KR20130035977A - Film for tire inner-liner and preparation method thereof - Google Patents

Abstract

PURPOSE: A tire inner-liner film is provided to have excellent sealability, to reduce the weight of a tire, to improve fuel efficiency, and to have high durability and fatigue resistance. CONSTITUTION: A film for a tire inner-liner(7) comprises a substrate film layer which includes a copolymer including a polyamide-based resin, polyamide-based segment, polyether-based segment, and a substrate film layer; and an adhesive layer which is formed on at least one layer of the substrate film layer and includes a resorcinol-formalin-latex-based adhesive. The segment content of the polyether-based copolymer is 15-50wt% based on total weight of the film layer and has a density of 1.050-1.125 g/cm^3 at 170 deg. C. [Reference numerals] (1) Tread; (2) Shoulder; (3) Sidewall; (4) Cap ply; (5) Belt; (6) Body ply; (7) Innerliner; (8) Apex; (9) Bead;

Description

FILM FOR TIRE INNER-LINER AND PREPARATION METHOD THEREOF}

The present invention relates to a film for tire innerliner and a method of manufacturing the same. More specifically, it is possible to lighten tires and improve fuel efficiency by implementing excellent airtightness even at a thin thickness, and for film inner tire liner and tire inner liner having mechanical properties such as high durability and fatigue resistance with excellent formability. It relates to a method for producing a film.

The tires support the load of the vehicle, alleviate the impact from the road surface, and transmit the driving or braking force of the vehicle to the ground. In general, a tire is a composite of fiber / steel / rubber and generally has a structure as shown in FIG. 1.

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): A layer of cord inside the tire, which must support loads, withstand impacts, and be resistant to fatigue during rolling.

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

Side Wall (3): refers to the rubber layer between the lower part of the shoulder (2) from the bead (9) and serves to protect the body ply (6) inside.

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 rests 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 filler 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 without the use of a tube are commonly 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. . However, when the content of the rubber component and the tire thickness increase, there is a problem in that the total tire weight increases and fuel economy of the vehicle decreases.

In addition, the rubber components have relatively low heat resistance, such 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, where repeated deformation occurs at high temperature conditions. There was a problem in changing form or physical properties. In addition, in order to couple the rubber components to the tire curker layer, a vulcanizing agent or a vulcanizing process had to be applied, and it was difficult to secure sufficient adhesive force.

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 molding or driving process of the tire.

However, any previously known method has had a limit in maintaining excellent air permeability and tire formability while sufficiently reducing the thickness and weight of the innerliner. In addition, 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 that 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 is to provide a tire innerliner film having excellent mechanical properties such as light weight and car fuel economy by implementing excellent airtightness even in a thin thickness, high durability and fatigue resistance with excellent formability.

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

The present invention is a substrate film layer comprising a polyamide-based resin, and a copolymer comprising a polyamide-based segment and a polyether-based segment; And an adhesive layer formed on at least one surface of the base film layer and including a resorcinol-formalin-latex (RFL) adhesive, wherein the content of the polyether segment of the copolymer is based on the total weight of the base film layer. 15 to 50% by weight, the base film layer is 1.050 g / cm ³ at 170 ℃ It provides a film for tire innerliner having a density of from 1.125 g / cm ³ .

The present invention also melts and extrudes a mixture of a polyamide-based segment and a copolymer comprising a polyether-based segment and a polyamide-based resin at 230 to 300 ° C, and extrudes 1.050 g / cm ³ to 1.125 g / at 170 ° C. forming a base film layer having a density of cm ³ , and forming an adhesive layer comprising a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the base film layer, wherein the airborne It provides a method for producing a film for tire innerliner, the content of the polyether-based segment of the copolymer is 15 to 50% by weight based on 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 an embodiment of the present invention, a base film layer including a polyamide-based resin and a copolymer including a polyamide-based segment and a polyether-based segment; And an adhesive layer formed on at least one surface of the base film layer and including a resorcinol-formalin-latex (RFL) adhesive, wherein the content of the polyether segment of the copolymer is based on the total weight of the base film layer. 15 to 50% by weight, the base film layer is 1.050 g / cm ³ at 170 ℃ A film for tire innerliner having a density of from 1.125 g / cm ³ may be provided.

As a result of the researches of the present inventors, when the copolymer including the polyether-based segment in a specific content and the base film layer formed by using the polyamide-based resin together, excellent airtightness is realized even at a thin thickness. It has been confirmed that the tire innerliner film can be provided by reducing the weight of the tire and improving the fuel efficiency of the vehicle, and exhibiting high heat resistance and excellent moldability and mechanical properties such as high durability and fatigue resistance. When the adhesive layer including the resorcinol-formalin-latex (RFL) -based adhesive is formed on the base film layer, it can be firmly bonded to the tire without applying an additional vulcanization process or greatly increasing the thickness of the adhesive layer. Confirmed.

