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WO2008013183A1 - Revêtement interne pour pneu, son procédé de fabrication et pneu - Google Patents

Revêtement interne pour pneu, son procédé de fabrication et pneu Download PDF

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Publication number
WO2008013183A1
WO2008013183A1 PCT/JP2007/064527 JP2007064527W WO2008013183A1 WO 2008013183 A1 WO2008013183 A1 WO 2008013183A1 JP 2007064527 W JP2007064527 W JP 2007064527W WO 2008013183 A1 WO2008013183 A1 WO 2008013183A1
Authority
WO
WIPO (PCT)
Prior art keywords
inner liner
layer
pneumatic tire
resin film
film layer
Prior art date
Application number
PCT/JP2007/064527
Other languages
English (en)
Japanese (ja)
Inventor
Daisuke Nakagawa
Daisuke Nohara
Daisuke Katou
Yuwa Takahashi
Original Assignee
Bridgestone Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2006200904A external-priority patent/JP4939863B2/ja
Application filed by Bridgestone Corporation filed Critical Bridgestone Corporation
Publication of WO2008013183A1 publication Critical patent/WO2008013183A1/fr

Links

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
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/12—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim
    • B60C5/14—Inflatable pneumatic tyres or inner tubes without separate inflatable inserts, e.g. tubeless tyres with transverse section open to the rim with impervious liner or coating on the inner wall of the tyre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
    • 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
    • B60C1/0008—Compositions of the inner liner
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C09J123/0861—Saponified vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
    • B29D2030/0682—Inner liners

Definitions

  • Inner liner for pneumatic tire for pneumatic tire, method for producing the same, and pneumatic tire
  • the present invention relates to an inner liner for a pneumatic tire, a method for producing the same, and a pneumatic tire including the inner liner.
  • the present invention improves rupture resistance during bending and suppresses the occurrence of cracks. It relates to a possible inner liner for a pneumatic tire.
  • a rubber composition mainly composed of butyl rubber, halogenated butyl rubber or the like has been used for an inner liner disposed as an air barrier layer on the inner surface of the tire in order to maintain the internal pressure of the tire.
  • the rubber composition mainly composed of these butyl rubbers has a low air-nore property, when the rubber composition is used for the inner liner, the thickness of the inner liner is reduced. It was necessary to be around lmm. Therefore, the weight of the inner liner in the tire is about 5%, which is an obstacle to reducing the tire weight and improving the fuel efficiency of the car!
  • an ethylene butyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) is known to have excellent gas barrier properties.
  • the EVOH has an air permeation amount that is 1/100 or less of the above-mentioned rubber composition for inner liners, so that it can greatly improve the tire internal pressure retention even at a thickness of 100 ⁇ m or less. In addition, the weight of the tire can be reduced.
  • Japanese Unexamined Patent Application Publication No. 2004-176048 discloses a pneumatic tire provided with an inner liner made of specific EVOH.
  • the inner liner disclosed in Japanese Patent Application Laid-Open No. 2004-176048 is used by being attached to an auxiliary layer made of an elastomer through an adhesive layer in order to improve the internal pressure retention of the tire. It is preferred to do, and it is said that.
  • the present inventors have examined an inner liner for a pneumatic tire using a resin film layer and a rubber-like elastic body layer.
  • the resin film layer and the rubber-like elastic body layer are different from each other. It was found that the resin film layer having low adhesion is easily peeled off from the rubber-like elastic layer.
  • JP-A-2004- 176048 even with the technique disclosed in JP-A-2004- 176048, and a still adhesion between the resin film layer and rubbery elastomer layer is susceptible force s for improvement in low immediately peeling strength .
  • the inner liner disclosed in Japanese Patent Application Laid-Open No. 2004-176048 is a power that can improve the air permeability of a pneumatic tire, and the inner liner has a low adhesiveness. There is room for improvement in peel resistance.
  • thermoplastic urethane elastomer may be disposed on the outer layer portion of the inner liner made of EVOH.
  • an object of the present invention is to improve the peel resistance between the resin film layer and the rubber-like elastic body layer, increase the fracture resistance at the time of bending, and prevent the occurrence of cracks. And providing a method for manufacturing the inner liner.
  • Another object of the present invention is to improve the adhesive strength of the adhesive layer so that it has durability that can withstand expansion during molding of the tire and to improve the peel resistance after vulcanization. , Increase rupture resistance during bending, It is an object of the present invention to provide an inner liner for a pneumatic tire capable of suppressing the generation of squeeze and a method for manufacturing the inner liner. Furthermore, another object of the present invention is to provide a pneumatic tire provided with such an inner liner.
  • an inner liner for a pneumatic tire in which a resin film layer and a rubber-like elastic body layer are joined via an adhesive layer.
  • the surface of the resin film layer at least on the side of the adhesive layer is modified to provide a pneumatic tire having excellent peeling resistance, excellent rupture resistance when bent, and suppressing occurrence of cracks. And found that an inner liner can be obtained.
  • the present inventors have determined that at least one surface of the resin film layer in the inner liner for a pneumatic tire comprising a laminate having a resin film layer and an adhesive layer.
  • the surface free energy above a certain value, it is possible to obtain an inner liner for tires that is durable enough to withstand expansion when molding tires, has excellent rupture resistance when bent, and suppresses the occurrence of cracks.
  • the present invention has been completed.
  • the resin film layer (A) and the rubber-like elastic body layer (B) are bonded via the adhesive layer (C).
  • the resin film layer (A) is characterized in that at least the surface on the adhesive layer (C) side is surface-modified.
  • the first inner liner for a pneumatic tire of the present invention it is preferable that at least a surface of the resin film layer (A) on the side of the adhesive layer (C) is subjected to surface oxidation treatment. Further, as the surface oxidation treatment, a corona discharge treatment is more preferable.
  • the second inner liner for a pneumatic tire of the present invention includes a resin film layer (A) and an adhesive layer (C) disposed on the resin film layer (A).
  • the surface free energy of at least one surface of the resin film layer (A) is 50 mN / m or more.
  • a modified ethylene butyl alcohol copolymer obtained by reacting the resin film layer (A) with an ethylene butyl alcohol copolymer ( At least a layer comprising D).
