WO2013048206A2 - 타이어 이너라이너용 필름 및 이의 제조 방법 - Google Patents
타이어 이너라이너용 필름 및 이의 제조 방법 Download PDFInfo
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- WO2013048206A2 WO2013048206A2 PCT/KR2012/007953 KR2012007953W WO2013048206A2 WO 2013048206 A2 WO2013048206 A2 WO 2013048206A2 KR 2012007953 W KR2012007953 W KR 2012007953W WO 2013048206 A2 WO2013048206 A2 WO 2013048206A2
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- WIPO (PCT)
- Prior art keywords
- film
- tire
- polyamide
- copolymer
- base film
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- 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
- B60C5/142—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 provided partially, i.e. not covering the whole inner wall
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- 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
- B60C2005/145—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 made of laminated layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/126—Copolymers block
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2461/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- 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
- C09J2461/00—Presence of condensation polymers of aldehydes or ketones
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- 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
- C09J2471/00—Presence of polyether
- C09J2471/006—Presence of polyether in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2477/00—Presence of polyamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- the present invention relates to a film for tire innerliner and a method of manufacturing the same. More specifically, it is possible to reduce tire weight and improve fuel efficiency of an automobile by implementing excellent airtightness even at a thin thickness, and to provide a method for manufacturing a tire inner liner film and a tire inner liner film having excellent molding stability and running durability. will be.
- the tires support the load of the vehicle, relieve the stratification from the road surface, and transmit the driving force or braking force of the vehicle to the ground.
- the tire is a composite of fiber / steel / rubber, and generally has a structure as shown in FIG. .
- Tread (1) It is a part in contact with the road surface, which provides the necessary frictional force for braking and driving, has good wear resistance, can withstand external stratification, and generates little heat.
- Body Ply (or Carcass) (6): This is a layer of cord inside the tire, which must support loads, withstand impacts and be resistant to flexing movements while driving.
- Belt (5) It is located between the body plies, and in most cases is composed of steel wire, which reduces the external stratification and keeps the tread grounding surface wide for excellent driving stability.
- Side Wall (3) It refers to the rubber layer between the lower part of the shoulder (2) and the bead (9), and serves to protect the inner body ply (6).
- Inner Liner (7) It is located inside the tire instead of the tube and prevents air leakage to enable pneumatic tires.
- BEAD (9) A square or hexagonal wire bundle with rubber coating on the wire that seats and secures the tire to the rim.
- CAP PLY (4) A special cord paper on the belt of some passenger radial tires that minimizes belt movement when driving.
- APEX (8) A triangular rubber layering material used to protect beads by minimizing the dispersion of beads and relieving external stratification and to prevent the inflow of air during molding.
- tire innerliners which are mainly composed of butyl rubber or halobutyl rubber rubber, which have relatively low air permeability. did. As the content and thickness of the rubber component increases, the total tire weight increases and the fuel economy of the vehicle decreases, and an air pocket or an inner liner is formed between the inner rubber and the inner liner of the carcass layer during the vulcanization process of the tire or the driving of the vehicle. The phenomena of the shape and physical properties were also changed.
- any previously known method has had a limit in maintaining excellent air permeability and tire formability while drastically reducing the thickness and weight of the inner liner.
- the inner liner obtained by the previously known method often did not have sufficient fatigue resistance, such as cracking caused by repeated deformation in the manufacturing process or running process of the tire.
- the previous tire innerliner does not have good adhesion to the carcass layer inside the tire, so that the tire innerliner may be separated or peeled off during the tire manufacturing process or the automobile driving process.
- the previous tire inner liner was not uniform in thickness, so that each part of the inner liner There was a problem of uneven stretching or deformation. As a result, the mechanical properties of the tire inner liner products have been degraded, and the thinner parts are elongated due to the relatively large elongation during the tire manufacturing process or the driving of automobiles, making it difficult to obtain a product having the durability that can be applied to the tire. Did.
- the present invention is to provide a film for a tire innerliner that can implement a superior airtightness even in a thin thickness to lighten the tire and improve the fuel economy of the vehicle, and can provide a tire having excellent molding stability and durability.
- this invention is providing the manufacturing method of the said film for tire innerliners.
- the present invention plyamide-based resin; And a copolymer comprising a polyamide-based segment and a 15 to 50% by weight polyether-based segment based on the total weight of the film. And an adhesive layer formed on at least one surface of the base film layer and including a resorcinol-formalin-latex (RFL) -based adhesive; wherein the difference between the maximum thickness and the average thickness and the minimum and average thickness of the base film layer is included.
- films for tire innerliners each having a difference of 6% or less of the average thickness.
- polyamide-based resin supplying a mixture of a copolymer including a polyamide-based segment and a polyether-based segment to an extrusion die through a raw material supply unit maintained at a temperature of 50 to 100 ° C. ; Melting and extruding the fed mixture at 230 to 30 CTC; Solidifying the extrudate in a cooling unit maintained at a temperature of 5 to 40 ° C.
- the base film comprises: It provides a method for producing a film for tire innerliner comprising 15 to 50% by weight of polyether segment.
- a polyamide-based resin comprising a polyamide-based segment and a polyether-based segment in an amount of 15 to 50 wt% based on the total weight of the film; and at least one of the base film layer
- An adhesive layer formed on one surface and including a resorcinol-formalin-latex (RFL) -based adhesive; wherein the difference between the maximum thickness and the average thickness and the difference between the minimum and average thickness of the base film layer is 63 ⁇ 4 of the average thickness, respectively.
- RTL resorcinol-formalin-latex
- Tire innerliner film comprising an adhesive layer comprising a
- it has a moldability and molding stability and can be firmly bonded to a tire without applying an additional vulcanization process or significantly increasing the thickness of the adhesive layer.
- the tire innerliner film obtained through the manufacturing method described below not only has a uniform thickness over the entire area, but also substantially does not exist in a relatively thick or thinner area than the surrounding part, No portion of the band or island form is observed in the figure film. Accordingly, the tire inner liner film may be uniformly formed over the entire film area when stretched or deformed, and may occur as a relatively thin or thin area exists. To prevent defects or damage to the film, and to have a uniform thickness and physical properties over the entire inner liner ' applied in the vehicle driving process; Excellent running durability can be ensured against repeated pressure and deformation.
- the difference between the maximum thickness and the average thickness of the base film layer and the difference between the minimum thickness and the average thickness may be 6% or less, preferably 3% or less, of the average thickness. That is, the base film layer provided by the manufacturing method mentioned later does not have a part too thick or thin compared with the total average thickness, and the whole film has a uniform thickness.
- the deviation between the thickness at any point on the base film layer and the thickness at a point located within 1 cm from the arbitrary point may be within 2%, preferably within. That is, the base film layer not only has a very uniform thickness over the entire area, but also has a feature that substantially no thick or thin area exists in the film as compared to the surrounding part.