In general, a film obtained by using a polymer resin may be stretched or crystallized to a certain degree even at room temperature, and may have a relatively high density. The film may be rapidly crystallized in a high temperature region of 100 ° C. or higher, thereby rapidly increasing the density or crystallinity. On the contrary, the base film layer may be prepared using a copolymer including a polyether-based segment and a polyamide-based segment of a specific content together with the polyamide-based resin to have specific density and crystallization characteristics.

Specifically, the base film layer may not be greatly crystallized even at a high temperature, and the rigidity of the film may not be significantly increased, for example, 1.050 g / cm ³ at 170 ° C. To 1.125 g / cm ³ . That is, the base film layer has a relatively low ratio of crystallization even at a high temperature, and thus may have a relatively low density range, and the modulus characteristics or moldability do not significantly decrease. Accordingly, such a base film layer has not only high modulus characteristics but also high elasticity or elastic recovery rate even at high temperatures, and not only exhibits excellent moldability in tire manufacturing, but also large deformation under high temperature conditions. In a tire manufacturing process or a vehicle driving process that is repeatedly applied, the film itself may be prevented from crystallization or damage such as cracks in the film.

And, the base film layer is 1.000 g / cm ³ at 30 ℃ It can have a density of 1.120 g / cm ³ , and thus the film for the tire innerliner may exhibit a not very high Molecular properties and appropriate elasticity near room temperature, at least to be secured during the tire manufacturing process or storage process It is possible to secure the durability and the like, it is easily applied to a molding machine used for manufacturing a tire can secure excellent moldability.

Specifically, the polyamide-based resin may have an absolute weight average molecular weight of 100,000 to 200,000. As the polyamide resin has an absolute weight average molecular weight in the above-described range, it can be easily mixed with the specific copolymer, the substrate film layer to be produced may have appropriate modulus characteristics and even if a high temperature condition is applied It is possible to prevent a phenomenon in which the modulus property is greatly increased or mechanical properties are degraded. Accordingly, the film for tire innerliner obtained by using the polyamide-based resin having the above-described weight average molecular weight can secure excellent moldability, and the film crystallizes or the film during the tire manufacturing process in which a large deformation is made under high temperature conditions. It is possible to prevent a phenomenon such as cracking inside.

The weight average molecular weight of the polyamide-based resin is less than 100,000, the base film layer to be prepared may not secure sufficient mechanical properties for use in the film for the inner liner, the chain mobility of the polyamide-based resin is greatly It may be increased, and the gas barrier property of the base film layer may be greatly reduced. In addition, when the weight average molecular weight of the polyamide-based resin exceeds 200,000, the modulus or crystallinity of the base film layer may be excessively increased when heated to a high temperature, and the density of the base film layer may be greatly increased. It may be difficult to secure elasticity or elastic recovery.

Meanwhile, the copolymer including the polyamide-based segment and 15 to 50% by weight of polyether-based segment based on the total weight of the film is 110,000 to 250,000, preferably 120,000 to 200,000 It may have an absolute weight average molecular weight of. As the copolymer has an absolute weight average molecular weight in the above-described range, it can be easily mixed with the polyamide-based resin, the substrate film layer to be produced may have appropriate modulus characteristics, even if a constant high temperature conditions are applied It is possible to prevent a phenomenon in which the modulus property is greatly increased or mechanical properties are degraded. Accordingly, the film for tire innerliner obtained by using the copolymer having the absolute weight average molecular weight described above may have the specific density characteristics described above, thereby ensuring excellent moldability and large deformation under high temperature conditions. In the tire manufacturing process, the film may be crystallized or cracks may be generated in the film.

Absolute weight average molecular weight of the copolymer is less than 110,000, it may be difficult to ensure the mechanical properties such as strength, heat resistance or durability sufficient for the base film layer to be used in the film for the inner liner. In addition, when the absolute weight average molecular weight of the copolymer is more than 260,000, the modulus or crystallinity of the base film layer may be excessively increased and the density of the base film layer may be greatly increased when heated to a high temperature, and should have an innerliner film. It may be difficult to secure elasticity or elastic recovery.

On the other hand, the base film layer manufactured using the polyamide-based resin having an absolute weight average molecular weight of 100,000 to 200,000 and the copolymer having an absolute weight average molecular weight of 110,000 to 260,000, has an absolute weight average molecular weight of 100,000 to 200,000. Can have The weight average molecular weight of such a base film layer changes the absolute weight average molecular weight of the polyamide resin used, the absolute weight average molecular weight of the said copolymer, mixing reaction time, an additive, or reaction conditions etc., as shown to the manufacturing method mentioned later. Adjustable by

In the solution containing the polymer material, light scattering occurs due to the chain of the polymer material. Using the light scattering phenomenon, the absolute weight average molecular weight of the polymer material can be measured. In particular, using Wyatt's Multi Angle Light Scattering (MALS) system, the absolute weight average molecular weight of the polymer can be obtained by applying the parameters from the measurement results to the Rayleigh-Gans-Debye equation.

