtyred tire axial maximum width part (because be the thinnest part of sidewall rubber (rubber thick for 5mm), the part so curing temperature the most easily rises, be sulphur and the most easily produce mobile part) the part (the substantial middle part (SW central part) of the tire axial width of sidewall rubber) of sidewall surface 2mm to the inside, get sidewall rubber sample (with reference to Fig. 1).
Equally, the sidewall rubber sample after aging from the test pneumatic tyre heat-obtaining after thermal ageing.
Use the sidewall rubber sample after the test pneumatic tyre after the thermal ageing obtained, sidewall rubber sample, thermal ageing, carry out following evaluation.Respectively test-results is shown in table 1,2.
(mensuration of sulfur content)
To sidewall rubber sample, change sulphur (S) into sulfurous gas (SO with process furnace
2), use carbon and sulfur analytical instrument, carry out chemical analysis (sulphur quantitative) by infrared detection.
(complex modulus (hardness) (E*), low oil consumption (tan δ))
Use rock this makings institute (strain) the visco-elasticity spectrometer made, 70 DEG C, the initial stage strains 10%, under the condition of dynamic strain 2%, frequency 10Hz, determine loss tangent (tan δ) and the complex modulus (E*) of each sidewall rubber sample.
Tan δ is less, and rolling resistance is low, more represents that low oil consumption is excellent.E* is larger, and driving stability is more excellent.
(tension test)
Use by No. 3 dumbbell shape test films of sidewall rubber composition of sample, according to JISK6251 " method of calculation of vulcanized rubber and thermoplastic elastomer-tensile properties ", in room temperature, implement tension test, measure elongation at break EB(%).EB is larger, represents that elongation at break is more excellent.Equally, to the sidewall rubber sample after thermal ageing, the elongation at break after thermal ageing and EB(% is also determined).Elongation at break after thermal ageing is larger, represents that the elongation at break after thermal ageing is more excellent.
(rotary drum weather resistance (the durable drum test of high loading))
Use cut-off knife, on the sidewall rubber of test after aging with the maximum wide portion of airtyred tire axial, with 45 degree of directions, the crack of the 20 wide 2mm in place, dark 0.2mm is circumferentially being set, under the condition of 140% load of the maximum load (maximum internal pressure condition) of JIS standard, make described tire with 80km/h speeds 80,000 km on rotary drum, by crack growth degree exponentiate.Moreover the situation that crack is stretched in inclination 45 degree of directions is many, but owing to there being deviation, therefore that 20 place's evaluation results are average, using the freedom from cracking growth property index of benchmark tire (embodiment 7) as 100, by the freedom from cracking growth property exponential representation of each tire.Moreover freedom from cracking growth property index is larger, more represent excellent in te pins of durability, good.
Table 1
Table 2
From table 1,2, it is a kind of pneumatic tyre with sidewall and carcass, sidewall is made up of the rubber composition for side wall of the divinyl rubber containing specified quantitative, sulphur, the steel wire cord of carcass is formed by steel wire cord rubber composition for coating is coated, the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating meets specific relational expression, and such tyre last is excellent.Again, obtain good driving stability, low oil consumption, elongation at break simultaneously.
In comparative example 1 ~ 3, the sulphur content of rubber composition for side wall is few, and Sulfur capacity easily moves from carcass to sidewall, therefore poor durability.In comparative example 4 ~ 6, the content of the sulphur of rubber composition for side wall is many, the extension at break rate variance after thermal ageing, therefore poor durability.Depart from the comparative example 7,8 of specified quantitative at the content of divinyl rubber, the extension at break rate variance after thermal ageing, therefore poor durability.In the difference of the content of the sulphur of rubber composition for side wall and the steel wire cord rubber composition for coating comparative example 3,9 more than 4.20, because Sulfur capacity easily moves to sidewall from carcass, therefore poor durability.In addition, though the difference of above-mentioned sulphur content is little, in the comparative example 4,5,6 of the content many (2.5 mass parts) of the sulphur of rubber composition for side wall, the elongation at break after the thermal ageing of sidewall rubber self is low, poor durability.
Claims (7)
1. a pneumatic tyre is the pneumatic tyre with sidewall and carcass, wherein,
Sidewall is made up of rubber composition for side wall, and in described rubber composition for side wall, the content of the divinyl rubber in 100 quality % rubber constituents is 30 ~ 70 quality %, relative to 100 mass parts rubber constituents, the content of sulphur more than 1.29 mass parts, less than 2.30 mass parts
The steel wire cord of carcass is coated by steel wire cord rubber composition for coating,
The sulphur content of rubber composition for side wall and steel wire cord rubber composition for coating meets following relational expression,
2.70 < (content relative to the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(content relative to the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 4.20.
2. pneumatic tyre as claimed in claim 1, wherein, the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating meets following relational expression,
2.80 < (content relative to the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(content relative to the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 3.70.
3. pneumatic tyre as claimed in claim 1 or 2, wherein, the steam filling temp of metal sulphide mould temperature or vulcanizer is 130 ~ 158 DEG C.
4. pneumatic tyre as claimed in claim 1, wherein, the total content of natural rubber, polyisoprene rubber, liquid polyisoprene rubber and styrene-butadiene rubber(SBR) in the rubber constituent 100 quality % of rubber composition for side wall is 30 ~ 70 quality %.
5. pneumatic tyre as claimed in claim 1, wherein, rubber composition for side wall comprises the divinyl rubber containing advising polyhutadiene crystal between 1,2-as divinyl rubber.
6. pneumatic tyre as claimed in claim 1, wherein, the content of the vulcanization accelerator of rubber composition for side wall, relative to 100 mass parts rubber constituents, is 0.3 ~ 0.8 mass parts.