- the tire inner liner film has not only uniform thickness characteristics but also physical properties such as excellent airtightness, high air pressure holding performance, and excellent moldability.
- the excellent physical properties of such a film for tire innerliner apply a base film layer including a copolymer (including polyamide-based segment-polyether-based segment) containing polyamide-based segment in a specific content together with polyamide-based resin. Seems to be.
- the base film layer may have a relatively low modulus with excellent airtightness by using the copolymer with the polyamide-based resin and the polyamide-based resin having a specific content to impart elastomeric properties.
- the polyamide-based resins included in the base film fill are excellent in airtightness due to their inherent molecular chain properties, for example, commonly used in tires at the same thickness. It exhibits airtightness of about 10 to 20 times compared to butyl rubber and the like, and shows not so high a modulus compared to other resins.
- the polyether-based segment of the copolymer is a polyamide-based segment or a polyamide-based segment
- the polyamide-based resin since the polyamide-based resin generally exhibits excellent airtightness, the polyamide-based resin has a role of allowing the base film layer to have low air permeability while having a thin thickness.
- an innerliner film having a relatively low modulus property is applied together with a copolymer including the specific content of polyether-based segments. It is possible to obtain the tire, thereby improving the moldability of the tire.
- the polyamide-based resin since the polyamide-based resin has excellent heat resistance and chemical stability, the inner liner film may be prevented from being deformed or modified when exposed to chemical substances such as high temperature conditions or additives applied in the tire manufacturing process.
- the polyamide-based resin is used with a copolymer comprising a polyamide-based segment and a polyether-based segment, and is relatively high relative to an adhesive (for example, a resorcinol-formalin-latex (RFL) -based adhesive).
- an adhesive for example, a resorcinol-formalin-latex (RFL) -based adhesive.
- RTL resorcinol-formalin-latex
- polyamide-based resins such as nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, and nylon 6/66.
- polyamide-based resins such as nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, and nylon 6/66.
- Nylon 6/66/610 copolymer nylon MXD6, nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer and nylon 66 / PPS copolymer;
- N-alkoxyalkylates for example 6-nylon methoxymethylate, 6-610-nylon methoxymethylate or 612-nylon methoxymethylate, nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610 or nylon 612 is preferred.
- Such polyamide-based resin may have a relative viscosity (96% sulfuric acid solution) of 3.0 to 3.5, more preferably 3.2 to 3.4.
- a relative viscosity 96% sulfuric acid solution
- the relative viscosity is less than 2.5, the elongation is not secured due to the decrease in toughness, and thus damage may occur when manufacturing a tire or driving a vehicle.
- the relative viscosity is higher than 4.0, the modulus or viscosity of the base film layer to be manufactured is unnecessary. It is possible to increase the efficiency, economic efficiency and the like of the manufacturing process, and the tire innerliner may be difficult to have a proper formability or elasticity.
- the relative viscosity of the polyamide-based resin refers to the relative viscosity measured using a 96% sulfuric acid solution at room temperature. Specifically, a sample of a certain polyamide-based resin (for example, 0.025 g) is dissolved in 96% sulfuric acid solution at different concentrations to prepare two or more measurement solutions (for example, a polyamide-based resin sample is 0.25 g / dL, O.lOg / dL, dissolved in 963 ⁇ 4 sulfuric acid to make three measurement solutions to a concentration of 0.05 g / dL), the relative viscosity of the measurement solution using a viscosity tube at 25 ° C (for example , The ratio of the average passage time of the measurement solution to the viscosity tube passage time of 96% sulfuric acid solution can be obtained.
- the polyamide-based resin may be included in the base film by mixing with the copolymer described above and melted, and also the monomer or oligomer, which is a precursor of the polyamide-based resin, may be used as an initiator or a catalyst.
- the combined reaction sikimeuroseo common with the above-described copolymer, along with it may be contained in the base film.
- the copolymer including the polyamide-based segment and the polyether-based segment is present in a bonded or dispersed state between the polyamide-based resins. It is possible to lower the modulus of the base film layer, to suppress the increase in the rigidity of the base film layer, and to prevent the crystallization at a high temperature.
- This copolymer is such as described above is included in the film layer according to the ⁇ Tire inner liner film has an excellent durability, heat resistance and fatigue resistance for While securing mechanical properties, high elasticity or elastic recovery rate can be realized.
- the inner liner film may exhibit excellent moldability, and the tire to which the inner liner film is applied may not be physically damaged or its own properties or performance may be deteriorated even during repeated driving and high heat.
- the copolymer is a polyamide segment; And 15 to 50% by weight, preferably 20 to 45%, of the polyether based segment based on the total weight of the film. If the content of the polyether-based segment is less than 10 weight 3 ⁇ 4> of the entire film, the modulus of the base film layer or the tire innerliner film is increased to reduce the moldability of the tire or to significantly decrease the physical properties due to repeated deformation. May appear.
- the airtightness of the film for the tire innerliner may be lowered i, the reactivity to the adhesive is lowered and the innerliner is easily adhered to the carcass layer
- the following may be difficult, and the elasticity of the base film layer may be increased, thereby making it difficult to manufacture a uniform film.
- the polyether-based segment may be present in the state of being bonded to the polyamide-based segment or dispersed between the polyamide-based resins. It is possible to suppress or prevent the base film layer from being easily broken.
- such a polyether-based segment can lower the modulus of the film for the tire inner liner, thereby allowing the tire to be easily stretched or deformed to fit the shape of the tire even when a very small force is applied during the tire forming.
- the polyether-based segment can suppress the increase in the rigidity of the film at low temperatures and prevent crystallization at high temperatures, and can prevent damage or tearing of the inner liner film due to repeated deformation.
- liner It is possible to improve the durability of the tire or innerliner by improving the recovery force against deformation to suppress the occurrence of wrinkles of the film due to permanent deformation.
- the polyamide-based segment may play a role in that the copolymer may have a certain level or more of physical properties but does not significantly increase the modulus properties.
- the base film layer may have a low thickness while having a thin thickness, and sufficient heat resistance and chemical stability may be ensured.
- the copolymer including the polyamide-based segment and the polyether-based segment may be a polyamide-based monomer or oligomer and a polyether-based monomer or oligomer It may be a copolymer obtained by reacting the polymer, the polymer comprising a polyamide segment and the polymer comprising a poly-ether segment may be a copolymer obtained by a polymerization reaction or crosslinking reaction.
- the copolymer including the polyamide-based segment and the polyether-based segment may be a block copolymer in which the segments form a block, and the segments are irregular. It can be a bonded random copolymer.
- the copolymer including the polyamide-based segment and the polyether-based segment may include a polymer including the polyamide-based segment and a polyether-based segment. It may be a copolymer including a polymerization reactant between polymers, or may be a crosslinked copolymer including a crosslinking reactant between a polymer including a polyamide-based segment and a polymer including a polyether-based segment.
