WO2014133174A1 - 空気入り安全タイヤ - Google Patents
空気入り安全タイヤ Download PDFInfo
- Publication number
- WO2014133174A1 WO2014133174A1 PCT/JP2014/055191 JP2014055191W WO2014133174A1 WO 2014133174 A1 WO2014133174 A1 WO 2014133174A1 JP 2014055191 W JP2014055191 W JP 2014055191W WO 2014133174 A1 WO2014133174 A1 WO 2014133174A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tire
- carcass ply
- group
- fiber
- rubber
- Prior art date
Links
Images
Classifications
-
- 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
- B60C9/0042—Reinforcements made of synthetic materials
-
- 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
- B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
- B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
-
- 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
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/0009—Tyre beads, e.g. ply turn-up or overlap features of the carcass terminal portion
- B60C15/0036—Tyre beads, e.g. ply turn-up or overlap features of the carcass terminal portion with high ply turn-up, i.e. folded around the bead core and terminating radially above the point of maximum section width
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
-
- 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
- B60C9/04—Carcasses the reinforcing cords of each carcass ply arranged in a substantially parallel relationship
- B60C2009/0475—Particular materials of the carcass cords
-
- 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
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/0009—Tyre beads, e.g. ply turn-up or overlap features of the carcass terminal portion
- B60C2015/009—Height of the carcass terminal portion defined in terms of a numerical value or ratio in proportion to section height
-
- 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
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C15/0603—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead characterised by features of the bead filler or apex
- B60C2015/061—Dimensions of the bead filler in terms of numerical values or ratio in proportion to section height
-
- 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
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C2015/0614—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead characterised by features of the chafer or clinch portion, i.e. the part of the bead contacting the rim
-
- 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
- B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
- B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
- B60C2017/0054—Physical properties or dimensions of the inserts
-
- 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
- B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
- B60C17/0009—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor comprising sidewall rubber inserts, e.g. crescent shaped inserts
- B60C2017/0054—Physical properties or dimensions of the inserts
- B60C2017/0072—Thickness
Definitions
- the present invention relates to a pneumatic safety tire (hereinafter, also simply referred to as “tire”).
- a side-reinforcement type tire that can safely travel a certain distance without losing its load-bearing capacity.
- Various safety tires have been proposed.
- a side-reinforced safety tire is a crescent-shaped side reinforcing rubber layer with a relatively high modulus on the inner surface of the carcass on the side wall of the tire to improve the rigidity of the side wall and reduce the side pressure when the internal pressure decreases.
- polyester cords such as polyethylene terephthalate (PET) are widely used.
- Aramid cords are also widely used.
- Patent Document 1 discloses a two-bath treatment in which PET is once immersed in an epoxy adhesive and then immersed again in an RFL adhesive. Yes.
- an object of the present invention is to provide a pneumatic safety tire with improved durability by improving the compression fatigue resistance of the carcass ply cord and improving the heat-resistant adhesion between the carcass ply cord and the rubber. It is in.
- the pneumatic safety tire of the present invention has a skeleton of a carcass made of at least one carcass ply extending between a pair of bead cores embedded in a pair of bead portions, and a tire width of a side wall portion of the carcass.
- a pneumatic safety tire provided with a side reinforcing rubber on the inner side in the direction, wherein in the cross section in the tire width direction, the area of the side reinforcing rubber is S1, and the area of the bead filler arranged on the outer side in the tire radial direction of the bead core is S2.
- the carcass ply reinforcing cord is made of polyester fiber and / or aramid fiber, and the carcass ply reinforcing cord is made of thermoplastic polymer (A), heat-reactive water-based urethane resin (B), and epoxide.
- the thermoplastic polymer is obtained by using an adhesive containing at least one of the compounds (C) as a one-bath treatment liquid and using a resorcin / formalin / latex adhesive as a two-bath treatment liquid.
- the main chain of (A) is substantially composed of an ethylenic addition polymer and / or a urethane-based high molecular polymer mainly composed of a linear structure, which does not substantially have an addition-reactive carbon-carbon double bond. And having at least one functional group having crosslinkability as a pendant group.
- the “pendant group” is a functional group that modifies the polymer chain.
- the pendant group is introduced into the polymer chain by a known method such as a method of polymerizing a monomer containing a pendant group or a method of introducing a pendant group into a polymer chain by a chemical modification reaction. It can be carried out.
- “Aqueous” in an aqueous resin means water-soluble or water-dispersible, and “addition-reactive carbon-carbon double bond” has resonance stability such as an aromatic six-membered ring. Does not include carbon-carbon double bonds.
- a pneumatic safety tire with improved durability can be realized by adopting the above configuration.
- (A)-(c) is the width direction one side sectional view which shows an example of the pneumatic safety tire of this invention. It is a partially cutaway perspective view showing still another example of the pneumatic safety tire of the present invention. It is explanatory drawing which shows the generation
- FIG. 1A shows a cross-sectional view in one side in the width direction showing an example of the pneumatic safety tire of the present invention.
- the pneumatic safety tire of the present invention has a carcass 2 including at least one carcass ply extending between a pair of bead cores 1 embedded in a pair of bead portions 11 as a skeleton.
- the illustrated tire includes two belt layers 3 on the outer side in the radial direction of the crown portion of the carcass 2 and so-called side reinforcing rubber 4 having a substantially crescent-shaped cross section on the inner side in the tire width direction of the sidewall portion 12 of the carcass 2. This is a side-reinforced safety tire.
- the side reinforcing rubber 4 having a substantially crescent-shaped cross section on the inner side in the tire width direction of the carcass ply in the vicinity of the maximum tire width.
- rubber having a high elastic modulus may be inserted in the vicinity of a portion where the carcass ply 2 and the bead core 1 are adjacent and in the vicinity of a portion where the rim and the tire are in contact with each other. It is effective.
- the rigidity of the sidewall portion can be controlled by the area S1 of the side reinforcing rubber 4, and the rigidity of the bead portion is the sum of the area S2 of the bead filler 5 and the area S3 of the rubber chafer 6 (S2 + S3). It is thought that it can be controlled by.
- the present inventor has prescribed the relationship between the area S1 of the side reinforcing rubber 4 and the sum of the areas of the bead filler 5 and the rubber chafer 6 (S2 + S3) according to the above formula (1).
- S2 + S3 the relationship between the area S1 of the side reinforcing rubber 4 and the sum of the areas of the bead filler 5 and the rubber chafer 6
- the present inventors have found that a tire capable of supporting the load stably even when the internal pressure is reduced by increasing the rigidity of the sidewall portion and the bead portion in a well-balanced manner has been found. If the value of (S2 + S3) / S1 is smaller than 0.10, the relative rigidity of the bead portion is lowered, and there is a possibility that the tire may fail early in the vicinity of the bead portion.
- the tire of the present invention has the following formula (3), 0.20 ⁇ (S2 + S3) /S1 ⁇ 1.50 (3) Shall be satisfied. Thereby, tire durability at the time of run flat running can be further improved.
- the area S2 of the bead filler 5 in the sum of the areas of the bead filler 5 and the rubber chafer 6 (S2 + S3) It is necessary that the value of the ratio S2 / (S2 + S3) satisfies the above formula (2).
- the value of S2 / (S2 + S3) is larger than 0.9, the compression input to the carcass ply increases along with the deformation of the sidewall portion when the tire is bent under load and the strength of the cord is increased. Decrease increases.
- the value of S2 / (S2 + S3) may be zero, that is, the bead filler 5 may not be arranged in the present invention.
- the tire of the present invention has the following formula (4): 0 ⁇ S2 / (S2 + S3) ⁇ 0.80 (4) Shall be satisfied. This makes it possible to avoid a decrease in cord strength after running.
- the area S1 of the side reinforcing rubber 4, the area S2 of the bead filler 5, and the area S3 of the rubber chafer 6 are the above formulas (1) and (2), preferably further As long as the above formulas (3) and (4) are satisfied, the specific composition of the rubber composition constituting each of the side reinforcing rubber 4, the bead filler 5 and the rubber chafer 6, the physical properties thereof, etc. There is no particular limitation.