  • the resin film layer (A) includes at least a layer containing the modified butyl alcohol copolymer (D). It may have another layer which is preferable, or it may be composed only of a layer containing the above-mentioned modified butyl alcohol copolymer (D).
  • the resin film layer (A) includes at least a layer containing the modified ethylene butyl alcohol copolymer (D)
  • the ethylene butyl alcohol copolymer The ethylene content of the coalescence is preferably 25-50 mono%. Further, the saponification degree of the ethylene butyl alcohol copolymer is preferably 90% or more. Furthermore, it is preferable that the modified ethylene-butyl alcohol copolymer (D) is obtained by reacting 1 to 50 parts by mass of an epoxy compound with respect to 100 parts by mass of the ethylene-butyl alcohol copolymer.
  • the layer containing the modified ethylene butyl alcohol copolymer (D) has a functional group that reacts with a hydroxyl group in the matrix made of the modified ethylene butyl alcohol copolymer (D), and has a Young's modulus of 500 MPa.
  • the resin composition (F) in which the following flexible resin (E) is dispersed is preferable.
  • the matrix here means a continuous phase.
  • the resin film Lum layer (A), 20 ° C, the oxygen permeability at 65% RH is 3.0 X 10- 12 cm 3 ' cm / cm 2 • seccmHg3 ⁇ 4T
  • the resin film layer (A) has a thickness of 100 Hm or less.
  • the resin film layer (A) is crosslinked! /.
  • the resin film layer (A) includes at least a layer containing the modified ethylene butyl alcohol copolymer (D)
  • the modified ethylene butyl alcohol copolymer is used.
  • the polymer (D) is preferably crosslinked.
  • the inner liner 1 for a pneumatic tire according to the present invention includes the modified ethylene-bule alcohol when the resin film layer (A) includes at least the layer containing the modified ethylene butyalcohol copolymer (D). It is preferable to provide one or more auxiliary layers (G) that also have an elastomeric force adjacent to the layer containing the copolymer (D).
  • the auxiliary layer (G) More preferably, it includes a plastic urethane elastomer.
  • the total thickness of the auxiliary layer (G) is more preferably in the range of 10 to 100 ⁇ m.
  • the second inner liner for a pneumatic tire of the present invention at least one surface of the coating liquid containing the adhesive composition (H) and the organic solvent is surface-modified.
  • the surface of the resin film layer (A) is applied and dried to form the adhesive layer (C), and the rubber-like elastic layer (B) is further bonded to the surface of the adhesive layer (C). It is obtained by performing a sulfur treatment.
  • the coating liquid containing the adhesive composition (H) and the organic solvent is used as the rubber-like elastic layer (B).
  • the adhesive layer (C) is formed by coating and drying on the surface of the adhesive layer, and the resin film layer (A) having at least one surface modified is bonded to the surface of the adhesive layer (C) and added. It can be obtained by sulfur treatment.
  • the rubbery elastic layer (B) contains butyl rubber and / or halogenated butyl rubber.
  • a first method for producing an inner liner for a pneumatic tire according to the present invention includes the step of modifying the surface of the resin film layer (A) with a coating solution containing an adhesive composition (H) and an organic solvent. The coated layer is coated and dried to form an adhesive layer (C). Next, the rubber-like elastic layer (B) is bonded to the surface of the adhesive layer (C) with! /, And vulcanized. It is characterized by performing processing.
  • a coating liquid containing an adhesive composition (H) and an organic solvent is applied to the rubber-like elastic layer (B).
  • a coating liquid containing an adhesive composition (H) and an organic solvent is applied to the rubber-like elastic layer (B).
  • Applied and dried to form an adhesive layer (C)
  • the surface of the resin film layer (A) is bonded to the surface of the adhesive layer (C).
  • the vulcanization treatment is performed.
  • a pneumatic tire according to the present invention is characterized by using the inner liner for a pneumatic tire.
  • the resin film layer and the rubber-like layer are bonded to the rubber-like elastic body layer via the adhesive layer, with the resin film layer having at least the adhesive layer side surface modified. It is possible to provide an inner liner for a pneumatic tire which has excellent resistance to peeling from an elastic layer and which has high fracture resistance when bent, and suppresses the occurrence of cracks, and a method for producing the inner liner. it can.
  • a laminate including a resin fine layer (A) having a surface free energy of at least a certain value or more on one side and an adhesive layer (B) disposed on the resin film (A) is used.
  • an inner liner for pneumatic tires that is durable enough to withstand expansion during molding of the tire, has excellent fracture resistance when bent, and suppresses the occurrence of cracks, and a method for manufacturing the inner liner can do. Further, it is possible to provide a pneumatic tire provided with an inner liner that is strong and capable.
  • FIG. 1 is a partial cross-sectional view of an example of a pneumatic tire according to the present invention.
  • FIG. 2 is a partial cross-sectional view of an example of an inner liner for a pneumatic tire according to the present invention.
  • FIG. 3 is a partial cross-sectional view of another example of an inner liner for a pneumatic tire according to the present invention.
  • the present invention is described in detail below.
  • the first inner liner for a pneumatic tire according to the present invention is for a pneumatic tire in which a resin film layer (A) and a rubber-like elastic body layer (B) are bonded via an adhesive layer (C). It is an inner liner, and at least the surface of the resin film layer (A) on the adhesive layer (C) side is surface-modified.
  • the first inner liner for a pneumatic tire of the present invention since the joint surface of the resin film layer (A) is surface-modified, the peel resistance is greatly improved.
  • the inner liner of the present invention also suppresses the generation of cracks having high rupture resistance during bending!
  • the resin film layer (A) is adhered to the adhesive layer (C) disposed on the surface of the resin film layer (A).
  • surface modification is required.
  • surface oxidation treatment is preferable.
  • corona discharge treatment plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, etc. are preferable, among which the equipment is inexpensive.
  • the corona discharge treatment is particularly preferable because it can be carried out in the atmosphere and at atmospheric pressure.
  • the second inner liner for a pneumatic tire of the present invention includes a resin film layer (A) and an adhesive layer (C) disposed on the resin film layer (A).
  • the surface free energy of at least one surface of the resin film layer (A) is 50 mN / m or more.
  • the surface free energy of at least one surface of the resin film layer (A) is 50 mN / m or more, so that the wettability is improved and the adhesive layer (C) The adhesive strength of can be improved.
