KR101386980B1 - Film for tire inner-liner and preparation method thereof - Google Patents

Abstract

The present invention is a substrate film comprising a copolymer or mixture of polyamide-based resin and polyether-based resin; And an adhesive layer comprising a resorcinol-formalin-latex (RFL) -based adhesive.

Description

TECHNICAL FIELD [0001] The present invention relates to a film for a tire innerliner,

The present invention relates to a film for a tire inner liner and a method of manufacturing the same, and more particularly, to a tire having an excellent airtightness even with a thin thickness, which makes it possible to reduce the weight of a tire and improve automobile fuel economy, And can exhibit excellent moldability and endothelial property, and a process for producing the 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): It is a part that comes into contact with the road surface, it should provide friction force necessary for braking and driving, good abrasion resistance, able to withstand external impact, and low heat generation.

Body Ply (Carcass, 6): It is the inner layer of the tire. It should support the load and withstand the impact.

Belt (5): It is located between the body fly. In most cases it is made of steel wire, which alleviates external shocks and keeps the ground surface of the tread wide.

Side Wall 3: A rubber layer between the lower portion of the shoulder 2 and the bead 9, and serves to protect the inner body ply 6.

Inner Liner (Inner Liner, 7): It is located inside the tire instead of the tube, which prevents air leakage and enables pneumatic tires.

Bead (BEAD, 9): A wire bundle (Wire Bundle) with square or hexagonal shape covered with rubber is used to seat and fix the tire on the rim.

CAP PLY (4): It is a special cloth paper placed on the belt of radial tires for some passenger cars, minimizing the movement of the belt when driving.

Apex (APEX, 8): This is a triangular rubber filler used to minimize the dispersion of beads and to protect the beads by alleviating external shocks and to prevent the inflow 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, a tire inner liner having rubber components such as butyl rubber or halobutyl rubber, which is relatively low in air permeability, was used. In this inner liner, the rubber content or the thickness of the inner liner had to be increased in order to obtain sufficient airtightness . As a result, the total weight of the tire is increased, fuel consumption of the vehicle is lowered, air pockets are formed between the inner rubber of the carcass layer and the inner liner, or the shape and physical properties of the inner liner are changed appear.

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 of the previously known methods have had limitations in maintaining excellent air permeability and moldability of the tire while sufficiently reducing the thickness and weight of the inner liner, The weight of the tire is increased and the fuel consumption of the automobile is lowered. In addition, the inner liner obtained by the previously known method has often failed to have sufficient fatigue resistance such as cracking due to repeated deformation in the manufacturing process or the running process of the tire.

Accordingly, the development of a thinner innerliner having a thinner thickness and being easily coupled to the inside of the tire to reduce the weight of the tire and having sufficient fatigue resistance to withstand repeated deformation and physical properties such as excellent air tightness and formability It is required.

The present invention relates to a tire innerliner which is capable of realizing excellent airtightness even with a thin thickness so as to make it possible to reduce the weight of the tire and to improve the automobile fuel economy and to firmly engage with the tire carcass layer, To provide a film for a liner.

The present invention also provides a method for producing the film for a tire innerliner.

The present invention, 50 to 95% by weight of a polyamide resin; And base material having a thickness of 30 to 300 ㎛ including a copolymer or a mixture of 5 to 50% by weight of a polyether resin; And an adhesive layer comprising an adhesive containing 2 to 32% by weight of a condensate of resorcinol and formaldehyde and 68 to 98% by weight of a latex.

In addition, the present invention comprises the steps of forming a copolymer or mixture of 50 to 95% by weight of polyamide-based resin and 5 to 50% by weight of polyether-based resin; Melting and extruding the copolymer or mixture to form a base film having a thickness of 30 to 300 μm; And forming an adhesive layer comprising an adhesive containing at least one surface of the condensate of resorcinol and formaldehyde and at least one surface of the base film layer, wherein the adhesive layer comprises from 2 to 32% by weight of condensate and from 68 to 98% by weight of latex. It provides a manufacturing method of a film for use.

Hereinafter, a film for a tire inner liner and a method of manufacturing the same according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the invention, 50 to 95% by weight of a polyamide resin; And base material having a thickness of 30 to 300 ㎛ including a copolymer or a mixture of 5 to 50% by weight of a polyether resin; And an adhesive layer comprising an adhesive containing 2 to 32% by weight of a condensate of resorcinol and formaldehyde and 68 to 98% by weight of a latex. The film for tire innerliner may be provided.

As a result of the researches of the present inventors, by using a base film prepared by copolymerizing or mixing a polyamide-based resin and a polyether-based resin in a specific content, excellent airtightness and high air pressure retention performance can be realized even at a thin thickness. In addition, the base film exhibits high reactivity with a certain adhesive, so that even a thin and lightweight adhesive layer can be firmly and uniformly bonded to the inside of the tire, and easily stretched or deformed even when a small force is applied when the tire is formed. It has been found that it can be exhibited excellent molding properties and improved fatigue resistance properties.

In addition, the base film may have high reactivity with the resorcinol-formalin-latex (RFL) -based adhesive having the specific composition due to the characteristic chemical structure, and the resorcinol-formalin-latex (RFL) having the specific composition. The adhesive can exhibit high and uniform adhesion to the tire carcass layer. Accordingly, the tire inner liner film may be firmly and uniformly fixed or combined with respect to the tire carcass layer, and is a tire manufacturing process to which a high temperature deformation or stretching step is applied. In the process, the bonding force between the inner liner film and the tire carcass layer may be greatly reduced, or the phenomenon of breaking between the base film and the adhesive layer may be prevented.

In addition, since the tire innerliner film does not require a large amount of additives or rubber components for improving physical properties, the manufacturing process can be simplified and the tire manufacturing cost can be reduced. Accordingly, the tire inner liner film can improve the fuel efficiency of the vehicle by reducing the weight of the tire, and maintain the proper air pressure even after long-term use, to prevent the fallover accident and fuel economy lowered caused by low air pressure, and also when driving Its excellent ability to withstand repeated fatigue ensures durability, and it is possible to manufacture tires with excellent performance even with a simple manufacturing process.

The 'copolymer of a polyamide-based resin and a polyether-based resin' refers to a copolymer of a polyamide-based resin in which polyamide-based repeating units are interposed and a polyether-based resin in which polyether- But also can encompass random copolymers of all types in which the polyamide-based repeating units and the polyether-based repeating units are bonded in any repetition number and order. For example, such a random copolymer can be obtained by copolymerizing a monomer or a precursor of the polyamide-based resin with a monomer or a precursor of the polyether-based resin, for example, a monomer or oligomers for producing them.

Some of the main characteristics of the film for a tire innerliner are that a base film obtained by copolymerizing or blending a polyether resin which gives elastomeric properties together with the polyamide resin in a specific amount range is applied see.

In the base film, the portion derived from the polyamide-based resin exhibits excellent airtightness due to its inherent molecular chain properties, for example, about 10 to 20 times higher than that of butyl rubber or the like generally used for tires at the same thickness. The modulus is not so high compared to other resins. Further, the modulus characteristic of the entire base film can be lowered due to the portion derived from the polyester resin, so that it is possible to exhibit excellent moldability in the tire manufacturing process, and the film for inner liner can be applied to the film layer It is possible to prevent an increase in the rigidity or deterioration of the mechanical properties of the substrate.

Generally, polyamide resins are known to be easily crystallized by heat, but the film for inner liners of the tire contains the polyether resin in a specific amount to inhibit the growth of crystals due to heat or external deformation in the film . Accordingly, the inner liner film is not easily crystallized by the heat generated in the tire, and the modulus or rigidity is not greatly changed even by long-term operation, and cracks that may occur during operation can be minimized.

On the other hand, the base film may have a thickness of 30 to 300 占 퐉, preferably 40 to 250 占 퐉, more preferably 40 to 200 占 퐉. Accordingly, the film for a tire inner liner of an embodiment of the present invention has a low thickness and a low air permeability, for example, an oxygen permeability of 200 cc / (m < 2 > have.

Further, as shown in Fig. 2, the base film can achieve excellent airtightness even at a lower thickness than the film for the inner liner of the prior art. Specifically, the base film can have a high airtightness even with the same thickness as the inner liner using the halobutyl rubber conventionally used in the related art, and can exhibit much better airtightness than the inner liner using natural rubber. In addition, although a general nylon 6 stretched film may exhibit high airtightness, the properties of the tire innerliner film including the base film may be deteriorated or deformed during a tire manufacturing process or an automatic running process, The change in physical properties or shape is insignificant and the moldability of the tire can be increased. 2, the abscissa represents the logarithmic scale of the film thickness, the ordinate represents the air permeability (OTR), NR represents natural rubber, Nylon film represents a general nylon 6 stretched film, Innerliner Rubber # 1 and # 2 A tire inner liner using a halobutyl rubber, and an inner liner film means a tire innerliner film of the invention.

The base film may include a copolymer of 50 to 95% by weight of a polyamide-based resin and 5 to 50% by weight of a polyether-based resin, and may contain 50 to 95% by weight of a polyamide- By weight, and may include both such copolymers and mixtures.

When the polyamide-based resin is used, excellent airtightness can be exhibited, so that the substrate film has a thin thickness and low air permeability. In addition, since a portion derived from such a polyamide-based resin exhibits a relatively high modulus as compared with other resins, even when it is mixed or copolymerized with a relatively low-content polyether-based resin or the like, It is possible to obtain a film for inner liner showing a modulus, thereby improving the moldability of the tire.

Also, Since the portion derived from the polyamide resin has sufficient heat resistance and chemical stability, it is possible to prevent deformation or denaturation of the inner liner film upon exposure to chemical substances such as high temperature conditions or additives applied in the tire manufacturing process. Since the portion derived from the polyamide-based resin can have a relatively high reactivity to a certain adhesive, for example, a resorcinol-formalin-latex (RFL) adhesive, So that the inner liner film can have sufficient fatigue resistance by preventing breakage of the interface due to heat or repetitive deformation occurring in the manufacturing process or running process of the tire.

As the component of the copolymer or the mixture, the polyamide-based resin may be contained in an amount of 50 to 95% by weight, preferably 70 to 90% by weight. When the polyamide-based resin is contained in an amount of less than 50% by weight, the density or airtightness of the base film may be lowered. When the polyamide-based resin is contained in an amount of more than 95% by weight, the modulus of the base film may be excessively high or the moldability of the tire may be deteriorated. In the high temperature environment occurring during the tire manufacturing process or the automobile running process, The amide resin can be crystallized and cracks can be generated by repeated deformation.

Examples of the polyamide resin that can be used for the base film include polyamide resins such as copolymers of nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, Nylon 6/66/610 copolymers, nylon MXD6, nylon 6T, nylon 6 / 6T copolymers, nylon 66 / PP copolymers and nylon 66 / PPS copolymers; 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.

On the other hand, in the process of forming the copolymer or the mixture of the polyamide-based resin and the polyether-based resin, a precursor of the polyamide-based resin may be used. Examples of the precursor of such a polyamide-based resin include monomers known to be used in the synthesis of the above-mentioned polyamide-based resin or oligomers thereof. For example, when the polyamide-based resin is nylon 6,? -Caprolactam may be used as a precursor thereof.

Such a polyamide-based resin may have a relative viscosity of 2.5 to 4.0. If the relative viscosity is less than 2.5, a sufficient elongation can not be secured due to a decrease in toughness, so that it may occur during tire production or automobile operation. When the relative viscosity is more than 4.0, the modulus or viscosity becomes unnecessarily high, And the like.

On the other hand, the portion derived from the polyether-based resin may exist in a state of being bonded or dispersed among the polyamide-based resins, and it may be preferable to inhibit the growth of large crystals in the substrate film during tire manufacturing process or automobile operation , It is possible to prevent the base film from breaking easily. Further, the portion derived from such a polyether-based resin can further lower the modulus of the film for a tire innerliner, so that even when a large force is applied at the time of tire formation, the tire can be stretched or deformed according to the shape of the tire Thereby making it possible to easily mold the tire. The portion derived from such a polyether-based resin can prevent the rigidity of the film from rising at a low temperature, and can prevent the inner liner film from being damaged or torn due to crystallization or repetitive deformation at a high temperature, It is possible to improve the durability of the tire or the inner liner by suppressing the occurrence of wrinkles of the film due to the permanent deformation.

As a component of the copolymer or the mixture, the polyether resin may be contained in an amount of 5 to 50% by weight, preferably 10 to 30% by weight. When the polyether resin is contained in an amount of less than 5% by weight, the modulus of the base film or the innerliner film for a tire becomes high, so that the moldability of the tire may deteriorate or the physical properties may deteriorate due to repeated deformation. When the polyether-based resin is contained in an amount of more than 50% by weight, the airtightness of the film for innerliner of the tire may be lowered and the reactivity to the adhesive may be lowered so that the innerliner is easily adhered to the carcass layer And the elasticity of the base film may increase, so that it may not be easy to produce a uniform film.

Examples of the polyether resin that can be used for the base film include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylenediamine, polyoxypropylenediamine, polyoxytetramethylenediamine, or copolymers thereof, Can be mixed and used. The weight average molecular weight of such a polyether resin may be 500 to 10,000, preferably 1,000 to 3,000. When the weight average molecular weight is less than 500, the polyether resin may not adequately suppress the growth of large crystals in the film for a tire inner liner or lower the modulus. In addition, when the weight average molecular weight is more than 10,000, the airtightness of the inner liner may be deteriorated.

In addition, in the process of forming the copolymer or the mixture of the polyamide-based resin and the polyether-based resin, the precursor of the polyether-based resin may be used. As such a precursor of the polyether-series resin, a monomer known to be used for the synthesis of the above-mentioned polyether-series resin or an oligomer thereof may be mentioned. For example, when the polyether-based resin is polyethylene glycol, oligomers of ethylene glycol or ethylene glycol may be used as the precursor thereof. In the case of polyoxyethylenediamine, ethylene glycol, ethylene glycol diamine or ethylene glycol diamine And the like can be used.

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On the other hand, the surface tension of the base film measured by ASTM D2578 may be 28 to 38 dyne / cm, preferably 30 to 36 dyne / cm. As the base film has the aforementioned surface tension, the adhesive layer may be uniformly and firmly bonded to the base film. If the surface tension of the base film is less than 28 dyne / cm, the difference in surface tension between the adhesive layer and the base film becomes large, so that the adhesive layer may be unevenly bonded to the base film or the bond strength between the base film and the adhesive layer may be deteriorated. When the surface tension of the base film is more than 38 dyne / cm, the difference in surface tension between the adhesive layer and the base film becomes large so that the adhesive layer can be unevenly bonded to the base film and the adhesive can not spread uniformly on the base film, And the aggregated adhesive may cause contamination during the manufacturing process or may reduce bonding force between the base film and the adhesive layer. The surface tension of such a base film may be a reagent index when the shape of the ACCU DYNE Test reagent (Diversified Enterprises Co., PEN TYPE reagent) applied on the film does not change.

Thus, the film for a tire innerliner can exhibit an improved adhesion to an adhesive or an adhesive layer owing to the characteristics of the base film described above, and it is not necessary to laminate an additional adhesive layer or rubber layer, and a thin and light- It can be firmly and uniformly fixed.

On the other hand, the base film may be an unstretched film. When the base film is an unstretched film, it can be suitably applied to a tire forming process in which high expansion occurs due to low modulus and high strain. 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 producing a film for a tire innerliner to be described later, a method of suppressing the orientation of the base film to the maximum, for example, a method of adjusting the viscosity through optimization of the melt extrusion temperature, The base film may be produced as an unoriented or unstretched film.

When an unoriented film is applied to the base film, the inner liner film can be easily formed into a cylindrical shape or a sheet shape in a tire manufacturing process. In particular, when the non-stretched sheet-like film is applied to the base film, it is not necessary to construct a film manufacturing facility for each tire size, and it is preferable because the impact and wrinkles applied to the film can be minimized during the transport and storage process. . In addition, when the base film is formed into a sheet shape, the step of adding an adhesive layer described later can be performed more easily, and the damage or dents that occur during the manufacturing process can be prevented due to the difference in specification from the 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 main characteristics of the above-described adhesive layer appears to include a specific resorcinol-formalin-latex (RFL) -based adhesive having a specific composition. In the past, an adhesive for tire innerliner was used, such as a rubber type tie gum, and 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. In addition, the base film and the tire carcass layer may be firmly bonded by pressing at high temperature heating conditions without increasing the thickness. 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.

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 contained in an amount of not less than 68% by weight based on the total amount of the adhesive layer for the flexibility of the material and an effective cross-linking reaction with the rubber, and not more than 98% by weight 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 20 μm or less, for example, 0.1 to 10 μm, preferably 0.2 to 7 μm, more preferably 0.3 to 5 μm, and one or both surfaces of the film for tire innerliner. It can be formed on. 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, 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.

On the other hand, the tire inner liner film may have an adhesive force of 15 to 40 kgf with respect to the tire carcass layer. This adhesion can be measured by the ASTM D 4394 method. In addition, 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 certain rubber component as a skeleton of a tire supporting a load of a vehicle body, and 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. As the tire cord included in the carcass layer, various natural fibers or rayon, nylon, polyester, kevlar, or the like may be used, and a steel cord braided with a thin wire may also be used.

On the other hand, the tire inner liner film, the adhesion to the tire carcass layer measured after the bending fatigue test according to the American Society for Testing and Materials Standard ASTM D 430 may be 10 to 40 kgf. The adhesive layer may be firmly bonded to the base film layer through constant reaction and bonding, and may be uniformly and firmly fixed to the tire carcass layer. The adhesive layer may be resorcinol-formalin-latex (RFL) of the specific component. By including the system adhesive, it is excellent in the ability to withstand repetitive shear force at high temperature, and the deterioration of the adhesive force or mechanical properties is small. Accordingly, the tire inner liner film including the base film and the adhesive layer may have excellent bending fatigue characteristics, and the inner liner film may break due to shear force that may occur between tire layers during driving of a vehicle (or during a tire manufacturing process). Interface breakage of the adhesive layer can be minimized or prevented.

On the other hand, the base film, a polyamide (poly-amide) segment; And a copolymer comprising 5 to 50% by weight of a poly-ether based segment based on the total weight of the film.

Accordingly, the film for inner liner can be distinguished from a film for a prior tire inner liner having a rubber component or a thermoplastic resin as a main component of the substrate, and does not require an additional vulcanizer . The term " substrate of the film " refers to a substrate of a resin or a rubber component that retains the shape of the film except for an additional dispersion component such as an additive in the film for a tire innerliner. The base material often contains various rubber components or resin components. By the way, the tire inner liner film according to an embodiment of the invention may include a polyamide-based resin and the like with the copolymer as a base material, but may also include only the copolymer, in this case other resin or rubber component It may not substantially include.

The polyamide segment may be a main repeating unit included in the polyamide resin described above. Specifically, the polyamide segment may include a repeating unit of Formula 1 or Formula 2.

[Chemical Formula 1]

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

(2)

R ₂ is a linear or branched alkylene group having 1 to 20 carbon atoms and R ₃ is a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched alkylaryl group having 7 to 20 carbon atoms It can be a ring.

In the present specification, an alkylene group means a divalent functional group derived from an alkyl group, and an arylalkylene group means a divalent functional group derived from an alkyl group into which an aryl group is introduced .

The polyether-based segment may be a main repeating unit included in the polyether-based resin described above. The polyether segment refers to a repeating unit including an alkyl oxide ('-Akyl-O-') group, and may be formed from a polyether resin or a precursor thereof that participates in a polymerization reaction. Specifically, the polyether-based segment may include a repeating unit represented by the following formula (5).

[Chemical Formula 5]

In Formula _5, R 5 may be an alkylene group of a straight-chain or branched-chain having 1 to 10, n can be an integer from 1 to 100. R ₆ and R ₇ may be the same or different from each other and may be a direct bond, -O-, -NH-, -COO- or -CONH-.

The tire innerliner film may further include a polyamide-based resin in order to improve mechanical properties or airtightness. Such polyamide-based resin may be present on the film in a mixed state or copolymerized state with the copolymer of the polyamide-based segment and the polyether-based segment described above. As shown in the manufacturing method to be described later, the polyamide-based resin may be included in the tire innerliner film by mixing with the copolymer of the polyamide-based segment and the polyether-based segment, and then melted and extruded.

The polyamide-based resin that may be further included may be used to improve mechanical properties such as heat resistance or chemical stability and airtightness of the film for a tire innerliner, but if the amount used is too large, The characteristics of the film for use can be deteriorated. In particular, even when the polyamide-based resin is further used, the total amount of the polyether-based segment or the polyamide-based resin in the film should be maintained at 5 to 50 wt% The sum of the content of the polyamide-based segment and other additives to be added should be 50 to 95% by weight.

The further usable polyamide based resin is not particularly limited and it is preferable to use a polyamide based resin containing the same or similar repeating unit as the polyamide based segment in order to improve compatibility with the copolymer .

On the other hand, according to another embodiment of the present invention, there is provided a process for producing a polyamide-based resin, comprising: forming a copolymer or a mixture of 50 to 95% by weight of a polyamide-based resin and 5 to 50% Melting and extruding the copolymer or mixture to form a base film having a thickness of 30 to 300 μm; And forming an adhesive layer comprising an adhesive containing at least one surface of the condensate of resorcinol and formaldehyde and at least one surface of the base film layer, wherein the adhesive layer comprises from 2 to 32% by weight of condensate and from 68 to 98% by weight of latex. The manufacturing method of the film for may be provided.

According to the manufacturing method, not only excellent thickness and high air pressure retention performance can be realized even at a thin thickness, but also the base film exhibits high reactivity with a certain adhesive, so that the thin and light weight adhesive layer can be applied to the inside of the tire. A film for a tire innerliner can be provided that can be firmly and uniformly coupled and can be easily elongated or deformed even when a small force is applied during tire forming, thereby exhibiting excellent molding properties and improved fatigue resistance.

In addition, the base film may have high reactivity with the resorcinol-formalin-latex (RFL) -based adhesive having the specific composition due to the characteristic chemical structure, and the resorcinol-formalin-latex (RFL) having the specific composition. The adhesive can exhibit high and uniform adhesion to the tire carcass layer, and is a tire manufacturing process in which a high temperature deformation or stretching step is applied. The breakage phenomenon between the inner layers can be prevented.

As described above, the tire innerliner film may have an adhesive force to the tire carcass layer measured by the ASTM D 4394 method of 15 to 40 kgf, and the tire carcass layer measured after the bending fatigue test according to ASTM D 430. Adhesion to can be 10 to 40 kgf. In addition, the surface tension of the base film may be 28 to 38 dyne / cm when measured by ASTM D2578. More specific information on the adhesion force and the surface tension after the adhesive force, bending fatigue test of the surface of the base film is as described above.

The step of forming a copolymer or mixture of 50 to 95% by weight of the polyamide-based resin and 5 to 50% by weight of the polyether-based resin is carried out by mixing 50 to 95% by weight of the polyamide-based resin or its precursor and the polyether- And 5 to 50% by weight of the precursor may be polymerized or mixed.

The step of forming such a copolymer or the mixture may change the reaction conditions depending on the specific type of resin or precursor used. For example, an acidic condition and a nitrogen atmosphere can be applied to the step of reacting a monomer (for example,? -Caprolactam, etc.) of a polyamide resin, and the polyamide-based resin or a precursor thereof; And the step of polymerizing the polyether resin may include a step of heating or melting at a temperature of 50 DEG C or more and may include a step of increasing or decreasing the pressure depending on the reaction step.

Meanwhile, various mixing, blending, or compounding methods known to be usable for mixing the polymer resin may be used for mixing the polyamide-based resin or the precursor thereof and the polyether-based resin or the precursor thereof without any particular limitation. In addition, the polymerization reaction of the polyamide-based resin or precursors thereof and polyether-based resins or precursors thereof may be used without any limitation. .

Specific details regarding the polyamide-based resin or its precursor and polyether-based resin or its precursor are as described above.

The temperature at which the copolymer or mixture of the polyamide-based resin or precursor thereof and the polyether-based resin or precursor thereof is melted may be 230 to 300 ° C, preferably 240 to 280 ° C. The melting temperature should be higher than the melting point of the polyamide compound, but if it is too high, carbonization or decomposition may occur and the physical properties of the film may be impaired, and bonding between the polyether resins may occur or orientation may occur in the direction of the fiber arrangement. It may be disadvantageous for producing a film.

On the other hand, the base film of the film for tire innerliner can be obtained by manufacturing the result of the melt extrusion step into an unstretched film having a thickness of 30 to 200 ㎛. The thickness of the extrudate can be adjusted according to the specifications of the apparatus such as the extruder used. In order to form an unstretched film, a method of adjusting the melt viscosity of the melt by adjusting the melt extrusion temperature, adjusting the discharge amount of the melt, changing the specification of the die, or controlling the winding speed of the film have.

For example, the Lip Opening of the retaining die can be set to around 1 mm, and the too narrowing of the Lip Opening may be undesirable because the pressure applied to the die shear may be too high. In addition, it is desirable that the winding speed of the film is maintained at a proper speed in order to prevent problems of poor cooling and increase in orientation. For example, it is preferable to set the speed at 100 m / min or less, preferably 50 m / min or less Can be applied.

In addition, the method for producing a film for a tire innerliner includes the step of forming an adhesive layer including a resorcinol-formalin-latex (RFL) -based adhesive on at least one surface of the film after the film step formation by the melt extrusion .

The step of forming the adhesive layer may be performed by coating a resorcinol-formalin-latex (RFL) -based adhesive on one surface or both surfaces of the substrate film formed above, followed by drying, Mu] m, preferably 0.1 to 10 [mu] m. 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.

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.

On the other hand, in the step of forming the copolymer or the mixture, or in the step of melting and extruding the copolymer, an additive 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 realize excellent airtightness even at a thin thickness, to reduce the weight of the tire and improve the fuel economy of the vehicle, to be firmly coupled to the tire carcass layer, and to exhibit excellent formability and fatigue resistance characteristics. A film for tire innerliner may be provided.

1 schematically shows the structure of a tire.
2 schematically shows the air permeability according to the material and thickness of the inner liner.

The invention will be described 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.

* In the following Examples and Comparative Examples, the thickness of the base film was measured using a gauge tester MITSUSTOYO Co., Ltd. The thickness of the adhesive layer was measured five times using FE-SEM instrument (JEOL) And the average value of the obtained results.

< Example : tire For inner liner  Manufacturing of Film>

One. Example  One

(1) Production of base film

60 wt% of a polyamide resin (nylon 6) having a relative viscosity of 3.4 and 40 wt% of a polyamide elastomer resin having a weight average molecular weight of 100,000 (a copolymer resin using 50 wt% of nylon 6 and polyoxyethylene glycol, respectively) And extruded into an annular die at a temperature of 260 ° C to prepare an unoriented base film having a thickness of 80 μm at a speed of 30 m / min without passing through the stretching and heat treatment sections.

(2) Preparation of Adhesive Layer Composition

Resorcinol and formaldehyde were mixed in a molar ratio of 1: 2, and then condensed to obtain a condensate of resorcinol and formaldehyde.

12% by weight of the condensate of resorcinol and formaldehyde and 88% by weight of styrene / 1,3-butadiene / vinylpyridine latex were mixed to obtain a mixture of resorcinol / formaldehyde / latex having a concentration of 20%.

(3) Manufacture of tire innerliner film

The resorcinol-formalin-latex (RFL) adhesive layer composition was applied to both surfaces of the substrate film (200 mm x 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 an adhesive layer having a thickness of 1.0 μm formed on both sides of the base film.

2. Example  2

A film for a tire innerliner was produced in the same manner as in Example 1, except that the components of the polyamide-based resin and the polyamide-based elastomer resin were used in amounts of 50% by weight and 50% by weight, respectively .

3. Example  3

It was found that the content of the condensation product of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex in the adhesive layer composition were changed to 15% by weight and 85% by weight, respectively, , A film for a tire innerliner was produced in the same manner as in Example 1.

4. Example  4

The content of styrene / butadiene-1,3 / vinylpyridine latex was varied to 15% by weight and 85% by weight respectively in the adhesive layer composition and the content of resorcinol / formaldehyde / latex mixture A film for a tire inner liner was prepared in the same manner as in Example 1 except that the concentration was changed to 25% and the adhesive layer was formed to a thickness of 1.6 탆.

5. Example  5

The content of styrene / butadiene-1,3 / vinylpyridine latex was varied to 15% by weight and 85% by weight respectively in the adhesive layer composition and the content of resorcinol / formaldehyde / latex mixture A film for a tire inner liner was prepared in the same manner as in Example 1 except that the concentration was changed to 30% and the adhesive layer was formed to a thickness of 2.0 탆.

6. Example  6

(1) Production of base film

A mole number of adipic acid such as polyoxyethylene diamine was mixed with a mixture of 70 wt% of? -Caprolactam and 30 wt% of polyoxyethylene diamine (Mw 1000) for resin polymerization for a base film, And then melted in a nitrogen atmosphere at 100 캜 for 30 minutes. The melt was heated at 250 ° C. for 3 hours and elevated to 8 kg / cm 2 to maintain pressure. Then, the pressure was reduced to 1 kg / cm 2 for 1 hour.

After the pressure-sensitive melt was prepared in a chip shape, the prepared chip was extruded into an annular die at a temperature of 260 ° C. to obtain a 100 탆 thick unstretched substrate film at a speed of 30 m / min without undergoing a 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 condensed to obtain a condensate of resorcinol and formaldehyde.

12% by weight of the condensate of resorcinol and formaldehyde and 88% by weight of styrene / butadiene-1,3 / vinylpyridine latex were mixed to obtain a mixture of resorcinol / formaldehyde / latex having a concentration of 20%.

(3) Manufacture of tire innerliner film

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

7. Example  7

A film for a tire inner liner was produced in the same manner as in Example 6, except that a mixture of 60 wt% of? -Caprolactam and 40 wt% of polyoxyethylene diamine (Mw 1,000) Respectively.

8. Example  8

Butadiene-1,3-vinylpyridine latex was changed to 15% by weight and 85% by weight, respectively, and the adhesive layer was formed to have an adhesive layer with a thickness of 0.6 탆 in the adhesive layer composition and the condensation product of resorcinol and formaldehyde and styrene / , A film for a tire inner liner was produced in the same manner as in Example 6. [

9. Example  9

The condensate of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex in the adhesive layer composition were varied to 15% and 85% by weight, respectively, and the mixture of the resorcinol / formaldehyde / latex A tire inner liner film was manufactured in the same manner as in Example 6 except that the concentration was changed to 25% and the adhesive layer was formed to a thickness of 0.9 μm.

10. Example  10

The condensate of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex in the adhesive layer composition were varied to 15% and 85% by weight, respectively, A tire inner liner film was manufactured in the same manner as in Example 6 except that the concentration was changed to 30% and the adhesive layer was formed to a thickness of 0.9 μm.

< Comparative Example : tire For inner liner  Manufacturing of Film>

One. Comparative Example  One

Except that the content of? -Caprolactam and polyoxyethylene diamine (Mw 1,000) was used in an amount of 30 wt% and 70 wt%, respectively, in the production process of the substrate film, Lt; / RTI &gt;

2. Comparative Example  2

The condensate of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex in the adhesive layer composition were varied to 35% and 65% by weight, respectively, and the mixture of the resorcinol / formaldehyde / latex A tire inner liner film was manufactured in the same manner as in Example 1 except that the concentration was changed to 30% and the adhesive layer was formed to a thickness of 9.0 μm.

3. Comparative Example  3

A tire inner liner film was manufactured in the same manner as in Comparative Example 2, except that the thickness of the adhesive layer was changed to 12 μm.

4. Comparative Example  4

The condensate of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex in the adhesive layer composition were varied to 35% and 65% by weight, respectively, and the mixture of the resorcinol / formaldehyde / latex A tire inner liner film was manufactured in the same manner as in Example 6 except that the concentration was changed to 30% and the adhesive layer was formed to a thickness of 9.0 μm.

5. Comparative Example  5

In the adhesive layer composition, the content of the condensate of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex were changed to 40% by weight and 60% by weight, respectively, and a mixture of resorcinol / formaldehyde / latex was used. Except for varying the concentration to 30%, except that the adhesive layer was formed to a thickness of 12.0㎛, a film for tire innerliner was prepared in the same manner as in Example 6.

6. Comparative Example  6

The content of the condensate of resorcinol and formaldehyde and the content of styrene / butadiene-1,3 / vinylpyridine latex in the adhesive layer composition was varied to 1% by weight and 99% by weight, respectively, and to the mixture of resorcinol / formaldehyde / latex. A tire inner liner film was manufactured in the same manner as in Example 6 except that the concentration was changed to 20% and the adhesive layer was formed to a thickness of 0.05 μm.

< Experimental Example : tire For inner liner  Measurement of physical properties of film>

delete

Experimental Example 2 . Measurement of surface tension of base film

The surface tension of the base films obtained in Examples 1 to 10 and Comparative Example 1 was measured by ASTM standard D2578. Specifically, after moistening a test reagent ACCU DYNE Test reagent (Diversified Enterprises, PEN TYPE reagent) on a cotton swab, and then lined the 5cm horizontal line on the surface of the substrate film obtained in the above Examples and Comparative Examples and then the shape of the solution for 5 seconds The surface tension was measured by observing the change of. If there was no change in the shape of the test reagent on the film, it was determined that the surface tension of the solution and the surface tension of the film were the same.

The results of 2 are shown in Table 1 below.

Measurement result of Experimental Example 2 division thickness
(탆) Surface tension
(dyne / cm ² ) Example 1 80 33 Example 2 80 35 Example 3 80 33 Example 4 80 33 Example 5 80 33 Example 6 100 32 Example 7 100 35 Example 8 100 32 Example 9 100 32 Example 10 100 32 Comparative Example 1 100 38

As shown in Table 1, the tire innerliner film of the embodiment exhibits a low surface tension of the surface tension with the adhesive so that the adhesive has a good spreadability on the surface of the base film to form a uniform adhesive layer, thereby providing excellent and uniform adhesion. It can have an effect of securing. In addition, the base film of the embodiment may have a high reactivity to a certain adhesive, it can be firmly and uniformly bonded to the tire carcass layer, and thus, even in a vehicle driving process subjected to repeated physical deformation for a long time with excellent adhesive properties Improved fatigue resistance can be realized to minimize changes in physical properties.

Experimental Example  3. Tire For inner liner  Adhesion of film Peel - Test ) Measure

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

Specifically, 1.6 mm rubber sheet, cord paper, the tire inner liner film, 1.6 mm rubber sheet, cord paper, 1.6 mm rubber sheet was laminated in this order, 150 ℃ at a pressure of 60 kg / cm ² Vulcanized at 30 minutes. Thereafter, the vulcanized sample was cut and cut to a width of 1 inch.

At this time, the 1.6 mm rubber sheet, cord paper, 1.6 mm rubber sheet to form a carcass layer, the rubber sheet was prepared using a rubber composition of the composition as shown in Table 2 below .

Composition of rubber sheet ingredient Content (parts by weight) caoutchouc 100 Zinc oxide 3 Carbon black 29.8 Stearic acid 2.0 Pin Tar 7.0 Mercaptobenzothiazole 1.25 sulfur 3.0 Diphenylguanidine 0.15 Phenylbetanaphthalamine 1.0 Sum 147.2

The cut sample was peeled off at 25 ° C. at a rate of 300 mm / min using a universal testing machine (Instron Co., Ltd.) to measure the adhesive force (kgf) of the innerliner film to the carcass layer. At this time, the average value of the load which arises at the time of peeling was calculated by adhesive force.

In addition, the standard deviation of the adhesive force was calculated according to the following formula (1).

[Equation 1]

In the formula, χ _i is the adhesive force of the sample, m is the average of the adhesive force, n is the number of samples.

Experimental Example  4. Tire For inner liner  Adhesion measurement after flexural fatigue test of film

The flexural fatigue test (Dynamic Fatigue test), which is a test for evaluating the fatigue resistance of the cord by repeatedly applying a bending strain to the films for tire innerliners obtained in the above Examples and Comparative Examples, was performed.

Specifically, according to the method of the American Society for Testing and Materials of Standard ASTM D 430, after the test piece length 250 mm and width 25 mm for the film for the inner tire liner, the bending fatigue test device (FT-4110, Ueshima Co.) Flexural fatigue tests were performed. At this time, the diameter of the friction roller was 25 mm, after treatment for 8 hours at a load 68 kgf, fatigue cycle 200 rpm at 80 ° C for 8 hours, the adhesion between the carcass layer and the film for the inner liner was measured. At this time, the average value of the load generated during peeling in the fatigue region of 40 mm by the friction roller was calculated as the adhesive force. The number of measurements was calculated by averaging three times.

The results measured in Experimental Examples 3 and 4 are shown in Table 3 below.

Results of Experimental Examples 3 and 4 division Adhesion evaluation Flexural Fatigue Test Evaluation / Adhesion (kgf) Adhesion
(kgf) Standard
Deviation Example 1 25.8 1.3 20.8 Example 2 22.4 1.9 18.9 Example 3 28.0 2.1 26.5 Example 4 31.4 2.1 16.5 Example 5 30.8 2.5 16.3 Example 6 24.2 1.5 22.7 Example 7 22.9 1.6 18.4 Example 8 27.0 1.8 24.7 Example 9 35.5 2.3 19.4 Example 10 32.4 2.8 18.8 Comparative Example 1 15.9 2.8 6.5 Comparative Example 2 22.2 6.0 Fracture Comparative Example 3 21.8 6.5 Fracture Comparative Example 4 23.5 5.5 Fracture Comparative Example 5 14.5 5.2 Fracture Comparative Example 6 8.6 1.5 Fracture

As shown in Table 3, the film for the tire innerliner of the example showed that the adhesive strength to the tire carcass layer measured by the American Material Testing Association standard ASTM D 4394 method was 20 kgf or more, and the standard deviation of the adhesive force was 1.3. To 2.8, a very uniform adhesive force distribution is shown. Accordingly, it was confirmed that the film for tire innerliner of the example can be bonded very uniformly and firmly to the tire carcass layer.

In addition, the adhesive force measured after the bending fatigue test also appeared to be more than 15 kgf, it was shown that the adhesion properties do not significantly decrease even in the long-term repeated deformation. That is, it was confirmed that the film for the tire innerliner of the example did not significantly degrade the adhesive property or fatigue resistance even during the tire manufacturing process to which the high temperature deformation / settling step was applied or the vehicle driving process to which the physical deformation was repeatedly applied for a long time.

On the other hand, it was confirmed that the film for tire innerliner of the comparative example was relatively low in adhesive force measured by the American Society for Testing and Materials Standard ASTM D 4394 method compared with the film for tire innerliner of the example. In addition, the film for the tire innerliner of the comparative example was measured after the bending fatigue test 10kgf or less, or the adhesive specimen was broken, which means that the retention of adhesion strength in case of repeated physical deformation for a long time is significantly reduced.

In addition, the tire innerliner film of Comparative Examples 2 to 4, the adhesive strength measured by the American Society for Testing and Materials Standard ASTM D 4394 method ranges from about 21.8 to 28.7 kgf, but the standard deviation of the adhesive force is about 5 to 6.5. It can be seen that it was not uniformly adhered to the tire carcass layer.

Experimental Example  5. Air Permeability Experiment

The air permeabilities of the base films obtained in Examples 1 to 2 and 6 to 7 were measured using an Oxygen Permeation Analyzer (Model 8000, manufactured by Illinois Instruments) by ASTM D 3895 under the atmosphere of 25 degrees and 60 RH%.

And the measurement results are shown in Table 4 below.

Air permeability measurement result division Air permeability
(cc / m &lt; 2 &gt; * 24hr * atm) Example 1 150 Example 2 165 Example 6 111 Example 7 145

As shown in Table 4, the film for the tire inner liner of the embodiment exhibits air permeability of 200 cc / m 2 * 24hr * atm or less, so that excellent airtightness can be realized even at a thin thickness, and the force is not so great during tire manufacturing. It can be easily stretched or deformed even if it is added, and it is confirmed that the moldability of the green tire or the final tire is excellent.

Tread
2. shoulder
3. Side Wall
4. CAP PLY
5. Belt
6. Body Ply
7. Inner Liner
8. Apex
9. BEAD

Claims (15)

A base film having a thickness of 30 to 300 μm comprising a polyamide based segment and a copolymer including 5 to 50 wt% of a polyether based segment and a polyamide based resin based on the total weight of the film; And
An adhesive layer comprising an adhesive comprising 2 to 32% by weight of a condensate of resorcinol and formaldehyde and 68 to 98% by weight of latex.
The method of claim 1,
The adhesive layer is formed on at least one surface of the base film, the film for tire innerliner having a thickness of 0.1 to 20 ㎛.
The method of claim 1,
A film for tire innerliner having an adhesion of 15 to 40 kgf to the tire carcass layer measured by the ASTM D 4394 method.
The method of claim 1,
A film for tire innerliner having an adhesion of 10 to 40 kgf to a tire carcass layer measured after a flexural fatigue test according to ASTM D 430.
The method of claim 1,
A film for tire innerliner, wherein the polyamide-based segment comprises a repeating unit represented by the following Chemical Formula 1 or Chemical Formula 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,
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,
Wherein the polyether-based segment comprises a repeating unit represented by the following formula (5):
[Chemical Formula 5]

In Chemical Formula 5,
R ₅ is a linear or branched alkylene group having 1 to 10 carbon atoms,
n is an integer from 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.
The method of claim 1,
The surface tension of the base film measured by ASTM D2578 is 28 to 38 dyne / cm.
The method of claim 1,
Wherein the base film is an unstretched film.
The method of claim 1,
The condensation molar ratio of the resorcinol and formaldehyde is 1: 0.3 to 1: 3.0 film for tire innerliner.
Mixing a polyamide-based copolymer with a polyamide-based segment and a polyether-based segment;
Melting and extruding the result of the mixing at 230 ° C. to 300 ° C. to form a base film having a thickness of 30 to 300 μm; And
Forming an adhesive layer on the at least one surface of the base film layer, the adhesive layer comprising an adhesive containing 2 to 32% by weight of a condensate of resorcinol and formaldehyde and 68 to 98% by weight of a latex,
Wherein the base film layer comprises 5 wt% to 50 wt% of the polyether-based segment in the total weight;
The manufacturing method of the film for tire innerliners of Claim 1.
delete delete 12. The method of claim 11,
Wherein the base film is an unstretched film.
12. The method of claim 11,
The adhesive layer is a method for producing a film for tire innerliner having a thickness of 0.1 to 20 ㎛.

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