Formula 1: Rayleigh-Gans-Debye equation

In Formula 1, M is the molar mass, and in the case of a polydisperse sample, the absolute weight average molecular weight (Mw), R (θ) is the excess Rayleigh ratio, and K = 4πn ₀ ² ( dn / dc ) ² λ ₀ ^-4 N _A ^-1 , C is the polymer concentration in solution (g / ml), and A ₂ is the second virial coefficient. And, in the K, n ₀ is the refractive index of the solvent, N _A is Avogadro's number, λ ₀ is the wavelength of the light source under vacuum, P (θ) = R (θ) / R ₀ , R ₀ is incident light.

On the other hand, the tire inner liner 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 a tire inner liner film are produced using the polyamide resin copolymer (including polyamide-based segment-polyether-based segment) and polyamide-based resin in the specific composition and have the specific density described above. It seems to be by applying the base film layer.

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 imparting elastomeric properties to the polyamide-based resin. The polyamide-based resin included in the base film layer exhibits excellent airtightness due to 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, and other resins. The modulus is not so high compared to. In addition, the polyether-based segment of the copolymer may be present in a bonded or dispersed state between polyamide-based segments or polyamide-based resins, thereby lowering the modulus of the base film layer, and 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 such polyamid resins exhibit a modulus that is not relatively high compared to other resins, an innerliner film exhibiting relatively low modulus characteristics can be obtained even when applied with a copolymer including the polyether-based segment having a specific content. This can improve the moldability of the tire. Also, Since the polyamide-based resin has sufficient heat resistance and chemical stability, the innerliner 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 polyamide-based resin is used in combination with a copolymer comprising a polyamide-based segment and a polyether-based segment, and thus relatively high relative to an adhesive (for example, a resorcinol-formalin-latex (RFL) -based adhesive). May indicate reactivity. Accordingly, the inner liner film may be easily adhered to the carcass portion, and the inner liner film may be sufficiently prevented by breaking the interface due to heat or repetitive deformation occurring during the tire manufacturing process or the driving process. Allow to have fatigue.

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, nylon 66, nylon Preference is given to using 46, nylon 11, nylon 12, nylon 610 or nylon 612.

In the manufacturing process of the base film, the polyamide-based resin may be included in the base film by mixing and melting with the copolymer described above, and the monomer or oligomer which is a precursor of the polyamide-based resin together with a reaction initiator or a catalyst It may also be included in the base film by reacting with the copolymer described above.

On the other hand, as described above, the copolymer including the polyamide-based segment and 15 to 50% by weight of the polyether-based segment based on the total weight of the film, between the polyamide-based resin By being present in a bonded or dispersed state, the modulus of the base film layer can be lowered more, the rigidity of the base film layer can be suppressed from rising, and the crystallization at high temperature can be prevented. As the copolymer is included in the base film layer, the tire innerliner film may realize high elasticity or elastic recovery while securing excellent mechanical properties such as 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 may be 15 to 50% by weight, 20 to 45% by weight, preferably 22 to 40% by weight based on the total weight of the base film layer. When the content of the polyether-based segment is less than 15% by weight of the entire film, the modulus of the base film layer or the tire inner liner film may be increased, thereby deteriorating the moldability of the tire or a large decrease in physical properties due to repeated deformation. have. When the content of the polyether-based segment exceeds 50% by weight of the entire film, the airtightness of the film for the tire innerliner may be lowered, and the reactivity to the adhesive is lowered so that the innerliner easily adheres to the carcass layer. It may be difficult, and the elasticity of the base film layer may be increased so that 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 is possible to suppress or prevent the base film layer from being easily broken.

In addition, such a polyether-based segment can lower the modulus of the film for the tire inner liner, thereby allowing the tire to be easily stretched or deformed to fit the shape of the tire even when a very small force is applied during the tire forming. Enable molding In addition, the polyether-based segment can suppress the increase in the rigidity of the film at low temperatures and prevent crystallization at high temperatures, and can prevent damage or tearing of the inner liner film due to repeated deformation, 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 the modulus properties. In addition, as the polyamide-based segment is applied, the base film layer may have a low air permeability while having a thin thickness, and may secure sufficient heat resistance and chemical stability.

The copolymer including the polyamide-based segment and the polyether-based segment may be a polyamide-based monomer or oligomer and a polyether-based monomer or oligomer It may be a copolymer obtained by reacting, and may be a copolymer obtained by polymerizing or crosslinking a polymer including a polyamide segment and a polymer comprising a polyether segment.

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. In addition, the copolymer including the polyamide-based segment and the polyether-based segment may include a polymer including the polyamide-based segment and a polyether-based segment. It may be a copolymer including a polymerization reactant between polymers, and may be a crosslinked copolymer including a crosslinking reactant between a polymer including a polyamide-based segment and a polymer including a polyether-based segment.

Meanwhile, in the base film layer, a copolymer including the polyamide-based resin, the polyamide-based segment, and the polyether-based segment is uniformly mixed, or polymerized or crosslinked. Through it may be in a combined state in part or the whole area.

