CN103717662A - Pneumatic tire - Google Patents
Pneumatic tire Download PDFInfo
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- CN103717662A CN103717662A CN201280035523.9A CN201280035523A CN103717662A CN 103717662 A CN103717662 A CN 103717662A CN 201280035523 A CN201280035523 A CN 201280035523A CN 103717662 A CN103717662 A CN 103717662A
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- rubber
- rubber composition
- mass parts
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- sulphur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0041—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/02—Carcasses
- B60C2009/0269—Physical properties or dimensions of the carcass coating rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- 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"
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C2200/00—Tyres specially adapted for particular applications
- B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
Abstract
Provided is a pneumatic tire which has excellent durability. The present invention relates to a pneumatic tire which has a sidewall and a casing and which is characterized in that: the sidewall is formed from a rubber composition for sidewalls, said composition containing 30-70% by mass of a butadiene rubber in 100% by mass of the rubber component, while containing more than 1.29 parts by mass but less than 2.30 parts by mass of sulfur per 100 parts by mass of the rubber component; the casing is obtained by covering a steel cord with a rubber composition for covering steel cords; and the sulfur content in the rubber composition for sidewalls and the sulfur content in the rubber composition for covering steel cords satisfy the following relational expression. 2.70 < (the sulfur content relative to 100 parts by mass of the rubber component in the rubber composition for covering steel cords) - (the sulfur content relative to 100 parts by mass of the rubber component in the rubber composition for sidewalls) < 4.20.
Description
Technical field
The present invention relates to pneumatic tyre.
Background technology
Pneumatic tyre also consists of various members such as sidewall, carcasses except the tyre surface being connected with road surface.In the past, in the Mixed Design of the rubber combination for each member, every kind of rubber combination of each member is carry out laboratory experiment all, and each member designs best rubber combination (for example, patent documentation 1～3).And, the evaluation result based on this laboratory test, each member that collocation consists of each best rubber combination is made pneumatic tyre.But the result from the independent laboratory sulfuration laboratory test of rubber combination, exists the airtyred weather resistance of made lower than the more problem of situation of the weather resistance of expecting.
Prior art
[patent documentation]
No. 4308289 communique of [patent documentation 1] Japanese Patent
[patent documentation 2] Japanese Patent Laid-Open 2008-24913 communique
No. 4246245 communique of [patent documentation 3] Japanese Patent
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 inventor concentrates on studies to above-mentioned problem, result is expected following hypothesis: in sulfuration or in use tire, sulphur moves between member, movement due to this sulphur, in each member, there is the variation of physical property, the weather resistance that the airtyred weather resistance that result is made is expected lower than the result from laboratory test.
And, find: be conceived to the movement for the sulphur of the steel wire cord rubber composition for coating of carcass, the content of the sulphur by the rubber composition for side wall that makes to use in steel wire cord rubber composition for coating and the sidewall as the adjoining members of carcass meets specific relational expression, the airtyred weather resistance of making is very excellent, further according to the distinctive estimated performance in sidewall, determine sulfur content, complete the present invention.
; the present invention relates to a kind of pneumatic tyre; it is the pneumatic tyre with sidewall and carcass; sidewall consists 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 %; with respect to 100 mass parts rubber constituents; the content of sulphur surpasses 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 < (with respect to the content of the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(with respect to the content of 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 < (with respect to the content of the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(with respect to the content of the sulphur of rubber constituent 100 mass parts of rubber composition for side wall) < 3.70
Preferably 130～158 ℃ of the steam filling temps of metal sulphide mould temperature or vulcanizer.
The total content 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 is 30～70 quality % preferably.
Rubber composition for side wall preferably comprises and contains the divinyl rubber of advising polyhutadiene crystal between 1,2-.
The content of the vulcanization accelerator of rubber composition for side wall, preferably with respect 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 consists of the rubber composition for side wall of the divinyl rubber that contains specified quantitative, sulphur, the steel wire cord of carcass is coated and forms by steel wire cord rubber composition for coating, the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating meets specific relational expression, so excellent in te pins of durability.Obtain good driving stability, low oil consumption, elongation at break again, simultaneously.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that shows sidewall portion periphery.
Embodiment
; pneumatic tyre of the present invention has sidewall and carcass; sidewall consists 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 %; with respect to 100 mass parts rubber constituents; the content of sulphur surpasses 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, in steel wire cord rubber composition for coating, rubber composition for side wall, the content of contained medicine all means the content in the rubber combination before sulfuration.That is, in steel wire cord rubber composition for coating, rubber composition for side wall, the content of contained medicine means the coated theoretical content of using medicine contained in unvulcanized rubber composition with unvulcanized rubber composition, sidewall of steel wire cord.The amount of the medicine of knocking down when here, theoretical content refers to preparation unvulcanized rubber composition.