  • the surface free energy on the surface on which the adhesive layer (C) is formed is set to 50 mN / m or more. Therefore, the peel resistance between the tire inner surface and the inner liner can be improved, and the surface free energy on the surface opposite to the surface on which the adhesive layer (C) is formed should be 50 mN / m or more. Therefore, it is possible to improve the shear adhesive strength of the joint where the inner liner is bonded in a ring shape. From the above, both effects can be obtained if the surface free energy on both surfaces of the resin film layer (A) is 50 mN / m or more.
  • the second inner liner for a pneumatic tire of the present invention requires that the surface free energy of at least one surface of the resin film layer (A) is 50 mN / m or more, and is 50 to 80 mN / m. Preferably there is.
  • the treatment is performed.
  • Preferred examples of the surface oxidation treatment include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, etc. Among these, corona discharge treatment is particularly preferred.
  • the resin that can be used for the resin film layer (A) is not particularly limited, and may be a specific resin alone, or other materials are dispersed in the specific resin. It may be a compound. As the power and mulch compound, those that form sea-island structures are preferred.
  • a thermoplastic resin is suitably used as the sea part of the sea-island structure.
  • the thermoplastic resin preferably has a Young's modulus of more than 500 MPa at 23 ° C.
  • ethylene-butyl alcohol copolymer-based resins have a low gas permeation and a very high gas barrier property.
  • the resin film layer (A) has a surface free energy, and therefore it is preferable that an oxygen-containing group is present on the surface of the resin film layer (A). More preferably, a functional group is present. Such a functional group can improve the wettability of the resin film layer (A). Accordingly, it is preferable that the resin film layer (A) is a thermoplastic resin having an ethylene butyl alcohol copolymer-based resin. For example, a modified ethylene obtained by reacting an ethylene butyl alcohol copolymer with an epoxy compound. -More preferred is a butyl alcohol copolymer (D). Since such a modified ethylene butyl alcohol copolymer (D) has a lower elastic modulus than a normal ethylene butyl alcohol copolymer, the rupture resistance during bending is high and cracks are difficult to occur. .
  • the resin film layer (A) includes at least a layer containing a modified ethylene butyl alcohol copolymer (D) obtained by reacting an ethylene butyl alcohol copolymer.
  • the ethylene Bulle alcohol copolymer forces S preferably ethylene content of 25 to 50 mol%, 30 to 48 mole 0/0, it is further preferred tool 35-45 mole 0/0 More preferably, it is. If the ethylene content is less than 25 mol%, the bending resistance, fatigue resistance, and melt moldability may deteriorate. On the other hand, if it exceeds 50 mol%, the gas barrier properties may not be sufficiently secured. Further, the ethylene-butyl alcohol copolymer preferably has a saponification degree of 90% or more, more preferably 95% or more, and still more preferably 99% or more. If the degree of saponification is less than 90%, gas barrier properties and Thermal stability at the time of molding may be insufficient.
  • the ethylene-butyl alcohol copolymer has a melt flow rate (MFR) of 190.degree. C. under a load of 2160 g, 0.;! To 30 g / 10 min. S, preferably 0.3 to 25 g / 10 min. More preferably it is.
  • MFR melt flow rate
  • the method for producing the modified ethylene butyl alcohol copolymer (D) is not particularly limited, the production is a reaction in which an ethylene butyl alcohol copolymer and an epoxy compound are reacted in a solution.
  • a method is preferably mentioned. More specifically, a modified ethylene-butyl alcohol copolymer (D) is added to an ethylene-vinyl alcohol copolymer solution in the presence of an acid catalyst or an alkali catalyst, preferably in the presence of an acid catalyst, and reacted. ) Can be manufactured.
  • the reaction solvent include non-proton polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
  • the acid catalyst examples include P-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, and boron trifluoride.
  • the alkali catalyst examples include sodium hydroxide, potassium hydroxide, and hydroxide. Examples include lithium and sodium methoxide.
  • the catalyst amount is preferably in the range of 0.0001 to 10 parts by mass with respect to 100 parts by mass of the ethylene-butyl alcohol copolymer.
  • the modified ethylene-butyl alcohol copolymer (D) is formed into a film, a sheet or the like at a melting temperature of preferably 150 to 270 ° C. by melt molding, preferably extrusion molding such as T-die method or inflation method. And used as the resin film layer (A).
  • a monovalent epoxy compound is preferable.
  • the monovalent epoxy compounds glycidol and epoxypropane are particularly preferred from the viewpoints of ease of production of the modified ethylene butyl alcohol copolymer, gas barrier properties, flex resistance and fatigue resistance.
  • the epoxy compound is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and more preferably 5 to 35 parts by mass with respect to 100 parts by mass of the ethylene butyl alcohol copolymer. It is more preferable to react.
  • the modified ethylene butyl alcohol copolymer (D) is preferably crosslinked. If the modified ethylene-butyl alcohol copolymer (D) is not cross-linked, the resin film layer (A) will deform significantly and become non-uniform in the vulcanization process for producing pneumatic tires. Therefore, the gas barrier properties, flex resistance, and fatigue resistance of the inner liner may be deteriorated.
  • the method for producing the modified ethylene-butyalcohol copolymer (D) it is possible to crosslink the modified ethylene-butyalcohol copolymer (D) by using a divalent or higher valent epoxy compound.
  • the modified ethylene-butalcohol copolymer (D) preferably has a saponification degree of 90% or more, more preferably 95% or more, and even more preferably 99% or more. Is more preferable. If the saponification degree is less than 90%, the gas barrier property and the thermal stability during molding will be insufficient.
  • the modified ethylene monobutyl alcohol copolymer (D) has a melt flow rate (MFR) of 190 ° C and a load of 2160g from the viewpoint of obtaining gas-noreness, bending resistance and fatigue resistance. Preferably 30-30 g / 10 min, more preferably 0.3-25 g / 10 min, and even more preferably 0.5-20 g / 10 min.
  • the layer containing the modified ethylene butyl alcohol copolymer (D) has a functional group that reacts with a hydroxyl group in a matrix composed of the modified ethylene butyl alcohol copolymer (D) and has a Young's modulus. It is preferable to use a resin composition (F) in which a flexible resin (E) of 500 MPa or less is dispersed. Dispersing the flexible resin (E) in a matrix that also has the modified ethylene-butyl alcohol copolymer (D) force significantly reduces the elastic modulus and suppresses the occurrence of breakage and cracks during bending. be able to.