Wherein the copolymer comprising the polyamide segment and the polyether segment is a copolymer of a polymer comprising a polyamide segment and a polymer comprising a polyether segment, Polymeric reactants or crosslinking reactants, the copolymer may comprise a polymer comprising a polyamide-based segment that is not involved in the polymerization or cross-linking reaction, or a polymer comprising a poly-ether-based segment have. Accordingly, the polymer including the polymerization reactant or the crosslinking reactant as well as the polymer including the polyamide-based segment or the polymer including the polyether-based segment may be present in a mixed or combined state with other components. have. Also in this case, the total sum of the content of the polyether segment and the content of the polymer including the polyether segment in the copolymer is in the range of 15 to 50% by weight based on the total weight of the base film layer , The physical properties of the film for the entire inner liner can be optimized.

The polyamide-based segment of the copolymer may include a repeating unit of Formula 1 or Formula 2.

[Formula 1]

In Formula 1, R ₁ is a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched arylalkylene group having 7 to 20 carbon atoms.

(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.

The polyamide-based segment may be the polyamide-based repeating unit when a base film layer is produced using a copolymer comprising a polyamide-based repeating unit and a polyether-based repeating unit. In addition, the polyamide-based segment may be derived from a polymer comprising a polyamide segment used in the production of the substrate film, or from a poly-amide-based monomer or oligomer.

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

[Formula 3]

In 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 are a direct bond, -O- , -NH-, -COO- or -CONH-.

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. In addition, the polyether segment may be derived from a polymer including a polyether segment, or a polyether monomer or oligomer used in the manufacturing process of the base film. .

On the other hand, the copolymer is a polyamide segment and a polyether segment in the range of 15 to 50% by weight based on the total weight of the film, the polyether segment 6: 4 to 3: 7, preferably 5: 5 to 4: 6.

As described above, when 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 deteriorating the moldability of the tire or a large decrease in physical properties due to repeated deformation. In addition, if the content of the polyether-based 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, in the base film layer, the polyamide-based resin and copolymer may be included in a weight ratio of 6: 4 to 3: 7, preferably 5: 5 to 4: 6. If the content of the polyamide-based resin is too small, the density or airtightness of the base film layer may be lowered. In addition, 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 lowered, and the polyamide-based resin may be Crystallization may occur and cracks may occur due to repeated deformation.

The base film layer may have a thickness of 30 to 300 ㎛, preferably 40 to 250 ㎛, more preferably 40 to 200 ㎛. Accordingly, the film for tire innerliner of one embodiment of the invention has a thinner thickness than previously known, but may have a low air permeability, for example, an oxygen permeability of 200 cc / (m 2 · 24hr · atm) or less. have.

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, it has a low modulus and a high strain rate and can be suitably applied to a tire forming process in which high expansion occurs. 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, adjusting viscosity by optimizing melt extrusion temperature, changing a die die specification, or adjusting a winding speed, etc. Through the method of the base film can be prepared in 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. 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 crushing occurring during the manufacturing process may be prevented due to a difference in specifications with a forming drum.

On the other hand, the base film may further include additives such as heat resistant antioxidants, heat stabilizers, adhesion promoters, or mixtures thereof. Specific examples of the heat resistant antioxidants include N, N'-hexamethylene-bis- (3,5-di- (t-butyl) -4-hydroxy-hydrocinnamamide (N, N'-Hexamethylene-bis- (Commercially available products such as 3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide such as rganox 1098), tetrakis [methylene (3,5-di- (t-butyl) -4-hydroxyhydrocinnanam Mate)] methane (commercially available products such as tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, such as Irganox 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 N, N'-bis (2). , 2,6,6-tetramethyl-4-piperidyl) -1,3-benzenedicarboxamide (N, N'-Bis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 3-benzenedicarboxamide), etc. However, the additive is not limited to the above examples, and may be used for the film for tire inner liner. It is known can be used without 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 It is possible to prevent breakage of the interface between the inner liner film and the carcass layer generated by the generated heat or repeated deformation so that the inner liner film may have sufficient fatigue resistance.

The main properties of the adhesive layer described above appear to be due to the inclusion of certain resorcinol-formalin-latex (RFL) based adhesives having a specific composition. Previously, adhesives for tire innerliners have been used, such as rubber type tie gums, and thus require additional vulcanization. In contrast, the adhesive layer includes a resorcinol-formalin-latex (RFL) -based adhesive having 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. The base film and the tire carcass layer may be firmly bonded. Accordingly, it is possible to reduce the weight of the tire and to improve the fuel efficiency of the automobile, and to prevent the phenomenon of separating the carcass layer and the inner liner layer or the base film and the adhesive layer even during repeated deformation in the tire manufacturing process or the automobile 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 driving, the adhesive force may be applied even during the manufacturing process under high temperature conditions or during the driving of a vehicle in which mechanical deformation is applied for a long time. 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. 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 may be 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. 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. In addition, the condensate of the 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 reaction for excellent adhesion, and may be included in less than 32% by weight in order to secure proper fatigue resistance properties. have.

The latex may be one or a mixture of two or more 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 more than 68% by weight relative to the total amount of the adhesive layer for the flexibility of the material and the effective crosslinking reaction with the rubber, it is included in 98% by weight or less for the chemical reaction with the base film and the rigidity of the adhesive layer.