2.70 < (with respect to the content of the sulphur of the rubber constituent of 100 mass parts steel wire cord rubber composition for coating)-(with respect to the content of the sulphur of the rubber constituent of 100 mass parts rubber composition for side wall) < 4.20
Carcass generally consists of the member 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 member by steel wire cord rubber composition for coating Cladding Steel silk cord as carcass.And, the necessary sulfur content of being combined with the coating of steel wire cord with rubber because steel wire cord is coated is rubber-coated the more than 1.5 times of necessary sulfur content of being combined with fiber cord of fiber cord, 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 member of steel wire cord rubber composition for coating Cladding Steel silk cord.
If dwindle this concentration difference and excessively increase sidewall sulfur content, 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, become large with the concentration difference of the sulphur of carcass, the sulphur of carcass moves to sidewall.In Fig. 1, medelling ground shows that sulphur moves to the situation on the sidewall that sulfur content is few and according to the distribution of the sulphur of the migration prediction of sulphur from the many carcasses of sulfur content.As the prediction distribution figure of this sulphur, be speculated as: the concentration gradient that produces sulphur in the rubber of sidewall, the part sulfur content having a common boundary with carcass is maximum, middle body from the part with carcass boundary to 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 on surface, sidewall.Moreover, compare 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, it is remarkable that the migration of sulphur also can become.On the other hand, expect, in the air retaining wall of good ventilation property, often to use halogenated butyl rubber.This halogenated butyl rubber, because polymer morphology is the form of tightening up, accepts unlike elastoprene the element sulphur that polarity is strong, therefore infers the situation that sulphur moves from carcass to air retaining wall direction that can occur hardly.
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, on the impregnation surface that covers carcass, easily generation is separated, and weather resistance significantly worsens.Further, in sulfuration or use in tire, the sulfur content of sidewall rubber surface becomes more than the sulfur content of rubber inside, sidewall, on the rubber surface of sidewall, forms hard formation, 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 inadequate to the coated sulphur working with being combined again of the sulphur between rubber of the coating of steel wire cord and steel wire cord, binding property and then weather resistance can decline.
On the contrary, when sulphur moves from sidewall to carcass, if amount of movement is many, the hardness on sidewall (Hs) reduces, and driving stability reduces.And sulfur content increases in carcass, improve with the binding property of steel wire cord, but the reduction of the flexibility of carcass, easily because fatigue cracks, weather resistance reduces.
Yet, in the present invention, when meeting above-mentioned relation formula due to the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating, the divinyl rubber, the sulphur that in rubber composition for side wall, contain specified quantitative, therefore can suppress the movement of sulphur, regulating the amount of movement of sulphur is appropriate amount, guarantees good driving stability, low oil consumption, elongation at break, obtains good weather resistance simultaneously.
Pneumatic tyre of the present invention has sidewall and carcass.
Carcass is the member consisting of steel wire cord and steel wire cord cladding rubber layer, is again casing.Particularly, the member as shown in Fig. 1 of Japanese Patent Laid-Open 2010-043180 communique waits.
Sidewall is the member that is disposed at the outside of carcass, and the Fig. 1 such as Japanese Patent Laid-Open 2010-043180 communique waits the member showing particularly.
In the present invention, sidewall consists 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 the airtyred weather resistance of suitable raising.Moreover 2.70 when following, steel wire cord and steel wire cord are coated to be reduced by the binding property between rubber, and weather resistance declines.Again, 4.20 when above, and sidewall (particularly top layer, sidewall) cross-linking density increases, and freedom from cracking growth property reduces, and weather resistance declines.
2.70 < (with respect to the content of the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(with respect to the content of 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 that is mixed in rubber combination.Here, bright sulfur composition for example refers to contained sulphur composition in the sulphur of oil-containing while using the sulphur of oil-containing as vulcanizing agent, in addition, for example, while using as vulcanizing agent the compound (alkylphenol sulfur subchloride condenses) that contains sulphur atom, the element sulphur composition containing 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, rubber composition for side wall, the steel wire cord rubber composition for coating using is in the present invention described.
(rubber composition for side wall)
As can for the vulcanizing agent of rubber composition for side wall without particular limitation of, can suitable use sulphur, alkylphenol sulfur subchloride condenses etc.The preferred sulphur of vulcanizing agent.
As sulphur, there are for example powder sulphur, precipitated sulfur, colloid sulphur, insoluble sulfur, polymolecularity sulphur etc.
