WO2014193146A1 - Film de polymère - Google Patents

Film de polymère Download PDF

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Publication number
WO2014193146A1
WO2014193146A1 PCT/KR2014/004729 KR2014004729W WO2014193146A1 WO 2014193146 A1 WO2014193146 A1 WO 2014193146A1 KR 2014004729 W KR2014004729 W KR 2014004729W WO 2014193146 A1 WO2014193146 A1 WO 2014193146A1
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WO
WIPO (PCT)
Prior art keywords
polyamide
copolymer
base film
weight
polymer
Prior art date
Application number
PCT/KR2014/004729
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English (en)
Korean (ko)
Inventor
정영한
권소연
정일
남궁현
Original Assignee
코오롱인더스트리 주식회사
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.)
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Publication date
Priority claimed from KR1020140063172A external-priority patent/KR102062816B1/ko
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to US14/894,386 priority Critical patent/US10173469B2/en
Publication of WO2014193146A1 publication Critical patent/WO2014193146A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2413/00—Belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • 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
    • 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
    • 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
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • 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
    • 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
    • C09J2477/00—Presence of polyamide
    • C09J2477/006—Presence of polyamide in the substrate

Definitions

  • the present invention relates to a polymer film. More specifically, it exhibits uniform physical properties in the entire film area and realizes excellent airtightness even with a thin thickness. When used as an inner liner film, it can lighten tires and improve automobile fuel economy, and has excellent moldability and high durability and fatigue resistance. It relates to a polymer film that can implement the mechanical properties of.
  • a tire is a composite of fiber / steel radish, and generally has a structure as shown in FIG. 1.
  • Tread (1) It is a part in contact with the road surface, which provides the necessary frictional force for braking and driving, has good abrasion resistance, can withstand external shocks and has low heat generation.
  • Body Ply (or Carcass) (6) A layer of cord inside the tire, which must support loads, withstand impacts, and be resistant to fatigue.
  • Belt (5) Located between the body plies, consisting of steel wires in most cases, to reduce external stratification and to maintain a wide tread grounding surface 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) On the belt of radial tires for some passenger cars It is a special cord paper located to minimize the movement of the belt when driving.
  • APEX (8) It is a triangular rubber filler used to minimize the dispersion of beads, to mitigate external shocks, to protect the beads, and to prevent the inflow of air during molding.
  • tire innerliners which consist mainly of rubber components such as butyl rubber or halo butyl rubber, which had relatively low air permeability.
  • the rubber content or the thickness of the inner liner had to be increased to obtain sufficient airtightness.
  • the content of the rubber component and the tire thickness increase, there is a problem that the total tire weight increases and fuel economy of the vehicle decreases.
  • the rubber components have a relatively low heat resistance, so that air pockets are formed between the inner rubber and the inner liner of the carcass layer or the inner liner of the carcass layer during the vulcanization process of the tire, or the driving of the car, which repeatedly undergoes deformation at high temperature.
  • a vulcanizing agent or a vulcanizing process had to be applied, and it was difficult to secure sufficient adhesive force.
  • any previously known method has a limit in maintaining excellent air permeability and tire formability while sufficiently reducing the thickness and weight of the innerliner.
  • the innerliner obtained by the previously known method may be deteriorated in its physical properties or cracks in the film during the manufacturing process of a tire which is repeatedly formed at a high temperature, or during the driving process of a vehicle in which high heat is generated. This phenomenon appeared.
  • the present invention exhibits uniform physical properties over the entire area of the film and realizes excellent airtightness even with a thin thickness.
  • an inner liner film When used as an inner liner film, it is possible to lighten tires and improve automobile fuel economy, and has excellent moldability and high durability and fatigue resistance. It is to provide a polymer film that can implement mechanical properties.
  • polyamide-based resin having a relative viscosity (96% solution of sulfuric acid) of 3.0 to 3.5; And a copolymer comprising a polyamide-based segment and a polyether-based segment; and a base film layer comprising: formed on at least one surface of the base film layer, and a resorcinol-formalin -An adhesive comprising a latex (RFL) adhesive, wherein the content of the polyether segment of the copolymer is at least 2% by weight and less than 15% by weight relative to the total weight of the base film layer, and a shear of 1000s ⁇ 1 .
  • a polymer film having a ratio of the melt viscosity of the copolymer to the melt viscosity of the polyamide-based resin may be 0.60 to 1.2.
  • a base film layer and such a base layer formed by using the copolymer comprising a specific content of the polyamide-based resin and a polyether-based segment may realize excellent airtightness even at a thin thickness to reduce tire weight and improve fuel efficiency of an automobile, and may have excellent moldability and mechanical properties while having high heat resistance. It has been found that it can be firmly bonded to the tire without applying an additional vulcanization process or significantly increasing the thickness of the adhesive layer.