7. pneumatic tyre as claimed in claim 1, described tire is heavy duty tire.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011181871 | 2011-08-23 | ||
| JP2011-181871 | 2011-08-23 | ||
| JP2012017256A JP5111670B1 (en) | 2011-08-23 | 2012-01-30 | Pneumatic tire |
| JP2012-017256 | 2012-01-30 | ||
| PCT/JP2012/070952 WO2013027690A1 (en) | 2011-08-23 | 2012-08-20 | Pneumatic tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103717662A CN103717662A (en) | 2014-04-09 |
| CN103717662B true CN103717662B (en) | 2015-12-09 |
Family
ID=47676426
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101296140A Pending CN102950979A (en) | 2011-08-23 | 2012-04-20 | Pneumatic tire |
| CN201280035523.9A Expired - Fee Related CN103717662B (en) | 2011-08-23 | 2012-08-20 | Pneumatic tyre |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101296140A Pending CN102950979A (en) | 2011-08-23 | 2012-04-20 | Pneumatic tire |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5111670B1 (en) |
| CN (2) | CN102950979A (en) |
| BR (1) | BR112014004208A2 (en) |
| WO (1) | WO2013027690A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5346390B2 (en) * | 2011-05-27 | 2013-11-20 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP5925527B2 (en) * | 2012-02-29 | 2016-05-25 | 東洋ゴム工業株式会社 | Rubber composition for tire sidewall and pneumatic tire |
| JP5981645B2 (en) * | 2013-04-30 | 2016-08-31 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP6195243B2 (en) * | 2013-11-01 | 2017-09-13 | 住友ゴム工業株式会社 | Pneumatic tire |
| CN104311908A (en) * | 2014-11-20 | 2015-01-28 | 三角轮胎股份有限公司 | Tire sidewall rubber combination comprising 1,2-syndiotactic polybutadiene |
| JP2018109198A (en) * | 2018-03-19 | 2018-07-12 | 住友ゴム工業株式会社 | tire |
| JP7196446B2 (en) * | 2018-07-20 | 2022-12-27 | 横浜ゴム株式会社 | Method for evaluating additive, rubber composition, metal-rubber composite, pneumatic tire, and method for producing pneumatic tire |
| JP7368698B2 (en) * | 2019-08-23 | 2023-10-25 | 横浜ゴム株式会社 | Pneumatic tires for heavy loads |
| JP7360021B2 (en) * | 2019-08-26 | 2023-10-12 | 横浜ゴム株式会社 | Pneumatic tires for heavy loads |
| JP7401734B2 (en) * | 2019-09-13 | 2023-12-20 | 横浜ゴム株式会社 | Pneumatic tires for heavy loads |
| CN111205522A (en) * | 2020-02-23 | 2020-05-29 | 湖北玲珑轮胎有限公司 | Rubber coating composition for steel wire carcass cords of all-steel radial tires |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0586727A1 (en) * | 1991-04-04 | 1994-03-16 | The Goodyear Tire & Rubber Company | Pneumatic tire having a multilayered innerliner |
| US5489628A (en) * | 1994-09-28 | 1996-02-06 | The Goodyear Tire & Rubber Company | Sulfur cured rubber composition containing epoxidized natural rubber and carboxylated nitrile rubber |
| JPH10250307A (en) * | 1997-03-17 | 1998-09-22 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| CN101142098A (en) * | 2005-03-15 | 2008-03-12 | 株式会社普利司通 | Pneumatic tire |
| CN101643004A (en) * | 2008-08-07 | 2010-02-10 | 住友橡胶工业株式会社 | Tire |
| JP2010188955A (en) * | 2009-02-20 | 2010-09-02 | Sumitomo Rubber Ind Ltd | Tire |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007269259A (en) * | 2006-03-31 | 2007-10-18 | Yokohama Rubber Co Ltd:The | Pneumatic radial tire |
-
2012
- 2012-01-30 JP JP2012017256A patent/JP5111670B1/en active Active
- 2012-04-20 CN CN2012101296140A patent/CN102950979A/en active Pending
- 2012-08-20 WO PCT/JP2012/070952 patent/WO2013027690A1/en active Application Filing
- 2012-08-20 CN CN201280035523.9A patent/CN103717662B/en not_active Expired - Fee Related
- 2012-08-20 BR BR112014004208A patent/BR112014004208A2/en not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0586727A1 (en) * | 1991-04-04 | 1994-03-16 | The Goodyear Tire & Rubber Company | Pneumatic tire having a multilayered innerliner |
| US5489628A (en) * | 1994-09-28 | 1996-02-06 | The Goodyear Tire & Rubber Company | Sulfur cured rubber composition containing epoxidized natural rubber and carboxylated nitrile rubber |
| JPH10250307A (en) * | 1997-03-17 | 1998-09-22 | Sumitomo Rubber Ind Ltd | Pneumatic tire |
| CN101142098A (en) * | 2005-03-15 | 2008-03-12 | 株式会社普利司通 | Pneumatic tire |
| CN101643004A (en) * | 2008-08-07 | 2010-02-10 | 住友橡胶工业株式会社 | Tire |
| JP2010188955A (en) * | 2009-02-20 | 2010-09-02 | Sumitomo Rubber Ind Ltd | Tire |
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| CN103717662A (en) | 2014-04-09 |
| JP2013060184A (en) | 2013-04-04 |
| JP5111670B1 (en) | 2013-01-09 |
| BR112014004208A2 (en) | 2017-03-14 |
| CN102950979A (en) | 2013-03-06 |
| WO2013027690A1 (en) | 2013-02-28 |
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