In rubber composition for side wall, the content of sulphur, with respect to rubber constituent 100 mass parts, surpasses 1.29 mass parts, preferably surpasses 1.40 mass parts, more preferably surpasses 1.50 mass parts, further preferably surpasses 1.60 mass parts.1.29 when mass parts is following, many from the inflow quantitative change of the sulphur of carcass, the freedom from cracking growth property of sidewall rubber, elongation at break, low oil consumption significantly worsen, and further, easily produce separatedly with the impregnation surface of carcass contact, weather resistance significantly worsens.Can not obtain sufficient driving stability again.Further, the sulphur of carcass is inadequate, reduces with the binding property of steel wire cord, and weather resistance declines.Again, should be containing quantity not sufficient 2.30 mass parts, preferred less than 2.20 mass parts.In 2.30 mass parts, when above, elongation at break (the particularly elongation at break after thermal ageing), freedom from cracking growth property worsen, and weather resistance worsens.
In rubber composition for side wall, use divinyl rubber (BR).As BR, be not particularly limited, such as using Japanese ZEON(strain) the contour BR along content of BR150B of BR1220, the emerging product of space portion (strain) system of system, VCR412, the VCR617 etc. of the emerging product of space portion (strain) system contain 1, between 2-, advise the BR of polyhutadiene crystal (SPB), the BR of the high-vinyl-content of the Europrene BR HV80 of Polimeri Europa society system etc., use the synthetic BR(rare earth BR of rare earth element series catalysts) etc., in tire industry general material.Also can use the tin modification divinyl rubber (tin modification BR) by tin compound modification again.
Especially, from guaranteeing good driving stability, low oil consumption, elongation at break, and the reason that obtains good weather resistance considers, preferably BR, the rare earth BR of the high-cis content of cis-content more than 95 quality %, the BR that contains SPB, more preferably contain the BR of SPB.
For the synthetic rare earth element series catalysts of rare earth BR, can use well-known, the catalyzer that for example have for example group of the lanthanides row rare-earth element compound, organo-aluminium compound, aikyiaiurnirsoxan beta, halogen contained compound, contains Lewis base as required.Especially, as group of the lanthanides row rare-earth element compound, particularly preferably used the Nd series catalysts of the compound that contains neodymium (Nd)..
As group of the lanthanides row rare-earth element compound, there are for example halogenide, carboxylate salt, alkoxide, sulfo-alkoxide, acid amides of the rare earth metal of atom sequence number 57～71 etc.Especially, from obtaining the viewpoint of the BR of high-cis content, low vinyl content, consider, preferably use as mentioned above Nd series catalysts..
As organo-aluminium compound, can use AlR
ar
br
c(R in formula
a, R
b, R
cidentical or different, represent the alkyl of water element or carbonatoms 1～8) material that represents.As aikyiaiurnirsoxan beta, there are for example chain aikyiaiurnirsoxan beta, ring-type aikyiaiurnirsoxan beta.As halogen contained compound, there is for example AlX
kr
d 3-k(in formula, X represents halogen, R
dthe alkyl, aryl or the aralkyl that represent carbonatoms 1～20, 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, suitable use have methyl ethyl diketone, ketone, an ethanol etc.
Above-mentioned rare earth element series catalysts can be used at the state that is dissolved in organic solvent (normal hexane, hexanaphthene, normal heptane, toluene, dimethylbenzene, benzene etc.) when polymerization divinyl, also can carry on the suitable carrier of silicon-dioxide, magnesium oxide, magnesium chloride etc. and use.As polymerizing condition, can be any of solution polymerization or mass polymerization, preferred polymerization temperature is-30～150 ℃, 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) is preferably more than 1.2, more preferably more than 1.5.During less than 1.2, the tendency that processibility has remarkable change to worsen.This Mw/Mn is preferably below 5, more preferably below 4.Surpass at 5 o'clock, have wear resistance to improve the tendency that effect diminishes.
The Mw of above-mentioned rare earth BR is preferably more than 300,000, more preferably more than 500,000, again preferably below 1,500,000, more preferably below 1,200,000.Further, the Mn that above-mentioned uncommon great soil group is BR is preferably more than 100,000, more preferably more than 150,000, again preferably below 1,000,000, more preferably below 800,000.Under Mw and Mn deficiency,, there is the tendency that wear resistance reduces or low oil consumption worsens in limited time.Surpass upper prescribing a time limit, the deterioration of processibility is worrying.
In addition, in the present invention, Mw, Mn are the values converting according to polystyrene standard with gel permeation chromatography (GPC).
The cis-content of above-mentioned rare earth BR is preferably more than 90 quality %, more preferably more than 93 quality %, further preferably more than 95 Quality amount %.During less than 90 quality %, wear resistance, low oil consumption may decline.
The contents of ethylene of above-mentioned rare earth BR is preferably below 1.8 quality %, more preferably below 1.0 quality %, further preferably below 0.5 quality %, particularly preferably below 0.3 quality %.While surpassing 1.8 quality %, wear resistance may decline.