- the side reinforcing rubber 4 is arranged between the end of the belt 3 and the bead portion 11 beyond the tire maximum width portion between the tire carcass ply 2 and the inner liner (not shown).
- the side reinforcement rubber 4 is not limited to when comprised with 1 type of rubber compositions, You may consist of the laminated structure and combined structure of multiple types of rubber
- the bead filler 5 is usually between a carcass ply main body portion 2A extending in a toroidal shape between the bead cores 1 and a carcass ply turn-up portion 2B which is folded around the bead core 1 from the inside to the outside.
- the bead core 1 is disposed on the outer side in the tire radial direction.
- the rubber chafer 6 is in a region where the lower end is inside the tire radial direction from the outer end in the tire radial direction of the bead core 1 and the upper end is a position in the range of 10 to 70% of the tire cross-section height. Be placed.
- the tire cross-sectional height means a height in the tire radial direction in a no-load state when the tire is assembled to an applicable rim and filled with a prescribed air pressure.
- the standard is an industrial standard that is effective in an area where tires are produced or used, which will be described later.
- the reinforcing cord of the carcass ply 2 is made of polyester fiber and / or aramid fiber.
- polyester fiber cords, aramid fiber cords or hybrid cords of polyester fibers and aramid fibers as the reinforcing cords for the carcass ply 2, these fibers have higher strength and rigidity per weight, so that less cords and rubber Thus, while maintaining the strength of the tire, it is possible to secure the roundness of the tire and obtain an excellent effect in maintaining the tire shape.
- Specific examples of the polyester fiber include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), and the like.
- PET, PEN, and an aramid fiber can be used suitably as a reinforcement cord of the carcass ply 2.
- PEN has a rigid molecular structure, tire shape retention can be improved.
- a polyester cord formed by twisting specific polyester filaments and then being subjected to an adhesive treatment can be suitably used as the polyester filament used for the carcass ply.
- the polyester filament used for the carcass ply it is preferable to use a specific polyester filament having a specific epoxy-based surface treatment agent attached to the fiber surface.
- the polyester filament suitable in the present invention is a fiber made of polyester having an intrinsic viscosity of 0.85 or more, the main repeating unit of which is ethylene terephthalate, and the amount of terminal carboxy groups in the fiber is 20 equivalents / ton or more.
- the long period by X-ray small-angle diffraction is 9 to 12 nm, and the polyester fiber is made of a surface treatment agent having an epoxy group attached to the fiber surface.
- the intrinsic viscosity of the polyester fiber needs to be 0.85 or more, and preferably 1.10 or less. More preferably, a polyester fiber having an intrinsic viscosity of 0.90 to 1.00 is used. When the intrinsic viscosity is less than 0.85, the strength of the polyester fiber is not sufficient, and in particular, the strength reduction in the tire vulcanization process cannot be sufficiently suppressed.
- the amount of terminal carboxy groups of the entire polymer is 20 equivalents / ton or more, and a surface treatment agent having an epoxy group is attached to the fiber surface.
- a polyester fiber used for tire reinforcement it has been a general technique to keep the carboxy group of a polymer at 15 equivalent / ton or less for the purpose of improving its heat deterioration resistance.
- the polyester fiber for tire reinforcement has a high necessity for maintaining adhesion to rubber in addition to maintaining the strength of the fiber, the long period by X-ray small angle diffraction is 9 to 12 nm as in the polyester fiber according to the present invention.
- the present inventors have found that a carboxy group amount of 20 equivalents / ton or more is most suitable for tire reinforcement when the surface is subjected to an epoxy treatment.
- the upper limit of the amount of carboxy groups in the polymer is preferably 40 equivalents / ton or less, and more preferably the amount of carboxy groups in the range of 21 to 25 equivalents / ton.
- the surface treatment agent having an epoxy group attached to the surface of the polyester fiber contains an epoxy compound which is one or a mixture of two or more epoxy compounds having two or more epoxy groups in one molecule. Those are preferred. More specifically, halogen-containing epoxies are preferred, and examples include those obtained by synthesis with epichlorohydrin polyhydric alcohols or polyhydric phenols, and compounds such as glycerol polyglycidyl ether are preferred.
- the adhesion amount of the surface treatment agent containing such an epoxy compound to the fiber surface is in the range of 0.05 to 1.5% by mass, preferably 0.10 to 1.0% by mass.
- the surface treatment agent may be mixed with a smoothing agent, an emulsifier, an antistatic agent, other additives and the like as necessary.
- the long period by X-ray small angle diffraction needs to be 9 to 12 nm.
- the long period by X-ray small angle diffraction here means the space
- This long period in the polyester fiber according to the present invention is characterized by a short point, and the number of tie molecules connecting the crystals increases. As a result, the strength retention rate when used as a tire reinforcing fiber is increased. You can keep it.
- the physical properties of the fibers can be made suitable for high modulus and low shrinkage tire reinforcing fibers.
- the lower limit of the long period range is 9 nm.
- the long period of the polyester fiber by X-ray small angle diffraction is in the range of 10 to 11 nm.
- the amount of terminal carboxy groups on the fiber surface (raw yarn surface) of the polyester fiber is preferably 10 equivalents / ton or less.
- the carboxy group amount of the whole polymer in the polyester fiber according to the present invention is required to be 20 equivalents / ton or more as described above, but the carboxy group amount on the fiber surface is an epoxy compound attached to the fiber surface. It is preferable that it is below 10 equivalent / ton or less by reaction with this.
- the polyester resin according to the present invention has extremely excellent adhesive performance. At this time, if the amount of terminal carboxy groups on the fiber surface is excessively large, heat resistance and adhesiveness tend to decrease.
- the polyester fiber preferably has a crystal size in the fiber transverse axis direction of 35 to 80 nm 2 .
- the polyester fiber according to the present invention has a short period of 12 nm or less, which is a crystal interval in the longitudinal direction of the fiber, but in order to obtain a high strength fiber, the size of the crystal is also necessary. It is preferable that the crystal size in the horizontal axis direction grows to 35 nm 2 or more. However, even if the crystal size is too large, the fiber becomes stiff and the fatigue property is lowered. Therefore, the crystal size is preferably 80 nm 2 or less.
- the crystal size in the fiber horizontal axis direction is more preferably in the range of 40 to 70 nm 2 .
- the crystal grows in the horizontal axis direction of the fiber, so that the tie molecules easily develop in the horizontal axis direction of the fiber, so that a three-dimensional structure is constructed in the vertical and horizontal direction of the fiber for tire reinforcement. It becomes a particularly suitable fiber. Furthermore, by taking such a three-dimensional structure, the loss factor tan ⁇ of the fiber is lowered. As a result, the amount of heat generated under repeated stress can be suppressed, and the adhesion performance after applying repeated stress can be kept high, which makes the fiber particularly preferable for tire reinforcement applications.
- the amount of terminal methyl groups in the fiber is preferably 2 equivalents / ton or less, and more preferably, no terminal methyl group is contained. This is because the methyl group in the polyester polymer has low reactivity and does not react with the epoxy group at all, and therefore tends to inhibit the reaction between the carboxy group and the epoxy group effective for improving the adhesiveness. If the polymer constituting the fiber has no or few terminal methyl groups, high reactivity with the epoxy group in the surface treatment agent is ensured, and high adhesion and surface protection performance can be ensured. It becomes possible.
- the titanium oxide content in the fiber is preferably 0.05 to 3.0% by mass.
- the titanium oxide content is less than 0.05% by mass, the smoothing effect for dispersing the stress acting between the roller and the fiber in the stretching process or the like tends to be insufficient. There is a risk of increasing the strength.
- the content of titanium oxide is more than 3.0% by mass, the titanium oxide acts as a foreign substance inside the polymer to obstruct stretchability, and the strength of the finally obtained fiber tends to decrease. .
- the polyester fiber has an epoxy index on the fiber surface of 1.0 ⁇ 10 ⁇ 3 equivalent / kg or less.
- the epoxy index per kg of the polyester fiber is preferably 0.01 ⁇ 10 ⁇ 3 to 0.5 ⁇ 10 ⁇ 3 equivalent / kg.
- the epoxy index of the fiber surface is high, there is a tendency that there are many unreacted epoxy compounds. For example, a large amount of viscous scum is generated in the twisting process, and the processability of the fiber decreases. At the same time, there arises a problem that causes a decrease in product quality such as twisted yarn spots.