In addition, the adhesive layer may further include at least one additive 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 modifier of the additive is applied for the uniform coating of the adhesive layer, but may cause a problem of the adhesive strength decrease when excessively added, 2 wt% or less or 0.0001 to 2 wt%, preferably based on the total adhesive layer 1.0 wt% or less, or 0.0001 to 0.5 wt%. At this time, 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 μm, preferably 0.1 to 10 μm, more preferably 0.2 to 7 μm, even more preferably 0.3 to 5 μm, and one surface of the film for tire innerliner or It can be formed on both surfaces. If the thickness of the adhesive layer is too thin, the adhesive layer itself may be thinner when the tire is inflated, the crosslinking adhesive force between the carcass layer and the base film may be lowered, and stress may be concentrated on a part of the adhesive layer, thereby reducing fatigue characteristics. In addition, when the adhesive layer is too thick, interfacial separation may occur in the adhesive layer, thereby reducing fatigue characteristics. And, in order to adhere 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.

In addition, the tire inner liner film can maintain a proper air pressure even after long-term use, for example, the tire inner liner film at 21 ℃ and 101.3 kPa in accordance with the method of ASTM F 1112-06 standards When the internal pressure retention (IPR) was measured for 90 days on the applied tire, the pneumatic retention rate as shown in the following general formula 2 may be 95% or more, that is, the pneumatic pressure reduction rate may be 5% or less. 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]

Meanwhile, according to another embodiment of the present invention, a mixture of a polyamide-based segment and a polyether-based segment and a mixture of a polyamide-based resin is melted and extruded at 230 to 300 ° C., and 1.050 g / cm ³ at 170 ° C. Forming a base film layer having a density of from 1.125 g / cm ³ to 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 polyether-based segment of the copolymer is 15 to 50% by weight based on the total weight of the base film layer, there may be provided a method for producing a film for tire innerliner.

As described above, the base film layer having a specific density is formed by using the polyamide resin and the specific copolymer (including 15 to 50 wt% of the polyether segment based on the total weight of the base film layer). The film for tire innerliner may be manufactured by forming an adhesive layer comprising a resorcinol-formalin-latex (RFL) adhesive on at least one surface of the base film layer.

The film for tire innerliner obtained by such a manufacturing method can realize excellent airtightness even at a thin thickness to reduce the weight of the tire and improve the fuel efficiency of the automobile, and can have excellent moldability and mechanical properties while having high heat resistance. However, it can be firmly bonded to the tire without applying additional vulcanization processes or significantly increasing the thickness of the adhesive layer.

The base film layer provided according to the manufacturing method is not greatly crystallized even at a high temperature and the rigidity of the film does not increase significantly, it may have a relatively low density range, specifically, at 170 ℃ 1.050 g / cm ³ To 1.125 g / cm ³ . Accordingly, such a base film layer has not only high modulus characteristics but also high elasticity or elastic recovery rate even at high temperatures, and not only exhibits excellent moldability in tire manufacturing, but also large deformation under high temperature conditions. In a tire manufacturing process or a vehicle driving process that is repeatedly applied, the film itself may be prevented from crystallization or damage such as cracks in the film.

And, the base film layer is 1.000 g / cm ³ at 30 ℃ It can have a density of 1.120 g / cm ³ , and thus the film for the tire innerliner may exhibit a not very high Molecular properties and appropriate elasticity near room temperature, at least to be secured during the tire manufacturing process or storage process It is possible to secure the durability and the like, it is easily applied to a molding machine used for manufacturing a tire can secure excellent moldability.

On the other hand, the crystallinity of the base film layer described above is due to the formation of the base film layer using the above-described polyamide-based resin and a copolymer including a specific content of the polyether-based segment and the polyamide-based segment. When the weight average molecular weight of the system resin and the copolymer is specifically applied, it may be more clearly expressed.

Specifically, the polyamide-based resin having an absolute weight average molecular weight of 100,000 to 200,000 and the copolymer having an absolute weight average molecular weight of 110,000 to 250,000 (15 to 50% by weight of the total weight of the polyamide-based segment and the base film layer The base film layer prepared using a copolymer comprising a polyether-based segment) is 1.050 g / cm ³ at 170 ℃ To 1.125 g / cm ³ .

In addition, according to the polyamide-based resin and copolymer having the above-described absolute weight average molecular weight, the base film layer may have an absolute weight average molecular weight of 100,000 to 200,000. The weight average molecular weight of such a base film layer changes the absolute weight average molecular weight of the polyamide resin used, the absolute weight average molecular weight of the said copolymer, mixing reaction time, an additive, or reaction conditions etc., as shown to the manufacturing method mentioned later. Adjustable by

On the other hand, in the method for producing a tire innerliner film, a polyamide-based resin having an absolute weight average molecular weight of 100,000 to 200,000 can be used, and air having an absolute weight average molecular weight of 10,000 to 250,000, preferably 120,000 to 200,000. Coalescing (including polyamide-based segments and 15-50% by weight of polyether-based segments based on the total weight of the film) may be used.

