WO2013002602A2

WO2013002602A2 - Film for an inner liner of a tire and method for manufacturing same

Info

Publication number: WO2013002602A2
Application number: PCT/KR2012/005187
Authority: WO
Inventors: 정영한; 권소연; 남궁현; 김성훈
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2011-06-30
Filing date: 2012-06-29
Publication date: 2013-01-03
Also published as: WO2013002602A3

Abstract

The present invention relates to a film for an inner liner of a tire, comprising: a base film layer having an absolute weight-average molecular weight of 50,000 to 1,000,000; and an adhesive layer. The present invention also relates to a method for manufacturing the film for the inner liner of the tire. The above-described inner liner of the tire can provide superior air-tightness despite having a thin thickness, thereby enabling a lightweight tire, improving the fuel efficiency of a vehicle, enabling easy molding in a tire manufacturing process, and exhibiting superior moldability and mechanical properties such as high durability, fatigue resistance, and superior adhesive force to a tire carcass layer.

Description

[Specifications

[Name of invention]

Tire innerliner film and manufacturing method thereof

Technical Field

The present invention relates to a film for a tire inner liner and a method of manufacturing the same, and more particularly, it is possible to realize excellent airtightness even at a thin thickness, thereby making it possible to reduce tire weight and improve automobile fuel efficiency, The present invention relates to a film for a tire innerliner and a method for producing the same, which can be easily formed and exhibit excellent adhesion to the tire carcass layer together with mechanical properties such as high durability and fatigue resistance together with excellent moldability.

Background Art

The tires support the load of the vehicle, alleviate the shock from the road surface, and transmit the driving or braking force of the vehicle to the ground. In general, the tire is a composite of fiber / steel / rubber, and generally has a structure as shown in FIG.

Tread (1): This part is to be in contact with the road surface to provide the necessary frictional force for braking and driving, to have good abrasion resistance, to withstand external shocks, and to generate little heat.

Body Ply (or Carcass) (6): The layer of cord inside the tire, which must support lower loads, withstand stratification, and be more fatigue-resistant to driving exercise.

Belt (5): Located between the body plies, consisting of steel wires in most cases to mitigate external shocks and maintain a wide tread grounding surface for excellent driving stability.

Side Wall (3): refers to the rubber layer between the bottom of the shoulder (2) and the beads (9) and serves to protect the inner ply (6).

Inner Liner (7): Located on the inside of the tire instead of the tube, it 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 placed on the belt of some passenger radial tires that minimizes belt movement when driving.

APEX (8): A triangular rubber layering funnel used to minimize the dispersion of beads, to mitigate external impacts, to protect the beads, and to prevent the ingress of air during molding.

Recently, tube-less tires in which high pressure air of about 30 to 40 psi is injected into the air without using a tube are generally used. To this end, a highly airtight inner liner is disposed in the carcass inner layer.

Previously, tire innerliners were used, with rubber components such as butyl rubber or halo butyl rubber, which had relatively low air permeability, and had to increase the rubber content or the thickness of the inner liner in order to obtain sufficient airtightness. . 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.

Accordingly, various methods have been proposed to reduce fuel consumption by reducing the thickness and weight of the inner liner, and to reduce the shape and physical properties of the inner liner generated during the vulcanization or driving process of the tire.

However, any previously known method has had a limit in maintaining excellent air permeability and formability of the tire while drastically reducing the thickness and weight of the innerliner, and additional tie-gum rubber to firmly bond to the carcass layer inside the tire. There was a problem that the weight of the tire is increased and the fuel economy of the vehicle is lowered using the lamp. In addition, 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. Accordingly, a thinner inner liner can be easily combined with the inside of the tire to reduce the weight of the tire, and develop a thinner inner liner having excellent fatigue resistance that can withstand repeated deformation and physical properties such as excellent air tightness and formability. This is required.

[Content of invention]

[Problem to solve]

The present invention can realize excellent airtightness even at a thin thickness, which enables not only to reduce the weight of the tire and improve the fuel efficiency of the automobile, but also to facilitate the molding in the tire manufacturing process, and to provide excellent moldability and high durability and fatigue resistance. It is to provide a film for tire innerliner that can exhibit excellent adhesion to the tire carcass layer together with mechanical properties such as.

Moreover, this invention is providing the manufacturing method of the said film for tire innerliners.

[Measures of problem]

The present invention, polyamide-based resin; And a copolymer comprising a polyamide-based segment and a polyether-based segment; and a base film layer comprising at least one surface of the base film layer, the resorcinol-formalin - latex (RFL) adhesive comprising an adhesive layer containing, a polyether content of the segment relative to the total weight of the base film layer 15 to 50 parts by weight ⁰ / of the copolymer, the base film layer is from 50,000 to It provides a film for tire innerliner having an absolute weight average molecular weight of 1,000,000.

In addition, the present invention, polyamide-based resin; And a copolymer comprising a polyamide-based segment and a polyether-based segment; melting and extruding the mixture at 230 to 300 ^° C. to 50,000 to

Forming a base film layer having an absolute weight average molecular weight of 1,000,000, and forming an adhesive layer comprising a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the base film layer, Of the copolymer The content of the poly ether segment provides 15 to 50 parts by weight ⁰ /. The method of manufacturing a film for a tire inner liner with respect to the total weight of the base film layer.

Hereinafter, a method for manufacturing the tire inner liner film and the tire inner liner film according to a specific embodiment of the present invention will be described in detail. According to one embodiment of the invention, a polyamide-based resin; And a copolymer comprising a polyamide-based segment and a polyether-based segment; and formed on at least one surface of the substrate film layer, the resorcinol-formalin- latex (RFL) adhesive comprising the adhesive layer comprising a poly content of the polyether-based segment of the copolymer is from 15 to 50 increased ^_0/0 relative to the total weight of the base film layer, the base film layer is from 50,000 to 1,000,000 A film for tire innerliner having an absolute weight average molecular weight of can be provided.

As a result of the researches of the present inventors, a base film layer having an absolute weight average molecular weight of 50,000 to 1000,000 formed by using a copolymer containing the poly-ether segment in a specific content together with the polyamide-based resin. By using it, it is possible to realize excellent airtightness even at a thin thickness to lighten the tire and improve the fuel efficiency of the car.Inner tires have high heat resistance and excellent moldability and high mechanical properties such as high durability and fatigue resistance. It has been confirmed that a film for use may be provided, and in particular, when an adhesive layer including a resolinol-formalin-latex (RFL) -based adhesive is formed on the base film layer, no additional vulcanization process is applied or the thickness of the adhesive layer is increased. It has been found that it can be firmly coupled to the tire without significantly increasing it.

In particular, the base film layer may have an absolute weight average molecular weight of 50,000 to 1,000,000, preferably 80,000 to 900,000, and thus, the tire innerliner film may have low modulus characteristics with sufficient strength, The crystallinity is not so great even at high temperature above 100 ^° C Therefore, the modulus characteristics, elasticity or elastic recovery rate, etc. are not significantly lowered, so that excellent formation can be ensured. In addition, the tire to which the tire innerliner film including the base film layer is applied may have mechanical properties such as high durability and fatigue resistance.

In the solution containing the polymer material, light scattering occurs due to the chain of the polymer material because the size of the polymer chain is smaller or similar to the wavelength of the light, and the polymer chains are polarized by the electric field of the incident light. Because. In the case of light scattering, scattering by large particles is much stronger than scattering by small particles when there is the same amount of scattering material. Therefore, the degree of light scattering is influenced by the size of the particles, so using this, it is possible to determine the characteristics of the polymer material such as molecular weight.

In addition, using the light scattering phenomenon, the absolute weight average molecular weight of the polymer material may be measured. In particular, using Wyatt's Multi Angle Light Scattering (MALS) system, the absolute weight average molecular weight of a polymeric material can be obtained by applying the parameters shown in the measurement results to the Rayleigh-Gans-Debye equation. .