  • the flexible resin (E) since the flexible resin (E) has a functional group that reacts with a hydroxyl group, the flexible resin (E) is uniformly dispersed in the matrix.
  • the functional group that reacts with a hydroxyl group include a maleic anhydride residue, a hydroxyl group, a carboxyl group, and an amino group.
  • Specific examples of the flexible resin (E) having a functional group that reacts with a hydroxyl group include maleic anhydride-modified hydrogenated styrene ethylene-butadiene-styrene block copolymer, maleic anhydride-modified ultra-low density polyethylene, and the like. It is done. Further, when the Young's modulus of the flexible resin (E) is 500 MPa or less, the elastic modulus of the resin film layer (A) can be lowered, and as a result, the bending resistance can be improved.
  • the ratio of the flexible resin (E) to the total of the modified ethylene butyl alcohol copolymer (D) and the flexible resin (E) is 10 to 10% from the viewpoint of improving the bending resistance and the gas barrier property. A range of 30% by weight is preferred.
  • the flexible resin (E) has an average particle size of 2 The following is preferable. If the average particle size exceeds 2, the bending resistance may not be sufficiently improved, and the gas barrier property may be lowered.
  • the average particle diameter of the flexible resin (E) in the resin composition (F) is observed, for example, by freezing the sample, cutting the sample with a microtome, and observing with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the resin film layer (A) preferably has a Young's modulus at 23 ° C of more than 500 MPa.
  • the resin film layer (A), the oxygen permeability at 20 ° C, 65% RH is 3.0 X 10- 12 cm 'cm / cm' sec ' that mosquitoes preferably cmUg than, 1.0 X 10 cm'
  • the force is more preferably cm / cm * sec'cmHg or less, and more preferably 5.0 ⁇ 10 cm'cm / cm'sec-cmHg or less.
  • the thickness of the resin film layer (A) is preferably 100 m or less, more preferably the lower limit is 0.1 m; and the range is from! To 40 m. More preferred is the range of 5-30 am! If the thickness of the resin film layer (A) exceeds 100 ⁇ m, the effect of reducing the weight will be less than that of a conventional butyl rubber-based inner liner when used for an inner liner, and the bending resistance and Fatigue resistance is reduced, and it is easy for fractures / cracks to occur due to bending deformation during rolling of the tire, and because the cracks are likely to extend, the internal pressure retention of the tire may be reduced compared to before use. On the other hand, if it is less than O.l ⁇ m, the gas barrier property is insufficient, and the tire internal pressure retention may not be sufficiently secured.
  • the resin film layer (A) is preferably crosslinked! /, Preferably! /. If the resin film layer (A) is cross-linked! /, N! /, The inner liner is significantly deformed and becomes non-uniform during the vulcanization process of the tire, and the gas barrier properties, flex resistance, and fatigue resistance of the inner liner are reduced. Sexuality may worsen.
  • the crosslinking method the method of irradiating energy rays is preferred. Examples of the energy rays include ionizing radiation such as ultraviolet rays, electron beams, X-rays, ⁇ -rays, ⁇ -rays. Lines are particularly preferred.
  • the electron beam irradiation is preferably performed after the resin film layer ( ⁇ ) is processed into a molded body such as a film sheet.
  • the electron beam dose Is preferably in the range of 10-60 Mrad, more preferably in the range of 20-50 Mrad.
  • the electron beam dose is less than lOMrad, crosslinking is difficult to proceed, whereas when it exceeds 60 Mrad, the deterioration of the compact tends to proceed.
  • the inner liner for a pneumatic tire according to the present invention has a resin film layer (A) that preferably uses the above-mentioned modified ethylene-butyl alcohol copolymer (D) for the resin film layer (A).
  • a multilayered film including a layer containing the modified ethylene butyl alcohol copolymer (D) may be used.
  • a method of multilayering for example, a method of co-extrusion of the resin composition (F) containing the modified ethylene butyl alcohol copolymer (D) and another resin, etc. can be mentioned.
  • the resin film layer (A) is further adjacent to the layer containing the modified ethylene butyl alcohol copolymer (D).
  • One provided with one or more auxiliary layers (G) made of an elastomer is preferably mentioned.
  • the auxiliary layer (G) uses an elastomer, it has high adhesion to the hydroxyl group of the modified ethylene-vinyl alcohol copolymer (D) and is difficult to peel off.
  • the elastomer used for the auxiliary layer (G) is preferably a thermoplastic urethane elastomer from the viewpoint of water resistance and adhesion to rubber.
  • the thermoplastic urethane elastomer is used for the auxiliary layer (G)
  • the generation and extension of cracks can be suppressed while making the auxiliary layer (G) thinner.
  • the thermoplastic urethane-based elastomer is obtained by a reaction of a polyol, an isocyanate compound, and a short chain diol. Polyol and short chain diol form a linear polyurethane by addition reaction with an isocyanate compound.
  • the polyol becomes a flexible part in the thermoplastic urethane elastomer, and the isocyanate compound and the short chain diol become a hard part.
  • the properties of the thermoplastic elastomeric elastomer can be changed over a wide range by changing the type of raw material, blending amount, polymerization conditions, and the like.
  • Preferred examples include polyether urethane.
  • the total thickness of the auxiliary layer (G) is preferably in the range of 10 to 100 m. If the thickness of the auxiliary layer is less than lO ⁇ m, the effect of disposing the auxiliary layer (G) is small. If it exceeds lOO ⁇ m, the weight of the tire cannot be reduced sufficiently.
  • a rubber-like elastic layer (B) is further provided on the surface of the adhesive layer (C) opposite to the resin film layer (A). It is preferable that the laminated body is provided.
  • the rubber-like elastic layer (B) by disposing the rubber-like elastic layer (B), the workability when the inner liner of the present invention is attached to the inner surface of the tire is greatly improved.
  • the rubber-like elastic body layer (B) includes butyl rubber and / or halogenated butyl rubber as a rubber component. It is preferable to contain.
  • the halogenated butyl rubber include chlorinated butyl rubber, brominated butyl rubber, and modified rubbers thereof.