In addition, the content of the polyether segment of the copolymer may be 15 to 50% by weight, 20 to 45% by weight, preferably 22 to 40% by weight based on the total weight of the base film layer.

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

The polyamide-based resin may be included in the base film by mixing or compounding with the above-mentioned copolymer, and then the monomer or oligomer, which is a precursor of the polyamide-based resin, may be mixed with the reaction initiator, And may be incorporated into the base film by mixing and reacting with a combination.

In addition, the copolymer including the polyamide-based segment and the polyether-based segment is a base film by melting the copolymer itself after mixing or compounding with the polyamide-based resin. Can be included.

In addition, after mixing or compounding a polymer including a polyamide-based segment and a polymer including a polyether-based segment and performing a polymerization reaction or a crosslinking reaction, the product of the polymerization reaction or the crosslinking reaction is The base film layer may be formed by mixing and melting the polyamide-based resin. In addition, by mixing or compounding a polymer comprising a polyamide-based segment and a polymer comprising a polyether-based segment, and mixing and melting such a mixture or compound with a polyamide-based resin, The polymer of may cause a polymerization reaction or a crosslinking reaction, and the base film layer may be formed through this process.

In the base film layer, a copolymer including the polyamide-based resin, the polyamide-based segment, and the polyether-based segment is uniformly mixed or polymerized or crosslinked. It may be coupled in some or all areas.

In the forming of the base film layer, in order to extrude a film having a more uniform thickness, the copolymer and the polyamide-based resin may 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 in the step of mixing them, staying at a raw material supply unit maintained at a constant temperature, or melting and extruding. 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. .

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 or appear uneven shape or region in the subsequent mixing, melting or extrusion step, and thus the film A base film layer having a uniform thickness can be formed over the entire area.

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 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, 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 lowered, and the polyamide-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.

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

As described above, the copolymer may include a polyamide-based segment and a polyether-based segment in a weight 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 temperature of 50 to 100 ℃. As the raw material supply unit is maintained at a temperature of 50 to 100 ℃, 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 the poor feeding of the raw material (feeding) phenomenon that occurs due to agglomeration of the mixture, it is possible to form a more uniform base film in the subsequent melting and extrusion process. The raw material supplier 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 to a large, and is a conventional raw material feeder (feeder) included in the extruder for producing a polymer resin, etc. Can be.

On the other hand, by melting and extruding the mixture supplied to the extrusion die through the raw material supply unit at 230 to 300 ℃, it is possible to form a base film layer. The temperature for melting the mixture may be 230 to 300 ℃, preferably 240 to 280 ℃. 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 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. The adjustment of the thickness of the film to be produced can be made 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.

In order to more uniformly control the thickness of the base film layer in the range of 30 to 300 μm, 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 stress 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 tire innerliner, a portion of an extrusion die corresponding to a position at which a non-uniform thickness appears by continuously measuring the thickness of the base film manufactured by the above-described steps, and feeding back a measurement result. For example, the film having a more uniform thickness can be obtained by reducing the deviation of the base film manufactured by adjusting the lip gap adjusting bolt of T-Die. In addition, the adjustment of the thickness measurement-feedback-extrusion die of such films can be configured by using an automated system such as an Auto Die system or the like.

On the other hand, the method for producing a film for tire innerliner may further comprise the step of solidifying the base film layer formed by melting and extruding in a cooling unit maintained at a temperature of 5 to 40 ℃, preferably 10 to 30 ℃. Can be.

The base film layer formed by melting and extruding may be provided on a film having a more uniform thickness by being solidified in a cooling unit 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.

In detail, the solidifying step may be performed by using an air knife, an air nozzle, an electrostatic charge device (Pinning device), or a combination thereof, on a cooling roll having the base film layer formed by melting and extruding at a temperature of 5 to 40 ° C. It may include the step of uniformly contact.

In the solidifying step, the base film layer formed by melting and extruding by using an air knife, an air nozzle, an electrostatic pinning device or a combination thereof is brought into close contact with a cooling roll. It is possible to prevent phenomena such as blowing in the air or cooling partially unevenly, so that a film having a more uniform thickness can be formed, and some areas of the film that are relatively thick or thin as compared to the surrounding part are substantially It may not be formed as.

Meanwhile, the melt extruded under the specific die gap condition may be attached or grounded to a cooling roll installed at a horizontal distance of 10 to 150 mm, preferably 20 to 120 mm, at a horizontal distance from the die outlet, thereby eliminating stretching and orientation. The horizontal distance from the die outlet to the chill roll may be the distance between the die outlet and the point where the discharged melt grounds to the chill roll. If the straight line distance between the exit of the die and the cold roll attachment point of the molten film is too small, the uniform flow of the molten extruded resin may be disturbed and the film may be unevenly cooled, and if the distance is too large, the stretching effect of the film may be achieved. Can not.

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 production of the polymer film, for example, screw diameter, screw rotational speed, or line speed, etc. Can be selected and used appropriately.