Formula 1: Rayleigh-Gans-Debye equation

The polymer material interacts with light to have a polarized charge and spreads the light radially. Equation 1 shows the amount of charge transfer and the radiation dose depending on the polarizability of the polymer material. This changing principle is used. That is, the molar mass and size of the polymer can be determined from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer material and a solvent. In Formula 1, M is the molar mass, and in the case of a polydisperse sample, the absolute weight average molecular weight (Mw), f is the excess Rayleigh ratio, Κ ^' = 4π ² η ₀ ² ^{(απ / αίί;) 2 λ} 0 - 4 Ν Α - a ^1, C is the polymer in the solution Concentration (g /) and A ₂ is the second virial coefficient. And, in K ^* , n ₀ is the refractive index of the solvent, N _A is the Avogadro's number, λ ₀ is the wavelength of the light source under vacuum, Ρ (Θ) = R _e / R ₀ , R ₀ Is incident light.

And, dn / dc is a specific refractive index increment, it means the change in refractive index (dn) according to the change in concentration (dc) of the lean solution obtained by dissolving a specific polymer material in an organic solvent. The refractive index may be obtained by injecting the lean solution into a flow cell of a differential refractometer, and the specific refractive index increment (dn / dc) may be obtained by measuring a change rate of refraction at a predetermined concentration change interval. .

According to the general formula 1, the intensity of the scattered light is proportional to the molecular weight and concentration, and thus the absolute weight average molecular weight of the polymer material may be obtained by measuring the intensity and the concentration of the scattered light through the MALS system.

The absolute weight average molecular weight is related to processability, moldability, or melt viscosity of a molded article such as a film manufactured using a high molecular material. Accordingly, the base film layer has an absolute value of 50,000 to 1,000,000, preferably 80,000 to 900,000. By having a weight average molecular weight, the strength and elongation at break of the tire innerliner film can be improved, the modulus properties can be lowered, and the moldability, elasticity and elastic recovery force can be improved. In addition, as the base film layer has an absolute weight average molecular weight in the above-described range, the film for tire innerliner may exhibit high-tightness even at a thin thickness. When the absolute weight average molecular weight of the base film layer is less than 50,000, the film for tire innerliner does not have sufficient strength, elongation at break, toughness, etc., so that the minimum mechanical—physical properties and molding for application in the tire manufacturing process. The tires produced may not have sufficient airtightness, durability, or fatigue resistance, so that defects such as cracks or cracks may occur in the inner liner during the vehicle driving process.

In addition, when the absolute weight average molecular weight of the base film layer is more than 1,000,000, ^' the modulus of the base film layer is greatly increased and high during film processing As the discharge pressure increases due to the viscosity, it is difficult to control the uniform thickness and the process efficiency and productivity are lowered, and it is difficult to secure sufficient formability during tire processing, and the modulus difference between the rubber and the inner liner of the tire is increased. As the inner liner is concentrated in the driving process or heat is generated, physical properties such as tire durability may be reduced.

On the other hand, in the film for the tire innerliner, the specific refractive index increment of the base film measured at 40 ^° C using a 1: 4 mixed solvent of m-cresol and chloroform containing tetramethyl ammonium chloride at a concentration of 0.02 M (dn / dc) may be 0.04 to 0.14 mL / g, preferably 0.05 to 0.13 mL / g.

The specific refractive index increment (dn / dc) refers to the change rate (dn) of the refractive index according to the change in concentration (dc) of the lean solution obtained by dissolving a specific polymer material in an organic solvent. The refractive index may be obtained by injecting the lean solution into a flow cell of a differential refractometer, and the specific refractive index increment (dn / dc) may be obtained by measuring a change rate of the refractive index at a predetermined concentration change interval.

The specific refractive index increment (dn / dc) is a value determined by the difference in refractive index between the polymer material and the organic solvent and the size of the polymer material, and is an absolute intrinsic value of the polymer material. In the solution containing the polymer material, light scattering occurs due to the chain of the polymer material because the size of the polymer chain is similar to that of the wavelength of the light, and the polymer chains are polarized by the electric field of the incident light. Because. In the case of light scattering, scattering by large particles is much stronger than scattering by small particles when the scattering material is not proportional to the amount of scattering material. Therefore, the degree of light scattering is influenced by the size of the particles, which can be used to determine the inherent characteristics of the polymer material.

More specifically, the polymer material has a polarized charge by interacting with light to spread light radially, and the amount of charge transfer and the amount of light radiation vary depending on the polarizability of the polymer material. Using the principle, it is possible to measure characteristics such as the molar mass and size of the polymer from the amount of scattered light and the angular variation measured by irradiating laser light to a solution containing any polymer material and solvent. You can decide. In particular, under a certain temperature and lean solution, since the polymer material has a constant refractive index change rate at a constant concentration change interval, the specific refractive index increment (dn / dc) becomes an absolute intrinsic value of the specific polymer material.

The '1: 4 mixed solvent of m-cresol and chloroform containing tetramethyl ammonium chloride at a concentration of 0.02M', respectively, is a solution of m-cresol and chloroform having a concentration of 99% or more (substantially 100%). Mean solution prepared by adding tetramethyl ammonium chloride to a solvent mixed with 4: 4 to a concentration of 0.02M.

Specific refractive index increments (dn / dc) of the base film measured using the specific conditions and solutions described above may be 0.04 to 0.14 mL / g, preferably 0.05 to 0.13 mL / g. As such, as the base film exhibits the specific refractive index increments (dn / dc) described above, the tire innerliner film may have excellent physical properties or properties such as excellent airtightness, low modulus, and high elastic recovery. . In addition, it is possible to realize excellent airtightness even with a relatively thin thickness compared to the previously known inner liner film, for example, a film using butyl rubber, thereby improving fuel efficiency and rolling resistance through weight reduction, thereby improving high-speed driving and automobile fuel economy. have. When the specific refractive index increment (dn / dc) of the base film layer is less than 0.04 mL / g, the oxygen permeability is poor and the modulus characteristics according to the elongation may be high, and the elastic recovery rate is low when it is more than 0.14 mL / g. The film may be damaged when the tire is deformed.

On the other hand, the base film layer may have a thickness of 30 to 300 kPa, preferably 40 to 250 urn, more preferably 40 to 200. Thus, while some embodiments of the invention cases Thai inner liner film is of a thickness thinner compared to a previously known, low air permeability, for ^{example, 200 cc / (in 2 -} . 24hr atm) have an oxygen transmission rate of less Can be. ^r Specifically, the above-described tire inner liner film is characterized in that the base film layer is prepared by using a copolymer including a polyether-based segment and a polyamide-based segment having a specific content together with the polyamide-based resin. .

More specifically, the base film layer may have a relatively low modulus with excellent airtightness by using a copolymer including a specific amount of a polyether-based segment that imparts elastomeric properties to the polyamide-based resin. The polyamide-based resin included in the substrate ^' film layer exhibits excellent airtightness due to its inherent molecular chain properties, for example, about 10 to 20 times higher than that of butyl rubber generally used in tires at the same thickness. The modulus is not so high compared to the resin. The pulley ether-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. The increase in the rigidity of can be suppressed and the crystallization at high temperature can be prevented.

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. In addition, since the plyamide-based resin exhibits modulus that is not relatively higher than that of other resins, the inner plyamide resin exhibits relatively low modulus characteristics even when applied with a copolymer including the specific content of the polyether-based segment. A film can be obtained and the moldability of a tire can be improved by this. In addition, 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. ^·

In addition, the ¾ liamide-based resin is used together with a copolymer comprising a polyamide-based segment and a polyether-based segment, and is relatively relative to an adhesive (for example, a resorcinol-formalin-latex (RFL) -based adhesive). High Can exhibit reaction. Accordingly, the inner liner film may be easily adhered to the carcass part, and the inner liner film may be divided into layers by preventing the breakage of the interface due to heat or repeated deformation occurring during the tire manufacturing process or the driving process. It makes it possible to have fatigue resistance. .

The polyamide-based resin is 3.0 to 3.5, preferably 3.2 to

It may have a relative viscosity of 3.4 (96% sulfuric acid solution). When the viscosity of the polyamide-based resin is less than 3.0, sufficient elongation may not be secured due to toughness deterioration, and thus, damage may occur during tire manufacturing or driving of a vehicle, and the airtightness of the base film layer as a film for tire innerliner or It may be difficult to secure physical properties such as moldability. In addition, when the viscosity of the polyamide-based resin exceeds 3.5, the modulus or viscosity of the base film layer to be produced may be unnecessarily high, and the tire innerliner may be difficult 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 0.25g / dL, 0.10g / dL and 0.05g / dL, and make three measuring solutions), and the relative viscosity of the measuring solution using a viscosity tube at 25 ^° C. For example, the ratio of the average passage time of the measurement solution to the passage time of the 96% sulfuric acid solution and the viscosity tube can be obtained.

Examples of the polyamide-based resin that can be used for the base film layer include 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; Or their N-alkoxyalkylates, for example methoxymethylate of 6-nylon, methoxymethylate of 6-610-nylon or methoxymethylate of 612-nylon, nylon 6, Preference is given to using nylon 66, nylon 46, nylon 11, nylon 12, nylon 610 or nylon 612.

In addition, the ^polyamide, the resin may be contained in the base film layer, as well as how to use the resin itself, using a monomer or a precursor of the polyamide resin of the polyamide resin by preparing a base film.

Meanwhile, as described above, 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 an increase in the rigidity of the base film layer, and to prevent crystallization from silver. As the co-polymer is included in the malleable film layer, the film for the tire inner liner may realize high elasticity or elastic recovery while securing mechanical properties such as excellent durability, heat resistance and fatigue resistance. Accordingly, 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 physical properties or performance may be degraded even during a vehicle driving process in which repeated deformation and high heat are continuously generated. have.

On the other hand, the content of the polyether segment of the copolymer is 15 to 50 weight ⁰ /., Preferably 20 to 45 weight ⁰ /. With respect to the total weight of the base film layer, more preferably 22 to 40 weight ⁰ / _{When 0} , the tire inner liner film may exhibit more excellent physical properties and performance. If the content of the polyether-based segment is less than 15 weight ⁰ /. Of the entire base film layer, the modulus of the base film layer or the tire inner liner film is increased to reduce the moldability of the tire or to decrease the physical properties due to repeated deformation. May appear large. The polyether-based segment, if the content of the film exceeds the total of 50 parts by weight ^_0/0, the tire. Air tightness requiring inner liner (Gas

Barrier is poor, and tire performance may be reduced. Reaction to the adhesive may be reduced, making it difficult for the innerliner to easily adhere to the carcass layer In addition, since the elasticity of the base film layer is increased, it may not be easy 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 can suppress or prevent that the said base film layer breaks easily.

In addition, such a polyether-based segment can lower the modulus of the film for the tire innerliner, 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. To be molded. And, the polyether-based segment can suppress the increase in the rigidity of the film at low temperatures, can prevent the crystallization at high temperatures, can prevent damage or tearing of the inner liner film due to repeated deformation, etc. By improving the resilience to the deformation of the liner to suppress the occurrence of wrinkles of the film due to permanent deformation it can improve the durability of the tire or innerliner.

The polyamide-based segment may serve to allow the copolymer to have a certain level or more of mechanical properties but not to significantly increase modulus properties. In addition, as the polyamide-based segment is applied, the base film layer may have a low thickness while having a thin thickness, and may secure a sufficient heat resistance and chemical stability. The polyamide-based segment of the copolymer may include a repeating unit of Formula 1 or Formula 2.

[Formula 1]

In Chemical Formula 1, is a straight or branched chain alkylene group having 1 to 20 carbon atoms or a straight or branched chain arylalkylene group having 7 to 20 carbon atoms. [Formula 2]

In Formula 2, 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.

In addition, the polyether segment of the copolymer may include a repeating unit represented by the following Formula 3.

[Formula 3]

In Chemical 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 ₆ and R ₇ may be the same or different from each other, and a direct bond, -0- Or -NH-, -COO- or -CONH-.

The absolute weight average molecular weight of the co-polymer including the polyamide-based segment and the polyether-based segment may be 50,000 to 1,000,000, preferably 80,000 to 900,000. When 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 mechanical properties that are sufficient for use in the film for the inner liner, and the film for the tire inner liner has sufficient gas barrier. It can be difficult to secure. In addition, when the absolute weight average molecular weight of the copolymer is more than 1,000,000, the modulus or crystallinity of the base film layer is excessively increased when heated to a high temperature, it may be difficult to secure the elasticity or elastic recovery rate to have as an inner liner film. On the other hand, the copolymer, wherein the polyether-based segment in the 15 to 50 parts by weight ^_0/0 in a range for the total weight of the film, a polyamide (p y-amide) based segment and a polyether (p y-ether) series Segments may be included in a weight ratio of 6: 4 to 3: 7, preferably 5: 5 to 4: 6. As described above, if the content of the polyether-based segment is too small, the modulus of the base film layer or the tire innerliner film may be increased, thereby reducing the moldability of the tire or a large decrease in physical properties due to repeated deformation. . In addition, if the content of the polyether segment is too large, the airtightness of the film for the tire inner liner may be lowered, the reactivity to the adhesive is lowered, it is difficult for the inner liner to easily adhere to the carcass layer, The elasticity of the film layer may be increased and thus it may not be easy to produce a uniform film.

In addition, the polyamide-based resin and the above-described copolymer in the base film layer may be included in an increase 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, when 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.

On the other hand, the base film layer may be an unstretched film. 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 can be suitably applied to a tire forming process in which high expansion occurs. In addition, since crystallization hardly occurs in the unstretched film, damage such as cracks can be prevented even by repeated deformation. In addition, 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. As shown in the method for manufacturing the tire innerliner film described below, a method of suppressing the orientation of the base film layer as much as possible, for example, viscosity adjustment through optimizing the melt extrusion temperature, changing the die die specification, or adjusting the winding speed, etc. Through this method, the base film can be prepared into an unoriented or unoriented film.

When the unstretched film is applied to the base film layer, the inner liner film can be easily manufactured in a cylindrical or sheet form in a tire manufacturing process. have. In particular, when 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. Do. In addition, when the base film is manufactured in a sheet form, a process of adding an adhesive layer to be described later may be more easily performed, and damage or distortion caused by manufacturing process increase due to a difference in specifications with a forming drum may be prevented. .

Meanwhile, the base film may further include additives such as a heat resistant antioxidant, a heat stabilizer, an adhesion promoter, or a mixture thereof. Specific examples of the heat-resistant antioxidants include Ν, Ν · -nuclear methylene-bis- (3,5-di- (t-butyl) -4-hydroxy-hydrocinnamamide (N, N'-Hexamethylene-bis- (Commercially available products such as 3,5-di-tert-butyl-4-hydroxyhydrocinnamamide such as rganox 1098), tetrakis [methylene (3,5-di- (t-butyl) -4-hydroxyhydrocinnanam Mate)

(tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, such as commercially available products such as I rganox 1010) or 4,4'-dicumyldiphenylamine (4,4'-di- cumyl-di-phenyl-amine such as Naugard 445). Specific examples of the heat stabilizer include benzoic acid, triacetonediamine, or Ν, Ν'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3 -Benzenedicarboxamide (Ν, Ν'-Bis (2,2,6,6-tetramethyl-4-piperidyl) -1,3-benzeneclicarboxamide). However, the additives are not limited to the above examples, and those known to be usable for the film for tire innerliner may be used without particular limitation. On the other hand, 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 fracture 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 sufficient fatigue resistance.

The main characteristic of the above-described adhesive layer appears to be the shade due to the inclusion of a specific resorcinol-forminine-latex (RFL) -based adhesive having a specific composition. Prior A rubber type tie gum or the like was used as the adhesive for the tire inner liner, and thus an additional vulcanization process was required. In contrast, the adhesive layer includes a resorcinol-formalin-latex (RFL) -based adhesive of a specific composition, and has high reactivity and adhesion to the base film, and is compressed under high temperature heating conditions without increasing the thickness thereof. The base film and the tire carcass layer can be firmly bonded. Accordingly, it is possible to reduce the tire weight and improve the fuel economy of the car, and to prevent the carcass layer and the inner liner layer or the base film and the adhesive layer from being separated even in the tire manufacturing process or repeated deformation in the vehicle driving process. Can be. In addition, since 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. The degradation of other physical properties can be minimized.

In addition, the resorcinol-formalin-latex (RFL) -based adhesive is capable of crosslinking between latex and rubber, thereby exhibiting adhesive performance, and since the latex is a physically latex polymer, it has a low curing degree and thus may have flexible properties such as rubber. And. 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, sufficient adhesion performance can be realized. The resorcinol-formalin-Latex (RFL) adhesive is re SOCIETE condensates of 2 to 32 parts by weight of the play and formaldehyde ⁰ /, preferably 10 to 20 parts by weight ⁰ /, latexes, 68 to 98 parts by weight ^_0/0 And preferably 80 to 90 weight ⁰ /.

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. In addition, the resorcinol and the condensation product of formaldehyde may be included to 2 parts by weight ⁰ /. Above with respect to the entirety of the adhesive layer total amount of the chemical banung side for good adhesion, as a 32% by weight or less in order to secure the properties in an appropriate endothelial May be included. 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 weight ⁰ /. Or more based on the total amount of adhesives for the flexibility of the material and effective crosslinking reaction with rubber, and includes 98 weight% or less for chemical reaction with the base film and rigidity of the adhesive layer. do.

In addition, the adhesive layer may further include one or more additives such as a surface tension modifier heat-resistant agent, an antifoaming agent, and a filler, together with a condensate and latex of resorcinol and formaldehyde. At this time, the surface tension control agent of the additive is applied for uniform application of the adhesive layer, but may cause a problem of adhesion loss when excessively added, 2 weight ⁰ /. Or less or Q.0001 to 2 weight ⁰ / Preferably less than 1.0 weight ⁰ / ^° or may be included in 0.0001 0.5 weight ⁰ / ^° . At this time, the surface tension modifiers sulfonate anionic surfactant, sulfate ester salt anionic surfactant, carboxylate anionic surfactant, phosphate ester salt anionic surfactant, fluorine surfactant, silicone surfactant and polysiloxane surfactant It may be one or more selected from the group consisting of.

The adhesive layer is 0.1 to 20 urn, preferably 0.1 to 10 / ini, more preferably 0.2 to 7! More preferably, it may have a thickness of 0.3 to 5, and may be formed on one or both surfaces of the film for tire innerliner. When 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 lowering fatigue characteristics. In addition, when the adhesive layer is too thick, interfacial separation may occur in the adhesive layer, thereby reducing fatigue characteristics. And on the carcass layer of tires _. In order to bond the inner liner film, it is common to form an adhesive layer on the surface of the base film, but according to the tire forming method and structural design such as applying a multilayer inner liner film or the inner liner film wrapping the bead part, When adhesion with rubber is desired, it is preferable to form an adhesive layer on both sides of the base film.

In addition, the tire inner liner film can maintain a proper air pressure even after long-term use, for example, 21 ^° C and according to the method of the American Society for Testing and Materials, ASTM F 1112-06. When the air pressure retention ratio (IPR, Internal Pressure Retention) was measured for 90 days with respect to the tire to which the tire inner liner film was applied at 101.3 kPa, the air pressure retention ratio as shown in the following general formula 2 was 95% or more, that is, the air pressure reduction ratio This may be less than 5%. Accordingly, by using the tire inner liner film, it is possible to prevent a rollover accident and fuel consumption reduction caused by low air pressure.

[Formula 2]

, ：：,. _{/ 0} ( _.. "( ^::; Ta ¾0 'air ^-90 sec ¾ 휙 b b 기

On the other hand, the tire innerliner film is used for the tire carcass layer.

It can have an adhesive force of 15 to 40 kgf. This adhesion can be measured by the ASTM D 4394 method. Further, the standard deviation of the adhesive force to the tire carcass layer of the tire inner liner film may be 5 or less, preferably 3 or less. Accordingly, the tire inner liner film may be very uniformly and firmly bonded to the tire carcass layer.

The tire carcass layer (or body ply) refers to a structure in which a tire cord is included in a predetermined rubber component as a skeleton of a tire supporting a load of a vehicle body. In general, the rubber component of the tire carcass layer is a tire inner liner. Combined with. The rubber component used in the carcass layer may be included without any limitation as long as it is a conventionally known material, and may include, for example, 30% by weight or more of synthetic rubber or natural rubber, and various other additives. have. Tire cords included in the carcass layer include various natural fibers or rayon, nylon, polyester and kevlar. Etc., a steel cord braided with a thin wire can also be used.

On the other hand, the base film may have a maximum load (Load At Specific Elongation, 100%) generated per unit thickness at 100% elongation at room temperature may be 10 to 35 gf / um. When the base film is stretched to 100% at room temperature, if a large load is generated, it is difficult to manufacture a proper tire shape at a low molding pressure of the tire forming machine, which results in crushing or tearing of the shape of the green tire after molding. Process problems may occur. In addition, when the base film has the load characteristics according to the above-described elongation, even if the tire is manufactured by changing the molding machine or the molding method, the black tensile that may occur in the automobile driving process due to the characteristics of the rigid film And external forces such as compressive deformation may be collected in a specific area of the film, and thus problems in product quality such as cracking or tearing of the film may occur.

In addition, the plyamide-based resin is generally known to be easily crystallized by heat, but the tire innerliner film includes the polyether-based segment in a specific content so that crystals grow in accordance with heat or external deformation in the film. It can be suppressed. Accordingly, the base film is not easily crystallized by heat generated inside the tire, and the modulus or stiffness does not change significantly even by long-term driving, and it is possible to minimize cracks that may occur during driving. On the other hand, according to another embodiment of the invention, polyamide-based resin; And a copolymer comprising a polyamide-based segment and a polyether-based segment; melting and extruding a mixture of 230 to 3 (xrc)

Forming a base film layer having an absolute weight average molecular weight of 50,000 to 1,000,000, and forming an adhesive layer comprising a resorcinol formalin-latex (RFL) -based adhesive on at least one surface of the base film layer. And the content of the polar ether segment of the copolymer With respect to the total weight of the film layer can be provided a method of 15 to 50 parts by weight ^_0/0 tire inner liner film.

Tire innerliner manufactured using a base film layer having an absolute weight average molecular weight of 50,000 to 1,000,000 formed using a polyamide-based resin together with a copolymer containing the polyether-based segment in a specific content. The film can realize excellent airtightness even at a thin thickness to lighten a tire and improve fuel efficiency of a vehicle, and can realize mechanical properties such as high durability and fatigue resistance while having high heat resistance and excellent moldability.

In particular, because of the properties of the base film layer, it is possible to exhibit high reaction resistance to an adhesive (for example, a resorcinol-formalin-latex (RFL) -based adhesive, etc.) Forming an adhesive layer comprising a knol-formalin-latex (RFL) -based adhesive can be firmly bonded to the tire without applying an additional vulcanization process or significantly increasing the thickness of the adhesive layer. ^'

The base film layer may have an absolute increase average molecular weight of 50,000 to 1,000,000, preferably 80,000 to 900,000. The details regarding the absolute weight average molecular weight are as described above.

In order to specify the absolute weight average molecular weight of the manufactured base film layer as 50,000 to 1,000,000, the relative viscosity or the absolute increase average molecular weight of the polyamide-based resin is adjusted, or the composition or the absolute weight average molecular weight of the copolymer is adjusted, or The mixing ratio of the polyamide-based resin and the copolymer may be adjusted, or the melting temperature and melting time of the mixture may be appropriately adjusted.

As described above, the specific refractive index increment of the base film measured at 40 ^° C. using a 1: 4 mixed solvent of m-cresol and chloroform containing tetramethyl ammonium chloride at a concentration of 0.02M (dn / dc) May be from 0.04 to 0.14 mL / g. More specific details regarding such specific refractive index increments (dn / dc) and the base film are as described above. As described above, 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. And, a polyether content based segment is 15 to 50 parts by weight ⁰ /, based on the total weight of the base film layer of the copolymer., Preferably 20 to 45 parts by weight ^_0/0, more preferably from 22 to 40 parts by weight ⁰ / It can be.

The base film may have a maximum load of 10 to 40 gf / um per unit thickness at 100% elongation. The tire innerliner film may have an adhesive force of 15 to 40 kgf on the tire carcass layer measured by ASTM D 4394 method, and the air permeability measured by the method of ASTM D 3895 is 200 cc / (n-24hr. Atm ) May be less than or equal to Specific contents related to these are as described above.

Details of the copolymer including the polyamide-based resin, the polyamide-based segment, and the polyether-based segment are as described above.

On the other hand, in the step of forming the base film layer, in order to extrude a film having a more uniform thickness, the copolymer and the polyamide-based resin can be adjusted to have a uniform size. As such, as the size of the copolymer and the polyamide-based resin are adjusted, mixing the copolymer and the polyamide-based resin, the raw material supply unit maintained at a constant temperature ^{: in} the step of staying or melting and extruding, the copolymer and the poly Amide-based resins can be more uniformly mixed, each of the copolymer and the polyamide-based resins can be prevented from agglomeration or the size of each other to increase the size, thereby forming a base film layer having a more uniform thickness Can be.

When the copolymer and the polyamide-based resin have a similar size, it is possible to minimize the phenomenon that the raw material chips agglomerate with each other or uneven shape or region appear in the subsequent mixing, melting or extrusion step, depending on the film A base film layer having a uniform thickness can be formed over the entire area. The size of the copolymer and the polyamide-based resin that can be used in the production method is not particularly limited. On the other hand, the tire innerliner film production method may further comprise the step of mixing the polyamide-based resin and the copolymer in an increase 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, when 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, and the plyamide-based resin may be Crystallization may occur and cracks may occur due to repeated deformation. In this mixing step, any device or method known to be used for mixing the polymer resin can be used without particular limitation.

After the polyamide-based resin and the copolymer are mixed, the polyamide-based resin and the copolymer may be injected into a raw material feeder, or may be mixed by being sequentially or simultaneously injected into the raw material feeder.

As described above, the copolymer may include polyamide-based segments and polyether-based segments in an increase ratio of 6: 4 to 3: 7.

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 specific temperature, for example, 50 to 100 ^° C. As the raw material supply part is maintained at a temperature of 50 to i (xrc, 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. In addition, it is possible to prevent a poor feeding of the raw materials (feeding) caused by the aggregates, etc., and to form a more uniform substrate film in the subsequent melting and extrusion process. As a part that serves to supply the raw material to the extrusion die or other part, the configuration is not particularly limited, and may be a conventional feeder included in an extruder for producing a polymer resin. On the other hand, by melting and extruding the mixture supplied to the extrusion die through the raw material supply at 230 to 300 ^° C, it is possible to form a base film layer. The temperature for melting the mixture may be 230 to 300 ^° C, preferably 240 to 280 ^° C. The molten silver 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 impaired. Unstretched may occur due to bonding between the polyether-based resins or orientation in a fiber array direction. It may be disadvantageous for producing a film.

The extrusion die may be used without any 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.

On the other hand, the step of forming the base film layer, the mixture of the copolymer comprising the polyamide-based resin, polyamide-based segments and polyether-based segments of 30 to 300 And extruding into a film of thickness. Control of the thickness of the film produced is extrusion conditions, for example. By adjusting 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.

In order to more uniformly adjust the thickness of the base film layer in the range of 30 to 300, the die gap of the extrusion die may be adjusted to 0.3 to 1.5 mm. In the step of forming the base film, if the die gap (Die Gap) is too small, 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 lowered If 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. In addition, in the method for producing a film for a tire inner liner, the thickness of the base film produced by the above-described steps is continuously measured, and the measurement result is fed back so that the uneven thickness of the extrusion die corresponds to the position where the uneven thickness appears. The film having a more uniform thickness can be obtained by reducing the deviation of the base film produced by adjusting the part, for example, the lip gap adjusting bolt of T-Die. It is also possible to configure automated process steps by using an automated system, such as an Auto Die system, to control the thickness measurement-feedback-extrusion die of such films.

On the other hand, the tire innerliner film manufacturing method, 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 base film layer formed by melting and extruding may be provided on a film having a more uniform thickness by being solidified at a corner portion maintained at a temperature of 5 to 40 ^° C. The substrate film layer obtained by melting and extruding may be grounded or adhered to the cooling unit maintained at the appropriate temperature so that the stretching may not occur substantially, and the substrate film layer may be provided as an unstretched film.

Specifically, the solidifying step may be performed by using an air knife, an air nozzle, an electrostatic charge device (Pinning device) or a combination thereof to maintain the base film layer formed by melting and extruding 1 " ^at a temperature of 5 to 40 ^° C. The method may include the step of bringing the cooling into uniformly.

In the solidifying step, the base film layer formed by melting and extruding by using an air knife, an air nozzle, a pinning device, or a combination thereof adheres to the angles of the base film layer after extrusion. It is possible to prevent phenomena such as blowing in the air or partially uneven angles, so that a film having a more uniform thickness can be formed, which is a relatively thick or thin area in the film compared to the surrounding portion. This may not be formed substantially.

On the other hand, the melt extruded under the above specific die gap conditions may be attached or grounded at a corner roll installed at 10 to 150 mm, preferably 20 to 120 mm, at a horizontal distance from the die outlet, thereby preventing stretching and orientation. The horizontal distance from the die outlet to the cooling is the die exit and the melt discharged. It can be the distance between points that ground cooling to. ^{If the} linear distance between the exit point of the die and the angle of attachment of the molten film is too small, the film may be unevenly angled by disturbing the uniform flow of the molten extruded resin, and if the distance is too large, suppressing the stretching effect of the film Cannot be achieved.

In the step of forming the base film, except for the specific steps and conditions described above, extrusion processing conditions of the film commonly used in the preparation of the polymer film, for example, screw diameter, screw rotation speed, or line speed, etc. Can be selected and used appropriately.

On the other hand, the method for manufacturing a tire innerliner film may include forming an adhesive layer including a resorcinol-formalin-latex (RFL) adhesive on at least one surface of the base film layer.

The adhesive layer including the resorcinol-formalin-latex (RFL) adhesive may be formed by applying a resorcinol-formalin-latex (RFL) adhesive to one surface of the base film layer. 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.

Preferably, 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, preferably 0.1 to 10 kPa. The resorcinol-formalin-latex (RFL) adhesive is resorcinol and the condensation product of formaldehyde, 2 to 32 parts by weight ⁰ /, latexes, 68 to 98 parts by weight ^_0/0, preferably 80 to 90 parts by weight ^_0/0 It may include.

More specific information regarding the resorcinol-formalin-latex (RFL) adhesive of the specific composition is as described above.

For the application of the adhesive, a coating or coating method or a method that is commonly used may be used without any particular limitation, but a knife coating method, a bar coating method, a gravure coating method, a spray method, or an immersion method may be used. Can be used. Knife coating, gravure coating or bar Use of the coating method is preferred in terms of uniform application and coating of the adhesive.

After the adhesive layer is formed on one surface or both surfaces of the base film, the drying and the adhesive reaction may be simultaneously performed, but after the drying step in consideration of the reactivity of the adhesive may be divided into heat treatment reaction step, In order to apply the thickness or adhesive of the adhesive layer, the adhesive layer forming and drying and reaction steps may be applied several times. In addition, after the adhesive is applied to the base film may be subjected to a heat treatment reaction by the method of solidifying and reacting under heat treatment conditions for about 30 seconds to 3 minutes at 100 ~ 150 ^° C.

In the forming of the copolymer or the mixture, or melting and extruding the copolymer, 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】

According to the present invention, it is possible to implement excellent airtightness even at a thin thickness to not only reduce the weight of the tire and improve the fuel economy of the vehicle, but also to facilitate the molding in the tire manufacturing process and to provide high durability and resistance with excellent formability. A film for tire innerliner that can exhibit excellent adhesion to the tire carcass layer together with mechanical properties such as fatigue property can be provided.

[Brief Description of Drawings]

1 schematically shows the structure of a pneumatic tire.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are only for exemplifying the present invention, and the contents of the present invention are not limited to the following examples. [Example: Gradation of film for tire inner liner; I

Example 1

(1) Production of base film

The relative viscosity (96% sulfuric acid solution) is 3.3 polyamide resin (nylon 6), 50 parts by weight ^_0/0, and the absolute weight average molecular weight of 145,000 in a copolymer resin (polyamide repeating units 55% by weight and polyether-based repeat units of 45 wt. 50 weight ⁰ /。 are mixed, extruded through a T-type die (die gap [1.0 mm) at 260 ^° C, maintaining a uniform melt flow and 25 ^° C). Air Knife was used on the angled roll surface to be adjusted, and the molten resin was solidified into a film of uniform thickness. And an unstretched base film having a thickness of 100 μm was obtained without passing through the stretching and heat treatment sections at a speed of 15 m / min.

(2) application of adhesive

Resorcinol and formaldehyde were mixed in a molar ratio of 1: 2, and then condensation reaction was carried out to obtain a condensate of resorcinol and formaldehyde. A resorcinol having a concentration of 20% by mixing 12 weight ⁰ /. Of the condensate of resorcinol and formaldehyde with 88 weight ⁰ /. Of styrene / butadiene -1,3 / vinylpyridine latex. A formalin-latex (RFL) based adhesive was obtained.

Then, this resorcinol-formalin-latex (RFL) -based adhesive was coated on the base film to a thickness of 1 um using a gravure coater, dried and reacted at 150 ^° C. for 1 minute to form an adhesive layer. Example 2

(1) Production of base film

Relative viscosity (96% solution of sulfuric acid) 3.3 polyamide-based resin (nylon 6) 40 weight ⁰ /。 and absolute weight average molecular weight 110,000 copolymer resin (polyamide-based repeat unit 40 weight ⁰ /。 and polyether repeat unit ⁶⁰ parts by weight ⁰ /. by including) 60 except that the sum of a common weight ^_0/0 and that of example 1, to obtain the same non-drawn all new base film having a thickness of 100um.

(2) application of adhesive An adhesive layer was formed on the prepared base film in the same manner as in Example 1. Example 3

(1) Production of base film

Relative viscosity (96% solution of sulfuric acid) 3.4 polyamide-based resin (nylon 6) 50 weight ⁰ /. And absolute weight average molecular weight 140,000 copolymer resin (polyamide repeating unit and polyether repeating unit 50 weight ⁰ / ₀ weight each) 50 weight ⁰ /. It was mixed, and extruded into a T-type die at 260 ^° C temperature to prepare an unstretched base film of 80 thickness at a rate of 30 m / min without going through the stretching and heat treatment section.

(2) Preparation of Adhesive Layer Composition

Resorcinol and formaldehyde were mixed in a molar ratio of 1: 2, and then condensation reaction was carried out to obtain a condensate of resorcinol and formaldehyde. A mixture of resorcinol / formaldehyde-latex having a concentration of 20% by mixing 12 weight ⁰ /. Of condensate of resorcinol and formaldehyde with 88 weight ⁰ /. Of styrene / 1,3-butadiene / vinylpyridine latex. Got.

(3) Production of tire inner liner film

The resorcinol formalin-latex (RFL) adhesive layer composition was applied to both sides of the substrate film (200 mm × 300 mm) using a gravure coater, respectively. Subsequently, drying and heat treatment at 150 ^° C. hot air oven for 60 seconds to prepare a film for a tire inner liner formed with an adhesive layer of 1.0 thickness on both sides of the base film. Example 4

(1) Production of base film

The relative viscosity (96% sulfuric acid solution) is 3.4 polyamide resin (nylon 6) 40, each weight ^_0/0, and the absolute weight average molecular weight of 140,000 in a copolymer resin (polyamide recurring units and polyether recurring units 50 weight ⁰ / 60 degrees ⁰ /。 The mixture was extruded into a T-type die at a temperature of 260 ^° C. to prepare an unstretched base film having a thickness of 80 at a rate of 30 m / min without undergoing stretching and heat treatment.

(2) Preparation of Adhesive Layer Composition

In the same manner as in Example 3, a mixture of lesosinol / formaldehyde-latex having a concentration of 20% was obtained.

(3) Manufacture of tire innerliner film

Except for using the substrate film prepared above, a film for tire innerliner was prepared in the same manner as in Example 3 in which an adhesive layer having a thickness of 1.0 pm was formed on both surfaces of the substrate film. Example 5

(1) Production of base film

The relative viscosity (96% sulfuric acid solution) is 3.4 polyamide resin (nylon 6), 30 parts by weight ⁰ /., And the absolute weight average molecular weight of 140,000 in a copolymer resin (polyamide, each based repeating unit, and polyether-based repeating units of 50 wt ⁰ / 70 weight ⁰ / ^{° was} mixed, and extruded to a T-type die at 260 ^° C temperature to prepare an unstretched base film of 80 thickness at a rate of 30 m / min without going through the stretching and heat treatment section.

(2) Preparation of Adhesive Layer Composition

(3) Manufacture of tire innerliner film

Except for using the prepared base film, a film for tire innerliner having a 1.0 / m thick adhesive layer formed on both surfaces of the base film was prepared in the same manner as in Example 3. Example 6

(1) Production of base film To a mixture of 70 wt% of ε-caprolactam and 30 wt ⁰ /. Of polyoxyethylene diamine (Mn 2000) for resin polymerization for the base film is mixed with a mole number of adipic acid such as polyoxyethylene diamine. And melted for 30 minutes under a nitrogen atmosphere of 100 ^° C. The melt was heated at 250 I: for 3 hours, and elevated to 8 kg / cirf to maintain pressure. Then, the pressure was reduced to 1 kg / cuf for 1 hour.

After manufacturing the reduced melt in the shape of a chip, the prepared chip is extruded into an annular die at a temperature of 260 ^° C to obtain an unstretched base film having a thickness of 100 / / m at a rate of 30 m / min without going through the stretching and heat treatment section Got it.

(2) Preparation of Adhesive Layer Composition

Resorcinol and formaldehyde were mixed in a molar ratio of 1: 2, and then condensation reaction was carried out to obtain a condensate of resorcinol and formaldehyde.

A mixture of resorcinol / formaldehyde-latex having a concentration of 20% by combining the condensate of resorcinol and formaldehyde 12 weight ⁰ /. And the styrene / butadiene -1,3 / vinylpyridine latex 88 weight. Got.

(3) Manufacture of tire innerliner film

The resorcinol formalin-latex (RFL) adhesive layer composition was applied to both sides of the base film (200 × 300 mm) using a gravure coater, respectively. Then, the film was dried and heat-treated at 150 ^° C. in a hot air oven for 60 seconds to prepare a film for tire innerliner having a 0.5-thick adhesive layer formed on both sides of the base film.

Comparative Example: Production of Tire Inner Film

Comparative Example 1

(1) Production of base film

Relative viscosity (96% solution of sulfuric acid) 3.3 polyamide-based resin (nylon 6) 60 weight ⁰ /。 and absolute weight average molecular weight 120,000 copolymer resin (polyamide repeat unit 80 weight ⁰ /。 and polyether repeat unit 20 weight ⁰ /。 inclusive) 40 A base film was produced in the same manner as in Example 1 except that the weight was ⁰ / ^° .

(2) application of adhesive

An adhesive layer was formed on the prepared base film in the same manner as in Example 1. Comparative Example 2

(1) Production of base film

Relative Viscosity (96% Sulfate Solution) 3.3 Polyamide Resin (Nylon 6) 20 weight ⁰ /。 and Absolute Weight Average Molecular Weight 100,000 Copolymer Resin (Polyamide Repeating Unit 20 Weight ⁰ /。 and Polyether Repeating Unit A base film was prepared in the same manner as in Example 1 except that 80 weights ⁰ / ^° were included.

(2) application of adhesive

An adhesive layer was formed on the prepared base film in the same manner as in Example 1. Comparative Example 3

A 100 unstretched tire innerliner film was obtained in the same manner as in Example 3 except that the base film was manufactured using only nylon 6 resin having a relative viscosity of 3.4 (96% sulfuric acid solution). Comparative Example 4

The manufacturing process of the base film, _ε - caprolactam, and polyoxyethylene diamine point to form a (Μη 2,000) content using in each 97 parts by weight ⁰ / and 3 parts by weight ^_0/0, and an adhesive layer of a thickness of 1.0. Except for, the film for tire innerliner was prepared in the same manner as in Example 6. Comparative Example 5 In the process of producing the base film, the content of _ε -caprolactam and polyoxyethylene diamine (Μη 2,000) was used at 50 weight ⁰ /。 and 50 weight ⁰ /。, respectively, and the adhesive layer was formed to a thickness of 1.2 ^ 皿. Except for, the film for tire innerliner was prepared in the same manner as in Example 6. Comparative Example 6

Relative Viscosity (96% Sulfate Solution) 3.3 Polyamide Resin (Nylon 6) 60 wt./。 and Copolymer Resin with Absolute Weight Average Molecular Weight 120,000 (80 wt% Polyamide Repeat Unit and 20 wt% Polyether Repeat Unit) ⁰ /. In increments) 40 Weight ⁰ /. »A base film was prepared in the same manner as in Example 3 except for the common points. Comparative Example 7

Relative viscosity (96% solution of sulfuric acid) 3.3 polyamide-based resin (nylon 6) 20 weight ⁰ /. And absolute weight average molecular weight 100,000 copolymer resin (polyamide-based repeat unit 20 weight% and polyether repeat unit 80 increase ^A base film was prepared in the same manner as in Example 3 except for mixing 80 weight ⁰ / ^° inclusive. '

Experimental Example: Measurement of Physical Properties of Tire Inner Liner Film

Experimental Example 1 Determination of Absolute Weight Average Molecular Weight and Specific Refractive Index Increment (dn / dc)

Experimental Example 1-1.

Tetramethylammonium chloride was used to determine the absolute molecular weight.

2.192g was weighed and placed in 1L Volumetric Flask to prepare m-cresol / Chlroform (1/4, V / V).

0.050 g of the base film obtained in Examples 1 and 2 and Comparative Example was further dissolved by adding 0.02 M-TMACm-cresol / chloroform 1/4 (V / V) lOiii. The solution in which the base film was completely dissolved was filtered through a 0.45 μm syringe filter, and then mounted in a MALS autosampler. At this time, specific measurement conditions were as follows.

(1) specific measurement conditions

injection volumn: 100ul

injector Temp .: 40 ^° C

flow rate: 1 in ^ / min

eluent: m-cresol / chloroform 1/4 (V / V) (containing 0.02 mol Tetramethyl ammonium chloride)

(2) measurement of dn / dc

The method of measuring specific refractive index increments (dn / dc) is as follows. A solution was prepared by adding 0.02 mol tetramethyl ammonium chloride to 1 L of a mixture of m-cresol and chloroform 1: 4. After adding 2 g of the base films obtained in Examples 1 to 4 and Comparative Example 1 to the mixed solvent 100 and completely dissolving it, the foreign matter was completely removed using a 0.45 um syringe filter. The obtained high concentration samples were distilled to make samples of 0.02g / m £, 0.010g / m ^, 0.005g and 0.002g / m ^ concentrations, respectively, and the refractive index values of the samples were measured using 0.45 syringe filters. Measured.

(3) dn / dc sample analysis method

-injection volumn: 0.9 ml ^'

-injector Temp .: 40 ^° C

-flow rate: 0.3ml / min

-eluent: m-Cresol + Chloroform (1: 4) solvent (contains 0.02 mol Tetramethyl ammonium chloride)

Table 1 Results of Experimental Example 1

Experimental Example 1-2.

Specific refractive index increments (dn / dc) of the base films obtained in Examples 3 to 6 and Comparative Examples 3 to 7 were measured. When the base films obtained in Examples and Comparative Examples were cut into small pieces to make the solvent easier to penetrate, added to an organic solvent, and injected into a flow cell of a differential refractometer in the form of an ash solution, the refractive index was detected. It is a value obtained by differentiating the change rate of the refractive index according to the change rate of the lean solution concentration, and is a value measured in the range of 0.002 to 0.02 g / ml in the concentration change section.

More specifically, specific refractive index increments were measured by the following method.

(1) pretreatment of samples for dn / dc measurement

A solution was prepared by adding 0.02 mol tetramethyl ammonium chloride to 1 L of a solvent in which m-cresol and chloroform were mixed at 1: 4. After adding 2 g of the base film obtained by the said Example and the comparative example to this mixed solvent 100, and fully melt | dissolving, the foreign material was completely removed using the 0.45um syringe filter. The samples of high concentrations were diluted to make samples of 0.02 g /, 0.010 g / m ^, 0.005 g / m, and 0.002 g, respectively, and the refractive index values of the samples were measured using 0.45 syringe filters, respectively.

(2) dn / dc sample analysis method

-injection volumn: 0.9

-injector Temp .: 40 ^° C

-flow rate: 0.3ml / min

Specific refractive index increments (dn / dc) measured above are shown in Table 1-2 below. TABLE 1-2 Result of Specific Index Increment (dn / dc) Measurement

As shown in Table 6-1, the base film obtained in Examples 3 to 6 has a specific refractive index of 0.0710 to 0.1107 mL / g (1 of m-cresol and chloroform containing tetramethyl ammonium chloride at a concentration of 0.02M). It was confirmed that it had a: 4 mixed solvent, 4C C). Experimental Example 2: Oxygen Permeability Experiment

Oxygen permeability of the tire innerliner film obtained in the above Examples and Comparative Examples was measured. The specific measuring method is as follows.

(1) Oxygen Permeability: Oxygen Permeation by the method of ASTM D 3895

Using an analyzer (Model 8000, manufactured by Illinois Instruments), the measurement was carried out at 25 degrees 60 RH% atmosphere. Experimental Example 3 Performance Measurement

Applying the tire inner liner film of the above Examples and Comparative Examples

Tires were manufactured according to the 205R / 65R16 standard. And the tires By using the ASTM F1112-06 method under a pressure of 101.3 kPa at 21 ^° C temperature, 90 days of air pressure retention according to the following formula (2) (IPR Internal Pressure Retention) was measured and evaluated.

Experimental Example 4. Measurement of maximum load per unit thickness of the base film at 100% elongation The maximum load value of 100% elongation of the base film obtained in Examples and Comparative Examples in the direction of machine direction (MD) was measured. The maximum load value per unit thickness was obtained by dividing the measured maximum load value by the thickness of the film.

The specific measuring method is as follows.

(1) Measuring instrument: Universal Testing Machine (Model 4204, Instron)

(2) Measuring condition:

i) Head Speed 300 mm / min,

ii) Grip Distance 100 mm,

iii) Sample Width 10 mm,

iv) measured under 25 ^° C and 60RH% atmosphere

(3) It measured 5 times each and calculated | required the average value of the obtained result. Experimental Example 5: Measurement of Ease of Molding

Tires were manufactured by applying the tire inner liner films of Examples and Comparative Examples to the 205R / 65R 6 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.

At this time, if the tire after the green tire or vulcanization is not crushed, and the standard deviation of the diameter is within 5% was evaluated as 'good'. And, green tires or If the tire is not properly manufactured due to crushing after vulcanization or the inner liner inside the tire is melted or torn or damaged, it is evaluated as a 'poor shape' when the standard deviation of the diameter exceeds 5%. The results of Examples 2 to 5 are shown in Table 2 below.

TABLE 2 Results of Experimental Examples 2 to 5

As confirmed in Table 2, in the embodiment, a base film layer having uniform physical properties may be formed in the entire film region, and the film for tire innerliner of the embodiment using the base film layer may have excellent moldability. In addition, it has high airtightness and pneumatic: holding performance. In addition, the film for the inner liner obtained in the embodiment has an oxygen permeability of 200 cc / (n-24hr · atm) or less not only has excellent airtightness, but also the load appears per unit thickness at 100% elongation at room temperature Maintained at 20 gf / um can have a proper formability in the tire manufacturing process, and can ensure excellent fatigue resistance against repeated deformation while having sufficient mechanical strength in the car driving process.

In addition, a tire manufactured by using the tire inner liner film of the embodiment is 90 days air pressure retention rate (IPR, Internal) of the tire to which the tire inner liner film is applied at 21 ^° C. and 101.3 kPa according to ASTM F1112-06. Pressure Retention) is maintained at 95% or more, thereby preventing overturning accidents and fuel consumption reduction caused by low air pressure.

On the contrary, the film for tire innerliner obtained in the comparative example is greatly inferior in airtightness (Comparative Examples 2 and 5), or the load generated per unit thickness at 100% elongation at room temperature is large, thereby ensuring proper formability in the tire manufacturing process. It was confirmed that the physical properties of the film itself could be greatly reduced by the deformation which is difficult to do or repeated (Comparative Examples 1, 4). Experimental Example 6. Measurement of Peel-Test of Tire Inner Liner Film

The adhesive force to the tire carcass layer of the film for tire innerliner obtained in the above Examples and Comparative Examples was measured by the method of the American Material Testing Association standard ASTM D 4394.

Specifically, after laminating the rubber sheet of 1.6 mm, cord paper, the rubber sheet of 1.6 mm rubber sheet, cord paper, 1.6 mm rubber sheet for the tire inner liner in order, 150 ^° C. ^at a pressure of 60 kg / cm ² 30 minutes. Thereafter, the vulcanized sample was cut and cut to a width of 1 inch.

In some cases, the 1.6 mm rubber sheet, cord paper, and 1.6 mm rubber sheet form a carcass layer, and the rubber sheet is prepared by using a rubber composition having a composition as described in Table 3 below. . Table 3 Composition of rubber sheet

Then, the cut sample was peeled off at 25 ^° C. at a rate of 300 mm / min using a universal testing machine (Instran) to measure the adhesive force (kgf) of the innerliner film to the carcass layer twice, and the average value thereof. Was obtained. At this time, the average value of the load which arises at the time of peeling was calculated by adhesive force.

Table 4 Results of Experimental Example 4

As shown in Table 4, the film for the tire innerliner of the embodiment was found to be more than 20kgf adhesive force to the tire carcass filling measured by the American Society for Testing and Materials Standard ASTM D 4394 method, accordingly, the tire inner of the embodiment The liner film is very uniform with respect to the tire carcass layer It has been found that it can be firmly combined. In addition, if the film for the tire inner liner of the embodiment is applied, even when the expansion pressure is applied in the tire manufacturing process, even stretching can be achieved, it was found that the production state of the green tire or the final tire is good.

In contrast, the tire innerliners of Comparative Examples 4 and 5 did not appear to have sufficient adhesion to the tire carcass layer.

[Explanation of code]

Tread

2. Solder

3. Side Wall

4. CAP PLY

5. Belt

6. Body Ply

7. Inner Uner

8. APEX

9. BEAD

Claims

[Patent Claims]

[Claim 11

Polyamide-based resins; And a copolymer comprising a polyamide-based segment and a polyether-based segment; and a base film layer comprising:

An adhesive layer formed on at least one surface of the base film layer and comprising a resorcinol-formalin-latex (RFL) -based adhesive,

The content of the poly ether segment in the copolymer is 15 to 50 parts by weight ^_0/0 relative to the total weight of the base film layer,

A film for tire innerliner, wherein the base film layer has an absolute weight average molecular weight of 50,000 to 1,000,000.

[Claim 2]

The method of claim 1,

The specific refractive index increment (dn / dc) of the base film measured at 40 ^° C. using a 1: 4 mixed solvent of m-cresol and chloroform containing tetramethyl ammonium chloride at a concentration of 0.02 M was 0.04 to 0.14 mL. / g Phosphorus, film for tire innerliner.

[Claim 3]

The method of claim 1,

The film for tire innerliner whose relative viscosity (96% solution of sulfuric acid) of the said polyamide resin is 3.0-3.5.

[Claim 4]

The method of claim 1,

A film for tire innerliner having an absolute weight average molecular weight of 50,000 to 1,000,000 of the copolymer including the polyamide segment and the polyether segment.

[Claim 5]

The method of claim 1,

Of the copolymer. Polyamide-based segment is represented by the formula

Film for tire innerliner comprising a repeating unit of formula (2):

[Formula 1]

In Chemical Formula 1, is a straight or branched chain alkylene group having 1 to 20 carbon atoms or a straight or branched chain arylalkylene group having 7 to 20 carbon atoms, [Formula 2]

[Claim 6]

The method of claim 1,

Polyether-based segment of the copolymer is a tire innerliner film comprising a repeating unit of the following formula (3):

[Formula 3]

In Chemical 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 ₆ and R ₇ may be the same as or different from each other, and are a direct bond, -O-, -NH-, -COO- or -CONH-, respectively.

[Claim 7]

The method of claim 1,

The copolymer is a film for a tire innerliner comprising a polyamide-based segment and a polyether-based segment in a weight ratio of 6: 4 to 3: 7.

[Claim 8]

The method of claim 1,

In the base film layer, the polyamide-based resin and copolymer is a tire inner liner film is included in a weight ratio of 6: 4 to 3: 7.

[Claim 9]

The method of claim 1,

The thickness of the base film layer is 30 to 300,

The film for tire innerliner whose thickness of the said contact bonding layer is 0.1-20.

[Claim 10]

The method of claim 1,

The film for tire innerliner whose said base film layer is an unstretched film.

[Claim 11]

The method of claim 1,

The resorcinol-formalin-latex (RFL) adhesive system is resorcinol and the formaldehyde condensates of 2 to 30 parts by weight ^_0/0; And a latex 68 to 98 weight ⁰ /.

[12.] ^"

Polyamide-based resins; And a copolymer comprising a polyamide-based segment and a polyether-based segment; a mixture having a absolute weight average molecular weight of 50,000 to 1,000,000 by melting and extruding the mixture at 230 to 30 ° C. Forming a film layer,

Forming an adhesive layer comprising a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the base film layer,

The process for producing a poly ether segment, a film for the base film layer is 15 to 50 parts by weight ^_0/0, based on the total weight, of claim 1 Thai inner liner included in the content of the copolymer.

[Claim 13]

The method of claim 12,

The relative viscosity (96% solution of sulfuric acid) of the polyamide-based resin is 3.0 to 3.5,

[Claim 14]

The method of claim 12,

The copolymer is a method for producing a tire innerliner film comprising a polyamide-based segment and a polyether (pc> ly-ether) segment in a weight ratio of 6: 4 to 3: 7.

[Claim 15]

The method of claim 12,

The substrate measured at 40 ^° C. using a 1: 4 mixed solvent of m-cresol and chloroform containing tetramethyl ammonium chloride at a concentration of 0.02 M The specific refractive index increment (dn / dc) of the film is 0.04 to 0.14 mL / g, the method for producing a film for tire innerliner.

[Claim 16]

The method of claim 12,

The step of forming the base film layer comprises the step of extruding the mixture into a film of the thickness of 30 to 300 ¬.

[Claim 17]

The method of claim 12,

The forming of the base film layer may include mixing the polyamide-based resin and a copolymer in a weight ratio of 6: 4 to 3: 7.

[Claim 18]

Clause 12,

The step of forming the adhesive layer, resorcinol and formaldehyde condensates of 2 to 30 parts by weight ^_0/0; And applying an adhesive comprising a latex 68 to 98 wt.

[Claim ¹ 19]

The method of claim 12,

The method of manufacturing a film for a tire innerliner further comprising the step of solidifying the base film layer formed by melting and extruding in the cooling unit maintained ^at 5 to 40 ^° C.