- the strength of the polyester fiber is preferably in the range of 4.0 to 10.0 cN / dtex.
- the strength is too low or too high, as a result, the durability in rubber tends to be inferior.
- the dry heat shrinkage of the fiber at 180 ° C. is preferably in the range of 1 to 15%. If the dry heat shrinkage is too high, the dimensional change during processing tends to be large, and the dimensional stability of a molded product using fibers tends to be inferior.
- the reinforcing cord of the carcass ply 2 is an adhesive containing at least one of a thermoplastic polymer (A), a heat-reactive aqueous urethane resin (B) and an epoxide compound (C).
- a thermoplastic polymer A
- B heat-reactive aqueous urethane resin
- C epoxide compound
- it is treated with an adhesive using a resorcin / formalin / latex adhesive as a two-bath treatment liquid.
- thermoplastic polymer (A) an acrylic polymer, acetic acid, the main chain of which has substantially no addition-reactive carbon-carbon double bond and mainly has a linear structure. It is composed of an ethylenic addition polymer such as a vinyl polymer, vinyl acetate / ethylene polymer, and / or a urethane polymer, and has at least one functional group having crosslinkability as a pendant group.
- the main chain of the thermoplastic polymer (A) is composed of an ethylenic addition polymer
- the thermoplastic polymer (A) is substantially composed of a monomer-derived unit having one carbon-carbon double bond, such as a conjugated diene monomer. It is preferable that the addition-reactive carbon-carbon double bond introduced by the above is 10% or less in terms of the monomer composition ratio.
- examples of the ethylenically unsaturated monomer having one carbon-carbon double bond include ⁇ -olefins such as ethylene, propylene, butylene and isobutylene; styrene ⁇ , ⁇ -unsaturated aromatic monomers such as ⁇ -methylstyrene, monochlorostyrene, vinyltoluene, vinylnaphthalene, styrene, sodium sulfonate; itaconic acid, fumaric acid, maleic acid, acrylic acid, methacrylic acid, Ethylene carboxylic acids such as butenetricarboxylic acid and salts thereof; acid anhydrides such as maleic anhydride and itaconic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, me
- monomers containing two or more carbon-carbon double bonds include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3 -Conjugated diene monomers such as halogen-substituted butadienes such as dimethyl-1,3-butadiene and chloroprene.
- the non-conjugated diene monomer include non-acting diene monomers such as vinyl nobornene, dicyclopentadiene, 1,4-hexadiene, and the like. You may use the above together.
- Urethane-based high molecular weight polymers are bonds resulting from the reaction between isocyanate groups and active hydrogen, such as urethane bonds and urea bonds obtained by polyaddition reaction of polyisocyanate and a compound having two or more active hydrogens. Is a high molecular polymer having a large number in the molecule. Not only bonds resulting from the reaction between isocyanate groups and active hydrogen, but also ester bonds, ether bonds, amide bonds, and uretdiones, carbodiimides, etc., produced by the reaction between isocyanate groups, contained in the active hydrogen compound molecule. May be included.
- the functional group having crosslinkability as the pendant group is at least one of oxazoline group, bismaleimide group, (blocked) isocyanate group, aziridine group, carbodiimide group, hydrazino group, epoxy group and epithio group, More preferred is an oxazoline group.
- a resin having a plurality of thermally dissociable blocked isocyanate groups in one molecule is preferably used as the heat-reactive aqueous urethane resin (B).
- a heat-reactive aqueous polyurethane compound represented by the following general formula is optimal.
- A represents an isocyanate residue of an organic polyisocyanate compound having 3 to 5 functional groups
- Y represents an active hydrogen residue of a blocking agent compound that liberates an isocyanate group by heat treatment
- Z represents at least 1 in the molecule.
- X is an active hydrogen residue of a polyol compound having 2 to 4 hydroxyl groups and an average molecular weight of 5000 or less.
- n is an integer of 2 to 4
- p + m is an integer of 2 to 4 (m ⁇ 0.25).
- the epoxide compound (C) can achieve the object of the present invention as long as it is a compound containing 2 or more, preferably 4 or more epoxy groups in one molecule, preferably, a compound containing an epoxy group, or The reaction product of polyhydric alcohols and epichlorohydrin.
- the epoxy compound include, for example, diethylene glycol diglycidyl ether, polyethylene diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Reaction of polychloridyl ether, trimethylolpropane / polyglycidyl ether, polyglycerol / polyglycidyl ether, pentaerythiol / polyglycidyl ether, diglycerol / polyglycidyl ether, sorbitol / polyglycidyl ether, and epichlorohydrin Product: Novolak epoxy resin such as phenol novolac epoxy resin and cresol novolac epoxy resin ; Like bisphenol A type epoxy resin. As the epoxide compound, sorbitol polyglycidyl ether or polyglycerol polyg,
- a mixed solution of the above components (A), (B) and (C) is used as a one-bath treatment solution.
- the ratio of each of these components is the dry weight ratio in the adhesive composition.
- the component (A) is 2 to 75%, the component (B) is 15 to 87%, and the component (C) is 11 to 70%. Is preferred.
- the carcass 2 is composed of at least one, for example, 1 to 3, especially 1 to 2, carcass plies formed by coating a plurality of reinforcing cords arranged in parallel with a coating rubber.
- the reinforcing cords of all carcass plies 2 are made of polyester fiber or aramid fiber, and are subjected to the above-mentioned specific adhesive treatment.
- the adhesive strength of the reinforcing cord of the carcass ply 2 is preferably 12 N / piece or more, and particularly preferably 15 N / piece or more.
- the said adhesive force is a value measured by the dynamic adhesion test mentioned later.
- the intermediate elongation at 66N of the carcass ply reinforcement cord in the crown portion taken out from the product tire is 3.5 to 6. It is preferably in the range of 5%, particularly 4.5 to 6.0%, and in the case of the carcass ply reinforcing cord made of aramid fibers, the range of 0.5 to 2.5%.
- the carcass ply 2 is folded around the bead core 1 from the inside to the outside as shown in the drawing.
- the carcass ply turn-up portion 2B is preferably located closer to the bead core 1 than the maximum thickness portion of the side reinforcing rubber 4 as shown in the figure. This is because the ply cord is less likely to be compressed and deformed, so that fatigue of the ply cord can be suppressed and the tire weight can be reduced.
- the folded portion 2B of the carcass ply the height H E from the center of the bead core 1, 30 mm or less, in particular, as being in the range of 5 ⁇ 25 mm, for example, shown in FIG. 1 (b) As described above, the height of the folded end portion of the carcass ply 2 is set low.
- the folded portion 2B of the carcass ply is set low to be positioned bead core 1 side than the maximum thickness of the side reinforcing rubber 4, in particular, when the height H E and 30mm or less, the rim flange compressed input is applied to the load at Since the organic fiber is not disposed in the vicinity of the contact point between the tire and the tire, it is possible to control the tire performance such as steering stability without considering the fatigue property of the cord. If the carcass ply turn-up portion 2B is too high, compression input acts on the rim flange portion, so the end of the nearby reinforcing cord becomes fatigued, which becomes a fracture nucleus, and induces peeling of the rubber layer, There are cases where the durability of the tire during normal running cannot be sufficiently improved.
- the bead filler 5 has a small shape so that the folded portion 2B of the carcass cord immediately follows the inner surface of the tire.
- the carcass cord exists outside the bending deformation, and only the tensile input, not the compression input, is applied to the cord. .
- the height of the bead filler 5 is set to 15 mm or less because the shape and the numerical value of the rim flange are standardized. This is because the carcass cord can be avoided. Further, when the bead filler 5 is 15 mm or less in height, there is a possibility that the compression input is applied to the end of the ply depending on the bending rigidity around the bead, the internal pressure condition, input, and the like. By setting the thickness to 10 mm or less, compression input can be reliably avoided regardless of the type of tire. There is no restriction
- the heights of the carcass ply 2 and the bead filler mean the height in the tire radial direction in a no-load state when the tire is assembled to an applicable rim and filled with a specified air pressure.