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

The forming of the adhesive layer may be performed by coating a resorcinol-formalin-latex (RFL) adhesive on one or both surfaces of the formed base film, and then drying the adhesive layer. May have a thickness of preferably 0.1 to 10 μm. The resorcinol-formalin-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 may include 2 to 30 wt% of a condensate of resorcinol and formaldehyde on at least one surface of the base film layer; And applying (coating) an adhesive including latex 68 to 98 wt% to a thickness of 0.1 to 20 μm.

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

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.

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

In forming the copolymer or 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.

According to the present invention, it is possible to reduce the weight and improve the fuel economy of the tire by implementing excellent airtightness even at a thin thickness, and for the film for the tire inner liner and the tire inner liner having high heat resistance characteristics and excellent moldability and mechanical properties Methods of making films can be provided.

1 schematically shows the structure of a tire.

The invention is explained in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  And Comparative example : tire For inner liner  Preparation of film]

< Example 1  To 3>

 (1) Production of base film

60 weight% of copolymer resin synthesize | combined using 60 weight% of polyethyleneglycol of an amine group, and 40 weight% of nylon 6 resin, and 40 weight% of polyamide-type resin (nylon 6) were mixed. In this case, the weight average molecular weight of each of the polyamide-based resin and the copolymer resin was as shown in Table 1 below. Then, the temperature of the raw material supply part was adjusted to 50 to 100 ° C., and the mixture was fed to the extrusion die while preventing the mixture from being fused in the extruder screw to cause feeding failure.

Then, the supplied mixture is extruded while maintaining a uniform melt flow through a T-type die (die gap [1.0 mm) at a temperature of 260 ° C., and an air knife is placed on a surface of a cooling roll controlled at 25 ° C. The molten resin was cooled and solidified into a film of uniform thickness. Then, 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. The weight average molecular weight of the obtained base film is as showing in following Table 1.

(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. 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%.

In addition, the 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.

< Comparative example  1 and 2>

As shown in Table 1 below, except that the weight average molecular weight of the polyamide-based resin (nylon 6) and the copolymer resin used was different, the base film layer and the adhesive layer were formed in the same manner as in the Example for the tire inner liner. A film was prepared.

< Experimental Example : tire For inner liner  Measurement of Film Properties>

Experimental Example 1 : Crystallisation  Measure

From each of the base film tire inner liner films of Examples and Comparative Examples, specimens having a width (30 mm * 30 mm in length) were obtained. The crystallinity was analyzed after peak seperation by X-ray diffraction analysis of the specimen at 0 ° to 60 ° using an X-RAY DIFFRACTION device at 25 ° C.

Experimental Example 2 . Modulous  Measure

From each of the base film tire inner liner films of Examples and Comparative Examples, specimens having a width (30 mm * 30 mm in length) were obtained. At 25 ° C., the modulus of 25% elongation of the specimen was measured by using an INSTRON apparatus and applying a constant rate of extension method.

Composition of Examples and Comparative Examples and Results of Experimental Examples 1,2 division Nylon 6
(Mw) Copolymer (Mw) Base film layer Mw Modulus at room temperature, 25% elongation (MPa) Density [30 ℃]
(g / cm ³⁾ density
[170 ℃]
(g / cm ³⁾ Example 1 106,910 150,020 111,740 16.07 1.108 1.118 Example 2 110,850 145,897 109,735 15.28 1.075 1.076 Example 3 113,657 151,972 120,698 15.58 1.111 1.112 Comparative Example 1 90,687 100,050 97,368 22.56 1.097 1.128 Comparative Example 2 206,160 287,362 241,760 23.51 1.127 1.136

* Mw. Of the nylon 6, the copolymer resin and the base film layer is the absolute weight average molecular weight measured using a MALS WYATT DAWIN8 + device.

As shown in Table 1, the base film layer of the film for tire innerliner of the embodiment is 1.076 g / cm ³ at 170 ℃ It has been confirmed that it has a density of from 1.118 g / cm ³ , 1.075 g / cm ³ at 30 ℃ It is confirmed that it has a density of 1.111 g / cm ³ , and in each of Examples 1 to 3, the density does not increase so much with temperature.

That is, in the base film layer of the embodiment, it was confirmed that the phenomenon that the density is greatly increased as the polymer arrangement is greatly changed or crystallized at high temperature, and thus the film for the innerliner of this embodiment has a modulus characteristic or molding It was confirmed that the sex and the like did not significantly decrease.

In addition, it was confirmed that modulus of 20 MPa or less appeared when the base film layer of the above example was stretched at 25% at room temperature. That is, the film for the tire inner liner of the embodiment can be easily applied to a molding machine used for manufacturing tires by exhibiting not so large crystallization characteristics or appropriate elasticity while ensuring minimum durability to be secured during tire manufacturing or storage. It has been confirmed that it has properties that can be.

On the contrary, the base film layer prepared in Comparative Example 1 exhibited a modulus of more than 20 MPa at 25% elongation at room temperature, so that the moldability, elasticity and elastic recovery rate were relatively low.