  • the two components may be uniformly mixed or combined without phase separation, and the prepared base film layer may have uniform physical properties over the entire area.
  • the base film layer manufactured as described above has not only high modulus characteristics but also high elasticity or elastic recovery rate, and thus not only exhibits excellent moldability during tire manufacturing, but also large deformation under high temperature conditions. Even in the tire manufacturing process or the vehicle driving process that is repeatedly applied to this made it is possible to prevent the phenomenon that the film itself crystallized or damage such as cracks inside the film.
  • the copolymer including the polyamide-based resin, the polyamide-based segment and the polyether-based segment may be a high temperature and a specific shear rate applied during the production of the base film pack. Even in the range, the ratio of the melt viscosity may not be significantly different. Accordingly, the two different components are unevenly mixed in the process of melting and mixing the copolymer including the polyamide resin, the polyamide segment, and the polyether segment. It is possible to minimize the phenomenon, and to minimize the parts that can cause a defect during the manufacturing of tires, it is possible to minimize the occurrence of cracks in the base film because the phase separation in the durability test after tire molding.
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the plyamide-based resin may be 0.60 to 1.2, at a shear rate of 1000s- 1 and a temperature of 260 ° C.
  • the shear rate of 1000s _1 and a temperature of 260 ° C may be a condition that can be applied in the process of mixing the polyamide-based copolymer with the polyamide-based segment and the polyether-based segment. .
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the polyamide-based resin may be 1.0 to 2.0.
  • the melt viscosity of the copolymer becomes very high compared to the melt viscosity of the polyamide-based resin in a state where the flow rate generated by the shear force is low, specifically, a shear rate of 100 s— 1 and
  • the copolymer is more than twice as high as the polyamide-based resin at a temperature of 260 ° C, the mixing of the polyamide-based resin and the copolymer is not easy, and the physical properties of the produced base film may also be greatly reduced.
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the polyamide-based resin may be a shear rate and 260 ° C temperature in 0.60 to 1.1 of the 2000s- 1, and a shear rate of 500s- 1 260 It may be 0.7 to 1.5 at a temperature of ° C.
  • the polyamide is selected according to the polyamide-based resin and the polyamide-based segment and the polyether-based segment, together with the polyamide-based resin having the specific relative viscosity, and the content of the polyether-segment in the copolymer.
  • the resin and the copolymer may have similar melting characteristics to each other in the melting and extruding steps, and may be mixed and melted without the phenomenon of agglomeration of each component or phase separation of other components.
  • the melt viscosity refers to the melt viscosity of the product produced in the discharge hole of a specific silver during the film processing. Since the melt viscosity of the production result is dependent on temperature, shear rate, and shear force, the stress and shear rate of the polymer in the discharged temperature range may be measured and applied to the following general formula (1).
  • ri is the melt viscosity
  • ⁇ is the shear stress
  • ⁇ is the shear rate
  • the polymer film of the embodiment may be used as a tire inner liner.
  • the polyamide-based resin may have a relative viscosity (96% solution of sulfuric acid) of 3.0 to 3.5, preferably 3.2 to 3.4. If the viscosity of the polyamide-based resin is less than 3.0, the elongation at break is reduced due to the decrease in toughness. It may not be secured and may cause damage during tire manufacturing or driving a car.
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the polyamide-based resin described above at a temperature of 260 ° C. and a total shear rate becomes very large, so that in the manufacturing process of the base film layer, the tire manufacturing process or the automobile driving process,
  • the polyamide-based resin and the copolymer may be phase separated from each other, and it may be difficult to secure physical properties such as airtightness or moldability that the base film filler should have as the tire innerliner.
  • the modulus or viscosity of the base film layer to be produced may be unnecessarily high, and it may be difficult for the tire innerliner to have proper moldability 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 of specimen) is dissolved in 96% sulfuric acid solution at different concentrations to prepare two or more measurement solutions (for example, a polyamide-based resin specimen). Dissolve in 96% sulfuric acid to make concentrations of 0.25 g / dL, 0.10 g / dL, and 0.05 g / dL, and make three measurement solutions), and 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 polymer film has excellent airtightness and high air pressure holding performance, and has physical properties such as high heat resistance, excellent moldability and high fatigue resistance.
  • the excellent physical properties of such polymer films seem to be due to the inclusion of a base film layer prepared using a polyamide-based resin having a specific relative viscosity and a copolymer comprising a specific content of a polyether-based segment and a polyamide-based segment. .
  • the base film layer may have a relatively low modulus with excellent airtightness by using a copolymer including a polyether-based segment having a specific content to impart elastomeric properties to the polyamide-based resin.
  • the polyamide-based resin included in the base film layer has excellent airtightness due to its inherent molecular chain properties, for example, the same. In terms of thickness, airtightness is about 10 to 20 times higher than that of butyl rubber, which is generally used in tires, and a moderus that is not so high compared to other resins.