- the applicable rim means a rim defined in the following standard
- the prescribed air pressure means an air pressure defined in accordance with the maximum load capacity in the following standard.
- the standard is an industrial standard effective in an area where tires are produced or used. For example, in the United States, the Tire and Rim Association Inc. In Europe, the European Tire and Rim Technical Organization Standards Manual in Japan, and in Japan, the Japan Automobile Tire Association JATMA Year book.
- the belt layer 3 is composed of a rubberized layer of cords, preferably a rubberized layer of steel cords, extending at an angle of 15 ° to 35 ° with respect to the tire equatorial plane, and the two belt layers 3 are usually belts.
- the cords constituting the layer 3 are laminated so as to intersect with each other across the equator plane to constitute a belt.
- the belt is composed of two belt layers 3.
- the number of belt layers constituting the belt is not limited thereto.
- a belt reinforcing layer (cap layer) covering the entire belt comprising a rubberized layer of cords arranged substantially parallel to the tire circumferential direction on the outer side in the tire radial direction of the belt 3,
- a pair of belt reinforcing layers (layer layers) covering only both ends of the cap layer can also be disposed.
- a turbulent-flow generating convex portion 7 may be disposed on the side portion.
- the provision of the turbulent flow generating convex portion 7 improves the heat dissipation effect from the tire surface, suppresses the temperature rise of the tire during run-flat running, and changes the ambient temperature of the carcass 2 to the fibers constituting the carcass 2. It becomes possible to maintain the cord near the temperature at which the heat shrinkage stress is high. As a result, it is possible to obtain an effect of suppressing the bending during the run-flat running, and it is possible to further improve the emergency running life of the run-flat tire.
- FIG. 3 is a partial cross-sectional view showing the vicinity of the surface of the run-flat tire of the present invention.
- the air flow S1 that has been in contact with the tire surface in the portion where the turbulent flow generating convex portion 7 is not formed is generated along with the rotation of the tire. It is peeled off from the tire surface and gets over the turbulent flow generating projection 7.
- a portion (region) S ⁇ b> 2 where the air flow stays is formed on the back side of the turbulent flow generation convex portion 7.
- the air flow S1 rebounds on the tire surface between the next turbulent flow generation convex portion 7 and is peeled off from the tire surface again by the next turbulent flow generation convex portion 7.
- a portion (region) S3 in which the air flow stays is formed on the back side of the next turbulent flow generating projection 7.
- a plurality of turbulent flow generating convex portions 7 are arranged in the tire circumferential direction, and these turbulent flow generating convex portions 7 are arranged as turbulent flow generating convex portions.
- the distance between adjacent turbulent flow generating convex portions 7 at a point at which the width w is divided into two at the center in the longitudinal direction is defined as pitch p
- the height of the turbulent flow generating convex portion 7 is defined as h.
- the value of p / h is less than 1.0, the air flow does not enter the tire surface sandwiched between the adjacent turbulent flow generating projections 7, while if it exceeds 50.0, the influence of turbulence is exerted. In any case, a region that does not reach is generated, and in any case, the heat dissipation efficiency of the portion where the turbulent flow generation convex portion 7 is provided becomes equivalent to the portion where the turbulent flow generating convex portion 7 is not provided.
- the value of p / h is more preferably 2.0 ⁇ p / h ⁇ 24.0, and more preferably 10.0 ⁇ p / h ⁇ 20.0.
- (pw) / w indicates the ratio of the width w of the turbulent flow generation convex portion 7 to the pitch p.
- the small value indicates that turbulent flow is generated with respect to the heat radiating surface. It means that the ratio of the area of the convex part 7 for use increases, that is, the area of the heat radiating surface decreases. Therefore, if the value of (p ⁇ w) / w is less than 1, the area of the heat radiating surface is too small, and a sufficient improvement effect of the heat radiating efficiency cannot be expected, and furthermore, the volume of rubber increases. There is concern about an increase in the heat generated by rubber.
- the value of (pw) / w is preferably 4.0 ⁇ (pw) /w ⁇ 39.0.
- the height h of the turbulent flow generating convex portion 7 satisfies 0.5 mm ⁇ h ⁇ 7 mm and the width w satisfies 0.3 mm ⁇ w ⁇ 4 mm.
- the volume of the turbulent flow generation convex portion 7 increases, heat generation at the turbulent flow generation convex portion 7 increases, and turbulent flow generation occurs.
- the area where the convex portion 7 covers the surface increases and heat is stored on the rubber surface.
- the turbulent flow generation convex portion 7 is arranged such that an angle ⁇ between the longitudinal direction a and the tire radial direction r is 70 ° or less. It is preferable that The air flow on the tire surface on which the turbulent flow generation convex portion 7 is disposed is slightly outward in the tire radial direction due to the centrifugal force generated by the rotation of the tire.
- the angle ⁇ formed by the longitudinal direction a of the turbulent flow generation convex portion 7 with respect to the tire radial direction r is set to 70 ° or less, so that air flows into the tire surface and the rear of the turbulent flow generation convex portion 7 Therefore, the heat retention efficiency can be improved by reducing the staying portions S2 and S3.
- the longitudinal direction “a” of the turbulent flow generation convex portion 7 may be in a range of a total of 140 ° including 70 ° on one side and 70 ° on the other side with reference to the tire radial direction r.
- the air flow velocity varies depending on the position in the tire radial direction r. Therefore, when a plurality of turbulent flow generating convex portions 7 are arranged in the tire radial direction, the angle ⁇ is set according to the position of the turbulent flow generating convex portion 7 in the tire radial direction. It is preferable to make it different for every seven.
- the shape of the turbulent flow generating convex portion 7 is not particularly limited, but preferably, as shown in the drawing, the turbulent flow generating convex portion 7 is at least at the inner side in the tire radial direction, the top portion 7A. It shall have.
- the turbulent flow generation convex portion 7 may have a shape in which the portion corresponding to the top portion 7A is a curved surface in addition to the shape having the four top portions 7A.
- the top portion 7A at least inward in the tire radial direction, a three-dimensional air flow is generated around the top portion 7A, and the heat dissipation effect is further improved.
- the turbulent flow generation convex portion 7 is divided in the longitudinal direction. If the turbulent flow generating projections 7 are divided in the longitudinal direction, the stagnation flow generating projections S2 and S3 generated behind the turbulent flow generating projections 7 during tire rotation are reduced. Average heat dissipation can be achieved over the entire portion where the portion 7 is provided.
- segmentation number of the convex part 7 for turbulent flow generation in this case is not specifically limited, It can select arbitrarily.
- the installation frequency of the turbulent flow generating convex portions 7 in the tire circumferential direction is set.
- the position varies depending on the position in the tire radial direction.
- the flow velocity of air varies depending on the position in the radial direction.
- the heat dissipation efficiency depends on the flow velocity of air flowing on the tire surface.
- a plurality of turbulent flow generating convex portions 7 are installed in the tire circumferential direction and in the radial direction, respectively, and the installation frequency of the turbulent flow generating convex portions 7 in the tire circumferential direction, that is, the number of installation is changed depending on the tire radial direction.
- the non-uniformity of the heat dissipation efficiency due to the difference in the position in the tire radial direction on the surface of the tire can be eliminated.
- a tread pattern is appropriately formed on the surface of the tread portion 13, and an inner liner (not shown) is formed on the innermost layer.
- an inert gas such as nitrogen can be used as the gas filled in the tire.
- 1670 dtex yarn converging bodies which are multi-filaments of general-purpose polyethylene terephthalate (PET) are twisted together with 40 twists per 10 cm in length to obtain 1670 dtex / 2, twist number 40 ⁇ 40
- PEN polyethylene naphthalate
- twist number 39 ⁇ 39 times / 10 cm
- poly Cords having a structure represented by 1670 dtex / 2 and a twist number of 39 ⁇ 39 (times / 10 cm) of paraphenylene terephthalamide (aramid, Kevler (manufactured by Toray DuPont)) were prepared.
- adhesive A is a blend of two bath dip solutions conventionally used in PET.
- Dip solution A-1 in the first bath is an epoxy adhesive, 1.20 parts by weight of diglycerol triglycidyl ether, 0.02 parts by weight of sodium dioctyl sulfosuccinate, 0.14 parts by weight of caustic soda (10% aqueous solution) And 98.64 parts by mass of soft water.