Particularly, the base film layer of Comparative Example 1 had a density of 1.097 g / cm ³ at 30 ° C., and the crystallinity of the film was greatly increased and the density rapidly increased to 1.128 g / cm ³ when heated to 150 ° C. Confirmed. That is, it was confirmed that the base film layer of Comparative Example 1 was low in heat resistance and deteriorated not only in elasticity and elastic recovery rate but also in mechanical properties when a certain high temperature condition was applied. That is, when the base film layer of Comparative Example 1 is applied to the tire inner liner, there is a possibility that damage such as cracks may occur in the tire manufacturing process or the vehicle driving process.

Then, the base film layer to be produced in Comparative Example 2, as well as indicate the over during a 25% elongation at room temperature 20MPa modulus, having a density of 1.127 g / cm ³ at 30 ℃ at 1500 ℃ of 1.136 g / cm ³ It was confirmed that having a density, it has a high density not only at room temperature but also at a high temperature region. That is, when using the base film layer of Comparative Example 2, it may be difficult to secure the appropriate formability in the tire manufacturing process, the vehicle running when the inner liner is stored or applied to the tire manufacturing equipment or repeated deformation In the process, damage to the film itself is likely to occur.

Claims (21)

A base film layer comprising a polyamide-based resin and a copolymer including a polyamide-based segment and a polyether-based segment; And
And an adhesive layer formed on at least one surface of the base film layer and including a resorcinol-formalin-latex (RFL) adhesive.
The content of the polyether segment of the copolymer is 15 to 50% by weight based on the total weight of the base film layer,
The base film layer was 1.050 g / cm ³ at 170 ° C. A film for tire innerliner having a density of from 1.125 g / cm ³ .
The method of claim 1,
The base film layer was 1.000 g / cm ³ at 30 ° C. A film for tire innerliner having a density of from 1.120 g / cm ³ .
The method of claim 1,
The film for tire innerliner, wherein the polyamide-based resin has an absolute weight average molecular weight of 100,000 to 200,000.
The method of claim 1,
The polyamide-based resin is nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, copolymer of nylon 6/66, nylon 6/66/610 copolymer, nylon MXD6, nylon 6T, Nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, methoxymethylated 6-nylon, methoxymethylated 6-610-nylon and methoxymethylated 612-nylon Tire innerliner film comprising one or more selected from the group consisting of.
The method of claim 1,
The copolymer for a tire innerliner having a polyamide-based segment and a polyether-based segment having an absolute weight average molecular weight of 110,000 to 250,000.
The method of claim 1,
Polyamide-based segment of the copolymer is a tire innerliner film comprising a repeating unit of the following formula (1) or (2):
[Chemical Formula 1]

In Formula 1, R ₁ is a linear or branched alkylene group having 1 to 20 carbon atoms or a straight or branched arylalkylene group having 7 to 20 carbon atoms,
(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.
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 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 are a direct bond, -O-, -NH-, -COO- or -CONH-, respectively.
The method of claim 1,
The copolymer is a tire inner liner film comprising a polyamide-based segment and a polyether-based segment in a weight ratio of 6: 4 to 3: 7.
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.
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 micrometers.
The method of claim 1,
The film for tire innerliner whose said base film layer is an unstretched film.
The method of claim 1,
The resorcinol-formalin-latex (RFL) -based adhesive may include 2 to 30% by weight of a condensate of resorcinol and formaldehyde; And 68 to 98% by weight of latex.
A mixture of a polyamide-based segment and a copolymer comprising a polyether-based segment and a polyamide-based resin was melted and extruded at 230 to 300 ° C., and 1.050 g / cm ³ at 170 ° C. Forming a base film layer having a density of from 1.125 g / cm ³ , and
Forming an adhesive layer including a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the base film layer,
The content of the polyether-based segment of the copolymer is 15 to 50% by weight based on the total weight of the base film layer, a method for producing a film for tire innerliner.
The method of claim 13,
The polyamide-based resin is a tire inner liner film having an absolute weight average molecular weight of 100,000 to 200,000.
The method of claim 13,
The copolymer for a tire innerliner having a polyamide-based segment and a polyether-based segment having an absolute weight average molecular weight of 110,000 to 250,000.
The method of claim 13,
The base film layer was 1.000 g / cm ³ at 30 ° C. A film for tire innerliner having a density of from 1.120 g / cm ³ .
The method of claim 13,
The method of manufacturing a film for a tire innerliner further comprising the step of mixing the polyamide-based resin and the copolymer in a weight ratio of 6: 4 to 3: 7.
The method of claim 13,
The copolymer is a method for producing a film for tire innerliner comprising a polyamide-based segment and a polyether-based segment in a weight ratio of 6: 4 to 3: 7.
The method of claim 13,
Forming the base film layer,
Method of producing a film for a tire innerliner comprising the step of extruding the mixture into a film having a thickness of 30 to 300 ㎛.
The method of claim 13,
And solidifying the base film layer formed by melting and extruding in a cooling unit maintained at 5 to 40 ° C.
The method of claim 13,
Wherein the step of forming the adhesive layer comprises:
2 to 30% by weight of a condensate of resorcinol and formaldehyde on at least one surface of the base film layer; And applying an adhesive comprising a latex 68 to 98% by weight to a thickness of 0.1 to 20 μm.

Images