Moreover in the present invention, the contents of ethylene of rare earth BR (1,2-bonding divinyl unit vol) and cis-content (cis-Isosorbide-5-Nitrae-bonding divinyl unit vol) can be measured by infrared absorption spectroscopy.
Containing the BR of SPB, can use at the general thing of tire industry, preferably 1, between 2-, advise the thing of polyhutadiene crystal and BR chemical bond merging dispersion.By contained 1, between 2-, advise polyhutadiene crystal and arrange to the direction of extrusion, obtain the sufficient complex modulus of tire circumferential direction, can improve rigidity, thereby obtain good driving stability.Again, the island structure of the BR that contains SPB has suppressed the growth in crack aptly, obtains outstanding freedom from cracking growth property, can suitable raising weather resistance.
Between 1,2-, advise the fusing point of polyhutadiene crystal preferably more than 180 ℃, more preferably more than 190 ℃.If 180 ℃ of less thaies, during mixing of rubber 1, advise polyhutadiene crystal and melt between 2-, rigidity may decline.Again, this fusing point is preferably below 220 ℃, more preferably below 210 ℃.While surpassing 220 ℃, the dispersiveness in rubber combination has the tendency of deterioration.
In containing the BR of SPB, between 1,2-, advise the content of polyhutadiene crystal preferably more than 2.5 quality %, more preferably more than 10 quality %.During less than 2.5 quality %, may not fully improve weather resistance.Again, this content is preferably below 20 quality %, more preferably below 18 quality %, further preferably below 15 quality %.While surpassing 20 quality %, the BR that contains SPB is difficult to be dispersed in rubber combination, and weather resistance has the tendency of decline.
The content of BR in rubber constituent 100 quality % is more than 30 quality %.During less than 30 quality %, can not get elongation at break, weather resistance after sufficient driving stability, low oil consumption, thermal ageing.The content of this BR is below 70 quality %, preferably below 50 quality %.If surpass 70 quality %, can not obtain elongation at break, weather resistance after sufficient elongation at break, thermal ageing.The content of BR in above-mentioned scope time, had both been guaranteed good driving stability, low oil consumption, elongation at break, the good weather resistance of getting back.
As can be for the rubber constituent of rubber composition for side wall except BR, be not particularly limited, such as the diene series rubber that has for example natural rubber (NR), polyisoprene rubber (IR), liquid polyisoprene rubber (L-IR), styrene-butadiene rubber(SBR) (SBR), styrene isoprene divinyl rubber (SIBR), chloroprene rubber (CR), paracril (NBR) etc.Rubber constituent can be used separately, 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 the good weather resistance of getting back, preferably NR, IR, L-IR and SBR, more preferably NR, IR, NR is further preferred.
As NR, be not particularly limited, such as using SIR20, RSS#3, TSR20 etc. at the general material of tire industry.As IR, be not particularly limited, such as using the general IR in tire industry such as IR2200.
The total content of NR, IR, L-IR and SBR in rubber constituent 100 quality % (preferably the total content of NR and IR, the more preferably content of NR) is preferably more than 30 quality %, more preferably more than 50 quality %.During less than 30 quality %, there are the elongation at break can not get after sufficient elongation at break, thermal ageing, the tendency of weather resistance.This content is preferably below 70 quality %.While surpassing 70 quality %, there are the elongation at break can not get after sufficient driving stability, low oil consumption, thermal ageing, the tendency of weather resistance.Above-mentioned content in above-mentioned scope time, had both been guaranteed good driving stability, low oil consumption, elongation at break, the good weather resistance of getting back.
In the present invention, as tenderizer, can use C5 through-stone oleo-resinous, C9 through-stone oleo-resinous, process oil, vegetables oil, coumarone-indene resin etc.Especially, from binding property, elongation at break, excellent, the cheap reason of resistance to ozone ageing, preferably C5 through-stone oleo-resinous.
C5 through-stone oleo-resinous is by by C5(carbonatoms 5) polymerization of through-stone petroleum hydrocarbon obtains.Here, C5 through-stone petroleum hydrocarbon refers to the C 5 fraction (cut of carbonatoms 5) that the thermolysis by petroleum naphtha obtains.The monoene class that has for example particularly the alkadiene of isoprene, 1,3-pentadiene, dicyclo pentane diene, m-pentadiene etc. or 2-methyl-1-butene alkene, 2-methyl-2-butene, cyclopentenes etc.
From the reason of appropriate binding property, elongation at break excellence, C5 through-stone oleo-resinous content is 1～5 mass parts, more preferably 1～3 mass parts preferably.
Can the relax degree of compacting of polymkeric substance of process oil, makes the movement of sulphur become easy.The mobile facilitation effect of the sulphur being 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, so the movability of medicine, sulphur is large.Thereby the few person of amount of process oil, can suppress the inflow from the sulphur of carcass.Therefore, process oil content is with respect to rubber constituent 100 mass parts, preferably below 10 mass parts, more preferably below 5 mass parts, further preferably below 0.5 mass parts.While surpassing 10 mass parts, from the influx of the sulphur of carcass, can increase, weather resistance may decline.
Also can mixed carbon black in rubber composition for side wall.By mixed carbon black, can improve reinforcement, can improve freedom from cracking growth property, weather resistance, driving stability, UV resistant deterioration.As the example of operable carbon black, there are for example GPF, FEF, HAF, ISAF, SAF etc., but are not particularly limited.
While using carbon black, the nitrogen adsorption specific surface area (N of carbon black
2sA) be preferably 20m
2more than/g, more preferably 60m
2more than/g.If N
2sA deficiency 20m
2/ g, freedom from cracking growth property, weather resistance, driving stability may decline.In addition the N of carbon black,
2the preferred 120m of SA
2below/g, more preferably 100m
2below/g.N
2sA surpasses 120m
2during/g, may can not get sufficient low oil consumption, processibility.
Moreover in this specification sheets, the nitrogen adsorption specific surface area of carbon black is tried to achieve according to JIS K6217-2:2001..
The content of carbon black is with respect 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 sufficient reinforcement, the tendency that has freedom from cracking growth property, weather resistance, driving stability to worsen.Again, the content of carbon black is with respect to rubber constituent 100 mass parts, preferably below 100 mass parts, more preferably below 70 mass parts, further preferably below 50 mass parts.While surpassing 100 mass parts, low oil consumption may worsen.
In above-mentioned rubber combination except described composition, can contain the mixture using in rubber industry in the past, such as the fillers such as silicon-dioxide, wax, antioxidant, anti-aging agent, vulcanization accelerator additive (stearic acid, zinc oxide etc.), mixed cross-linker (HTS, the PK900 etc. of Flexsys society system), vulcanization accelerator etc..
As vulcanization accelerator, have for example that guanidine system, aldehyde-amine system, aldehyde-ammonia system, thiazole, sulfinyl amine system, thiocarbamide system, thiuram system, dithiocar-bamate (or ester) are, a compound of xanthonate system etc.These vulcanization accelerators can be used separately, two or more use of also can arranging in pairs or groups.Especially, from the stability of the dispersiveness rubber, sulfuration physical property, consider, preferably sulfinyl amine is 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 is with respect 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, obtains suitable cross-linking density, freedom from cracking growth property as sidewall rubber, the amount of movement of sulphur can be adjusted to appropriate amount, obtains effect of the present invention preferably.
The manufacture method of rubber composition for side wall can be used known method, for example, can manufacture by above-mentioned each composition being adopted the compounding rubber devices such as mill, Ben Baili Banbury mixer carry out mixing method etc.
(steel wire cord rubber composition for coating)
Can for the rubber of steel wire cord rubber composition for coating without particular limitation of, can use the diene series rubber same with rubber composition for side wall.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 the good weather resistance of getting back is considered, preferred NR.
As NR, be not particularly limited, can use the NR identical with rubber composition for side wall.
The content of NR in rubber constituent 100 quality % is preferably more than 50 quality %, more preferably more than 80 quality %, and further preferred 100 quality %.When the content of NR is above-mentioned amount, good driving stability, low oil consumption, elongation at break had both been guaranteed, the good weather resistance of getting back.
As the vulcanizing agent that can use, be not particularly limited, can use the vulcanizing agent identical with rubber composition for side wall.
In steel wire cord rubber composition for coating, the content of sulphur, with respect to rubber constituent 100 mass parts, preferably surpasses 3.0 mass parts, more preferably surpasses 4.50 mass parts, further preferably surpasses 4.80 mass parts.If below 3.0 mass parts, low with the binding property of steel wire cord, weather resistance may decline.May not obtain sufficient low oil consumption, elongation at break again.Again, preferred less than 6.00 mass parts of this content, more preferably less than 5.80 mass parts, further preferred less than 5.30 mass parts.If more than 6.00 mass parts, elongation at break, freedom from cracking growth property reduce, and weather resistance declines.May not obtain sufficient low oil consumption again.The content of sulphur in the above range time, had both been guaranteed good driving stability, low oil consumption, the 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.
As the tenderizer that can use, be not particularly limited, can the suitable use tenderizer identical with rubber composition for side wall.
From the reason of appropriate binding property, elongation at break excellence, C5 through-stone oleo-resinous content is 1～5 mass parts, more preferably 1～3 mass parts preferably.
The content of process oil is with respect to rubber constituent 100 mass parts, preferably below 10 mass parts, more preferably below 5 mass parts, further preferably below 0.5 mass parts.While surpassing 10 mass parts, from the discharge of the sulphur of carcass, increase, weather resistance may decline.
Also can mixed carbon black in steel wire cord rubber composition for coating.By mixed carbon black, can improve reinforcement, can improve weather resistance, driving stability.
While using carbon black, the nitrogen adsorption specific surface area (N of carbon black
2sA) be preferably 40m
2more than/g, more preferably 60m
2more than/g.If N
2sA deficiency 40m
2/ g, weather resistance, driving stability may decline.In addition the N of carbon black,
2the preferred 150m of SA
2below/g, more preferably 100m
2below/g.N
2sA surpasses 150m
2during/g, bad dispersibility, may can not get sufficient low oil consumption.
The content of carbon black is with respect 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 sufficient reinforcement, weather resistance, driving stability have the tendency of deterioration.Again, the content of carbon black is with respect to rubber constituent 100 mass parts, preferably below 100 mass parts, more preferably below 80 mass parts.While surpassing 100 mass parts, low oil consumption may worsen.
Fusible object for raising with steel wire cord, the preferred mixed organic acid cobalt of steel wire cord rubber composition for coating.Organic acid cobalt play a part to make rubber and steel wire cord crosslinked, therefore, by containing organic acid cobalt, can improve the binding property between steel wire cord and rubber.
As organic acid cobalt, there are for example cobalt stearate, cobalt naphthenate, new cobalt decanoate, boron 3 new cobalt decanoates, sylvic acid cobalt etc.Especially, excellent from processibility (viscosity), easily carry out vulcanization reaction consideration, preferably cobalt stearate.
The content of organic acid cobalt, with respect to rubber constituent 100 mass parts, is scaled cobalt, more than being preferably 0.05 mass parts, more preferably more than 0.07 mass parts.If less than 0.05 mass parts, 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 surpass 0.15 mass parts, 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 contain the mixture using in rubber industry in the past, such as the filler of silicon-dioxide etc., wax, antioxidant, anti-aging agent, vulcanization accelerator additive (stearic acid, zinc oxide etc.), vulcanization accelerator etc.
The content of zinc oxide is with respect 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, both guaranteed good driving stability, low oil consumption, the 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 be used the thing identical with rubber composition for side wall, from and cord between the reason of binding property excellence, more preferably DCBS, TBSI.
The combined amount of vulcanization accelerator is with respect 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, obtains with the suitable cross-linking density of rubber, the amount of movement of sulphur to be adjusted to appropriate amount as steel wire cord is coated, obtains effect of the present invention preferably.
As the manufacture method of steel wire cord rubber composition for coating, can use the method identical with rubber composition for side wall.
Pneumatic tyre of the present invention is used above-mentioned rubber combination according to usual method manufacture.That is, will mix as required the rubber combination of various additives, the unvulcanized stage according to the shape of each member (situation on sidewall, by rubber composition for side wall according to the shape on sidewall; The situation of carcass, in the unvulcanized stage by the steel wire cord rubber composition for coating of sheet according to the shape of the carcass of the extrusion cladding up and down from steel wire cord) extrusion processing, on tyre building machine, with usual method, be shaped, be bonded together with other structural tire part, form not after vulcanized tyre, in vulcanizer (preferably dome type vulcanizer), heating and pressurizing is vulcanized, and manufactures tire.
Preferably 130～158 ℃ of metal sulphide mould temperature while carrying out the sulfuration of tire or the steam filling temps of vulcanizer, more preferably 130～155 ℃, further preferably 130～152 ℃, particularly preferably 130～145 ℃, most preferably 130～140 ℃.Curing temperature is higher, and the thin sidewall of gauge, by overvulcanize, reversion easily occurs, and sulphur moves to sidewall from carcass and easily promoted, weather resistance declines.Herein, reversion refers to temporary transient sulfur-crosslinked being cut off forming, and sulphur falls the sagging phenomenon of shape at a side polymer chain to hang down, or the phenomenon of the molecular chain of polymkeric substance self cut-out.
As steel wire cord, be not particularly limited, such as single layer of twisting with the fingers steel wire cord, k+m structure that can exemplify 1 * n structure, twist with the fingers steel wire cord etc.Here, 1 * n structure single to twist with the fingers steel wire cord be to make the monofilament twisted of n thigh and the twisted steel wire cord of 1 layer that obtains.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 and have k thigh monofilament, skin to have the steel wire cord of m thigh monofilament to 2 layers of structure, internal layer of, the lay pitch.N is 1～27 integer, and k is 1～10 integer, and m is 1～3 integer.The surface of steel wire cord is due to the initial stage binding property having improved with respect to rubber combination, therefore preferably with plating such as brass (brass), Zn.
Pneumatic tyre of the present invention is as uses such as riding tire for vehicles, heavy tire for heavy load use, suitablely especially as heavy duty, reuses tire used.Moreover the heavy tire for heavy load use in this specification sheets is the tire that weather resistance is excellent especially, there is for example industrial tyre that the industrial vehicle of truck bus tire for vehicles, heavy equipment etc. uses etc.It is all wire tyre of steel wire cord that heavy tire for heavy load use is used the cord using in carcass, buffer layer (breaker) conventionally.
[embodiment]
According to embodiment, the present invention is specifically described, but the present invention is not limited to this.
Then, the various medicines that use in embodiment and comparative example are carried out to general description.
NR：TSR20
IR:JSR(strain) IR2200 of system
BR1: the BR150B(cis-content of the emerging product of space portion (strain) system: 97 quality %)
The CB24(of BR2: ラ Application Network セ ス (strain) is used BR, Tg:-116 ℃ synthetic, cis-content of Nd series catalysts: 96 quality %, contents of ethylene: 0.7 quality %, ML
1+4(100 ℃): 45, Mw/Mn:2.69, Mw:50 ten thousand, Mn:18.6 ten thousand)
BR3: the BR, 1 that the VCR450(of the emerging product of space portion (strain) system contains SPB, advises the content of polyhutadiene crystal: 3.8 quality %) between 2-
BR4: the BR, 1 that the VCR412(of the emerging product of space portion (strain) system contains SPB, advises the content of polyhutadiene crystal: 12 quality %) between 2-
Carbon black 1: DIABLACK H(N330, the N of Mitsubishi Chemical's (strain) system
2sA:78m
2/ g)
C5 resin: ball is apt to the マ Le カ レ ッ Star T-100AS(C5 through-stone oleo-resinous of petrochemical industry (strain) system)
Zinc oxide: No. 1, the zinc oxide of Mitsui Metal Co., Ltd.'s mining industry (strain) system
Stearic acid: the stearic acid " camellia " of day oil (strain) system
Anti-aging agent: Sumitomo Chemical (strain) ア Application processed チ ゲ Application 6C(N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine)
The insoluble sulfur that contains 10% oil: Japanese destructive distillation industry (strain) セ イ processed ミ OT
TBBS: the Nocceler NS(N-tertiary butyl-2-[4-morpholinodithio base sulfinyl amine of the emerging chemical industry of imperial palace (strain) system)
Carbon black 2: DIABLACK LH(N326, the N of Mitsubishi Chemical's (strain) system
2sA:84m
2/ g)
Cobalt stearate: the cost-F(cobalt contents of large Japanese ink chemical industry (strain) system: 9.5 quality %)
The insoluble sulfur that contains 20% oil: four countries change into the ミ ュ ー Network ロ OT-20 of (strain) system
DCBS: the emerging chemical industry of imperial palace (strain) Nocceler DZ(N processed, N-dicyclohexyl-2-[4-morpholinodithio base sulfinyl amine)
Embodiment and comparative example
About rubber composition for side wall, according to the mixed content shown in 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, under the condition of 160 ℃, by mixing 5 minutes of the material except vulcanizing agent and vulcanization accelerator, obtain mixing thing.Then, in the mixing thing obtaining, add sulphur and vulcanization accelerator, use mill, under the condition of 105 ℃ mixing 3 minutes, make unvulcanized rubber composition.
Then, if make steel wire cord rubber composition for coating, the thickness that unvulcanized rubber composition obtaining is configured as to 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, is configured as sidewall shape (the thick 5mm of being of sidewall rubber of the tire axial maximum width of tire).And, according to the combination shown in table 1,2, with other structural tire part laminatings, by carrying out compression molding 12 minutes with dome type vulcanizer at table 1,2 temperature that show, made test with pneumatic tyre (whole steel wire radial tyre) (295/80R22.5).
In the coated Yong Xiang Jiao Group compound of steel wire cord, with respect to NR100 mass parts, mixed the insoluble sulfur that contains 20% oil (scale shown in table 1,2 shows bright sulfur composition), the 1 mass parts DCBS of the amount shown in 60 mass parts carbon black 2,1 mass parts cobalt stearates, 10 mass parts zinc oxide, 2 mass parts C5, table 1,2.
At the air of 80 ℃, fill in baking box the test obtaining is used to standing 3 weeks of pneumatic tyre, as the test pneumatic tyre after thermal ageing.
From airtyred tire axial maximum width part for resulting test (because be the thinnest part of sidewall rubber (rubber is thick is 5mm), the part so curing temperature the most easily rises, be sulphur and the most easily produce mobile part) surface, the sidewall part of the 2mm substantial middle of the tire axial width of sidewall rubber (part (SW central part)) to the inside, get sidewall rubber sample (with reference to Fig. 1).