- Dip solution A-2 in the second bath is an RFL adhesive, and includes 518.59 parts by mass of soft water, 15.12 parts by mass of resorcin, 16.72 parts by mass of formaldehyde (37% aqueous solution), and caustic soda (10% aqueous solution).
- the dip solution in the first bath is B-1, Epocross K1010E (manufactured by Nippon Shokubai Co., Ltd.) 16.5% by mass (solid content weight), Elastron BN27 (Daiichi Kogyo) It consists of 6% by mass (solids weight) manufactured by Pharmaceutical Co., Ltd., 7.5% by mass (solids weight) manufactured by Nagase Chemical Industries, Ltd., and 70% by mass of water.
- Is B-2 524.01 parts by weight of water, 15.12 parts by weight of resorcin, 16.72 parts by weight of formalin (37%) and 4.00 parts by weight of caustic soda (10%), vinylpyridine-styrene-butadiene 233.15 parts by mass of polymer latex (JSR0655, manufactured by JSR Corporation, solid concentration 41%), styrene-butadiene copolymer latex (JSR2108, manufactured by JSR Corporation, solid) Concentration of 40%) consisting of 207.00 parts by weight.
- the twisted cord obtained above is immersed in the dipping solution of the first bath, in a trizone at 160 ° C for 60 seconds under a tension of 2.0 kg / piece, for a hot zone of 240 ° C Then, heat treatment was performed for 60 seconds under a tension of 2.0 kg / piece. After that, it is again immersed in the dip solution of the second bath with a dip tension of 200 g, and again under a tension of 2.0 kg / piece, in a dry zone at 240 ° C. for 60 seconds, a hot zone of 0.5 to 1.5 kg / piece Heat treatment was applied for 60 seconds under tension for a total of 240 seconds to produce a cord coated with an adhesive. For the PET cord, the tension of the last hot zone in the dipping process was finely adjusted so that the intermediate elongation at 66 N load of the cord was 3.8%.
- FIG. 5 is a perspective view showing a rubber test piece used in the dynamic adhesion test.
- the tire reinforcing polyester cords 22 of the examples and comparative examples are embedded in a rubber matrix so that the cord layers are parallel to each other, and the width W is 50 mm, the length L is 500 mm, and the height.
- Each rubber test piece 21 was produced at H: 5.5 mm.
- the number of cords to be driven was 50/50 mm, the distance h 1 between cords was 2.5 mm, and the distance h 2 from the cord center to the surface was 1.5 mm. As shown in FIG.
- each rubber test piece 21 obtained was hung on a pulley 23 ( ⁇ 50 mm), a load of 50 kg / inch was applied in the cord axis direction, and tension and compressive force were circulated 300,000 times cyclically at 100 rpm. Loaded.
- the above test was carried out in a thermostatic bath capable of keeping the atmospheric temperature constant, and the dynamic adhesion at a high temperature of 100 ° C. was tested. After the test, the sample was cooled and then the tensile strength of the cord on the tensile side was measured (N / piece) to determine the dynamic adhesive strength.
- the rubber matrix used for the sample preparation was natural rubber 60.0 parts by mass, styrene butadiene rubber (SBR) 40.0 parts by mass, carbon black (HAF) 45.0 parts by mass, softener (spindle oil) 2 0.0 part by mass, 3.0 parts by mass of zinc white, 1.0 part by mass of anti-aging agent (NOCRACK 6C, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), vulcanization accelerator (Noxeller NS, Ouchi Shinsei Chemical Industry ( Co., Ltd.) 0.8 parts by mass, 1.0 parts by mass of stearic acid and 3.0 parts by mass of sulfur.
- the pulling speed during the adhesion test was 300 mm / min.
- the rubber test piece was produced under vulcanization conditions of 160 ° C. ⁇ 20 minutes.
- cords obtained above were covered with rubber to obtain rubber-cord composites of Examples and Comparative Examples.
- a treat with 50 shots / 50 mm was produced and applied to a carcass ply to produce a pneumatic safety tire of tire size 225 / 45R17.
- This test tire has a carcass made of a single carcass ply extending between a pair of bead cores embedded in a pair of bead portions, and the outer side in the tire radial direction of the carcass is ⁇
- the belt had two layers of belts (material: steel) that were arranged to intersect each other at an angle of 40 °, and one layer layer (material: nylon) covering the entire width of the belt layer.
- side reinforcement rubber is provided on the inner side in the tire width direction of the sidewall portion of the carcass, a bead filler is disposed on the outer side in the tire radial direction of the bead core, and a rubber chafer is disposed on the outer side in the tire width direction of the bead filler and the bead core. It had been. Tests for each example and comparative example were made so that the area S1 of the side reinforcing rubber, the area S2 of the bead filler, and the area S3 of the rubber chafer in the tire width direction cross section satisfy the conditions shown in the following table. A tire was produced. In Comparative Examples 7 and 8 and Examples 18 to 25, no bead filler was provided.
- Adhesive A Dip solution A-1 in the first bath (1.20 parts by mass of diglycerol triglycidyl ether, 0.02 parts by mass of sodium dioctyl sulfosuccinate, 0.14 parts by mass of caustic soda (10% aqueous solution)) And 98.64 parts by weight of soft water), Dip solution A-2 for the second bath (518.59 parts by weight of soft water, 15.12 parts by weight of resorcin, 16.72 parts by weight of formaldehyde (37% aqueous solution), caustic soda (10% Aqueous solution) 11.00 parts by mass, vinylpyridine-styrene-butadiene latex (41% concentration) 216.58 parts by mass and styrene-butadiene latex (40% concentration) 221.99 parts by mass).
- Adhesive B Dip solution B-1 for the first bath (Epocross K1010E (manufactured by Nippon Shokubai Co., Ltd.) 16.5% by mass (solid content weight), Elastron BN27 (Daiichi Kogyo Seiyaku Co., Ltd.
- polyester fiber or aramid fiber is used for the carcass ply reinforcement cord, and a predetermined adhesion treatment is performed, and the area of the side reinforcement rubber, bead filler, and rubber chafer in the cross section of the tire width direction is determined.
- the ratio satisfies the predetermined relationship defined by the formulas (1) and (2), compared to the test tire of the comparative example that does not satisfy the above relationship, It was confirmed that the adhesive strength, run flat durability and drum durability were improved as a whole.
- Polyester fibers as shown below were prepared by using a polyethylene terephthalate chip having an intrinsic viscosity of 1.03 and having a high carboxy group end, performing high-speed spinning and multistage drawing by a melt spinning method, and performing epoxy treatment on the surface.
- the oil agent used for the epoxy treatment adhered to 0.2 parts by mass with respect to 100 parts by mass of the fiber, and the amount of polyglycerol polyglycidyl ether, which is an epoxy compound component, was 0.12% by mass. It was.
- This polyester fiber has mechanical properties of an intrinsic viscosity of 0.91, a fineness of 1130 dtex, 384 filament, a strength of 6.9 cN / dtex, an elongation of 12%, and a dry heat shrinkage of 10.5%.
- the amount of carboxy groups is 22 equivalents / ton, the long period by X-ray small angle diffraction is 10 nm, the amount of terminal carboxy groups on the fiber surface is 7 equivalents / ton, the crystal size in the fiber horizontal axis direction is 45 nm 2 , and the amount of terminal methyl groups is
- the content was 0 equivalent / ton, the titanium oxide content was 0.05 mass%, and the surface epoxy group content (epoxy index) was 0.1 ⁇ 10 ⁇ 3 equivalent / kg.
- the intrinsic viscosity, strength and elongation of the polyester fiber, dry heat shrinkage rate, terminal carboxy group amount, long period by X-ray small angle diffraction and crystal size in the fiber transverse axis direction, terminal carboxy group amount on the fiber surface, terminal The methyl group content, titanium oxide content, and surface epoxy group content were measured according to the following. The same applies to the following.
- ⁇ Titanium oxide content> The content of each element was measured using a fluorescent X-ray apparatus (manufactured by Rigaku Corporation, Model 3270E), and quantitative analysis was performed.