  • the halogenated butyl rubber may be a commercially available product, such as “Enjay Butyl HT10-66” (registered trademark) [Chlorinated butyl rubber manufactured by ENGAI Chemical Co., Ltd.], “Bromob utyl 2255” (registered) Trademarks) [manufactured by JSR, brominated butylene rubber], “Bromobutyl 2244” (registered trademark) [manufactured by JSR, brominated butyl rubber] and the like.
  • Examples of the chlorinated or brominated modified rubber include “Expro50” (registered trademark) [manufactured by Exxon].
  • the content of butyl rubber and / or halogenated butyl rubber in the rubber component in the rubber-like elastic layer (B) is preferably 50% by mass or more from the viewpoint of improving air permeation resistance. 70 to 100% is more preferable.
  • the rubber component in addition to butyl rubber and halogenated butyl rubber, it is possible to use gen-based rubber, epic chlorohydrin rubber, or the like. These rubber components may be used singly or in combination of two or more.
  • the rubber-like elastic layer (B) contains a compounding agent usually used in the rubber industry, such as a reinforcing filler, a softening agent, an anti-aging agent, a vulcanizing agent, A rubber vulcanization accelerator, a scorch inhibitor, zinc white, stearic acid and the like can be appropriately blended depending on the purpose.
  • a compounding agent usually used in the rubber industry such as a reinforcing filler, a softening agent, an anti-aging agent, a vulcanizing agent, A rubber vulcanization accelerator, a scorch inhibitor, zinc white, stearic acid and the like can be appropriately blended depending on the purpose.
  • these compounding agents commercially available products can be suitably used.
  • an adhesive composition (H) containing at least 0.1 part by mass of at least one kind of P-dinitrosobenzene it is preferable to use an adhesive composition (H) containing at least 0.1 part by mass of at least one kind of P-dinitrosobenzene.
  • the adhesive layer (C) With respect to the resin film layer (A) and the rubber-like elastic body layer (B) The adhesiveness is improved, and the peel resistance between the resin film layer (A) and the rubber-like elastic layer (B) can be improved.
  • Examples of the rubber component (I) used in the adhesive composition (H) include chlorosulfonated polyethylene, butyl rubber, halogenated butyl rubber, and Gen rubber. Among these, chlorosulfonated polyethylene, and Butyl rubber and / or halogenated butyl rubber is preferred.
  • the above chlorosulfonated polyethylene is a synthetic rubber having a saturated main chain structure obtained by chlorination and chlorosulfonization of polyethylene using chlorine and sulfurous acid gas, and is weather resistant, ozone resistant, heat resistant. Excellent gas barrier properties.
  • the chlorosulfonated polyethylene a commercially available product can be used, and examples thereof include trade name “HIVALON” [manufactured by DuPont].
  • the content of the chlorosulfonated polyethylene in the rubber component (I) is preferably 10% by mass or more from the viewpoint of improving the peeling resistance.
  • butyl rubber and halogenated butyl rubber are as described in the rubber-like elastic layer (B), and the content of butyl rubber and / or halogenated butyl rubber in the rubber component (I) is 50% by mass. % Or more is preferable.
  • the rubber component (I) may be used alone or in combination of two or more.
  • the adhesive composition (H) is a maleimide derivative having two or more reactive sites in the molecule and / or as a crosslinking agent and a crosslinking aid in order to improve the peel resistance after heat treatment.
  • Includes poly-P-dinitrosobenzene and examples of the maleimide derivative include 1,4-phenylene dimaleimide, among which 1,4-phenylene dimaleimide is preferable.
  • One of these crosslinking agents and crosslinking assistants may be used alone, or two or more thereof may be used in combination.
  • the blending amount of the maleimide derivative and / or poly-P-dinitrosobenzene in the adhesive composition (H) is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the rubber component (1). Yes. If the blending amount of the maleimide derivative and / or poly-p-dinitrosobenzene is less than 0.1 parts by mass, the peeling resistance after vulcanization cannot be sufficiently improved! /.
  • the adhesive composition (H) preferably further contains a rubber vulcanization accelerator, a filler, a tackifier such as a resin and a low molecular weight polymer, and the like.
  • a softening agent, an anti-aging agent, a vulcanizing agent, an anti-scorch agent, zinc white, stearic acid and the like may be appropriately blended according to the purpose! /.
  • an inner liner for a pneumatic tire of the present invention for example, at least one surface of a coating liquid in which the adhesive composition (H) is dispersed or dissolved in an organic solvent is surface-modified.
  • the adhesive layer (C) is formed by coating and drying on the surface of the resin film layer (A), preferably the resin film layer (A) having at least one surface subjected to surface oxidation treatment, and then the adhesive layer Examples thereof include a method in which the rubber-like elastic layer (B) is bonded to the surface of (C) and vulcanized.
  • the coating liquid is applied to the surface of the rubber-like elastic layer (B) and dried to form an adhesive layer (C).
  • the surface of the agent layer (C) is laminated with the surface of the resin film layer (A) whose surface has been modified on at least one side, and preferably the surface of the resin film layer (A) which has been subjected to surface oxidation treatment on at least one side. Processing may be performed.
  • the vulcanization temperature is preferably 120 to 120 ° C or more, more preferably 125 to 200 ° C, more preferably 130 to 180 ° C.
  • the method of mixing the adhesive composition (H) and the organic solvent is carried out by a conventional method !, and the concentration of the adhesive composition (H) in the coating solution prepared by such a method is 5 The range of ⁇ 50 mass% is preferred, and the range of 10-30 mass% is more preferred.
  • examples of the organic solvent include toluene, xylene, n-hexane, cyclohexane, black mouth form, methyl ethyl ketone, and the like. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
  • the Hildebrand solubility parameter ( ⁇ value) is preferably in the range of 14 to 20 MPa 1/2 .
  • the affinity between the organic solvent and the rubber component (I). Becomes higher.
  • FIG. 1 is a partial cross-sectional view of an example of the pneumatic tire of the present invention.
  • the tire shown in FIG. 1 has a pair of bead portions 1 and a pair of sidewall portions 2, and a tread portion 3 connected to both sidewall portions 2, and extends in a toroidal shape between the pair of bead portions 1.
  • the carcass 4 is composed of one or more carcass plies that reinforce these parts 1, 2, and 3, and an inner liner 5 is disposed on the inner surface of the tire inside the carcass 4.
  • the carcass 4 includes a main body portion extending in a toroidal shape between a pair of bead cores 6 embedded in the bead portion 1 and the inner side in the tire width direction around each bead core 6.
  • the force composed of the folded portion wound outward in the radial direction toward the outside In the pneumatic tire of the present invention, the number of plies and the structure of the carcass 4 are not limited thereto.
  • a belt 7 composed of two belt layers is disposed on the outer side in the tire radial direction of the crown portion of the carcass 4, and the belt 7 in the illustrated example includes two sheets.
  • the number of belt layers constituting the belt 7 is not limited to this.
  • the belt layer is usually composed of a rubberized layer of a cord extending obliquely with respect to the tire equatorial plane, and the two belt layers have the cords constituting the belt layer intersecting each other across the equator plane. The belt 7 is thus laminated.
  • the illustrated tire has a force S including a belt reinforcing layer 8 disposed so as to cover the entire belt 7 outside the belt 7 in the tire radial direction, and the pneumatic tire of the present invention has a belt reinforcing layer 8.
  • the belt reinforcing layer having another structure may be provided.
  • the belt reinforcing layer 8 is usually composed of a rubberized layer of cords arranged substantially parallel to the tire circumferential direction.
  • FIG. 2 is a partial cross-sectional view of an example of an inner liner for a pneumatic tire according to the present invention.
  • the inner liner shown in Fig. 2 The rum layer (A) 9 and the rubber-like elastic layer (B) 10 are joined via the adhesive layer (C) 11.
  • the rubber-like elastic layer (B) 10 is joined to the tire inner surface inside the carcass 4 in the pneumatic tire.
  • the illustrated inner liner 1 has a force S including the rubber-like elastic layer (B) 10, and the second inner liner 1 for a pneumatic tire according to the present invention does not have the rubber-like elastic layer. May be.
  • the adhesive layer (C) 11 is directly bonded to the inner surface of the tire inside the carcass 4.
  • the resin film layer (A) 9 has only one layer containing, for example, a modified ethylene butyl alcohol copolymer (D).
  • a modified ethylene butyl alcohol copolymer (D) One may have other layers as shown in FIG.
  • FIG. 3 is a partial cross-sectional view of another example of the inner liner 1 of the present invention.
  • the inner liner of the illustrated example includes, as a resin film layer (A) 12, a layer 13 containing the modified ethylene-butyl alcohol copolymer (D) and two layers of heat disposed adjacent to the layer 13. And a layer 14 made of a plastic urethane elastomer.
  • the same reference numerals as those in Fig. 2 indicate the same members.
  • the pneumatic tire of the present invention can be manufactured by a conventional method using the inner liner 1 described above.
  • the gas filled in the tire it is possible to use normal air or air having a changed oxygen partial pressure, or an inert gas such as nitrogen.
  • ethylene-butyl alcohol copolymer with an ethylene content of 44 mol% and a saponification degree of 99.9% 190 ° C, MFR under 216 Og load: 5.5 g / 10 min
  • 2 parts by mass and N- 8 parts by mass of methyl-2-pyrrolidone was charged, and heated and stirred at 120 ° C for 2 hours to completely dissolve the ethylene-vinyl alcohol copolymer.
  • modified ethylene-butyl alcohol copolymer (D) After heating, precipitate in 100 parts by weight of distilled water, and use a large amount of distilled water to sufficiently dissolve N-methyl-2-pyrrolidone and unreacted ether. Poxypropane was washed to obtain a modified ethylene-butyl alcohol copolymer (D). Furthermore, after the obtained modified ethylene butyl alcohol copolymer (D) was vigorously reduced to a particle size of about 2 mm with a pulverizer, it was thoroughly washed again with a large amount of distilled water. The washed particles were vacuum-dried at room temperature for 8 hours and then melted at 200 ° C. using a twin-screw extruder to be pelletized. The resulting modified ethylene butyl alcohol copolymer (D) had a Young's modulus of 1300 MPa at 23 ° C.
  • the Young's modulus at 23 ° C of the modified ethylene-butyl alcohol copolymer (D) was measured by the following method.
  • a single-layer film having a thickness of 20 m was produced using a twin-screw extruder manufactured by Toyo Seiki Co., Ltd. under the following extrusion conditions.
  • a strip-shaped test piece having a width of 15 mm was prepared and left in a temperature-controlled room at 23 ° C. and 50% RH for one week, and then autograph [AG- A500] was used to measure the S-S curve (stress-strain curve) at 23 ° C and 50% RH under conditions of chuck spacing of 50 mm and tensile speed of 50 mm / min. Young's modulus was determined.
  • Screw 20mm ⁇ , full flight
  • Cylinder, die temperature setting: C1 / C2 / C3 / die 200/200/200/200 (.C)
  • the ethylene content and the saponification degree of the above ethylene butyl alcohol copolymer were determined by 1 H-NMR measurement using deuterated dimethyl sulfoxide as a solvent [JN M-GX-500 type manufactured by JEOL Ltd.] Is a value calculated from the spectrum obtained in [Use].
  • melt flow rate (MFR) of the above ethylene monobutyl alcohol copolymer was measured at 190 ° C by filling a sample into a cylinder with an inner diameter of 9.55 mm and a length of 162 mm of a melt indexer L244 [manufactured by Takara Kogyo Co., Ltd.] After melting, an even load is applied using a plunger with a weight of 2160g and a diameter of 9.48mm, and the amount of resin extruded per unit time from a 2.1mm diameter orifice provided in the center of the cylinder (g / 10 Min).
  • melt flow rate MF R
  • Maleic anhydride-modified hydrogenated styrene ethylene butadiene styrene block copolymer was synthesized by a known method and pelletized.
  • the resulting maleic anhydride-modified hydrogenated styrene ethylene butadiene styrene block copolymer had a Young's modulus power of 3 MPa, a styrene content of 20%, and a maleic anhydride content of 0.3 meq / g.
  • the Young's modulus of the maleic anhydride-modified hydrogenated styrene ethylene butadiene styrene block copolymer was measured by the above method.
  • Screw single-flight full flight type, surface nitrided steel
  • Cylinder, die temperature setting: C1 / C2 / C3 / Adapter / Die 180/200/210 / 210/210 (° C)
  • the resin composition (F) was prepared by kneading the modified ethylene butyl alcohol copolymer (D) obtained in the synthesis example and the flexible resin (E) with a twin-screw extruder, in the same manner as the production of the film A1.
  • a monolayer film having a thickness of 20 m was obtained.
  • the content of the flexible resin (E) in the resin composition (F) is 20% by mass.
  • the average particle diameter of the flexible resin (E) in the resin composition (F) is determined by freezing a sample of the obtained resin composition (F) and then cutting the sample with a microtome. It was 1.0 when measured with a transmission electron microscope.
  • thermoplastic polyurethane Using the modified ethylene butyl alcohol copolymer (D) pellets obtained in the synthesis example and thermoplastic polyurethane [Kuraray 3190, Kuraray Co., Ltd.], the following co-extrusion equipment was used. A three-layer film (thermoplastic polyurethane layer / modified EVOH (D) layer / thermoplastic polyurethane layer, thickness: 20 ⁇ m / 20 ⁇ m / 20 ⁇ m) was prepared under extrusion molding conditions.
  • Thermoplastic polyurethane 25mm ⁇ Extruder —25—18 AC [Osaka Seiki Co., Ltd.
  • T-die specification 500mm width, 2 types, 3 layers [Plastic Engineering Laboratory Co., Ltd.] Cooling roll temperature: 50 ° C
  • thermoplastic polyurethane layer was produced in the same manner as the production of the film A2.
  • the film was conditioned at 20 ° C. and 65% RH for 5 days. Using the two humidity-adjusted films obtained, using MOCON OX—TRAN2 / 20, manufactured by Modern Control, in compliance with JIS K7126 (isobaric method) at 20 ° C and 65% RH Then, the oxygen transmission coefficient was measured and the average value was obtained. [0086]
  • Butyl rubber SR Co., Ltd., Butyl 268 100 parts by mass, GPF carbon black [Asahi Carbon Co., Ltd., # 55] 60 parts by mass, SUNPAR2280 [Nihon Sun Sekiyu Co., Ltd.] 7 parts by mass, Stearic acid [Asahi Denka Kogyo Co., Ltd.] 1 part by mass, Noxeller DM [Ouchi Shinsei Chemical Co., Ltd.] 1.3 parts by mass, Zinc oxide [Shiramizu Chemical Co., Ltd.] 3 parts by mass and sulfur [ Tsurumi Chemical Co., Ltd.] A rubber composition was prepared by blending 0.5 part by mass, and an unvulcanized rubber-like elastic layer (B) having a thickness of 500 am was produced using the rubber composition. .
  • Brominated butyl rubber [JSR Co., Ltd., Bromobutyl 2244] 100 parts by mass of carbon black [Tokai Carbon Co., Ltd., Seast NB] 10 parts by mass, phenolic resin [Sumitomo Beichikrite Co., Ltd., PR-SC-400] 20 parts by mass, stearic acid manufactured by Nippon Rika Co., Ltd., 50S] 1 part by mass, zinc oxide [by Hakutech Co., Ltd.] 3 parts by mass, poly-P-dinitrosobenzene [Ouchi Shinsei Chemical Industry Co., Ltd., Barnock DNB] 3 parts by mass, 1,4-phenylene dimaleimide [Ouchi Shinsei Chemical Co., Ltd., Barnock PM] 3 parts by mass, vulcanization accelerator ZTC [Ouchi Eshin Chemical Industry Co., Ltd., Noxeller ZTC, Zinc dibenzyldithiocarbamate] 1 part by mass, Vulcanization accelerator DM
  • film A1 was irradiated with an electron beam under the conditions of a quick calorie voltage of 200 kV and an irradiation energy of 30 Mrad to perform crosslinking treatment. After that, on the surface of the obtained cross-linked film, a corona discharge treatment device “Corona Master PS-1M” manufactured by Shinko Electric Instruments Co., Ltd. was used under the conditions of electrode spacing lm m, discharge voltage 7 kV, frequency 15 kHz. Corona discharge treatment (surface oxidation treatment) was performed.
  • a pneumatic tire was produced in the same manner as in the above Example; 1-1 except that the resin film layer (A) and rubber-like elastic layer (B) shown in Table 2 were used.
  • the resin film layer (A) and rubber-like elastic layer (B) shown in Table 2 were used, and instead of the corona discharge treatment as a surface oxidation treatment, a plasma irradiation surface modification device manufactured by Kasuga Electric Co., Ltd.
  • a pneumatic tire was produced in the same manner as in the above Example; 1-1 except that the plasma discharge treatment was performed under the condition of an output of 10 kV using “PS-601C type”.
  • a pneumatic tire was produced in the same manner as in the above Example; 1-1 except that the surface oxidation treatment was not performed.
  • a pneumatic tire was produced in the same manner as in Comparative Example 1-1, except that the resin film layer (A) and rubber-like elastic layer (B) shown in Table 2 were used. [0095] Next, a durability test of the obtained tire was performed by the following method to evaluate the presence or absence of a failure. The results are shown in Table 2.
  • Each prototype tire is assembled with a rim, the internal pressure is 175 kPa, the load is 4.5 kN, the speed is 80 km / h, the temperature is 20 ° C, and the drum running test is performed. After running 10,000 km, the inner liner appearance of the tire is visually observed. Observed. By visual observation, the case where no failure was detected was determined to be good, and the case where cracks or cracks occurred, or peeling or lifting was determined to be defective.
  • film A2 was irradiated with an electron beam under the conditions of a quick calorie voltage of 200 kV and an irradiation energy of 30 Mrad, and then subjected to crosslinking treatment. After that, on the surface of the obtained crosslinked film, Shinko Electric Meter Using a corona discharge treatment device “Corona Master PS-1M” (electrode spacing lmm, frequency 15kHz) manufactured by Sou Co., Ltd., surface oxidation treatment was performed on at least one side of the crosslinked film under the conditions shown in Tables 3-4. did.
  • ⁇ is the surface free energy (mN / m)
  • y d is the surface free energy dispersive component (mN / m)
  • ⁇ ⁇ is the surface free energy dipole attractive component (mN / m)
  • ⁇ 11 is the hydrogen bond component of surface free energy (mN / m)
  • ⁇ H is the contact angle of water (°)
  • ⁇ 1 is the contact angle of jode methane (°)
  • e D is the contact angle (°) of n-hexadecane.
  • Each prototype tire was assembled on a rim, the internal pressure was 175 kPa, the load was 4.5 kN, the speed was 80 km / h, the temperature was 20 ° C, and the drum running test was performed. After running 10,000 km, the inner surface of the tire was visually inspected. . When no failure was found by visual observation, “ ⁇ ” was assigned, and when cracks or cracks were observed, or when peeling or lifting was observed, “X” was assigned.
  • the tire inner liners of Examples 2-3 to 2-7 have a surface free energy of 50 mN / m or more on the A-1 surface of the resin film layer (A). It can be seen that it has the durability to withstand the expansion of. Also, Example 2-;! To 2-2 and 2-8 The inner liner of this tire has a force that the surface free energy on the A-1 surface of the resin film layer (A) is less than 50 mN / m, and the surface free energy on the A-2 surface is 50 mN / m or more.
  • the adhesive strength of the agent layer (C) has been improved, and it has the durability that can be produced without any problem as a tire!

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne un revêtement interne pour pneus, ledit revêtement étant obtenu en joignant une couche de résine (A) (9) avec une couche élastique de type caoutchouc (B) (10) par une couche adhésive (C) (11). Au moins la surface de la couche de résine (A) (9) du côté de la couche adhésive (C) (11) est modifiée et la résistance à la séparation entre la couche de résine et la couche élastique de type caoutchouc est améliorée. Le revêtement interne pour pneus présente une grande résistance à la rupture par flexion et est très peu touché par les craquelures. Il est préférable qu'au moins la surface de la couche de résine (A) (9) du côté de la couche adhésive (C) (11) soit soumise à une oxydation de surface.
PCT/JP2007/064527 2006-07-24 2007-07-24 Revêtement interne pour pneu, son procédé de fabrication et pneu WO2008013183A1 (fr)

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JP2006200904A JP4939863B2 (ja) 2006-07-24 2006-07-24 空気入りタイヤ用インナーライナー及びその製造方法、並びに空気入りタイヤ
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008143188A1 (fr) * 2007-05-17 2008-11-27 Bridgestone Corporation Pneu à carcasse radiale pour charge lourde
JP2010069828A (ja) * 2008-09-22 2010-04-02 Bridgestone Corp タイヤ内面処理方法及びタイヤ内面処理装置
WO2015079384A1 (fr) * 2013-11-29 2015-06-04 Pirelli Tyre S.P.A. Pneu auto-obturant pour roues de véhicules et pneu auto-obturant
US9832428B2 (en) 2012-12-27 2017-11-28 Kateeva, Inc. Fast measurement of droplet parameters in industrial printing system
US11207919B2 (en) 2016-06-21 2021-12-28 Bridgestone Americas Tire Operations, Llc Methods for treating inner liner surface, inner liners resulting therefrom and tires containing such inner liners
US11697260B2 (en) 2016-06-30 2023-07-11 Bridgestone Americas Tire Operations, Llc Methods for treating inner liners, inner liners resulting therefrom and tires containing such inner liners
US11697306B2 (en) 2016-12-15 2023-07-11 Bridgestone Americas Tire Operations, Llc Sealant-containing tire and related processes
US11794430B2 (en) 2016-12-15 2023-10-24 Bridgestone Americas Tire Operations, Llc Methods for producing polymer-containing coatings upon cured inner liners, methods for producing tires containing such inner liners, and tires containing such inner liners
US12103338B2 (en) 2016-12-15 2024-10-01 Bridgestone Americas Tire Operations, Llc Sealant layer with barrier, tire containing same, and related processes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001113908A (ja) * 1999-09-22 2001-04-24 Goodyear Tire & Rubber Co:The 空気透過防止層を有するタイヤ
JP2005103760A (ja) * 2003-09-26 2005-04-21 Yokohama Rubber Co Ltd:The 積層体及びそれを用いた空気入りタイヤ
WO2006059621A1 (fr) * 2004-12-03 2006-06-08 Bridgestone Corporation Stratifie, son procede de production et pneu l’utilisant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001113908A (ja) * 1999-09-22 2001-04-24 Goodyear Tire & Rubber Co:The 空気透過防止層を有するタイヤ
JP2005103760A (ja) * 2003-09-26 2005-04-21 Yokohama Rubber Co Ltd:The 積層体及びそれを用いた空気入りタイヤ
WO2006059621A1 (fr) * 2004-12-03 2006-06-08 Bridgestone Corporation Stratifie, son procede de production et pneu l’utilisant

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008143188A1 (fr) * 2007-05-17 2008-11-27 Bridgestone Corporation Pneu à carcasse radiale pour charge lourde
JP2010069828A (ja) * 2008-09-22 2010-04-02 Bridgestone Corp タイヤ内面処理方法及びタイヤ内面処理装置
US9832428B2 (en) 2012-12-27 2017-11-28 Kateeva, Inc. Fast measurement of droplet parameters in industrial printing system
WO2015079384A1 (fr) * 2013-11-29 2015-06-04 Pirelli Tyre S.P.A. Pneu auto-obturant pour roues de véhicules et pneu auto-obturant
US11207919B2 (en) 2016-06-21 2021-12-28 Bridgestone Americas Tire Operations, Llc Methods for treating inner liner surface, inner liners resulting therefrom and tires containing such inner liners
US12030350B2 (en) 2016-06-21 2024-07-09 Bridgestone Americas Tire Operations, Llc Methods for treating inner liner surface, inner liners resulting therefrom and tires containing such inner liners
US11697260B2 (en) 2016-06-30 2023-07-11 Bridgestone Americas Tire Operations, Llc Methods for treating inner liners, inner liners resulting therefrom and tires containing such inner liners
US11697306B2 (en) 2016-12-15 2023-07-11 Bridgestone Americas Tire Operations, Llc Sealant-containing tire and related processes
US11794430B2 (en) 2016-12-15 2023-10-24 Bridgestone Americas Tire Operations, Llc Methods for producing polymer-containing coatings upon cured inner liners, methods for producing tires containing such inner liners, and tires containing such inner liners
US12103338B2 (en) 2016-12-15 2024-10-01 Bridgestone Americas Tire Operations, Llc Sealant layer with barrier, tire containing same, and related processes

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