  • polyether-based segment of the copolymer may be present in a bonded or dispersed state between polyamide-based segments or polyamide-based resins to lower the modulus of the base film layer, and the base film
  • the increase in the rigidity of the layer can be suppressed and the crystallization at high temperature can be prevented.
  • the base film layer may have a thickness of 30 to 300, preferably 40 to 250 m, more preferably 40 to 200 kPa. Accordingly, the polymer film of one embodiment of the present invention may have a thinner thickness than that previously known, and may have a low air permeability, for example, an oxygen permeability of 200 cc / (m 2 .24hr. Atm) or less.
  • Polyamide-based resins that can be used include polyamide-based resins such as nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66 copolymer, nylon 6/66 / 610 copolymer, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer and nylon 66 / PPS copolymer; Or N—alkoxyalkylates thereof, for example mesoxymethylate of 6 'nylon, mesoxymethylate of 6-610-nylon or mesoxymethylate of 612-nylon, nylon 6, nylon 66, nylon Using 46, nylon 11, nylon 12, nylon 610 or nylon 612 is preferred.
  • polyamide-based resins such as nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612 is preferred.
  • the polyamide-based resin may be included in the base film by mixing with the copolymer described above to melt, and also reacts the monomer or oligomer which is a precursor of the polyamide-based resin . It may also be included in the base film by reacting with the copolymer described above with an initiator or a catalyst.
  • 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.
  • the modulus of the base film layer can be lowered, and the base film layer It is possible to suppress the increase in the rigidity and to prevent the crystallization from the silver.
  • the copolymer is included in the base film layer, the polymer film may realize high elasticity or elastic recovery while securing mechanical properties such as excellent durability, heat resistance, and fatigue resistance. Accordingly, the polymer film may exhibit excellent moldability, and the tire to which the polymer film is applied may not be physically damaged or its physical properties or performance may be degraded even during a vehicle driving process in which repeated deformation and high heat are continuously generated.
  • the content of the polyether segment of the copolymer may be 2% by weight or more and less than 15% by weight, preferably 3 to 14% by weight, more preferably 5 to 13% by weight based on the total weight of the base film layer. have.
  • the content of the polyether-based segment is too low in the entire base film layer, the modulus of the base film layer or the polymer film is high, the moldability of the tire may be lowered, or the physical properties may be largely reduced due to repeated deformation.
  • the gas barrier (Gas Barrier) of the polymer film 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 manufacture a uniform film.
  • the content of the polyether-based segment of the copolymer in the total weight of the base film layer is outside the above-described range, that is, the content of the polyether-based segment in the copolymer is too small or too large, the polyamide-based
  • the melt viscosity of the resin and the melt viscosity of the copolymer may vary greatly. Accordingly, the two different components are not uniformly mixed or combined in the process of mixing and melting the polyamide-based resin and the copolymer. Phase separation or cracking may occur in the base film.
  • the copolymer including the polyamide amide segment and the polyether segment may be a polyamide monomer or a oligomer and a polyether monomer. Or oligomers It may be a co-polymer obtained by the reaction, 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 comprising a polymerization reactant between polymers, and may be a crosslinked copolymer including a crosslinked semi-product 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, polymerization reaction or crosslinking reaction Through it may be in a combined state in part or the whole area.
  • 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.
  • the polyamide-based segment of the copolymer may include a repeating unit of Formula 1 or Formula 2.
  • 3 ⁇ 4 is a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or a straight chain having 7 to 20 carbon atoms. Or a branched arylalkylene group.
  • 3 ⁇ 4 is a linear or branched alkylene group having 1 to 20 carbon atoms
  • .3 ⁇ 4 is a linear or branched alkylene group having 1 to 20 carbon atoms
  • a branched arylalkylene group is
  • polyether segment of the copolymer may include a repeating unit represented by the following Formula 3.
  • 3 ⁇ 4 is a linear or branched alkylene group having 1 to 10 carbon atoms, n is an integer of 1 to 100, R 6 and R 7 Are the same as or different from each other, and are each 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 monomer or oligomer Can be.
  • the absolute weight average molecular weight of the copolymer including the polyamide-based segment and the polyether-based segment may be 50,000 to 300,000, preferably 110,000 to 250, 000. If the absolute weight average molecular weight of the copolymer is less than 50, 000, the base film layer to be produced may not be able to secure the mechanical properties that are sufficient for use in the film for the inner liner, it is difficult to have good physical properties that can be a gas barrier , Of the copolymer If the absolute weight average molecular weight is more than 300,000, the modulus or crystallinity of the base film filling may be excessively increased when heated to a high temperature, and thus it may be difficult to secure elasticity or elastic recovery rate to have as an innerliner film.
  • the absolute weight average molecular weight of the polymer material can be measured.
  • MALS Wyatt's Multi Angle Light Scattering
  • M is the molar mass, which is the absolute weight average molecular weight (Mw) for the polydisperse sample, and R (e) The excess Rayleigh rain
  • the copolymer is a polyamide segment and a polyether segment in a range of 15 to 50% by weight based on the total weight of the film, the polyether segment 1: It may be included in the weight ratio of 9 to 9: 1.