- a fluorescent X-ray apparatus manufactured by Rigaku Corporation, Model 3270E
- a test molded body having a flat surface was produced under a pressure of 7 MPa, Measurements were performed.
- the X-ray diffraction of the polyester composition / fiber was performed using an X-ray diffractometer (manufactured by Rigaku Corporation, RINT-TTR3, Cu-K ⁇ ray, tube voltage 50 kV, current 300 mA, parallel beam method).
- the long-period interval is a meridional interference diffraction line obtained by irradiating at a right angle to the fiber axis with a conventionally known method using a small-angle X-ray scattering measurement apparatus, using a Cu-K ⁇ ray with a wavelength of 1.54 mm as a radiation source. From this, it was calculated using the Bragg equation.
- the crystal size was determined from the X-ray wide angle diffraction using the half-width of the (010) (100) intensity distribution curve of the equator scan using the shirare equation.
- the rubber used in the adhesive treatment is the same as in Example 1 above, except that the adhesive shown in the table below is used.
- -Cord composites were prepared, and test tires of the examples and comparative examples were prepared.
- the polyester fiber is used for the reinforcing cord of the carcass ply, the predetermined adhesion treatment is performed, and the ratio of the area of the side reinforcing rubber, the bead filler and the rubber chafer in the tire width direction cross section is as follows:
- the adhesive strength compared with the test tire of the comparative example that does not satisfy the above relationship, It was confirmed that run-flat durability and drum durability were improved as a whole.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Tires In General (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
0.10≦(S2+S3)/S1≦2.50 (1)
0≦S2/(S2+S3)≦0.9 (2)
を満足し、前記カーカスプライの補強コードがポリエステル繊維および/またはアラミド繊維からなり、かつ、該カーカスプライの補強コードが、熱可塑性重合体(A)、熱反応型水性ウレタン樹脂(B)およびエポキシド化合物(C)のうちの少なくとも一種を含む接着剤を1浴処理液として用いるとともに、レゾルシン・ホルマリン・ラテックス系接着剤を2浴処理液として用いて接着剤処理されてなり、該熱可塑性重合体(A)の主鎖が、付加反応性のある炭素間2重結合を実質的に有さず、直鎖状構造を主体としたエチレン性付加重合体および/またはウレタン系高分子重合体よりなり、ペンダント基として架橋性を有する官能基を少なくとも1つ有することを特徴とするものである。
図1(a)に、本発明の空気入り安全タイヤの一例を示す幅方向片側断面図を示す。図示するように、本発明の空気入り安全タイヤは、一対のビード部11にそれぞれ埋設された一対のビードコア1間に延在する少なくとも1枚のカーカスプライからなるカーカス2を骨格とする。図示するタイヤは、カーカス2のクラウン部タイヤ半径方向外側に2枚のベルト層3を備え、カーカス2のサイドウォール部12のタイヤ幅方向内側に断面略三日月状のサイド補強ゴム4を備える、いわゆるサイド補強タイプの安全タイヤである。
0.10≦(S2+S3)/S1≦2.50 (1)
0≦S2/(S2+S3)≦0.9 (2)
を満足する点が重要である。これは、以下のような理由による。
0.20≦(S2+S3)/S1≦1.50 (3)
を満足するものとする。これにより、ランフラット走行時におけるタイヤ耐久性をより高めることができる。
0≦S2/(S2+S3)≦0.80 (4)
を満足するものとする。これにより、走行後のコード強力の低下を避けることが可能となる。
(式中、Aは官能基数3~5の有機ポリイソシアネート化合物のイソシアネート残基を示し、Yは熱処理によりイソシアネート基を遊離するブロック剤化合物の活性水素残基を示し、Zは分子中、少なくとも1個の活性水素原子および少なくとも1個のアニオン形成性基を有する化合物の活性水素残基を示し、Xは2~4個の水酸基を有し平均分子量が5000以下のポリオール化合物の活性水素残基であり、nは2~4の整数であり、p+mは2~4の整数(m≧0.25)である。)
汎用のポリエチレンテレフタレート(PET)のマルチフィラメントである1670dtexのヤーン収束体2本の下撚りおよび上撚りを、長さ10cmあたり40回の撚り数で撚り合わせて、1670dtex/2、撚り数40×40(回/10cm)で表される構造のPETコードを得た。同様にして、ポリエチレンナフタレート(PEN,原糸タイプNo.Q904(帝人(株)製))の1670dtex/2、撚り数39×39(回/10cm)で表される構造のコード、および、ポリパラフェニレンテレフタルアミド(アラミド,Kevler(ケブラー)(東レ・デュポン(株)製))の1670dtex/2、撚り数39×39(回/10cm)で表される構造のコードをそれぞれ準備した。
図5は、動的接着試験に用いたゴム試験片を示す斜視図である。
図示するように、コード層が互いに平行になるように、各実施例および比較例のタイヤ補強用ポリエステルコード22をゴムマトリックス中に埋設して、幅W:50mm、長さL:500mmおよび高さH:5.5mmにて、各ゴム試験片21を作製した。コードの打込み数は50本/50mmとし、コード間距離h1は2.5mm、コード中心から表面までの距離h2は1.5mmとした。図6に示すように、得られた各ゴム試験片21をプーリ23(φ50mm)に掛け、コード軸方向に50kg/inchの荷重を掛け、100rpmにて30万回にわたって循環的に張力および圧縮力を負荷した。上記試験は雰囲気温度を一定に保持できる恒温槽の中にて実施して、100℃の高温時における動的接着性を試験した。試験後、サンプルを冷却した後に引張側コードの引き起こし接着力(N/本)を測定して、動的接着力とした。ここで、サンプル作製に使用したゴムマトリックスは、天然ゴム60.0質量部、スチレンブタジエンゴム(SBR)40.0質量部、カーボンブラック(HAF)45.0質量部、軟化剤(スピンドルオイル)2.0質量部、亜鉛華3.0質量部、老化防止剤(ノクラック6C,大内新興化学工業(株)製)1.0質量部、加硫促進剤(ノクセラーNS,大内新興化学工業(株)製)0.8質量部、ステアリン酸1.0質量部および硫黄3.0質量部よりなる。接着試験時の引張り速度は300mm/分とした。ゴム試験片は、160℃×20分の加硫条件にて作製した。
各供試タイヤをJATMAに規定される標準リムにリム組みした後、ドラム試験機に取り付け、バルブコアを抜いて内圧を除去し、JATMAに規定される最大荷重の65%の荷重をかけてランフラット耐久試験を実施し、故障に至るまでの走行距離を測定した。結果は、比較例1を100としたときの指数で表した。この数値が大きいほど、走行距離が長くランフラット耐久性に優れていることを示す。
各供試タイヤをJATMAに規定される標準リムにリム組みした後、ドラム試験機に取り付け、内圧100kPaを充填し、JATMAに規定される最大荷重を負荷して、ドラム上を20000km走行させた。試験終了後に、各供試タイヤを解剖して、カーカスプライの残存強力を測定し、新品時からの強力保持率を評価した。結果は、比較例1の強力保持率を100としたときの指数で表示し、数値が大きいほど、ドラム耐久性に優れていることを表す。その結果を、下記の表中に併せて示す。
*2)A:カーカスプライの折返し部の、ビードコアの中心からの高さHEが、60mmである構造。B:カーカスプライの折返し部の、ビードコアの中心からの高さHEが、30mmである構造。C:カーカスプライの折返し部の、ビードコアの中心からの高さHEが、15mmである構造。
固有粘度1.03の高カルボキシ基末端を有するポリエチレンテレフタレートチップを用い、溶融紡糸法により高速紡糸、多段延伸を行って、表面にエポキシ処理を施すことにより、下記のようなポリエステル繊維を準備した。なお、エポキシ処理に用いた油剤は、繊維100質量部に対して0.2質量部付着しており、エポキシ化合物成分であるポリグリセロールポリグリシジルエーテルの繊維表面付着量は0.12質量%であった。
ポリエステルチップ、ポリエステル繊維を、100℃、60分間でオルトクロロフェノールに溶解した希薄溶液を、35℃でウベローデ粘度計を用いて測定した値から求めた。