Equally, the sidewall rubber sample after the test from thermal ageing uses pneumatic tyre heat-obtaining aging.
The sidewall rubber sample after pneumatic tyre, sidewall rubber sample, thermal ageing for test after the thermal ageing that use obtains, carries out following evaluation.Respectively test-results is shown in to table 1,2.
(mensuration of sulfur content)
To sidewall rubber sample, with process furnace, change sulphur (S) into sulfurous gas (SO
2), use carbon and sulfur analytical instrument, by infrared detection, carry out chemical analysis (sulphur quantitatively).
(complex modulus (hardness) (E*), low oil consumption (tan δ))
The visco-elasticity spectrometer that uses rock this makings institute (strain) to make, under 70 ℃, the condition of initial stage strain 10%, dynamic strain 2%, frequency 10Hz, has measured 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 JIS K6251 " method of calculation of vulcanized rubber and thermoplastic elastomer-tensile properties ", is implemented tension test in room temperature, 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, also measured elongation at break and the EB(% after thermal ageing).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 wide portion of maximum of airtyred tire axial, with 45 degree directions, the crack of the 20 wide 2mm in place, dark 0.2mm is set on circumference, under the condition of 140% load of the maximum load (maximum internal pressure condition) of JIS standard, make described tire on rotary drum with 80km/h speed 80,000 km that travel, by crack growth extent index.Moreover the situation that stretch in the 45 degree directions that tilt in crack 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 consists of the rubber composition for side wall of the divinyl rubber that contains specified quantitative, sulphur, the steel wire cord of carcass is coated and forms by steel wire cord rubber composition for coating, 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.Obtain good driving stability, low oil consumption, elongation at break again, simultaneously.
In comparative example 1～3, the sulphur content of rubber composition for side wall is few, and Sulfur capacity easily moves to sidewall from carcass, so 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, so poor durability.Content at divinyl rubber departs from the comparative example 7,8 of specified quantitative, the extension at break rate variance after thermal ageing, so poor durability.The difference of the content of the sulphur of rubber composition for side wall and steel wire cord rubber composition for coating surpasses in 4.20 comparative example 3,9, because Sulfur capacity easily moves to sidewall from carcass, so poor durability.In addition,, though the difference of above-mentioned sulphur content is little, in the comparative example 4,5,6 of the content of the sulphur of rubber composition for side wall many (2.5 mass parts), 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 consists 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 %, with respect to 100 mass parts rubber constituents, the content of sulphur surpasses 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 < (with respect to the content of the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(with respect to the content of 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 < (with respect to the content of the sulphur of rubber constituent 100 mass parts of steel wire cord rubber composition for coating)-(with respect to the content of 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 ℃.
4. the pneumatic tyre as described in any one of claim 1～3, 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. the pneumatic tyre as described in any one of claim 1～4, wherein, rubber composition for side wall comprises and contains the divinyl rubber of advising polyhutadiene crystal between 1,2-as divinyl rubber.
6. the pneumatic tyre as described in any one of claim 1～5, wherein, the content of the vulcanization accelerator of rubber composition for side wall, with respect to 100 mass parts rubber constituents, is 0.3～0.8 mass parts.
7. the pneumatic tyre as described in any one of claim 1～6, described tire is heavy tire for heavy load use.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011181871 | 2011-08-23 | ||
| JP2011-181871 | 2011-08-23 | ||
| JP2012-017256 | 2012-01-30 | ||
| JP2012017256A JP5111670B1 (en) | 2011-08-23 | 2012-01-30 | Pneumatic tire |
| PCT/JP2012/070952 WO2013027690A1 (en) | 2011-08-23 | 2012-08-20 | Pneumatic tire |
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| Publication Number | Publication Date |
|---|---|
| CN103717662A true CN103717662A (en) | 2014-04-09 |
| CN103717662B CN103717662B (en) | 2015-12-09 |
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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 |
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| Application Number | Title | Priority Date | Filing Date |
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| 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 |
|---|---|---|---|---|
| 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 |
Families Citing this family (10)
| 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 |
| EP2985310B1 (en) * | 2013-04-30 | 2018-02-21 | Sumitomo Rubber Industries, Ltd. | 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 |
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| 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 |
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| 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 BR BR112014004208A patent/BR112014004208A2/en not_active IP Right Cessation
- 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
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 |
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| 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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| CN102950979A (en) | 2013-03-06 |
| CN103717662B (en) | 2015-12-09 |
| BR112014004208A2 (en) | 2017-03-14 |
| JP5111670B1 (en) | 2013-01-09 |
| WO2013027690A1 (en) | 2013-02-28 |
| JP2013060184A (en) | 2013-04-04 |
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