- the copolymer including the polyamide-based resin, the polyamide-based segment, and the polyether-based segment is uniformly mixed, polymerized, or crosslinked. Through it may be in a combined state in part or the whole area.
- the copolymer including the polyamide-based segment and the polyether-based segment may be a polyamide-based segment.
- the copolymer may include a polyamide-based segment that does not participate in the polymerization or crosslinking reaction. It may also include polymers comprising polymers or polyether based segments.
- the polymer including the polymerization reactant or the crosslinking reactant as well as the polymer including the polyamide-based segment or the polymer including the poly-ether-based segment may be present in a mixed state or in combination with other components.
- the sum of the content of the polyether-based segmant and the content of the polymer including the polyether-based segment of the copolymer is increased by 15 to 50% by weight based on the total weight of the base film layer.
- the physical properties of the entire innerliner film can be optimized.
- the polyamide-based segment of the copolymer may include a repeating unit of Formula 1 or Formula 2.
- Ri is a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched arylalkylene group having 7 to 20 carbon atoms.
- R 2 is a linear or branched alkylene group having 1 to 20 carbon atoms
- R 3 is a straight or branched alkylene group having 1 to 20 carbon atoms or a straight or branched arylalkyl having 7 to 20 carbon atoms. It's Rengi.
- the polyamide segment is a substrate film layer using a copolymer comprising a polyamide repeat unit and a polyether repeat unit.
- the polyamide-based repeating unit may be used.
- the polyamide-based segment may be derived from a polymer comprising a polyamide-based segment used in the manufacturing process of the base film, or a polyamide-based monomer or oligomer.
- polyether segment of the copolymer may include a repeating unit represented by the following Formula 3.
- R 5 is a linear or branched alkylene group having 1 to 10 carbon atoms
- n is an integer of 1 to 100
- R 7 may be the same or different from each other, and a direct bond, -0—, -NH-, -C00- or -C0NH-.
- the polyether segment may be the polyether repeating unit when a base film layer is manufactured using a copolymer including a polyamide repeating unit and a polyether repeating unit.
- the polyether segment is derived from a polymer containing a polyether segment used in the manufacturing process of the base film, or a polyether ether monomer or oligomer Can be.
- the absolute weight average molecular weight of the co-polymer including the polyamide segment and the polyether segment may be 50,000 to 300,000, preferably 110,000 to 250,000. If the weight average molecular weight of the copolymer is less than 50,000, and the base film layer to be manufactured may not secure sufficient mechanical properties for use in the innerliner film, and if the weight average molecular weight of the copolymer is more than 300,000, When heating, the modulus or crystallinity of the base film layer may be excessively increased, and thus it may be difficult to secure the elasticity or elastic recovery rate to have as the innerliner film. In the solution containing the polymer material, light scattering occurs due to the chain of the polymer material. If used, the absolute weight average molecular weight of a polymeric material can be measured. Especially
- the absolute weight average molecular weight of the polymer can be obtained by applying the parameters from the measurement results to the Rayleigh—Gans-Debye equation.
- M is the molar mass, and in the case of a polydisperse sample, the absolute weight average molecular weight (Mw), R e is the excess Rayleigh ratio, ⁇ :: ⁇ !! /; ⁇ ⁇ ⁇ — 4 ⁇ — 1 , C is the polymer concentration in solution (g /), and A 2 is the second virial coefficient.
- the polyamide-based segment preferably has properties similar to those of the polyamide resin used, for example, relative viscosity, so that the polyamide-based segment has a relative viscosity of 3.0 to 3.5 (sulfuric acid). 96% solution)
- the polyamide-based segment has a relative viscosity in a range similar to that of the polyamide resin, both components may be uniformly mixed without phase separation in manufacturing the base film.
- the base film layer may have a uniform physical property as a whole, high airtightness and air pressure holding ability, excellent moldability, high durability and fatigue resistance It may have the physical properties such as.
- the polyether segment unit may be derived from a monomer, oligomer or polymer having an absolute weight average molecular weight of 500 to 10,000, preferably 1,000 to 3,000.
- the tire when the weight average molecular weight of the precursor of the polyether segment unit is less than 500 It may not be possible to appropriately suppress the growth of large crystals in the innerliner film or lower the modulus.
- the weight average molecular weight of the precursor of the polyether segment unit is more than 10,000, the airtightness of the inner liner may be reduced.
- the copolymer is a polyamide-based segment and a polyether segment in the range of 15 to 50% by weight based on the total weight of the film, the polyether segment 6: 4 to 3: 7, preferably 5: 5 to 4: 6 by weight.
- the modulus of the base film layer or the film for the tire inner liner may be increased, thereby reducing the moldability of the tire, or the physical property decrease due to repeated deformation.
- the content of the polyether segment is too large, the airtightness of the film for the tire inner liner may be lowered, the reaction resistance to the adhesive is lowered, it is difficult for the inner liner to easily adhere to the carcass layer, The elasticity of the base film layer may be increased and thus it may not be easy to produce a uniform ' film.
- the polyamide-based resin and copolymer may be included in a weight ratio of 6: 4 to 3: 7, preferably 5: 5 to 4: 6. If the content of the polyamide-based resin is too small, the density or airtightness of the base film layer may be lowered. In addition, if the content of the polyamide-based resin is too large, the modulus of the base film layer may be excessively high or the moldability of the tire may be reduced, the polyamide-based resin in a high temperature environment during the tire manufacturing process or driving Crystallization may occur and cracks may occur due to repeated deformation.
- the base film layer may include 1.3 to 2.5 Equ / E6g, preferably 1.5 to 2.4 Equ / E6g of the amine group on the surface
- the base film layer is according to the adhesive known to be used in the polymer resin film It has high responsiveness, and can be firmly and uniformly bonded to the inside of the tire or the carcass layer even with a thin and lightweight adhesive layer. have.
- RTL resorcinol-formalin-latex
- the tire inner liner film may exhibit improved adhesion to the adhesive or the adhesive layer due to the characteristics of the above-described base film, and may be applied to the carcass layer as a thin and light weight adhesive layer without the need for laminating additional adhesive layers or rubber layers. It can be fixed firmly and evenly.
- the base film layer may have a thickness of 30 to 300 im, preferably 40 to 250 pm, more preferably 40 to 200 // m. Accordingly, the film for tire innerliner of one embodiment of the invention has a thinner thickness than previously known, but has a low air permeability, for example, an oxygen permeability of 200 cc / (m J. 24hr ⁇ atm) or less. Can be. Of
- the base film layer may be an unstretched film.
- the base film layer When the base film layer is in the form of an unstretched film, it has a low modulus and a high strain rate and can be suitably applied to a tire forming process in which high expansion occurs.
- crystallization hardly occurs in the unstretched film, damage such as cracks and the like can be prevented even by repeated deformation.
- the unoriented film since the unoriented film does not have a large variation in the orientation and physical properties in a specific direction, an inner liner having uniform physical properties can be obtained.
- a method of suppressing the orientation of the base film layer as much as possible for example, adjusting viscosity by optimizing melt extrusion temperature, changing a die specification, or adjusting a winding speed, etc.
- the method of the base film can be prepared in an unoriented or unoriented film.
- the inner liner film can be easily manufactured in a cylindrical or sheet form in a tire manufacturing process.
- the base film layer is applied as an unstretched sheet-like film, it is not necessary to construct a film manufacturing facility for each tire size, and the lamination and wrinkle applied to the film during the transport and storage process are not required. It is preferable because it can be minimized.
- a process of adding an adhesive layer to be described later may be more easily performed, and damage or crushing occurring during the manufacturing process may be prevented due to the difference in specifications with the forming drum.
- the base film may further include additives such as heat resistant antioxidants, heat stabilizers, adhesion promoters, or mixtures thereof.
- heat resistant antioxidants include ⁇ 1 ⁇ '-nuclemethylene-bis- (3,5-di- (1; -butyl) -4-hydroxy-hydrocinnamamide (N, N'-Hexamethylene-b is- (3,5-di-tert-butyl -4-hydroxy-hydroc i nnamam i de, for example, commercially available products such as rganox 1098), tetrakis [methylene (3, 5-di- (t-butyl) ) -4-hydroxyhydrocinnamate)] methane (commercially available as tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, eg Irganox 1010) or 4,4'-d-cue Mildiphenylamine
- heat stabilizer benzoic acid (Bezoic acid), triacetone diamine ( triacetonediamine), or ⁇ 1 -bis (2,2,6,6—tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide ( ⁇ , ⁇ '— Bis (2,2,6 , 6-tetramethyl-4-piperidyl) -l, 3-benzenedicarboxamide), but the additives are limited to the above examples. It is not, it is known as being used for the film for a tire inner liner can be used without limitation.
- the adhesive layer comprising the resorcinol-formalin-latex (RFL) -based adhesive has excellent adhesion and adhesion retention performance to the base film layer and the tire carcass layer, and thus in the manufacturing process or running process of the tire By preventing the breakage of the interface between the inner liner film and the carcass layer generated by the generated heat or repeated deformation, the inner liner film may have a layered fatigue resistance.
- RTL resorcinol-formalin-latex
- the main properties of the adhesive layer described above appear to be due to the inclusion of certain resorcinol-forminine-latex (RFL) -based adhesives having a specific composition.
- RRL resorcinol-forminine-latex
- adhesives for tire innerliners have been used such as rubber-type tie gums, which required an additional vulcanization process.
- the adhesive layer is Resorcinol-formalin-latex (RFL) -based adhesives of a particular composition, including high resilience and adhesion to the substrate film, as well as compression under high temperature heating conditions without increasing the thickness of the substrate film and tire The carcass layer can be firmly bonded.
- the adhesive layer may exhibit high fatigue resistance against physical and chemical deformations that may be applied during tire manufacturing or automobile driving, the adhesive force may be applied even during a high temperature manufacturing process or a vehicle driving process subject to long-term mechanical deformation. It can minimize the deterioration of other physical properties.
- the resorcinol-formalin-latex (RFL) -based adhesives are capable of crosslinking between latex and rubber, thereby exhibiting adhesive performance, and because they are physically latex polymers, have low curing properties and thus have flexible properties such as rubber. Chemical bonding between the end group and the base film of the methi of the lesosinol-formalin polymer is possible. Accordingly, when the resorcinol formalin-latex (RFL) -based adhesive is applied to the base film, high moldability and elasticity can be realized together with the adhesive performance.
- the resorcinol-formalin-latex (RFL) -based adhesive is 2 to 32% by weight, preferably 10 to 20% by weight and latex 68 to 98% by weight, preferably 80 to 80%, of a condensate of resorcinol and formaldehyde. And 90 weight percent.
- the condensate of resorcinol and formaldehyde may be obtained by mixing the resorcinol and formaldehyde in a molar ratio of 1: 0.3 to 1: 3.0, preferably 1: 0.5 to 1: 2.5, and then condensation reaction.
- the condensate of resorcinol and formaldehyde may be included in an amount of 2 weight or more relative to the total amount of the adhesive layer in terms of chemical reaction for excellent adhesion, and may be included in less than 32 weight 3 ⁇ 4 «to secure the proper fatigue resistance. have..
- the latex may be one or two or more kinds selected from the group consisting of natural rubber latex, styrene / butadiene rubber latex, acrylonitrile / butadiene rubber latex, chloroprene rubber latex and styrene / butadiene / vinylpyridine rubber latex. .
- the latex may be included in an amount of 68% by weight or more based on the total amount of the adhesive layer for flexibility of the material and an effective crosslinking reaction with the rubber, and 98% by weight or less for the chemical reaction with the base film and the rigidity of the adhesive layer.
- the adhesive layer may further include at least one additive such as a surface tension modifier, a heat resistant agent, an antifoaming agent, and a filler, together with a condensate and latex of resorcinol and formaldehyde.
- the surface tension modifier of the additive is applied for uniform application of the adhesive layer, but may cause a problem of adhesion loss when excessively added, 2% by weight or less based on the total amount of the adhesive layer or 0.0001 to 2% by weight, preferably May be included in an amount of 1.0 weight% or less or 0.0001 to 0.5 weight%.
- the surface tension modifiers sulfonate anionic surfactant, sulfate ester salt anionic surfactant, carboxylate anionic surfactant, phosphate ester salt anionic surfactant, fluorine-based surfactant, silicone-based surfactant and polysiloxane-based surfactant
- sulfonate anionic surfactant sulfate ester salt anionic surfactant
- carboxylate anionic surfactant phosphate ester salt anionic surfactant
- fluorine-based surfactant silicone-based surfactant
- silicone-based surfactant and polysiloxane-based surfactant
- the adhesive layer may have a thickness of 0.1 to 20 pm, preferably 0.1 to 10 ⁇ , more preferably 0.2 to 7 am, even more preferably 0.3 to 5 // m, and one of the films for tire innerliner It can be formed on the surface or on both surfaces. If the thickness of the adhesive layer is too thin, the adhesive layer itself may be thinner when the tire is inflated, the crosslinking adhesive force between the carcass layer and the base film may be lowered, and stress may be concentrated on a part of the adhesive layer, thereby reducing fatigue characteristics. In addition, when the adhesive layer is too thick, interfacial separation may occur in the adhesive layer, thereby reducing fatigue characteristics.
- the base film layer may further include additives such as heat resistant antioxidants, heat stabilizers, adhesion promoters, or mixtures thereof.
- heat resistant antioxidants include ⁇ -nucleated methylene-bis- (3,5-di- (butyl) -4-hydroxy-hydrocinnamamide ( ⁇ , ⁇ '-Hexamethylene-bi s- (3, 5-di-tert-but y 1-4-hydr oxy-hydr oc i nnamam i de, such as commercially available products such as rganox 1098), tetrakis [methylene (3,5-di- (t-butyl) -4) -Hydroxyhydrocinnamate)] methane (commercially available products such as tetrakis [methyl ene (3, 5—di t t -but y 1-4-hydroxyhydroc i nnaraat e) methane, eg Irganox
- thermal stabilizer examples include benzoic acid and triacetone diamine. (triacetonediamine), or ⁇ , ⁇ '—bis (2,2,6,6-tetramethyl-4—piperidyl) -1,3-benzenedicarboxamide (N, N'-Bis (2,2 , 6,6-tetramethyl-4- piperidyl) -l, 3-benzened ic ar boxam i de), etc. It is not limited to the example, What is known to be usable for the film for tire innerliner can be used without a restriction
- the maximum stress (stress) that appears when the tire inner liner film 100% elongated at room temperature may be 10 to 30 Mpa.
- the tire inner liner film having such stretching characteristics not only has excellent moldability in the tire manufacturing process, but also can stably maintain physical properties even in the severe deformation during tire forming, and even if a small force is applied during tire forming, It can be stretched or modified to suit.
- the tire to which the tire innerliner film is applied may not significantly change the modulus or the rigidity even after long-term driving, and may minimize the crack of the inner structure of the tire that may occur during the driving.
- the tire inner liner film can maintain the proper air pressure even after long-term use, for example, for the tire inner liner at 21 ° C and 101.3 kPa according to the method of the ASTM F 1112-06 standard
- the air pressure retention ratio as shown in the following general formula 2 may be 95% or more, that is, the air pressure reduction rate may be 5% or less. Accordingly, by using the tire inner liner film, it is possible to prevent overturning accidents and fuel economy reduction caused by low air pressure.
- polyamide-based resin having a melt viscosity deviation of 3% or less, polyamide-based segments and polyether-based segments (3) or less
- a method for manufacturing the film for tire innerliner which includes 15 to 50 weight 3 ⁇ 4, may be provided.
- the melt viscosity variation of each copolymer and the polyamide-based resin including the polyamide-based segment and the polyether-based segment, which are raw materials used in the production of the base film is uniformly controlled to 3% or less,
- these mixtures are melted and extruded by feeding them to the extrusion die through a raw material supply unit maintained at a temperature of 50 to 100 ° C., not only have a uniform thickness over the entire film area, they are relatively thicker than the surrounding parts, or It was confirmed that the base film layer in which the thin part ⁇ region was substantially absent can be obtained.
- the difference between the maximum thickness and the average thickness of the base film layer and the difference between the minimum thickness and the average thickness may be 6% or less, preferably 3% or less, of the average thickness.
- the deviation of the thickness at any point on the base film ' layer and the point located within lcm from the arbitrary point may be within 2%, preferably within 1%.
- the base film layer of the tire innerliner film provided according to the manufacturing method not only has a uniform thickness over the entire area. It is characterized by the fact that some areas in the film that are relatively thick or thin as compared to the surrounding part are substantially free. Therefore, the tire inner liner film may be uniformly stretched or deformed over the entire area of the film during a tire forming process, etc., and may prevent defects or damage of the film that may occur due to the existence of a relatively thick or thin area. In addition, it has a uniform thickness and physical properties over the entire area of the inner liner, thereby ensuring excellent driving durability against repeated pressures and deformations applied during the vehicle driving process.
- the tire innerliner film produced by forming an adhesive layer containing resorcinol-formalin-latex (RFL) adhesive on the surface provides excellent airtightness even at a thin thickness to reduce tire weight and improve automobile fuel economy. It can have excellent moldability and molding stability resulting from uniform thickness with excellent mechanical properties such as high durability or fatigue resistance, and firmly bonded to the tire without applying additional vulcanization process or greatly increasing the thickness of the adhesive layer. Can be.
- RTL resorcinol-formalin-latex
- the copolymer including the polyamide-based segment and the polyether-based segment and each of the polyamide-based resins may have a uniform melt viscosity, and specifically, may have a melt viscosity variation of 33 ⁇ 4 or less.
- the deviation of the melt viscosity means the difference between the average value and the maximum value (or minimum value) of the melt viscosity of the entire resin or copolymer.
- the copolymer or polyamide-based resin has a melt viscosity deviation of 3% or less, the maximum value of the melt viscosity of each of the copolymer or polyamide-based resin is 103% or less of the average value and the minimum value of the melt viscosity the average value of a sense of 'more than 97%.
- Criteria for the measurement of the melt viscosity of each of the copolymer and polyamide-based resin are not particularly limited, and may vary depending on the specific examples of the copolymer and polyamide-based resin used or the process conditions to be applied. It may be measured under a temperature of 230 to 300 ° C and a shear rate of 100 / sec to 300 / sec.
- melt viscosity of each of the copolymer and the polyamide-based resin is not particularly limited, but the melt viscosity measured at a temperature of 260 ° C. and a shear rate of 200 / sec may be 5000 poise to 7000 poise. However, as described above, the melt viscosity deviation of each of the copolymer and the polyamide-based resin may be 33 ⁇ 4 or less, preferably 2% or less.
- the copolymer and the polyamide-based resin has a uniform melt viscosity, in the step of mixing them, ' staying or melting and extruding the raw material supply unit maintained at the constant temperature, and the like,
- the polyamide-based resin may be more uniformly mixed, and the copolymer and the polyamide-based resin may be prevented from increasing in size by being aggregated with each other or with each other, whereby a base film layer having a more uniform thickness may be obtained. Can be formed.
- the size of the copolymer and the polyamide-based resin that can be used in the production method is not particularly limited, and for example, each maximum diameter may be 2mm to 3mm.
- each maximum diameter may be 2mm to 3mm.
- the polyamide-based resin may be included in the base film by melting or after mixing or compounding with the above-described copolymer, and may further include monomers or oligomers, which are precursors of the polyamide-based resin, together with a reaction initiator or a catalyst. It can also be included in the base film by reacting with one copolymer.
- copolymer including the polyamide-based segment and the polyether-based segment is melted after mixing or compounding the copolymer itself with the polyamide-based resin. Can be included.
- the base film layer may be formed by mixing and melting with the polyamide-based resin.
- by mixing or compounding a polymer comprising a polyamide-based segment and a polymer comprising a polyether-based segment, and mixing and melting such a mixture or compound with a polyamide-based resin The polymer of the species may cause a polymerization reaction or crosslinking reaction, and through this process, the base film layer may be formed.
- the uriamide resin and the. Copolymers comprising polyamide (p 0 ly- am id e ) segments and polyether-based segments may be homogeneously mixed or bound in some or all regions through polymerization or crosslinking reactions. Can be.
- the method for manufacturing the tire innerliner film may further include mixing the polyamide-based resin and the copolymer in a weight ratio of 6: 4 to 3: 7. If the content of the polyamide-based resin is too small, the substrate The density or airtightness of the film layer may be reduced.
- the modulus of the base film layer may be excessively high or the formation of tires may be degraded, and the polyamide may be formed in a high Amide-based resin may be crystallized, and the stack may occur due to repeated deformation.
- the polyamide-based resin and the copolymer may be injected into a feeder after being mixed, or may be mixed by being sequentially or simultaneously injected into the raw material supply.
- the mixture of the polyamide-based resin and the copolymer may be supplied to the extrusion die through a raw material supply unit maintained at a temperature of 50 to 100 ° C.
- the mixture of the polyamide-based resin and the copolymer has physical properties such as proper viscosity, and can easily move to other parts of the extrusion die or the extruder.
- it is possible to prevent a poor feeding of the raw material (feeding) phenomenon caused by agglomeration of the mixture it is possible to form a more uniform substrate film in the subsequent melting and extrusion process.
- the raw material supplied to the extruder may slide rapidly on the surface of the extruder screw or the raw material may be unevenly supplied to the extruder, and if the temperature is maintained above ioo ° c May melt on the surface of the extruder screw, resulting in poor supply.
- the raw material supply part is a part that serves to supply the raw material injected from the extruder to the extrusion die or any other part, the configuration is not greatly limited, a conventional feeder (feeder) included in the extruder pillar for manufacturing the polymer resin Can be.
- the temperature for melting the mixture may be 230 to 300 ° C, preferably 240 to 280 ° C.
- the melting temperature should be higher than the melting point of the polyamide compound, but if it is too high, carbonization or decomposition may occur, causing Physical properties may be inhibited, and bonding between the polyether resins may occur or orientation may occur in a fiber array direction, and thus may be disadvantageous in manufacturing an unstretched film.
- the extrusion die may be used without any limitation as long as it is known to be used for extrusion of the polymer resin, but a T-type die is used to make the thickness of the base film more uniform or to prevent orientation of the base film. It is desirable to.
- the die gap of the extrusion die may be adjusted to 0.3 to 1.5 mm.
- the die gap Die Gap
- the die shear pressure of the melt extrusion process is too high and the shear force is so high that it is difficult to form a uniform shape of the extruded film and the productivity is reduced
- the die gap is too large, the stretching of the melt-extruded film may be too high, the orientation may occur, the difference in physical properties between the longitudinal and transverse direction of the substrate film to be produced may be increased.
- a part of an extrusion die corresponding to a position where a non-uniform thickness appears by continuously measuring the thickness of the base film manufactured by the above-described steps and feeding back a measurement result, eg
- the film having a more uniform thickness can be obtained by reducing the variation of the base film manufactured by adjusting the lip gap (Vt) adjustment bolt of T-Die.
- Vt lip gap
- the method for producing a tire innerliner film the step of solidifying the base film layer formed by melting and extruding at the corner portion maintained at a temperature of 5 to 40 ° C, preferably 10 to 30 ° C. It may include.
- the film having a more uniform thickness as the base film layer formed by melting and extruding is solidified in the cooling unit maintained at the temperature of 5 to 40 ° C. May be provided. Titrating the base film layer obtained by melting and extruding By stretching or grounding the cooling part maintained at a temperature, it is possible to substantially prevent stretching, and the base film layer may be provided as an unstretched film.
- the temperature of the indentation is less than 5 ° C, water condensation may occur in the cooling unit to cause non-uniform cooling phenomenon, and thus, the base film layer formed by melting and extruding may be difficult to adhere to the indentation.
- the temperature of the corner portion is greater than 40 ° C, it may be difficult to sufficiently angle the base film layer formed by melting and extruding.
- the temperature of the corner portion is too high, the base film layer adheres to the surface of the corner portion. I can throw it away.
- the solidifying step may be performed using an air knife, an air nozzle, an electrostatic charge device (Pinning device), or a combination thereof, in which the base film layer formed by melting and extruding is maintained at a temperature of 5 to 40 ° C. It may include the step of uniformly contact.
- an air knife an air nozzle, an electrostatic charge device (Pinning device), or a combination thereof, in which the base film layer formed by melting and extruding is maintained at a temperature of 5 to 40 ° C. It may include the step of uniformly contact.
- the base film layer formed by melting and extruding by using an air knife, an air nozzle, an electrostatic impinger (Pinning device), or a combination thereof is brought into close contact with cooling, so that the base film layer is subjected to air after extrusion.
- Phenomena such as flying or partially non-uniform angles in the middle of the film may be prevented, and thus a film having a more uniform thickness may be formed, and a portion of the film may be substantially thicker or thinner than the surrounding portion. It may not be formed.
- the melt extruded under the specific die 3 ⁇ 4 conditions can be attached or grounded to the ground angle installed at 10 to 150mm, preferably 20 to 120mm at a horizontal distance from the die outlet to exclude the stretching and orientation.
- the horizontal distance from the die outlet to the cooling can be the distance between the die outlet and the point where the discharged melt grounds the angle of depression. If the straight line distance between the exit point of the die and the molten film attachment point is too small, it may interfere with the uniform flow of the molten extruded resin and cause film angular unevenness, and if the distance is too large, suppress the stretching effect of the film. Can not.
- extrusion processing conditions of the film commonly used in the preparation of the polymer film for example, screw diameter, screw rotational speed, or line speed, etc. Can be selected and used appropriately.
- the thickness of the molten resin sheet discharged by combining the extruder discharge amount and the width of the die or 3 ⁇ 4, the winding speed of cooling, or the like, or optionally, as described above, Air Knife and Air nozzle can be adjusted to 30 to 300 m by uniformly adhering to each other using an electrostatic Edge Pinnig device.
- the method for producing a film for tire innerliner may include forming an adhesive layer including a resorcinol-formalin-latex (RFL) adhesive on at least one surface of the base film layer.
- RTL resorcinol-formalin-latex
- the adhesive layer comprising the resorcinol-formalin-latex (RFL) -based adhesive may be formed by coating a resorcinol-formalin-latex (RFL) -based adhesive on one surface of the base film layer, and the resorcinol- It can also be formed by laminating an adhesive film comprising a formalin-latex (RFL) -based adhesive on one side of the base film layer.
- the step of forming the adhesive layer may be carried out by coating a resorcinol-formalin-latex (RFL) -based adhesive on one or both surfaces of the formed base film and then drying.
- the formed adhesive layer may have a thickness of 0.1 to 20 im, preferably 0.1 to 10.
- the resorcinol-formalin-latex (RFL) -based adhesive may include 2 to 32 weight 3 ⁇ 4 of condensate of resorcinol and formaldehyde and 68 to 98 weight% of latex, preferably 80 to 90 weight%.
- RTL resorcinol-formalin-latex
- the coating or coating method or apparatus conventionally used for the application of the adhesive may be used without any limitation, but may be a knife coating method, a bar coating method, a gravure coating method or a spray method, or a dipping method. Can be used. Knife coating, gravure coating or The use of the bar coating method is preferred in terms of uniform application and coating of the adhesive.
- the drying and the adhesive reaction may be simultaneously performed, but may be divided into the heat treatment reaction step after the drying step in consideration of the reactivity of the adhesive,
- the adhesive layer forming, drying and reaction steps may be applied several times.
- the heat treatment may be performed by a method of solidifying and reacting under heat treatment conditions at about 30 seconds to 3 minutes at 100-150 ° C.
- additives such as a heat resistant antioxidant or a heat stabilizer may be further added. Details of the additives are as described above.
- the present invention it is possible to reduce the tire weight and improve the fuel efficiency of the vehicle by implementing excellent airtightness even at a thin thickness, has a uniform thickness, film and tire inner liner for tire inner liner having excellent molding stability and running durability
- the manufacturing method of the film for may be provided.
- FIG. 1 schematically shows the structure of a tire.
- each of the polyamide-based resin and the elastomer resin has a maximum diameter of 2 mm to 3mm, had a melt viscosity of 6000 poise at a temperature of 260 ° C and a shear rate of 200 / sec, and the polyamide-based resin and The variation in the melt viscosity of each of the copolymer resins (the difference in the ratio of the maximum value (or minimum value) to the average value of the melt viscosity of the entire resin or the copolymer) was adjusted to 2%.
- the mixture is controlled to prevent coarsening between chips below 100 ° C.
- the temperature of the raw material supply part is adjusted to 50 to 100 ° C while the mixture is fused in the extruder screw to prevent feeding failure. It was fed to an extrusion die.
- the supplied mixture is extruded through a T-type die (Die Gap] -1.0 mm) at a temperature of 260 ° C. while maintaining a uniform melt flow, and cooled to 25 ° C. on the surface of the air. Knife was used and the molten resin was cooled and solidified into a film of uniform thickness. Then, an unstretched base film having a thickness of Table 1 was obtained without undergoing stretching and heat treatment sections at a speed of 15 m / min.
- Resorcinol and formaldehyde were mixed at a molar ratio of 1: 2, and then condensed to obtain a condensate of resorcinol and formaldehyde.
- 12% by weight of the condensate of resorcinol and formaldehyde and 88% by weight of styrene / butadiene ⁇ 1,3 / vinylpyridine latex were mixed to obtain a resorcinol-formalin-latex (RFL) adhesive having a concentration of 20%.
- RTL resorcinol-formalin-latex
- the resorcinol-formalin-latex (RFL) -based adhesive was coated on the base film at a thickness of 1 ⁇ m using a gravure coater, dried and reacted at 150 ° C. for 1 minute to form an adhesive layer.
- Example 2 40% by weight of polyamide-based resin (nylon 6) having a relative viscosity of 3.4 and a copolymer resin having an absolute weight average molecular weight of 150,000 (synthesized using 40% by weight of polyethylene glycol at the end of the amine group and 60% by weight of nylon 6 resin) 60
- a tire innerliner film was prepared in the same manner as in Example 1 except that the weight% was mixed.
- nylon 6 60% by weight of polyamide-based resin (nylon 6) having a relative viscosity of 3.4 and a copolymer resin having a weight average molecular weight of 150,000 (synthesized using 50% by weight of polyethylene glycol at the end of the amine group and 50% by weight of nylon 6 resin)
- a film for tire innerliner was prepared in the same manner as in Example 1 except for mixing 40% by weight.
- the release agent and the processing agent were added to the butyl rubber, mixed, and refined to obtain a tire inner liner film having the thickness shown in Table 1 below, and an adhesive rubber (tie gum) having a thickness of 1; ⁇ was formed on the inner liner film.
- a tire innerliner film was prepared in the same manner as in Example 1 except that the weight% was mixed.
- a resorcinol-formalin-latex (RFL) -based adhesive was prepared in the same manner as in Example 1, and was then coated and dried on the base film to form an adhesive layer having a thickness of 1 urn. Comparative Example 3
- a resorcinol-formalin-latex (RFL) -based adhesive was prepared in the same manner as in Example 1, and was then coated and dried on the base film to form an adhesive layer having a thickness of 1 urn.
- the temperature of the raw material supply portion was adjusted to 120 ° C., except that the mixture was extruded using an annular die was prepared in the same manner as in Example 1 film for the tire innerliner.
- the stress generated when 100% elongated in the direction of the machine direction (MD) was measured.
- the specific measuring method is as follows.
- Oxygen permeability of the tire innerliner film obtained in the above Examples and Comparative Examples was measured.
- the specific measuring method is as follows.
- Oxygen permeability The method of ASTM D 3895 was measured using the Oxygen Permeation Analyzer (Model 8000, the product of Illinois Instruments) in 25 degreeC 60 RH% atmosphere.
- Experimental Example 4 Performance measurement of air pressure holding
- Tires were manufactured by applying the tire inner liner films of Examples and Comparative Examples to the 205R / 65R16 standard. In addition, the manufactured tires were evaluated under the pressure of 101.3 kPa at 21 ° C. using the ASTM F1112-06 method, and the air pressure retention (IPR Internal Pressure Retention) was measured for 90 days according to the following general formula (2).
- the film for tire innerliner of the embodiment was confirmed not only to have a uniform thickness over the entire area, but also within 2% of the thickness variation at two points adjacent to each other within 1 cm.
- the film for the tire inner liner of the embodiment not only shows excellent airtightness (low oxygen permeability) even at a thin thickness, but also shows excellent pneumatic holding performance, and a small load occurs even at 100% elongation at room temperature, thereby forming actual tires. It was confirmed that excellent moldability could be expressed at the time.
- the film for tire innerliner of Comparative Example 1 manufactured using butyl rubber is not only very uneven in thickness but also easy to pressure. Due to the nature of the soft rubber itself, it was difficult to constantly measure the thickness of the film by pressure contact. And when it has a thickness similar to the film for tire innerliners of an Example, it was confirmed that it has airtightness (high oxygen permeability) which is difficult to use as an inner liner.
- Comparative Example 2 and Comparative Example 3 which had different compositions of the raw materials used, showed uniformity in the range similar to that of Example, but Comparative Example 2 had a very large load at 100% elongation at room temperature. As a result, it was impossible to actually form the tire, and it was confirmed that Comparative Example 3 had airtightness (high oxygen permeability), which was difficult to use as an inner liner.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Tires In General (AREA)
- Tyre Moulding (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12837146.5A EP2762519B1 (en) | 2011-09-30 | 2012-09-28 | Film for an inner liner for a tire, and method for manufacturing same |
CN201280059291.0A CN103958580B (zh) | 2011-09-30 | 2012-09-28 | 用于轮胎内衬层的膜及其制备方法 |
US14/346,069 US9492981B2 (en) | 2011-09-30 | 2012-09-28 | Film for tire inner liner and method for manufacturing the same |
JP2014533215A JP5893147B2 (ja) | 2011-09-30 | 2012-09-28 | タイヤインナーライナー用フィルムおよびその製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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KR10-2011-0100238 | 2011-09-30 | ||
KR20110100238 | 2011-09-30 | ||
KR10-2012-0108585 | 2012-09-28 | ||
KR1020120108585A KR102023166B1 (ko) | 2011-09-30 | 2012-09-28 | 타이어 이너라이너용 필름 및 이의 제조 방법 |
Publications (2)
Publication Number | Publication Date |
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WO2013048206A2 true WO2013048206A2 (ko) | 2013-04-04 |
WO2013048206A3 WO2013048206A3 (ko) | 2013-07-04 |
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PCT/KR2012/007953 WO2013048206A2 (ko) | 2011-09-30 | 2012-09-28 | 타이어 이너라이너용 필름 및 이의 제조 방법 |
Country Status (6)
Country | Link |
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US (1) | US9492981B2 (ko) |
EP (1) | EP2762519B1 (ko) |
JP (1) | JP5893147B2 (ko) |
KR (1) | KR102023166B1 (ko) |
CN (1) | CN103958580B (ko) |
WO (1) | WO2013048206A2 (ko) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016047710A1 (ja) * | 2014-09-24 | 2016-03-31 | 株式会社ブリヂストン | タイヤ |
US20180086140A1 (en) * | 2015-04-10 | 2018-03-29 | Bridgestone Corporation | Polyamide-based thermoplastic elastomer and tire |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101475494B1 (ko) * | 2010-12-30 | 2014-12-31 | 코오롱인더스트리 주식회사 | 타이어 이너라이너용 필름 및 이의 제조 방법 |
US20150053324A1 (en) * | 2013-08-22 | 2015-02-26 | The Goodyear Tire & Rubber Company | Tire having laminated innerliner with reinforced splice |
KR102123626B1 (ko) * | 2013-09-30 | 2020-06-16 | 코오롱인더스트리 주식회사 | 고분자 필름 |
WO2016047708A1 (ja) | 2014-09-24 | 2016-03-31 | 株式会社ブリヂストン | タイヤ |
US10533078B2 (en) | 2014-09-30 | 2020-01-14 | Kolon Industries, Inc. | Polymer film and method for preparing polymer film |
US9889703B2 (en) | 2014-12-16 | 2018-02-13 | The Goodyear Tire & Rubber Company | Tire with spliced film innerliner |
KR102202591B1 (ko) * | 2014-12-30 | 2021-01-12 | 코오롱인더스트리 주식회사 | 공압출 필름 |
US20160303907A1 (en) | 2015-04-16 | 2016-10-20 | The Goodyear Tire & Rubber Company | Tire with spliced multilayered film innerliner |
KR102288987B1 (ko) * | 2015-09-30 | 2021-08-10 | 코오롱인더스트리 주식회사 | 인플레이션 필름 및 이의 제조 방법 |
US10160263B2 (en) | 2016-01-11 | 2018-12-25 | The Goodyear Tire & Rubber Company | Tire with non-spliced multilayered film innerliner |
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US6079465A (en) * | 1995-01-23 | 2000-06-27 | The Yokohama Rubber Co., Ltd. | Polymer composition for tire and pneumatic tire using same |
JP3217239B2 (ja) * | 1995-01-23 | 2001-10-09 | 横浜ゴム株式会社 | タイヤ用ポリマー組成物およびそれを使用した空気入りタイヤ |
JP3692370B2 (ja) * | 1995-10-13 | 2005-09-07 | 住友ゴム工業株式会社 | 空気入りタイヤ |
JPH11170339A (ja) | 1997-12-12 | 1999-06-29 | Unitika Ltd | ポリアミドフィルムの製造方法 |
JP3868757B2 (ja) * | 2001-04-25 | 2007-01-17 | 株式会社神戸製鋼所 | ゴム系組成物の混練装置および混練方法 |
JP2005219565A (ja) | 2004-02-04 | 2005-08-18 | Yokohama Rubber Co Ltd:The | 空気入りタイヤ |
KR101063972B1 (ko) * | 2004-06-24 | 2011-09-14 | 코오롱인더스트리 주식회사 | 공기 타이어의 이너라이너 |
KR101085033B1 (ko) | 2004-06-28 | 2011-11-18 | 코오롱인더스트리 주식회사 | 공기 타이어의 다층 공기투과방지층 |
JP5001721B2 (ja) * | 2007-06-01 | 2012-08-15 | 東洋ゴム工業株式会社 | 空気入りタイヤ |
US20100258230A1 (en) * | 2007-11-28 | 2010-10-14 | Marco Cantu | Method for manufacturing tyres for vehicles wheels |
JP4435253B2 (ja) * | 2008-03-26 | 2010-03-17 | 住友ゴム工業株式会社 | インナーライナーおよび空気入りタイヤ |
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-
2012
- 2012-09-28 US US14/346,069 patent/US9492981B2/en active Active
- 2012-09-28 JP JP2014533215A patent/JP5893147B2/ja not_active Expired - Fee Related
- 2012-09-28 CN CN201280059291.0A patent/CN103958580B/zh active Active
- 2012-09-28 KR KR1020120108585A patent/KR102023166B1/ko active IP Right Grant
- 2012-09-28 WO PCT/KR2012/007953 patent/WO2013048206A2/ko active Application Filing
- 2012-09-28 EP EP12837146.5A patent/EP2762519B1/en active Active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016047710A1 (ja) * | 2014-09-24 | 2016-03-31 | 株式会社ブリヂストン | タイヤ |
US20180086140A1 (en) * | 2015-04-10 | 2018-03-29 | Bridgestone Corporation | Polyamide-based thermoplastic elastomer and tire |
Also Published As
Publication number | Publication date |
---|---|
US20140242370A1 (en) | 2014-08-28 |
KR102023166B1 (ko) | 2019-09-20 |
CN103958580A (zh) | 2014-07-30 |
CN103958580B (zh) | 2017-03-08 |
JP5893147B2 (ja) | 2016-03-23 |
KR20130035938A (ko) | 2013-04-09 |
WO2013048206A3 (ko) | 2013-07-04 |
EP2762519A4 (en) | 2015-07-08 |
EP2762519A2 (en) | 2014-08-06 |
JP2014534103A (ja) | 2014-12-18 |
US9492981B2 (en) | 2016-11-15 |
EP2762519B1 (en) | 2016-12-28 |
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