粉砕機を用いて粉末状にしたポリエステルサンプル40.00gおよびベンジルアルコール100mlをフラスコに加え、窒素気流下で215±1℃の条件下、4分間にてポリエステルサンプルをベンジルアルコールに溶解させた。溶解後、室温までサンプル溶液を冷却させた後、フェノールレッドのベンジルアルコール0.1質量%溶液を適量添加し、N規定の水酸化ナトリウムのベンジルアルコール溶液によって、速やかに滴定し、変色が起こるまでの滴下量をAmlとした。ブランクとして、100mlのベンジルアルコールにフェノールレッドのベンジルアルコール0.1質量%溶液を同量添加し、N規定の水酸化ナトリウムのベンジルアルコール溶液によって、速やかに滴定し、変色が起こるまでの滴下量をBmlとした。それらの値から、下記式によって、ポリエステルサンプル中の末端COOH基含有量を計算した。
末端COOH基含有量(eq/100g)=(A-B)×103×N×106/40
なお、ここで使用したベンジルアルコールは、試薬特級グレードのものを蒸留し、遮光瓶内で保管したものである。N規定の水酸化ナトリウムのベンジルアルコール溶液としては、定法により事前に濃度既知の硫酸溶液によって滴定し、規定度Nを正確に求めたものを使用した。
ポリエステルを加水分解して酸成分、グリコール成分にした後、ガスクロマトグラフィーにてメチルエステル成分を定量し、この値から算出した。
各元素の含有量は、蛍光X線装置((株)リガク製,3270E型)を用いて測定し、定量分析を行った。この蛍光X線分析の際には、圧縮プレス機にて、ポリエステル繊維樹脂ポリマーサンプルを2分間260℃にて加熱しながら、7MPaの加圧条件下で平坦面を有する試験成形体を作製し、測定を実施した。
ポリエステル組成物・繊維のX線回折については、X線回折装置((株)リガク製,RINT-TTR3,Cu-Kα線,管電圧50kV,電流300mA,平行ビーム法)を用いて行った。長周期間隔はX線小角散乱測定装置を用いて、従来公知の方法、すなわち、波長1.54ÅのCu-Kα線を線源とし、繊維軸に直角に照射して得られる子午線干渉の回折線より、ブラッグの式を用いて算出した。結晶サイズはX線広角回折から赤道線走査の(010)(100)強度分布曲線の半価幅より、シエラーの式を用いて求めた。
JIS K0070-3.1項 中和滴定法に準じて、繊維表面のカルボキシ基量(酸価)を求めた。すなわち、繊維試料約5gにジエチルエーテル/エタノール=1/1溶液50mlを加え、指示薬としてフェノールフタレイン溶液を数滴添加し、室温で15分間超音波振とうした。この溶液に、0.1ml水酸化カリウムエタノール溶液(ファクター値f=1.030)で滴定し、指示薬のうすい紅色が30秒間続いたときを終点として指示薬滴下量を測定し、以下の式から酸価を算出した。
酸価A(eq/ton)=(B×1.030×100)/S
(ここで、Bは0.1ml水酸化カリウムエタノール溶液滴定量(ml)、Sは試料量(g)を表す)
引張荷重測定器((株)島津製作所製オートグラフ)を用いて、JIS L-1013に従って測定した。
JIS-L1013に従い、20℃、65%RHの温湿度管理された部屋で、24時間放置後、無荷重状態で、乾燥機内で180℃×30分間熱処理し、熱処理前後の試長差より算出した。
加温処理後のポリエステル繊維について、JIS K-7236に従ってエポキシ指数(EI:繊維1kgあたりのエポキシ当量数)を測定した。
Claims (11)
- 一対のビード部にそれぞれ埋設された一対のビードコア間に延在する少なくとも1枚のカーカスプライからなるカーカスを骨格とし、該カーカスのサイドウォール部のタイヤ幅方向内側にサイド補強ゴムを備える空気入り安全タイヤであって、
タイヤ幅方向断面において、前記サイド補強ゴムの面積をS1、前記ビードコアのタイヤ半径方向外側に配置されたビードフィラーの面積をS2、該ビードフィラーおよび該ビードコアのタイヤ幅方向外側に配置されたゴムチェーファーの面積をS3としたとき、下記式(1)および(2)、
0.10≦(S2+S3)/S1≦2.50 (1)
0≦S2/(S2+S3)≦0.9 (2)
を満足し、前記カーカスプライの補強コードがポリエステル繊維および/またはアラミド繊維からなり、かつ、該カーカスプライの補強コードが、熱可塑性重合体(A)、熱反応型水性ウレタン樹脂(B)およびエポキシド化合物(C)のうちの少なくとも一種を含む接着剤を1浴処理液として用いるとともに、レゾルシン・ホルマリン・ラテックス系接着剤を2浴処理液として用いて接着剤処理されてなり、該熱可塑性重合体(A)の主鎖が、付加反応性のある炭素間2重結合を実質的に有さず、直鎖状構造を主体としたエチレン性付加重合体および/またはウレタン系高分子重合体よりなり、ペンダント基として架橋性を有する官能基を少なくとも1つ有することを特徴とする空気入り安全タイヤ。 - 下記式(3)および(4)、
0.20≦(S2+S3)/S1≦1.50 (3)
0≦S2/(S2+S3)≦0.80 (4)
を満足する請求項1記載の空気入り安全タイヤ。 - 前記カーカスプライの補強コードの接着力が、12N/本以上である請求項1記載の空気入り安全タイヤ。
- 前記カーカスプライが、前記ビードコアの周りにタイヤ内側から外側に向かい折り返されてなり、該カーカスプライの折り返し端部が、前記サイド補強ゴムの最大厚み部分よりもタイヤ半径方向内側に位置している請求項1記載の空気入り安全タイヤ。
- 前記ビードフィラーの高さが15mm以下である請求項1記載の空気入り安全タイヤ。
- 前記カーカスプライが、前記ビードコアの周りにタイヤ内側から外側に向かい折り返されてなり、該カーカスプライの折り返し端部が、該ビードコアの中心から30mm以下の高さに位置する請求項1記載の空気入り安全タイヤ。
- 前記カーカスプライの補強コードがポリエステル繊維からなり、製品タイヤから取り出した、クラウン部における該カーカスプライの補強コードの66Nでの中間伸度が、3.5~6.5%の範囲である請求項1記載の空気入り安全タイヤ。
- 前記カーカスプライの補強コードがアラミド繊維からなり、製品タイヤから取り出した、クラウン部における該カーカスプライの補強コードの66Nでの中間伸度が、0.5~2.5%の範囲である請求項1記載の空気入り安全タイヤ。
- 前記ペンダント基としての架橋性を有する官能基が、オキサゾリン基、ビスマレイミド基、イソシアネート基、アジリジン基、カルボジイミド基、ヒドラジノ基、エポキシ基およびエピチオ基のうち少なくとも1つである請求項1記載の空気入り安全タイヤ。
- 前記ペンダント基としての架橋性を有する官能基が、オキサゾリン基である請求項9記載の空気入り安全タイヤ。
- 前記カーカスプライの補強コードが、エチレンテレフタレートを主たる繰り返し単位とする、固有粘度が0.85以上のポリエステルからなる繊維であって、繊維中の末端カルボキシ基量が20当量/ton以上であり、X線小角回折による長周期が9~12nmであり、繊維表面にエポキシ基を有する表面処理剤が付着してなるポリエステル繊維よりなる請求項1記載の空気入り安全タイヤ。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480011247.1A CN105026185B (zh) | 2013-02-28 | 2014-02-28 | 充气安全轮胎 |
EP14757004.8A EP2946948B1 (en) | 2013-02-28 | 2014-02-28 | Pneumatic safety tire |
US14/767,325 US20160001601A1 (en) | 2013-02-28 | 2014-02-28 | Pneumatic safety tire |
JP2015503074A JP6280539B2 (ja) | 2013-02-28 | 2014-02-28 | 空気入り安全タイヤ |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013039805 | 2013-02-28 | ||
JP2013-039805 | 2013-02-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014133174A1 true WO2014133174A1 (ja) | 2014-09-04 |
Family
ID=51428431
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/055191 WO2014133174A1 (ja) | 2013-02-28 | 2014-02-28 | 空気入り安全タイヤ |
Country Status (5)
Country | Link |
---|---|
US (1) | US20160001601A1 (ja) |
EP (1) | EP2946948B1 (ja) |
JP (1) | JP6280539B2 (ja) |
CN (1) | CN105026185B (ja) |
WO (1) | WO2014133174A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017043083A1 (ja) * | 2015-09-08 | 2017-03-16 | 株式会社ブリヂストン | タイヤ用繊維、ゴム・繊維複合体及びタイヤ |
WO2019021747A1 (ja) * | 2017-07-28 | 2019-01-31 | 横浜ゴム株式会社 | 空気入りタイヤ、及び空気入りタイヤの製造方法 |
WO2020085498A1 (ja) * | 2018-10-26 | 2020-04-30 | 株式会社ブリヂストン | ランフラットタイヤ |
WO2020090851A1 (ja) * | 2018-10-31 | 2020-05-07 | 株式会社ブリヂストン | タイヤ |
JP7402337B2 (ja) | 2019-11-29 | 2023-12-20 | ブリヂストン ヨーロッパ エヌブイ/エスエイ | 空気入りタイヤの補強層用コードの処理方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10882978B2 (en) | 2016-05-02 | 2021-01-05 | Bridgestone Americas Tire Operations, Llc | Tire with component comprising cured rubber composition having high dielectric constant and related methods |