  • the modulus of the base film layer or the polymer film may be increased, thereby deteriorating moldability of the tire or greatly decreasing physical properties due to repeated deformation.
  • the content of the polyether segment is too large, the polymer The airtightness of the film may be lowered, the reaction resistance to the adhesive may be lowered, and it may be difficult for the innerliner to easily adhere to the carcass layer, and the elasticity of the base film layer may be increased, making it difficult to manufacture a uniform film. You may not.
  • the polymer 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 firm and uniform to the carcass layer even with a thin and lightweight adhesive layer without the need for laminating additional adhesive layers or rubber layers. Can be fixed.
  • 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, the base film layer has a low modulus and a high strain, and thus is suitably applied to a tire forming process in which high expansion occurs. can do.
  • crystallization hardly occurs in the unstretched film, damage such as cracks and the like can be prevented even by repeated deformation.
  • 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 maximally suppressing the orientation of the base film layer for example, a method of adjusting viscosity by adjusting melt extrusion temperature, changing a die die specification, or adjusting a winding speed Through 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. have.
  • the non-stretched sheet-like film is applied to the base film layer, it is not necessary to construct a film manufacturing facility for each tire size, and the impact and wrinkles applied to the film during the transport and storage process can be minimized.
  • the base film into a sheet it can be carried out more easily a process of adding the "adhesive layer that will be described later, due to the forming drum and the standard difference can be prevented from damage or distortion, etc. generated during the manufacturing process .
  • the base film layer may further include an olefin polymer compound.
  • the base film layer is the polyamide-based resin and the copolymer containing the polyamide-based segment and the poly-ether (poly-ether) segment together with the olefin resin compound by using together, the polymer film of the embodiment is a high temperature
  • the olefin-based polymer compound serves to increase the softness of the base film layer and improve the ability to absorb the impact applied from the outside, and also greatly reduce the modulus of the base film layer.
  • the internal structure of the compound or polymer contained in the base film layer is changed to prevent the phenomenon of crystallization.
  • the base film layer may include 0.1% by weight to 40% by weight, or 1% by weight to 30% by weight, or 2% by weight to 25% by weight of the olepin-based polymer compound. If the content of the olefinic polymer compound is too small, the degree of action and effect according to the olefinic polymer compound may be insignificant. In addition, when the content of the olefin-based polymer compound is too large, it is possible to reduce the physical properties and effects expressed from the polyamide-based resin and the copolymer, when manufacturing the tire by applying the polymer film of the embodiment as an inner liner film Moldability may be lowered.
  • the base film layer includes the olefinic polymer compound
  • the content of the polyether segment of the copolymer is not increased so much.
  • a polymer film or innerliner that can realize high elasticity, durability and fatigue resistance for a long time, even if the base film contains 2% by weight or more and less than 15% by weight of the polyether-based segment of the copolymer.
  • a film for use can be provided.
  • the olephine-based polymer compound may include an olefin-based polymer, an olephine-based copolymer, dicarboxylic acid or an olephine-based polymer or copolymer grafted with an acid anhydride thereof, or a mixture of two or more thereof.
  • the olefinic polymer may include polyethylene, polypropylene, or a combination thereof.
  • the olefin copolymer may include an ethylene-propylene copolymer.
  • the olefin polymer compound may include an olefin polymer or copolymer grafted with dicarboxylic acid or an acid anhydride thereof, and the dicarboxylic acid may be maleic acid, phthalic acid, itaconic acid, or citraconic acid.
  • the dianhydride of the acid may be the dicarboxylic dianhydride of the examples described above.
  • the content of the carboxylic acid grafted dicarboxylic acid or acid anhydride grafted dicarboxylic acid or acid anhydride thereof may be 0.05% by weight or more, preferably 0.1% by weight to 50% %, Or 0.1% to 10% by weight.
  • the grafting ratio of such dicarboxylic acid or its acid anhydride can be measured from the result obtained by acid-base titrating the said olefin type high molecular compound. For example, about lg of the lelpene-based high molecular compound was added to 150 m £ of xylene saturated with water, refluxed for about 2 hours, and then a small amount of 1% by weight of thymol blue-dimethylformamide solution was added, and 0.05 N sodium hydroxide-ethyl alcohol.
  • the olefinic polymer compound may have a density of 0.820 g / cuf to 0.960 g / cm 3 , or 0.840 g / ciii 3 to 0.920 g / cii.
  • the base film 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 (N, N'-Hexamethyl ene— b is- ( Commercially available products such as 3,5-di-tert-butyl-4 hydroxy one hydrocinnamamide such as rganox 1098), tetrakis [methylene (3,5-di- (t-butyl) -4—hydroxyhydrocinnamate) Tetrakis [methylene (3 ( 5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, such as commercially available products such as Irganox 1010) or 4,4'-dicumyldiphenylamine (4,4 ' ⁇ ) di-cumyl-di-phenyl-amine,
  • thermal stabilizer examples include benzoic acid, triacetonediamine, or ⁇ , ⁇ ' ⁇ bis (2). , 2,6,6-tetramethyl-4 ′ piperidyl) -1,3-benzenedicarboxamide (N, N'-Bis (2,2,6,6-tetraniethyl-4- p iper i dy 1) -1, 3-benzenedi carboxami de), etc.
  • the additive is It is not, it is known as being used in the polymer film can be used without limitation.
  • the adhesive layer containing 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 heat or repeated deformation occurring, the polymer film can have sufficient fatigue resistance.
  • RTL 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 a reso .
  • Synol ⁇ formalin—latex (RFL) based adhesives including high reactivity and adhesion to the substrate film, as well as thickness
  • the substrate film and the tire carcass layer may be firmly bonded by pressing under high temperature heating conditions without too much stretching.
  • the adhesive layer may exhibit high fatigue resistance against physical / chemical deformations that may be applied during tire manufacturing or driving, the adhesive force may be applied even during high-temperature manufacturing or during driving of a vehicle for a long time. The degradation of other physical properties can be minimized.
  • 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 flexibility such as rubber. Chemical bonding between the metirol end of the lesosinol-formalin polymer and the base film is possible. Accordingly, when the resorcinol formalin-latex (RFL) -based adhesive is applied to the base film, sufficient adhesion performance can be realized.
  • 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 more than 2% by weight relative to the total amount of the adhesive layer in terms of chemical resistance for excellent adhesion, and may be included in less than 32% by weight to ensure proper fatigue resistance properties. have.
  • the latex may be a mixture of one or two subphases 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. have.
  • the latex is the flexibility of the material It may be included in an amount of 68% by weight or more based on the total amount of the adhesive layer for 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 may further include one or more additives such as a surface tension modifier heat-resistant agent, antifoaming agent, and filler together with a condensate and latex of resorcinol and formaldehyde.
  • a surface tension modifier heat-resistant agent such as a surface tension modifier heat-resistant agent, antifoaming agent, and 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 1.0 weight% or less, or 0.0001 to 0.5 weight% may be included.
  • 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 It may be one or more selected from the group consisting of.
  • the adhesive layer may have a thickness of 0.1 to 20 urn, preferably 0.1 to 10, more preferably 0.2 to 7, even more preferably 0.3 to 5, and may be formed on one or both surfaces of the polymer film. Can be.
  • 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 the stress may be concentrated on a part of the adhesive to reduce fatigue characteristics.
  • interfacial separation may occur in the adhesive layer, which may reduce fatigue properties.
  • the inner liner film in order to bond the inner liner film to the carcass layer of the tire, it is common to form an adhesive layer on one surface of the base film, but in the case of applying a multilayer inner liner film or the inner liner film wrapping the bead part, etc. And it is preferable to form an adhesive layer on both sides of the base film when rubber and adhesion on both sides according to the structural design.
  • the polymer film can maintain a proper air pressure even after long-term use, for example, for the tire to which the polymer film is applied 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) can be 95% or more, that is, the air pressure reduction can be 5% or less. Accordingly, by using the polymer film it is possible to prevent the fallover accident and fuel economy lowering caused by low air pressure.
  • the polyamide-based resin may be included in the base film by melting or after mixing or compounding with the above-described co-polymer, and further includes 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 substrate by mixing and co-mixing with one copolymer.
  • copolymer comprising 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 the mixture 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 plyamide-based resin The polymer of the species may cause a polymerization reaction or a crosslinking reaction,
  • the base film layer may be formed through the process.
  • a copolymer including the polyamide-based resin, the polyamide-based segment, and the polyether-based segment is uniformly mixed, or through a polymerization reaction or a crosslinking reaction. It may be coupled in some or all areas.
  • the copolymer and the polyamide-based resin in order to extrude a film having a more uniform thickness, can be adjusted to have a uniform size. As such, as the size of the copolymer and the polyamide-based resin are adjusted, the copolymer and the polyamide-based resin may be mixed, mixed in the raw material supply unit maintained at a constant temperature, or melted and extruded. The 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 formed. .
  • copolymer and the polyamide-based resin have a similar size, it is possible to minimize the phenomenon of agglomeration of raw material chips or the appearance of non-uniform shapes or regions in a subsequent mixing, melting or extrusion step, and thus the entire film.
  • a base film layer having a uniform thickness can be formed over the region.
  • the manufacturing method of the polymer film may further comprise the step of 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 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 appearing in the tire manufacturing process or automobile driving process May crystallize and cracks may occur due to repeated deformation.
  • any device or method known to be used for mixing the polymer resin can be used without particular limitation.
  • the polyamide-based resin and the co-polymer may be injected into a feeder after being mixed, or may be mixed by being injected sequentially or simultaneously with the feeder.
  • the copolymer may include a polyamide-based segment and a polyether-based segment in a weight ratio of 1: 9 to 9: 1.
  • 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 K rc.
  • the raw material supply unit is maintained at a temperature of 50 to ioo ° c
  • the mixture of the polyamide-based resin and the copolymer has a physical property such as an appropriate viscosity can be easily moved to another part of the extrusion die or extruder
  • it is possible to prevent a poor raw material feeding (feeding) phenomenon caused by agglomeration of the mixture it is possible to form a more uniform base film in the subsequent melting and extrusion process.
  • the raw material supply part is a part that serves to supply the raw material injected from the extruder to the extrusion die or other parts, the configuration is not limited significantly, and is a conventional raw material feeder (feeder) included in an extruder for manufacturing a polymer resin, etc. Can be.
  • the temperature for melting the mixture is 230 to 300 ° C., preferably 240 to
  • the melting temperature should be higher than the melting point of the polyamide-based compound, but if it is too high, carbonization or decomposition may occur and the physical properties of the film may be hindered. Unstretched may occur due to bonding between the polyether-based resins or orientation in the fiber array direction. It may be disadvantageous for producing a film.
  • the extrusion die may be used without limitation as long as it is known that it can be used for extrusion of the polymer resin, but in order to make the thickness of the base film more uniform or to prevent the orientation of the base film from using a T-type die It is preferable.
  • Adjustment of the thickness of the film to be produced may be achieved by adjusting the extrusion conditions, for example, the extruder discharge amount or the gap of the extrusion die, or by changing the winding speed of the cooling process or recovery process of the extrudate. .
  • the mixture of the polyamide-based resin and the copolymer including the polyamide-based segment and the polyether-based segment may further include the olefin-based polymer compound described above.
  • the content of the olefin polymer compound is as described above.
  • the die gap of the extrusion die may be adjusted to 0.3 to 1.5 kPa.
  • the die gap Die Gap
  • the die shear pressure of the melt extrusion process is too high and the shear stress is so high that it is difficult to form a uniform shape of the extruded film and the productivity is lowered
  • 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.
  • the part of the extrusion die corresponding to the position where the non-uniform thickness appears by continuously measuring the thickness of the base film manufactured by the above-described steps and feeding back the measurement result, for example, T
  • the lip gap adjustment bolt of the die By adjusting the lip gap adjustment bolt of the die, the film having a more uniform thickness can be obtained by enjoying the variation of the base film produced by adjusting the lip gap adjustment bolt of the die.
  • an automated system such as an Auto Die system, to control the thickness measurement and feedback-extrusion die of such films. .
  • the manufacturing method of the polymer film may further comprise the step of solidifying the base film layer formed by melting and extruding in the cooling unit maintained at a temperature of 5 to 40 ° C, preferably 10 to 30 ° C. have.
  • 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.
  • the base film layer obtained by melting and extruding may be grounded or adhered to a cooling part maintained at the appropriate temperature to substantially prevent stretching, and the base film filling may be provided as an unstretched film.
  • 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 the substrate film layer formed by using the air knife, the air nozzle, the electrostatic charge device (Pinning device), or a combination thereof closely adheres to the cooling. It is possible to prevent phenomena such as blowing off or partially unevenly cooling, thereby forming a film having a more uniform thickness, and in the film, a portion of the region that is relatively thicker or thinner than the surrounding portion is substantially It may not be formed as.
  • the melt extruded under the specific die gap conditions may be attached or grounded at a horizontal angle of 10 to 150 kPa, preferably 20 to 120 kPa at a horizontal distance from the die outlet, to prevent stretching and orientation.
  • the horizontal distance from the die outlet to the angle of incidence can be the distance between the die outlet and the point at which the discharged melt grounds cooling. If the linear distance between the outlet of the die and the point of attachment of the cooling of the molten film is too small, the uniform flow of the molten extruded resin may be disturbed and the film may be unevenly angled. If the distance is too large, suppression of the stretching effect of the film may be achieved. 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 manufacturing method of the polymer film may include forming an adhesive layer including a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the base film layer.
  • the forming of the adhesive layer may be performed by coating a resorcinol-formalin-latex (RFL) -based adhesive on one or both surfaces of the formed base film and then drying the adhesive layer. 1, preferably may have a thickness of 0.1 to 10.
  • the resorcinol-formin-latex (RFL) -based adhesive may comprise 2 to 32% by weight of condensate of resorcinol and formaldehyde and 68 to 98% by weight of latex, preferably 80 to 90% by weight. That is, the forming of the adhesive layer, on at least one surface of the base film layer, the condensate of resorcinol and formaldehyde 2 to
  • 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. However, it is preferable to use a knife coating method, a gravure coating method, or a bar coating method in terms of uniform application and coating of the adhesive.
  • the drying and the adhesive reaction may be simultaneously performed, but the drying may be performed after the drying step in consideration of the side reaction of the adhesive.
  • the adhesive layer forming and 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 KXKL50 ° C.
  • additives such as a heat resistant antioxidant or a heat stabilizer may be further added. Details of the additives are as described above. ⁇ Effects of the Invention ⁇
  • even thin thickness is excellent.
  • airtightness it is possible to reduce the weight of the tire and improve automobile fuel economy, and to provide a polymer film and a method of manufacturing a polymer film having high heat resistance and excellent moldability and mechanical properties.
  • FIG. 1 schematically shows the structure of a tire.
  • Polyamide-based resin (nylon 6) having a relative viscosity (96% solution of sulfuric acid) 3.3, copolymer resin having an absolute weight average molecular weight of 145,000 (45% by weight of polyethylene glycol at the end of the amine group and 55% by weight of nylon 6 resin) (0.7 wt 3 ⁇ 4>) ethylene-propylene copolymer (density: 0.870 g / cu) grafted with maleic anhydride was mixed at a weight ratio of 4: 4: 2. At this time, by adjusting the temperature of the raw material supply unit to 50 to 100 ° C. while the mixture is fused in the extruder screw to prevent the feeding failure, it was supplied to the 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 air cooled at 25 ° C.
  • Molten resin was solidified into a film of uniform thickness.
  • an unstretched base film having a thickness of 100 ⁇ m was obtained without passing through the stretching and heat treatment sections at a speed of 15 m / min.
  • Resorcinol and formaldehyde are mixed in a molar ratio of 1: 2, and then condensed A condensate of resorcinol and formaldehyde was obtained. 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
  • this resorcinol-formalin-latex (RFL) -based adhesive was coated on the base film to a thickness of 1 urn using a gravure coater, dried and reacted at 150 ° C. for 1 minute to form an adhesive layer.
  • RTL resorcinol-formalin-latex
  • Polyamide-based resin (nylon 6) having a relative viscosity (96% solution of sulfuric acid) 3.3, co-polymer resin having an absolute weight average molecular weight of 145, 000 (45% by weight of polyethylene glycol at the end of the amine group and 55% by weight of nylon 6 resin) Synthesized) and maleic anhydride grafted (0.7 wt%) ethylene-propylene copolymer (density: 0.870 g / ciif) in a weight ratio of 3.5: 6.5: 2. Except for the point, a base film was prepared in the same manner as in Example 1.
  • a base film was prepared in the same manner as in Example 1, except that a nylon 6 resin of 2.54 was used.
  • a base film was prepared in the same manner as in Example 2, except that a nylon 6 resin of 2.54 was used.
  • polyamide-based resin nylon 6
  • nylon 6 resin having an absolute weight average molecular weight of 150, 000 (80% by weight of polyethylene glycol at the end of the amine group and 20% by weight of nylon 6 resin)
  • a lobster film was prepared in the same manner as in Example 1, except that 50% by weight of the compound) was used.
  • nylon 6 50% by weight of polyamide-based resin (nylon 6) having a relative viscosity (96% solution of sulfuric acid) 2.54 and a copolymer resin having an absolute weight average molecular weight of 150,000 (80% by weight of the polyethylene glycol at the end of the amine group and 20% by weight of the nylon 6 resin)
  • a base film was prepared in the same manner as in Example 1, except that 50% by weight of the compound was synthesized using%).
  • melt viscosity of each of the nylon 6 and the copolymer resin used in each of the above Examples and Comparative Examples was measured using a G0TTFERT Rheo-tester 2000 device, and the orifice melt viscosity at a temperature of 260 ° C and shear rate shown in Table 1 below. It measured at diameter 1mm * length 20mm.
  • 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 in the atmosphere of 25 degree
  • Tires were manufactured by applying tire inner liner films of Examples and Comparative Examples to 205R / 65R16. Then, the manufactured tires were subjected to the following method under the pressure of 101.3kPa at 21 ° C using ASTM F1112—06 method. 90 days of air pressure retention (IPR Internal Pressure Retention) according to the formula 2 was measured and evaluated.
  • Tires were manufactured according to the 205R / 65R16 standard. During the tire manufacturing process, the manufacturing ease and appearance were evaluated after the production of green tires, and the final appearance of the tires after vulcanization was examined.
  • the polyamide-based resin having a relative viscosity of 96% (96% sulfuric acid solution) and the specific copolymer resin were 22.5% by weight and 39% by weight in the base film, respectively.
  • the tire innerliner films of Examples 1 and 2 obtained using%) have a ratio of the melt viscosity (at 260 ° C.) of the copolymer to the melt viscosity of the polyamide-based resin, at a shear rate of 100 s " It was confirmed that it was in the range of 1.0 to 2.0, in the range of 0.7 to 1.5 at the shear rate of 500s _1 , in the range of 0.65 to 1.2 at the shear rate of 1000s- 1 , and in the range of 0.65 to 1.1 at the shear rate of 2000s _1 .
  • the polyamide-based resin and the copolymer may be uniformly kneaded and melted with each other to form a base film layer having uniform physical properties in the entire region of the film.
  • the polymer film of the embodiment using the base film layer not only has excellent moldability, but also has high airtightness and air pressure holding performance.
  • Comparative Example 3 if the shear rate of the poly-amide and less than the silver is the resin shear rate and 260 ° C the ratio of the melt viscosity of the copolymer to the melt viscosity of 100s- 1 1.0, 500s- 1 and It was found to be less than 0.7 at a silver temperature of 260 ° C. and less than 0.65 at a shear rate of 1000 s " 1 and a temperature of 2601 :. That is, the polyamide-based resin and the copolymer used in Comparative Example 3 were stirred to form a base film layer. In this case, the melt density is greatly different, so that not only mixing is easy, but also phase separation between the two components may occur. In addition to this drastic fall, it was confirmed in Experimental Examples 2 and 3 that the airtightness and air pressure holding performance were not secured enough for the actual tire application. The.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Tires In General (AREA)

Abstract

La présente invention concerne un film de polymère comprenant : une couche de film de base qui comprend une résine à base de polyamide ayant une viscosité relative prédéterminée et un copolymère comprenant des teneurs prédéterminées en segments à base de polyester et en segments à base de polyamide ; et une couche adhésive formée sur au moins une surface de la couche de film de base, le rapport de la viscosité à l'état fondu du copolymère à celle de la résine à base de polyamide à un taux de cisaillement de 1000 s-1 et une température de 260 °C étant compris entre 0,65 et 1,2.
PCT/KR2014/004729 2013-05-27 2014-05-27 Film de polymère WO2014193146A1 (fr)

Priority Applications (1)

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US14/894,386 US10173469B2 (en) 2013-05-27 2014-05-27 Polymer films

Applications Claiming Priority (4)

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KR10-2013-0059969 2013-05-27
KR20130059969 2013-05-27
KR10-2014-0063172 2014-05-26
KR1020140063172A KR102062816B1 (ko) 2013-05-27 2014-05-26 고분자 필름

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WO2014193146A1 true WO2014193146A1 (fr) 2014-12-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109641484A (zh) * 2016-06-30 2019-04-16 可隆工业株式会社 充气轮胎

Citations (5)

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KR20010038924A (ko) * 1999-10-28 2001-05-15 유현식 내충격성이 우수한 폴리카보네이트계 수지 조성물
KR20020052509A (ko) * 2000-12-26 2002-07-04 구광시 폴리아미드 수지 조성물
KR20050088660A (ko) * 2004-03-02 2005-09-07 현대자동차주식회사 내충격성 열가소성 수지조성물
KR20110120885A (ko) * 2009-02-06 2011-11-04 바스프 에스이 개선된 내후성을 갖는 스티렌 공중합체 및 폴리아미드 기재 열가소성 성형 조성물
KR20130035975A (ko) * 2011-09-30 2013-04-09 코오롱인더스트리 주식회사 타이어 이너라이너용 필름 및 이의 제조 방법

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
KR20010038924A (ko) * 1999-10-28 2001-05-15 유현식 내충격성이 우수한 폴리카보네이트계 수지 조성물
KR20020052509A (ko) * 2000-12-26 2002-07-04 구광시 폴리아미드 수지 조성물
KR20050088660A (ko) * 2004-03-02 2005-09-07 현대자동차주식회사 내충격성 열가소성 수지조성물
KR20110120885A (ko) * 2009-02-06 2011-11-04 바스프 에스이 개선된 내후성을 갖는 스티렌 공중합체 및 폴리아미드 기재 열가소성 성형 조성물
KR20130035975A (ko) * 2011-09-30 2013-04-09 코오롱인더스트리 주식회사 타이어 이너라이너용 필름 및 이의 제조 방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109641484A (zh) * 2016-06-30 2019-04-16 可隆工业株式会社 充气轮胎

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