CN106004256A (zh) * | 2016-07-08 | 2016-10-12 | 中国化工集团曙光橡胶工业研究设计院有限公司 | 一种具有特殊胎侧结构的飞机轮胎 |
CN106339542B (zh) * | 2016-08-25 | 2019-08-23 | 中策橡胶集团有限公司 | 一种轮胎的整体带束层安全倍数计算方法 |
FR3061188A1 (fr) * | 2016-12-22 | 2018-06-29 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc renforcee |
US20200365935A1 (en) * | 2018-01-10 | 2020-11-19 | Tdk Corporation | All-solid lithium ion secondary battery |
JP7034835B2 (ja) * | 2018-05-31 | 2022-03-14 | 株式会社ブリヂストン | ランフラットタイヤ |
CN110962509A (zh) * | 2019-12-26 | 2020-04-07 | 正新橡胶(中国)有限公司 | 一种缺气保用轮胎 |
CN113861827A (zh) * | 2021-11-09 | 2021-12-31 | 烟台恒诺新材料有限公司 | 一种油性耐磨损抗冲击耐腐蚀涂层材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000355875A (ja) | 1999-06-10 | 2000-12-26 | Teijin Ltd | ポリエステル繊維コードの処理方法 |
JP2002046411A (ja) * | 2000-08-04 | 2002-02-12 | Bridgestone Corp | 空気入りラジアルタイヤ |
JP2012148661A (ja) * | 2011-01-19 | 2012-08-09 | Bridgestone Corp | ランフラットタイヤ |
JP2012162230A (ja) * | 2011-02-09 | 2012-08-30 | Yokohama Rubber Co Ltd:The | ランフラットタイヤ |
JP2012214136A (ja) * | 2011-03-31 | 2012-11-08 | Bridgestone Corp | ランフラットタイヤ |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001098245A (ja) * | 1999-09-30 | 2001-04-10 | Bridgestone Corp | 接着剤組成物、樹脂材料、ゴム物品、および空気入りタイヤ |
US20040261928A1 (en) * | 2003-06-27 | 2004-12-30 | Imhoff Serge Julien Auguste | Polyester cords and their use in runflat tires |
EP1842958A4 (en) * | 2005-01-21 | 2012-10-24 | Toray Industries | POLYESTER FIBER WIRE FOR STRENGTHENING RUBBER AND METHOD FOR PRODUCTION THEREOF |
JP4627519B2 (ja) * | 2006-07-11 | 2011-02-09 | 本田技研工業株式会社 | 引張り具の支持構造 |
JP5123587B2 (ja) * | 2007-07-13 | 2013-01-23 | 住友ゴム工業株式会社 | ランフラットタイヤ |
-
2014
- 2014-02-28 US US14/767,325 patent/US20160001601A1/en not_active Abandoned
- 2014-02-28 JP JP2015503074A patent/JP6280539B2/ja active Active
- 2014-02-28 WO PCT/JP2014/055191 patent/WO2014133174A1/ja active Application Filing
- 2014-02-28 CN CN201480011247.1A patent/CN105026185B/zh active Active
- 2014-02-28 EP EP14757004.8A patent/EP2946948B1/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000355875A (ja) | 1999-06-10 | 2000-12-26 | Teijin Ltd | ポリエステル繊維コードの処理方法 |
JP2002046411A (ja) * | 2000-08-04 | 2002-02-12 | Bridgestone Corp | 空気入りラジアルタイヤ |
JP2012148661A (ja) * | 2011-01-19 | 2012-08-09 | Bridgestone Corp | ランフラットタイヤ |
JP2012162230A (ja) * | 2011-02-09 | 2012-08-30 | Yokohama Rubber Co Ltd:The | ランフラットタイヤ |
JP2012214136A (ja) * | 2011-03-31 | 2012-11-08 | Bridgestone Corp | ランフラットタイヤ |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017043083A1 (ja) * | 2015-09-08 | 2017-03-16 | 株式会社ブリヂストン | タイヤ用繊維、ゴム・繊維複合体及びタイヤ |
CN107949667A (zh) * | 2015-09-08 | 2018-04-20 | 株式会社普利司通 | 轮胎用纤维、橡胶/纤维复合体和轮胎 |
WO2019021747A1 (ja) * | 2017-07-28 | 2019-01-31 | 横浜ゴム株式会社 | 空気入りタイヤ、及び空気入りタイヤの製造方法 |
WO2020085498A1 (ja) * | 2018-10-26 | 2020-04-30 | 株式会社ブリヂストン | ランフラットタイヤ |
WO2020090851A1 (ja) * | 2018-10-31 | 2020-05-07 | 株式会社ブリヂストン | タイヤ |
JP2020069897A (ja) * | 2018-10-31 | 2020-05-07 | 株式会社ブリヂストン | タイヤ |
JP7099932B2 (ja) | 2018-10-31 | 2022-07-12 | 株式会社ブリヂストン | タイヤ |
JP7402337B2 (ja) | 2019-11-29 | 2023-12-20 | ブリヂストン ヨーロッパ エヌブイ/エスエイ | 空気入りタイヤの補強層用コードの処理方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105026185B (zh) | 2017-05-10 |
EP2946948A4 (en) | 2016-10-26 |
JP6280539B2 (ja) | 2018-02-14 |
US20160001601A1 (en) | 2016-01-07 |
CN105026185A (zh) | 2015-11-04 |
EP2946948A1 (en) | 2015-11-25 |
EP2946948B1 (en) | 2019-04-24 |
JPWO2014133174A1 (ja) | 2017-02-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6280539B2 (ja) | 空気入り安全タイヤ | |
EP2813376B1 (en) | Pneumatic radial tire | |
US9463669B2 (en) | Tire | |
EP1671813B1 (en) | Pneumatic radial tire | |
JP6280538B2 (ja) | 空気入り安全タイヤ | |
JP6423177B2 (ja) | 空気入りタイヤ | |
JP6383577B2 (ja) | 空気入りタイヤ | |
JP5631801B2 (ja) | ランフラットタイヤ | |
JP6208438B2 (ja) | 空気入り安全タイヤ | |
JP6133625B2 (ja) | 空気入り安全タイヤ | |
JP2009046783A (ja) | ゴム付き繊維材料及び空気入りタイヤ | |
JP5956724B2 (ja) | ランフラットタイヤ | |
JP6004731B2 (ja) | ランフラットタイヤ | |
JP6162978B2 (ja) | 空気入り安全タイヤ | |
JP2010120400A (ja) | 空気入りタイヤ | |
JP2009045864A (ja) | ゴム付き繊維材料の製造方法及び空気入りタイヤ | |
JP2009051280A (ja) | 空気入りラジアルタイヤ | |
JP2010115952A (ja) | 空気入りラジアルタイヤ | |
JP2012214140A (ja) | タイヤ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480011247.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14757004 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015503074 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14767325 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014757004 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |