JP2008274074A - Easily adhesive polyester film or polyester film for easy rubber adhesion and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an easily adhesive polyester film having excellent adhesiveness to a rubber and adhesion durability and a laminate that is obtained by laminating the rubber to the easily adhesive polyester film and has excellent elasticity and sealability. <P>SOLUTION: The easily adhesive polyester film is obtained by forming an adhesive layer (a) containing a polyamide-imide-based resin having a polyacrylonitrile butadiene structure in the molecule on one side of a polyester film orientated in at least a uniaxial direction. The laminate is obtained by laminating rubber through the adhesive layer (a) to the easily adhesive polyester film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an easily-adhesive polyester film used by being bonded to a resin, particularly rubber, and a laminate obtained by bonding the film and rubber. More specifically, the present invention relates to an easily-adhesive polyester film excellent in adhesiveness and adhesion durability with a resin, particularly rubber, and a laminate excellent in elasticity and sealing properties obtained by bonding a resin, particularly rubber, to the film. .

  Since rubber has excellent elasticity, it is used for sealing materials and cushion materials in a wide range of industrial fields. However, since the rubber film is flexible, it is inferior in workability when incorporated in an apparatus or a part. On the other hand, plastic base materials such as polyester film are harder than rubber, have good dimensional stability, have excellent workability when incorporated into equipment and parts, and have good sliding properties. It is used in. However, plastic films are generally unsuitable as sealing materials and cushioning materials because of their low elasticity and sealing properties.

As a method for solving the above problems, a composite body in which various films such as a polyester film and a rubber film are bonded together has been proposed. (For example, see Patent Documents 1 and 2)
The polyester film is excellent in heat resistance, dimensional stability and the like, and is excellent in economic efficiency, and is suitable as a base film for a composite with the rubber. A composite in which a film is bonded to a rubber film via an adhesive is disclosed. However, an epoxy resin is used as the composite adhesive disclosed in the examples of the patent document, and the adhesiveness between the rubber layer and the adhesive interface is insufficient.

  As one of the uses of the rubber composite, it may be used as a constituent member of various molded products. By using a rubber composite as the member, distortion generated in the molding of the molded body can be relaxed by utilizing the elasticity of the rubber. For example, the surface state of the molded body can be improved. In addition, the external force applied to the molded body in the use of the molded body can be relaxed by the elasticity of the rubber, and as a result, for example, it is possible to impart effects such as improving the durability of the molded body. .

  In the use method as described above, the rubber composite requires high moldability and high adhesion between the rubber and the polyester film in the rubber composite.

  Further, as one of the above usage methods, there is a case where a rubber composite is used in combination with the surface of the molded body, and in one of the usage methods, the polyester film side is incorporated into the molded body as the outermost layer, and the polyester is used. There are cases where printing, painting, or laminating metal thin films or metal foils on the surface of the film by vapor deposition or laminating methods. By the correspondence, the effect of reducing the gas permeability of the surface of the molded body and oxygen gas, water vapor and the like can be exhibited.

  In this method of use, the adhesive layer at the interface between the rubber and the polyester film is eroded by the solvent used in printing, painting, laminating, etc., and the adhesiveness is lowered. In addition, the molded body may be used under severe conditions such as outdoor use, and it is necessary to maintain excellent adhesion between rubber and polyester film even under the severe conditions. Is done.

JP 2001-322167 A JP 2001-330881 A

  An object of the present invention is to provide an easily adhesive polyester film excellent in adhesiveness and adhesion durability with a resin, particularly rubber, and a resin, particularly rubber, bonded to the easily adhesive polyester film. The object is to provide an excellent laminate.

  The easily-adhesive polyester film of the present invention that can solve the above-mentioned problems and the laminate obtained by bonding it to rubber have the following constitution.

  (1) An easily adhesive polyester film in which an adhesive layer (a) containing a polyamidoimide resin having a polyacrylonitrile butadiene structure in the molecule is formed on at least one surface of a film oriented in a uniaxial direction.

  (2) A laminate obtained by bonding rubber and the above-mentioned easily adhesive polyester film via the adhesive layer (a).

  The easy-adhesive polyester film particularly suitable for bonding to rubber according to the present invention forms an adhesive layer (a) having a polyacrylonitrile butadiene (hereinafter sometimes abbreviated as NBR) structure in the molecule. , Improved affinity at the interface with rubber, resulting in excellent adhesion, and a polyamide-imide skeleton, resulting in good solvent resistance and heat resistance, and excellent adhesion durability .

The easy-adhesive polyester film of the present invention comprises a polyamideimide resin having a polyacrylonitrile butadiene (NBR) structure in the molecule on one side of the base material, the base film being a polyester film oriented in at least uniaxial direction. (A) is formed.
Moreover, the laminated body of this invention consists of a structure which bonded rubber | gum and the easily-adhesive polyester film through the contact bonding layer (a).
Hereinafter, the easily adhesive polyester film and the laminate will be described in detail.

(1) Easy-adhesive polyester film (i) Base material First, the raw material of the polyester film used as a base material by this invention is demonstrated.
The polyester constituting the polyester film of the base material contains ethylene glycol and terephthalic acid as main components. As long as the object of the present invention is not impaired, a dicarboxylic acid component other than terephthalic acid or a glycol component other than ethylene glycol may be copolymerized within a range of 15 mol% or less.

  Examples of dicarboxylic acid components other than terephthalic acid include isophthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxybenzophenone, bis- (4-carboxyphenylethane), adipine Examples include acid, sebacic acid, 5-sodium sulfoisophthalic acid, cyclohexane-1,4-dicarboxylic acid, and the like.

  Examples of glycol components other than ethylene glycol include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, ethylene oxide adducts such as bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, oxycarboxylic acid components such as p-oxybenzoic acid can also be used.

  The polyester may contain fine particles in order to impart functions such as handling properties (sliding property, blocking resistance, winding property, etc.) and scratch resistance. Examples of the fine particles include known inorganic fine particles and heat-resistant resin fine particles.

  Examples of the inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate. Examples of the heat-resistant resin fine particles include crosslinked PMMA particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. The average particle diameter of the fine particles is appropriately selected within the range of 0.05 to 2.0 μm as necessary.

  Furthermore, in the polyester forming the film, various additives such as a wax, an antioxidant, an antistatic agent, a crystal nucleating agent, and a viscosity reducing agent are used depending on the function required for the intended use. , Heat stabilizers, coloring pigments, anti-coloring agents, ultraviolet absorbers and the like can be contained.

Next, the manufacturing method of the polyester film of a base material is demonstrated.
In the present invention, the polyester film of the substrate is a film stretched and oriented in at least a uniaxial direction, and a biaxially stretched polyester film is particularly preferable. Hereinafter, a method for producing a biaxially stretched polyester film will be described as a representative example.

  The polyester film is obtained by sequentially or sequentially converting an unstretched film (unstretched laminated film or unstretched laminated sheet) obtained by melting and extruding a polyester chip as a raw material in the longitudinal direction (longitudinal direction) and the transverse direction (width direction). At the same time, the film is biaxially stretched, then heat-set, and wound into a roll.

  As a method for obtaining an unstretched sheet, polyethylene terephthalate-based resin pellets containing fine particles for the purpose of imparting slipperiness are sufficiently dried, then supplied to an extruder, and melt-extruded into a sheet at about 285 ° C. A method of cooling and solidifying the molten sheet with a cooling roll can be suitably employed.

  In addition, a well-known method can be applied to rapidly cool an unstretched sheet while bringing the sheet-like melt into close contact with the rotary cooling drum. For example, a method of using an air knife on the sheet-like melt or an electrostatic charge can be applied. A method of imprinting is preferably applicable. In those methods, the latter is preferably used.

  As a method for cooling the air surface of the sheet-like material, a known method can be applied. For example, a method in which the sheet surface is brought into contact with the cooling liquid in the tank, and a liquid that is evaporated by a spray nozzle on the sheet air surface. You may use together the method of apply | coating, and the method of spraying a high-speed airflow and cooling. The unstretched sheet thus obtained is stretched in the biaxial direction to obtain a film.

  As a method of stretching the film in the biaxial direction, the obtained unstretched sheet is stretched in the longitudinal direction by a roll or a tenter-type stretching machine, and then stretched in the width direction orthogonal to the first-stage stretching direction. A sequential biaxial stretching method or a simultaneous biaxial stretching method of a pantograph type or a linear motor drive type is preferable.

Hereinafter, the sequential biaxial stretching method will be described as a representative example.
In the stretching in the longitudinal direction, the stretching temperature is 75 to 120 ° C., and the stretching ratio in the longitudinal direction is 2.5 to 4.5 times, preferably 3.0 to 4.3 times. If the stretching temperature in the longitudinal direction is less than 75 ° C., the film tends to break, which is not preferable. On the other hand, when the temperature exceeds 120 ° C., the thickness unevenness of the obtained film is deteriorated, which is not preferable. When the draw ratio in the longitudinal direction is less than 2.5 times, the flatness of the obtained film is deteriorated, which is not preferable. On the other hand, if it exceeds 4.6 times, the orientation in the longitudinal direction becomes strong, and the frequency of breakage increases in stretching in the transverse direction, which is not preferable.

  When stretching in the width direction, the stretching temperature is 80 to 210 ° C, preferably 130 to 200 ° C. If the stretching temperature in the width direction is less than 80 ° C., the film tends to break, which is not preferable. Moreover, when it exceeds 210 degreeC, since the planarity of the obtained film worsens, it is not preferable. The draw ratio in the width direction is 3.0 to 5.0 times, preferably 3.6 to 4.8 times. If the draw ratio in the width direction is less than 3.0 times, the thickness unevenness of the obtained film is deteriorated, which is not preferable. If the draw ratio in the width direction exceeds 5.0 times, the frequency of breaking increases in the drawing, which is not preferable.

  Subsequently, heat setting is performed. The temperature in the heat setting treatment step is preferably 180 ° C. or higher and 240 ° C. or lower. If the temperature of the heat setting treatment is less than 180 ° C., the absolute value of the heat shrinkage rate is increased, which is not preferable. On the other hand, if the temperature of the heat setting treatment exceeds 240 ° C., the film tends to become opaque and the frequency of breakage increases, which is not preferable.

  Moreover, in order to give functionality to a film, it is good also as a laminated polyester film which has a multilayer structure of two or more layers. If the surface on which the slippery layer or the adhesive layer is applied is the A layer, the opposite surface is the B layer, and the other surface is the C layer, the layer structure in the film thickness direction is A / B, A / C / B, or Examples of the configuration include A / C / E / D / B. The layers A to E may be made of the same material or different materials.

  The thickness of the polyester film used as the substrate in the present invention is, for example, 20 μm or more and 400 μm or less, and is set to an appropriate thickness within the above thickness range depending on the application.

(Ii) Adhesive layer (a)
As for the easily-adhesive polyester film of this invention, an adhesive layer (a) is formed in the single side | surface of the polyester film of the said base material. This adhesive layer (a) is designed with an adhesive resin so that excellent adhesion and adhesion durability can be obtained especially when bonded to rubber.

  In the present invention, the adhesive resin used for the adhesive layer (a) is characterized in that it contains a polyamidoimide resin having a polyacrylonitrile butadiene (NBR) structure in the molecule. In the present invention, the ratio of the NBR structure of the polyamideimide resin is preferably 10% by mass to 60% by mass when the entire polyamideimide resin is 100% by mass.

  The lower limit of the NBR structure ratio of the polyamide-imide resin is more preferably 20% by mass, and the upper limit is more preferably 50% by mass. By setting the ratio of the NBR structure to the entire polyamideimide resin to 10% by mass or more, the affinity between the rubber and the adhesive layer (a) becomes sufficient, and excellent adhesiveness can be stably expressed. On the other hand, by setting the ratio of the NBR structure to the whole polyamideimide resin to 50% by mass or less, it is possible to suppress a decrease in solvent resistance of the adhesive layer (a) due to a decrease in the polyamideimide skeleton, and further, rubber and polyester Excellent adhesion at the interface with the film can be maintained.

  The “polyamideimide resin” described in the present invention includes not only those having both an amide bond and an imide bond in the molecule, but also a resin containing other bonding groups such as a slight urethane bond, urea bond, and ester bond. When the total number of functional groups is 100%, the total number of amide bonds and imide bonds is preferably 60% or more from the viewpoint of enhancing durable adhesion and solvent resistance. More preferably, it is 70% or more.

  The polyamideimide resin can be produced by a known method such as an acid chloride method or an isocyanate method.

  In addition to trimellitic acid and its anhydride and chloride, pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylether Tetracarboxylic acids such as tetracarboxylic acid, ethylene glycol bis trimellitate and propylene glycol bis trimellitate and their anhydrides, oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, di Aliphatic dicarboxylic acids such as carboxypoly (acrylonitrile-butadiene), dicaluboxypoly (styrene-butadiene), 1,4-cyclohexanedicarboxylic acid, 1,3cyclohexanedicarboxylic acid, 4,4′-di Black hexyl methane dicarboxylic acid, alicyclic dicarboxylic acids such as dimer acid, terephthalic acid, isophthalic acid, diphenyl sulfone dicarboxylic acid, diphenylether dicarboxylic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.

  Among these, trimellitic anhydride is more preferable in terms of reactivity, heat resistance, adhesiveness, solubility, and the like. Further, trimellitic anhydride in which a part thereof is replaced with 1,4-cyclohexanedicarboxylic acid is more preferable in order to improve the solubility in a general-purpose solvent.

  Examples of diamines (corresponding diisocyanates) used in the production of polyamideimide resins include aliphatic diamines such as ethylenediamine, propylenediamine, and hexamethylenediamine, and their diisocyanates, 1,4-cyclohexanediamine, 1,3 cyclohexanediamine, and isophorone. Diamines, alicyclic diamines such as 4,4′-dicyclohexylmethanediamine, and diisocyanates thereof, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4 Aromatic diamines such as' -diaminodiphenylsulfone, benzidine, o-tolidine, 2,4-tolylenediamine, 2,6-tolylenediamine, xylylenediamine, and their diisocyanates And the like.

  Among these, 4,4'-diaminodiphenylmethane (diisocyanate), isophonediamine (diisocyanate), and the like are preferable from the viewpoints of heat resistance, adhesiveness, solubility in general-purpose solvents, and the like.

  In the polyamideimide resin, a urethane bond can be introduced into the molecule by copolymerizing a diol component in addition to the acid component and the diamine (diisocyanate) component. Examples of the diol component include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetota ethylene glycol, polytetraethylene glycol, polyester diol, and carbonate diol.

  Moreover, as a means for introducing the NBR structure into the polyamideimide resin, for example, a raw material monomer constituting the polyamideimide resin such as dicarboxypoly (acrylonitrile-butadiene) or dihydroxypoly (acrylonitrile-butadiene) And a method of copolymerizing a raw material having a functional group that reacts with.

  In general, the characteristics of NBR are determined by the copolymerization ratio of acrylonitrile. If the copolymerization amount of acrylonitrile is large, the oil resistance is improved, and if it is small, the rubber elastic behavior at low temperature is improved.

  In the present invention, the NBR copolymerized with the polyamideimide resin is preferably a medium nitrile or high nitrile type having an acrylonitrile copolymerization amount of 25% by mass or more. If the acrylonitrile copolymerization amount is less than 25% by mass, the compatibility with the other components constituting the polyamide-imide resin will be reduced and the reactivity will be reduced, so the copolymer may not be sufficiently copolymerized in the molecule. There is.

  In the case of polymerizing the polyamideimide resin by the isocyanate method, in a polar solvent such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, γ-butyrolactone, 60 to 200 It can be easily produced by stirring while heating to ° C.

  Further, when the above polyamideimide resin is used as an adhesive resin, the polymerization solution is poured into a solvent immiscible with the polymerization solution, preferably acetone or water, and re-precipitated, and washed to remove the polymerization solvent. It can be dried and redissolved in another solvent. Examples of the solvent used for redissolving include alcohols such as methanol, ethanol and butanol, aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran and dioxane, and ketones such as cyclopentanone and cyclohexanone.

  In the present invention, the adhesive resin containing a polyamide-imide resin preferably satisfies low-temperature adhesiveness, heat resistance, and adhesive strength. Therefore, it is preferable that the polyamideimide resin has a glass transition temperature of 120 ° C. or higher, a logarithmic viscosity of 0.1 dl / g or higher, and a tensile elastic modulus of less than 1500 MPa.

  When the glass transition temperature is less than 120 ° C., the heat resistance may be insufficient. When the logarithmic viscosity is less than 0.1 dl / g, or when the tensile elastic modulus is 1500 MPa or more, the resin becomes brittle and the adhesive strength is increased. There may be a shortage.

  In the adhesive resin used in the adhesive layer (a), it is preferable to blend a crosslinking agent in order to improve low-temperature adhesiveness and adhesive strength within a range not impairing heat resistance. Examples of the crosslinking agent include bifunctional or higher polyfunctional epoxy compounds, melamine compounds, and isocyanate compounds. Moreover, the blending amount is preferably 1 to 40 parts by mass, particularly preferably 3 to 20 parts by mass with respect to 100 parts by mass of the polyamideimide resin. If the cross-linking agent is less than 1 part by mass, the effect of improving the low-temperature adhesiveness and adhesive strength may not be exhibited, and if it exceeds 40 parts by mass, the heat resistance may be reduced.

  The adhesive resin used in the adhesive layer (a) is a resin other than an inorganic or organic pigment, a dye, an antistatic agent, a leveling agent, or a polyamideimide resin, for example, within a range not impairing the effects of the present invention. , Polyester resin, polyamide resin, polyimide resin, polyurethane resin, and the like can be appropriately blended.

  The method for forming the adhesive layer (a) includes, for example, a method in which a solution obtained by blending a polyamideimide resin solution with a crosslinking agent or an additive is applied to one side of a polyester film as a base material and dried. After applying a solution in which a crosslinking agent or additive is blended to a resin-based resin solution to one side of the polyester film of the base material and drying it, it is laminated with rubber and pressure-bonded with a heating roll or heat press, and if necessary heat curing treatment The method of performing is mentioned.

  In this case, if the solvent remains in the adhesive layer (a), foaming may occur during the bonding process, or the heat resistance itself may decrease. For this reason, in order to increase the efficiency of drying, it is more preferable to replace the high boiling point solvent used in the polymerization with a low boiling point solvent such as alcohol, aromatic hydrocarbon, ether, ketone or the like.

  When coating a coating solution containing an adhesive resin and a solvent on one side of a polyester film as a base material, it is described in "Progress in the latest coating technology" (authored by Yuji Harasaki, published by General Technology Center Co., Ltd.). A general coating apparatus can be used.

(2) Laminate The laminate of the present invention is composed of a rubber layer / adhesive layer (a) / base material (orientated polyester film), and an easily adhesive polyester composed of an adhesive layer (a) / base material. Rubber is bonded to the adhesive layer (a) of the film. Hereinafter, the rubber layer will be described.

  Examples of the rubber component constituting the rubber layer include natural rubber (NR), silicone rubber (Q), ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), acrylic rubber ( ACM), a rubber selected from the group of fluorine rubber (FKM), or a mixture thereof. The rubber component may be appropriately selected depending on the properties required for the rubber in each application in the application in which the laminate of the present invention is used.

It is preferable to add an adhesion improver to the rubber layer.
As the adhesion improver, a compound containing a reactive group active against a radical reaction is preferable. Examples of this compound include acrylic acid derivatives, methacrylic acid derivatives, and allyl derivatives.

  Among these, derivatives having 2 or more, particularly 3 or more unsaturated bonds are more preferable. These compounds are widely used as rubber co-crosslinking agents, such as polyhydric alcohol acrylic acid esters and methacrylic acid esters, polyhydric carboxylic acid allyl esters, triallyl isocyanurate, triallyl cyanurate and the like. Can be mentioned.

  The polyhydric alcohol acrylic ester or methacrylic ester is an ester compound obtained by esterifying two or more alcoholic hydroxyl groups of a polyhydric alcohol having two or more alcoholic hydroxyl groups with acrylic acid or methacrylic acid. Ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol acrylate, 1,4-butanediol methacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2,2′-bis (4-acryloxydiethoxyphenyl) propane, 2,2 ′ Bis (4-methacryloxydiethoxyphenyl) prone, glycerin dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylol methane diacrylate, tetramethylol methane dimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol tetraacrylate, tetramethylol tetramethacrylate, dimer diol Acrylate, dimer diol dimethacrylate and the like.

  Among these polyhydric alcohol acrylic acid esters and methacrylic acid esters, compounds containing three or more allylic acid esters or methacrylic acid esters are particularly preferred. In addition, although said compound illustrated each single ester compound of acrylic acid and phthalacrylic acid, the mixed ester of acrylic acid and methacrylic acid may be sufficient.

  Examples of the allyl ester of polyvalent carboxylic acid include phthalic acid diarylate, trimellitic acid diarylate, pyromellitic acid tetraarylate, and the like.

  Any one of the rubber layer adhesion improvers may be used alone, or two or more may be used in combination.

  0.2-20 mass parts is preferable with respect to 100 mass parts of all rubber components, and, as for the compounding quantity of said adhesive improvement agent, Most preferably, it is 0.5-10 mass parts. By setting the compounding ratio of the adhesion improver with respect to the total rubber component to 0.2% by mass or more, the adhesive strength with the base film becomes sufficient. On the other hand, from the viewpoint of adhesive strength, it is preferable that the compounding ratio of the adhesion improving agent is large, but when the compounding ratio of the adhesive improving agent with respect to all rubber components exceeds 20% by mass, the effect of improving the adhesive strength reaches saturation, And the physical properties of the rubber are reduced.

  Moreover, in order to promote the expression of the adhesive improvement effect by the above-mentioned adhesive improver, it is possible to add a peroxide compound to the rubber layer so that the delamination strength between the rubber and the base material (oriented polyester film) is increased. From the viewpoint of further improvement, this is a more preferred embodiment.

  The peroxide compound may be either acyl-based or alkyl-based, such as benzoyl peroxide, monochlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-bis-t-butylperoxy-3,3,5- Examples thereof include trimethylcyclohexane, di-t-butyl peroxide, and t-butylcumyl peroxide.

  The compounding amount of the peroxide compound is preferably 0.05 to 10 parts by mass, particularly 1 to 8 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount is less than 0.05 parts by mass, the expression of the adhesion improving effect is not promoted, and when it exceeds 10 parts by mass, the above promoting effect is saturated and the physical properties of the rubber film are lowered.

When rubber other than silicone rubber is used, it is preferable to blend uncrosslinked silicone rubber in the rubber layer. The uncrosslinked silicone rubber is an organopolysiloxane represented by an average unit formula: RaSiO _{(4-a) / 2} .

  In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, a vinyl group, an allyl group, or a butenyl group. Group, alkenyl group such as pentenyl group and hexenyl group, aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aralkyl group such as benzyl group and phenethyl group, -Halogenated alkyl groups such as -chloropropyl group and 3,3,3-trifluoropropyl group. Among these, a methyl group, a vinyl group, a phenyl group, and a 3,3,3-trifluoropropyl group are preferable.

In the above formula, a is a number in the range of 1.9 to 2.1. The silicone rubber component is represented by the above average unit formula. Specific siloxane units constituting the silicone rubber component are, for example, R ₃ SiO _1/2 units, R ₂ (HO) SiO _1/2 units, R ₂ SiO _2/2 units, RSIO _3/2 units and SiO _4/2 units.

The main component of the silicone rubber component is a linear polymer essentially comprising R ₂ SiO _2/2 units and R ₃ SiO _1/2 units or R ₂ (HO) SiO _1/2 units. A small amount of RSIO _3/2 unit and / or R ₃ SiO _1/2 unit may be contained to introduce a branched structure into a part. Further, a resinous polymer composed of R ₃ SiO _1/2 units and SiO _4/2 units can be blended with a part of the silicone rubber component. Thus, the silicone rubber component may be a mixture of two or more polymers.

  The molecular structure of the uncrosslinked silicone rubber component includes, for example, linear, partially branched linear, branched, and resinous. It is a chain polymer or a mixture mainly composed of a linear polymer.

Examples of the silicone rubber component include, for example, molecular chain both ends trimethylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped methylphenylpolysiloxane, molecule Trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, both ends of the chain trimethylsiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, trimethylsiloxy group-capped dimethylsiloxane / methyl (3,3) 3,3-trifluoropropyl) siloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, both ends of molecular chain dimethyl Nylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylphenylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane Copolymer, dimethylvinylsiloxy group-capped dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group, dimethylvinylsiloxy group-capped dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer Dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, silanol group-blocked dimethylpolysiloxane, molecular chain Silanol group-blocked methylvinylpolysiloxane, molecular chain both-end silanol-blocked methylphenylpolysiloxane, molecular chain both-end silanol-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both-end silanol-blocked dimethylsiloxane / methylphenyl Siloxane copolymer, silanol group-capped dimethylsiloxane / methyl (3,3,3-trifluoropropyl) siloxane copolymer, both chain end-capped dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane Polymer, molecular chain both ends trimethoxysiloxy-blocked dimethylpolysiloxane, molecular chain both ends trimethoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethoxysiloxane Si-blocked dimethylsiloxane / methylphenylsiloxane copolymer, trimethoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, both ends of the molecular chain, from R ₃ SiO _1/2 unit and SiO _4/2 unit An organopolysiloxane copolymer comprising an R ₂ SiO _2/2 unit and an RSi O _3/2 unit, an R ₃ SiO _1/2 unit, an R ₂ SiO _2/2 unit and an RS ₃ O _{3 /} Examples thereof include an organopolysiloxane copolymer composed of ₂ units, and a mixture of two or more of these.

  The viscosity at 25 ° C. of the silicone rubber component is practically preferably 100 centistokes or more, particularly 1,000 centistokes or more.

  The blending amount of the uncrosslinked silicone rubber is preferably 5 to 100 parts by mass, particularly preferably 10 to 70 parts by mass with respect to 100 parts by mass of the ethylene propylene rubber. When the blending amount is less than 5 parts by mass, the improvement of the adhesion improving effect is not promoted. On the contrary, when the blending amount exceeds 100 parts by mass, the above promoting effect reaches saturation and is not economical. In addition, the heat resistance of rubber | gum may improve by mix | blending silicone rubber.

  Also, instead of blending uncrosslinked silicone rubber into the rubber layer, an intermediate layer may be provided between the rubber composite polyester and the rubber layer to improve the delamination strength between the rubber composite polyester and the rubber layer. Good. The intermediate layer is preferably composed of an uncrosslinked silicone rubber composition containing an adhesion improver. As the uncrosslinked silicone rubber constituting the intermediate layer, the same ones as described above can be used, and as the adhesion improver, the same ones as those blended in the rubber layer can be used.

  Moreover, the compounding quantity of the adhesive improvement agent with respect to silicone rubber is 0.5-30 mass parts with respect to 100 mass parts of silicone rubbers in the case of the said methacrylic acid ester, Especially 1-20 mass parts is preferable. When the blending amount of the adhesion improver with respect to the silicone rubber is less than 0.5 parts by mass, the adhesive strength with the base film becomes insufficient, and when it exceeds 30 parts by mass, the strength is saturated, which is economically disadvantageous. Become.

  Moreover, it is preferable that the thickness of said uncrosslinked silicone rubber layer is 0.5-50 micrometers.

  For the intermediate layer, if necessary. Reinforcing fillers, pigments, dyes, antioxidants, antioxidants, mold release agents, flame retardants, thixotropy imparting agents, filler dispersants, and the like can be blended. Moreover, in order to promote the adhesive improvement effect by said adhesive improvement agent, a peroxide can be mix | blended as an adhesive improvement promoter.

  Examples of a method of blending the above compounding agent with rubber include a method of using a rubber kneader such as a two-roll, Banbury mixer, or dough mixer (kneader) when preparing a rubber compound. In addition, when a rubber is dissolved in a solvent and a film is formed by a casting method, a method of adding and blending the rubber compound in a solvent to prepare a solution or after forming the solution may be used. .

  As a method for producing a laminate comprising the rubber / film substrate of the present invention. For example, a method is preferred in which the adhesive layer (a) is provided on one side of a base material made of an oriented polyester film, an uncrosslinked rubber layer is laminated, and then the rubber component is crosslinked. In this method, it is a more preferable embodiment to incorporate the above-mentioned adhesion improver into the rubber layer. By using this method, a laminate comprising a rubber / film substrate can be produced economically.

  As a method of laminating the rubber layer, for example, a solution obtained by dissolving a rubber composition in a solvent is applied to the surface of the adhesive layer (a) of the easy-adhesive polyester film, and dried to form a rubber layer. A method of forming a rubber layer by extruding the rubber composition under high pressure on the surface of the adhesive layer (a) of the easily adhesive polyester film, or a calendar method on the surface of the adhesive layer (a) of the easily adhesive polyester film. And a method of forming a rubber layer by molding a rubber composition into a layer. Moreover, when using liquid rubber like liquid silicone rubber, it can apply without diluting with a solvent.

  As a method of crosslinking the rubber component, for example, thermal crosslinking may be used, or crosslinking using high energy active rays such as electron beams and γ rays may be used. In particular, a method using an active ray is preferable. This method does not require the addition of radicals such as peroxides, so there is no deterioration in rubber properties due to residues of these additives, and it can be crosslinked efficiently, resulting in productivity. There is an advantage that is high.

  Further, it is a more preferable method that an uncrosslinked rubber layer dissolved in a solvent is applied to the surface of the adhesive layer (a) of the easy-adhesive polyester film, dried, and subsequently crosslinked to produce the rubber. . At this time, interfacial cross-linking occurs between the rubber layer and the NBR structure in the adhesive layer (a) together with the cross-linking of the rubber layer, and a stronger adhesiveness is expressed.

3. Other function improving layers of an easily adhesive film (i) Anchor layer (b)
In the easily adhesive polyester film of the present invention, it is preferable to provide the anchor layer (b) made of a crosslinked polymer on the surface of the oriented polyester film of the substrate before providing the adhesive layer (a). By providing the anchor layer (b), the adhesion between the adhesive layer (a) and the substrate film becomes better. As a result, the adhesion between the rubber layer and the easily adhesive polyester film becomes better.

  The thickness of the anchor layer (b) is preferably 0.01 or more. The lower limit of the thickness of the anchor layer (b) is more preferably 0.03 μm, particularly preferably 0.05 μm, from the viewpoint of adhesiveness to the adhesive layer (a), that is, adhesiveness between the rubber layer and the easily adhesive polyester film. . On the other hand, the upper limit of the thickness of the anchor layer (b) is preferably 5 μm or less, more preferably 3 μm, and particularly preferably 1 μm from the economical point of view. This is because even if the anchor layer (b) is thicker than 5 μm, the effect of improving the adhesion between the easily adhesive polyester film and the rubber layer is saturated.

  The cross-linked polymer constituting the anchor layer (b) is, for example, a resin, monomer or oligomer having a functional group such as an amino group, a phenol group, an epoxy ring, an isocyanate group, a vinyl group or a carboxylic acid, and a polyester. The polymer layer is irradiated with heat, electron beam, radiation, etc. on the coating layer containing at least one polymer selected from polyurethane and acrylic acid polymers, and the polymer resin is crosslinked with water or insoluble. Is obtained. The polymer may be used alone, or two or three different types may be combined. Alternatively, self-crosslinking may be performed using a polymer having a functional group capable of crosslinking reaction as described above.

  The above polyester has an ester bond in the main chain or side chain, and is obtained by polycondensation of a dicarboxylic acid and a diol.

  Examples of the carboxylic acid component constituting the polyester include aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1 , 2-bisphenoxyethane-p, p′-dicarboxylic acid, phenylindanedicarboxylic acid, and the like can be used. Among these, from the viewpoint of strength and heat resistance, a polyester having a ratio of aromatic dicarboxylic acid to all dicarboxylic acid components of 30 mol% or more, more preferably 35 mol% or more, and most preferably 40 mol% or more is used. preferable.

  Examples of the aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. Acids, 1,4-cyclohexanedicarboxylic acid, and the like, and ester-forming derivatives thereof.

  Examples of the glycol component of the polyester resin include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1, 3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2 , 2,4-trimethyl-1,6-hexanediol, 1 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropyl Examples include redenephenol, 4,4′-isopropylidenebin diol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, and the like.

  In addition, when using polyester as an aqueous solution as a coating solution, in order to facilitate water-solubilization or water-dispersion of the polyester, a compound containing a sulfonate group, a compound containing a phosphonate group, and a carboxylate group are included. It is preferred to copolymerize the compound.

  Examples of the compound containing a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, 1,2, 3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) -3-cyclohexene-1,2-dicarboxylic acid, cyclopentanetetracarboxylic acid, 2,3 , 6,7-Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene glycol bis trimellitate 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, etc., or alkali metal salts, alkaline earth metal salts, ammonium salts thereof .

  Examples of the compound containing a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo Examples include -1,4-bis (hydroxyethoxy) benzene, and alkali metal salts, alkaline earth metal salts, and ammonium salts thereof.

  Examples of the compound containing a phosphonate group include phosphoterephthalic acid, 5-phosphosophthalic acid, 4-phosphoisophthalic acid, 4-phosphonaphthalene-2,7-dicarboxylic acid, phospho-p-xylylene glycol, 2-phospho- Examples include 1,4-bis (hydroxyethoxy) benzene and alkali metal salts, alkaline earth metal salts, and ammonium salts thereof.

  Moreover, as said polyester, modified polyester copolymers, such as a block copolymer modified with acryl, urethane, an epoxy, etc., a graft copolymer, can also be used, for example.

  Preferred polyesters include terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid as the acid component, and a copolymer selected from ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl glycol as the glycol component. Can be mentioned.

  In order to form the anchor layer (b) by in-line coating, the polyester is preferably a water-dispersible or water-soluble copolymer polyester, more preferably a copolymer polyester containing a water-dispersible sulfonic acid metal base. .

  Further, when water resistance is required, a copolymer using trimellitic acid as its copolymer component instead of 5-sodium sulfoisophthalic acid is also suitable.

  Said polyester can be manufactured with the following manufacturing methods. For example, a polyester resin composed of terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid as a dicarboxylic acid component, and ethylene glycol and neopentyl glycol as a glycol component will be described. Terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and A first stage reaction in which ethylene glycol or neopentyl glycol is directly esterified, or terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and ethylene glycol or neopentyl glycol are transesterified, and this first stage The method of manufacturing is mentioned by the 2nd step reaction which polycondensates the reaction product of this.

  At this time, as the reaction catalyst, for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used.

  Further, as a method for obtaining a polyester resin having a large amount of carboxylic acid at the terminal and / or side chain, JP-A-54-46294, JP-A-60-209073, JP-A-62-240318, JP-A-53-26828, JP-A-53-26829, JP-A-53-98336, JP-A-56-116718, JP-A-61-124684, JP-A-62-240318 Although it can be produced from a resin obtained by copolymerization of a trivalent or higher polyvalent carboxylic acid described in Japanese Patent Publication No. Gazette, etc., other methods may be used.

  When a urethane resin is used as the polymer for forming the anchor layer (b), the urethane resin may be a known polyisocyanate containing a urethane component, a polyol, a polyurethane resin having an anionic group, or a polyurethane resin based on them. Is mentioned.

For example, the anionic group of the urethane resin is preferably a sodium salt, potassium salt, lithium salt, magnesium salt or ammonium salt of —SO ₃ ^— , —OSO ₂ ^— , —COO ^— . The heat-reactive water-dispersible urethane resin in which the terminal isocyanate group is blocked with the above salts has an organic polyisocyanate having two or more isocyanate groups in the molecule and two or more active hydrogen atoms in the molecule. It is prepared from a compound having a molecular weight of 200 to 20000 or a prepolymer obtained by reacting a chain extender having two or more active hydrogen atoms in the molecule.

  As a method for providing the anchor layer (b) made of a crosslinked polymer, for example, a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method, etc. The method used can be applied.

  As the step of applying the anchor layer (b) to one side of the polyester film, any method such as a method of applying before stretching of the film, a method of applying after longitudinal stretching, or a method of applying to the film surface after the orientation treatment is used. Is possible.

(Ii) Surface treatment layer (c)
In the easily adhesive polyester film of this invention, it can have a surface treatment layer (c) on the opposite surface of an adhesive layer (a).
The surface treatment layer (c) enables printing on the surface opposite to the surface on which the rubber is bonded, a hard coat layer is provided to prevent the film from being scratched, other material layers are provided, It means a functional layer provided for imparting a function such as improvement. In addition, it is the concept also including surface-treating an oriented polyester film. Examples of other material layers include metals, resin films, paper, cloth, and spunbond.

  The surface treatment layer (c) is provided by a method of providing a resin layer by in-line coating or offline coating, a method of corona treatment or plasma treatment, and a layer made of metal or metal oxide in the same manner as the provision of the crosslinked polymer layer. There are methods such as vapor deposition and sputtering.

  Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that the present invention is not limited by the following examples, and can be implemented with appropriate modifications within a range that can be adapted to the gist of the present invention. Included in the scope.

In addition, the evaluation method of the characteristic value used in this specification is as follows.
(1) Glass transition temperature Dynamic viscoelasticity was measured and determined from the inflection point of the storage elastic modulus.

(2) Logarithmic viscosity Using a solution obtained by dissolving 0.5 g of a polymer in 100 ml of NMP, the viscosity was measured at 25 ° C. using an Ubbelohde viscosity tube.

(3) Resin composition Resin was dissolved in DMSO-d ₆ and a resin composition ratio was determined by ¹ H-NMR using a nuclear magnetic resonance analyzer (NMR) “Gemini-200” manufactured by Varian.

(4) Tensile modulus A polymer film was prepared and measured using a tensile tester manufactured by Toyo Baldwin.

(5) Interlaminar peel strength A knife is inserted into the adhesive layer (a) at the interface between the rubber layer and the plastic film of the laminate comprising a rubber / film substrate, and stress is applied to the part with a finger to cause interfacial delamination. The peel strength was measured by a T-type peel method according to -K6854.

(6) Adhesive durability After immersing the laminate comprising a rubber / film substrate in toluene adjusted to 25 ° C. for 72 hours, the sample was taken out and wiped off with toluene, and the delamination strength was measured by the above method.

(7) Ink adhesion strength In accordance with the cross-cut evaluation described in JIS-K5400, after printing the following ink on the printing surface of the film (coating layer A in the present invention), a 1 mm grid is cut using a cross-cut guide. After making 100 pieces with a blade, the adhesive strength of the grid portion was evaluated using an adhesive tape (manufactured by Nichiban Co., Ltd., cellophane tape).

  Adhesion strength with UV curable ink is UV curable ink (manufactured by Toka Dye Co., Ltd., Best Cure 161), and the surface of the coating layer (covering layer A of the present invention) is irradiated with 100 mJ of UV after printing with an RI tester. And evaluated according to the above method. Also, using another UV curable ink (Seiko Advance Co., Ltd., UVA), the surface of the coating layer (coating layer A of the present invention) was irradiated with 500 mJ of UV after # 300 screen printing, and the same procedure was followed. Evaluated.

Example 1
[Film Production Example 1]
As a water-dispersible urethane resin, 11.5 parts by mass of a self-crosslinking polyurethane resin having an isocyanate group blocked with sodium bisulfite (Elastoron H-3, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and a water-dispersible copolymer polyester As above, 7.5 parts by mass of sodium sulfonate-containing copolymer polyester (MD-1250, manufactured by Toyobo Co., Ltd.) was added to a mixed solution of 39 parts by mass of water and 39 parts by mass of isopropyl alcohol, and mixed well. .

  Furthermore, 0.24 parts by mass of a catalyst of Elastron H-3, which is a self-crosslinking polyurethane resin (Elastotron Cat-64, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), is added to the above mixed solution, and an anionic surfactant ( 0.06 part by mass of Dainippon Ink & Chemicals, Inc., MegaFace F444) was added and mixed thoroughly with stirring.

  Next, 0.02 part by mass of aggregate silica (manufactured by Fuji Silysia Co., Ltd., Silicia 310) was dispersed in 2.68 parts by mass of water with a homogenizer at 1000 rpm for 1 hour, and then the water-dispersible urethane resin and the water-dispersible resin were dispersed. To 97.5 parts by mass of the polyester copolymer resin mixed solution, 2.7 parts by mass of an aqueous dispersion of aggregate silica was added with stirring to obtain a coating solution.

Polyethylene terephthalate resin having an intrinsic viscosity of 0.62 dl / g is melt-extruded by a single screw extruder and cooled by a 25 ° C. casting roll. A polyester resin sheet having a thickness of 800 μm is obtained at 85 ° C. The film was stretched 8 times to obtain a uniaxially stretched polyester film. The coating liquid is applied to both surfaces of this film using a coating roll having a roundness and cylindricity of 3/1000 with a surface of 0.2S or less by ultra hard chrome plating finish, and the wet coating amount is After coating at 6.5 g / m ² and drying at a temperature of 110 ° C., the film was stretched 4 times at 110 ° C. in the width direction, then heat-set at 220 ° C. An axially stretched polyester film was obtained. On the film, an anchor layer (b) and a surface treatment layer (c) made of a crosslinked polymer were provided by applying and drying the coating solution during film formation.

[Method for producing rubber-adhesive polyester film]
An adhesive layer (a) was provided on the obtained polyester film under the following conditions.

(Synthesis Example 1)
(Production of polyamide-imide resin A)
Dicarboxypoly (acrylonitrile-butadiene of 0.475 mol trimellitic anhydride (TMA), 0.475 mol 1,4-cyclohexanedicarboxylic acid, molecular weight 3500 in a four-necked flask equipped with a condenser and a nitrogen gas inlet ) (Ube Industries CTBN 1300 × 13) 0.05 mol and isophorone diisocyanate (IPDI) were charged together with γ-butyrolactone so that the solid concentration was 50% by mass, and the temperature was raised to 150 ° C. with stirring for about 2 hours. The temperature was further raised to 180 ° C., and the reaction was carried out for about 5 hours.

  The obtained polyamide-imide resin A had a glass transition temperature of 190 ° C., a logarithmic viscosity of 0.48 dl / g, and a copolymerization amount of acrylonitrile-butadiene skeleton of 30% by mass. This polymer solution was poured into stirring water, coagulated, washed with water and dried, and then dissolved in a mixed solution of ethanol / toluene = 50/50 (mass ratio) so that the solid content was 25% by mass. This solution was cast on a polypropylene film and dried at 100 ° C. for about 10 minutes to obtain a film having a thickness of 30 μm. The tensile elastic modulus of this film was 1089 MPa. These results are shown in Table 1 together with the resin composition.

(Formation of adhesive layer)
The resin of Synthesis Example 1 was applied onto the film by bar coating so that the thickness after drying was 5 μm.

[Formation of laminate of rubber and film]
EPDM (manufactured by Nippon Synthetic Rubber, EP21; ethylene content 34%) as rubber, zinc salt of 2-mercaptobenzimidazole (manufactured by Ouchi Shinsei Chemical Industry, Nocrack MBZ) as anti-aging agent A, and anti-aging agent B Each of 4,4- (α, α-dimethylbenzyl) diphenylamine (Ouchi Shinsei Chemical Co., Ltd., Nocrack CD) was used and kneaded in a conventional manner at the following blending ratio.

(Composition composition)
-EPDM: 100.0 parts by mass-Polyethylene glycol (molecular weight 4000): 2.5 parts by mass-Stearic acid: 0.5 parts by mass-Anti-aging agent A: 1.5 parts by mass-Anti-aging agent B: 0.7 -Phenol formaldehyde resin: 2.0 parts by mass-MAF carbon: 30.0 parts by mass-FT carbon: 40.0 parts by mass-Polybutene: 15.0 parts by mass-N, N'-m-phenylene dimaleimide: 1.5 parts by mass-2,5-dimethyl-2,5-di (t-butylperoxy) hexane: 5.0 parts by mass

(Rubber and film laminate manufacturing method)
The kneaded rubber was formed into a sheet having a thickness of 3 mm. This unvulcanized rubber sheet is cut into 1 cm square pieces, which are weighed so that the mass ratio with respect to toluene is 30%, and put together with toluene into a stirrer equipped with a vacuum defoaming device. After stirring for 15 hours and dissolving the above strips in toluene, pentaerythritol tetraacrylate was added to the solution so as to be 8 parts by mass with respect to 100 parts by mass of EPDM rubber, and after stirring uniformly, The vacuum deaerator was driven, and the mixture was further stirred for 20 minutes under vacuum with a gauge pressure of −750 mmHg for defoaming.

  Next, the EPDM rubber solution obtained by the above dissolution and defoaming was supplied to a roll coater and applied to the adhesive layer of the polyester film so that the thickness after drying was 150 μm. Subsequently, it was introduced into an oven, dried at 80 ° C., and a mat processed film sheet having a thickness of 35 μm made of a copolymer of poly-4-methylpentene-1 on the surface of the EPDM rubber (manufactured by Mitsui Petrochemical, Opulan X- 60YMT4) was laminated so that the matted surface thereof was directed to the EPDM rubber surface, and was continuously laminated using a pressure roll at a pressure of 5 kgf / cm.

  The obtained laminate was further continuously introduced into an electron beam irradiation apparatus, and pre-crosslinking was performed by irradiating an electron beam with an energy of 200 KV and 3 Mrad from the polyester film side. Thereafter, the cover sheet was peeled off to obtain a composite comprising an EPDM rubber layer and a polyester film. Then, this composite was further introduced into an electron beam irradiation apparatus, and post-crosslinking was performed by electron beam irradiation of 200 KV and 30 Mrad from the EPDM rubber layer side to obtain a rubber / plastic substrate laminate and wound into a roll.

Examples 2 to 8 and Comparative Example 1
The above-mentioned adhesion test samples were prepared using the polyamideimide resins A to I obtained in the following Synthesis Examples 1 to 8 and Comparative Synthesis Example 1, and the results subjected to delamination strength and adhesion durability evaluation are shown in Table 2. It was shown to.

(Synthesis Examples 2 to 5)
[Production Examples of Polyamideimide Resins B, C, D, E]
According to the resin composition shown in Table 1, polyamide imide resins B, C, D, and E were synthesized in the same manner as in the synthesis method of polyamide imide resin A in Synthesis Example 1, and synthesis examples 2, 3, 4, 5 were respectively performed. It was. The resin properties similar to those of the polyamide-imide resin A are shown in Table 1.

(Synthesis Example-6)
[Production Example of Polyamideimide Resin F]
Trimellitic anhydride (TMA) 0.95 mol, molecular weight 3500 dicarboxypoly (acrylonitrile-butadiene) (Ube Industries CTBN 1300 × 13) 0.05 mol in a four-necked flask equipped with a condenser and a nitrogen gas inlet And 4,4′-diphenylmethane diisocyanate (MDI) together with dimethylacetamide (DMAc) so that the solid concentration is 40% by mass, the temperature is raised to 150 ° C. with stirring, and the temperature is further raised to 180 ° C. for about 2 hours. The reaction was allowed to warm for about 5 hours.

  The obtained polyamideimide resin F had a glass transition temperature of 205 ° C., a logarithmic viscosity of 0.54 dl / g, and a copolymerization amount of an acrylonitrile-butadiene skeleton of 34% by mass. Toluene was added to this polymer solution to dilute the solid content concentration to 30% by mass. This solution was applied onto a 50 μm-thick polypropylene film (non-corona-treated surface) and dried at 100 ° C. for about 5 minutes. Subsequently, the coating layer was peeled from the polypropylene film, and further dried on a Teflon (registered trademark) sheet at 130 ° C. for 10 hours to obtain a film having a thickness of 0.03 mm. The tensile elastic modulus of this film was 1700 MPa. These results are shown in Table 1 together with the resin composition.

(Synthesis Examples 7 and 8)
[Production example of polyamideimide resins G and H]
According to the resin composition shown in Table 1, polyamide imide resins G and H were synthesized in the same manner as the synthesis method of polyamide imide resin F of Synthesis Example 6, and were designated as Synthesis Examples 7 and 8, respectively. The resin characteristics similar to those of the polyamide-imide resin F are shown in Table 1.

(Comparative Synthesis Example 1)
[Production of Polyamideimide Resin I]
In accordance with the resin composition shown in Table 1, a polyamideimide resin I was synthesized in the same manner as in the synthesis method of the polyamideimide resin A in Synthesis Example 1 to obtain Comparative Synthesis Example 1. The resin properties similar to those of the polyamide-imide resin A are shown in Table 1.

  The above Comparative Synthesis Example 1 is an example in the case of not having a polyacrylonitrile butadiene structure.

Abbreviations shown in the table. The following compound names are meant.
TMA: trimellitic anhydride CHDA: 1,4-cyclohexanedicarboxylic acid NBRDC: dicarboxypoly (acrylonitrile-butadiene) having a molecular weight of 3500 (Ube Industries, CTBN 1300 × 13)
IPDI: isophorone diisocyanate MDI: 4,4′-diphenylmethane diisocyanate

Example 9
In Example 1, a film and a laminate were obtained in the same manner except that the stretching temperature of the film was 110 ° C. for longitudinal stretching, 120 ° C. for lateral stretching, and 180 ° C. for heat setting.

Example 10
In Example 1, the same method except that only one anchor layer (b) made of a crosslinked polymer was provided on one surface of the uniaxially stretched polyester film by coating the above coating solution, and no surface treatment layer was provided. A film and a laminate were obtained.

  A laminate comprising a rubber / film substrate obtained by laminating the easily-adhesive polyester film of the present invention with rubber is excellent in adhesion between the rubber and the film substrate and adhesion durability, and is laminated in applications where the laminate is used. Since the external force applied to the body can be relaxed by the elasticity of the rubber, it is particularly suitable for applications that require durability, such as pen input touch panels and membrane switches that are repeatedly pressed with fingers. .

Claims (6)

  An easily adhesive polyester film comprising an adhesive layer (a) containing a polyamideimide resin having a polyacrylonitrile butadiene structure in a molecule formed on at least one side of a polyester film oriented in a uniaxial direction.   2. The easily adhesive polyester film according to claim 1, wherein the content ratio of the polyacrylonitrile butadiene structure is 10% by mass to 60% by mass when the entire polyamideimide resin is 100% by mass.   An anchor layer (b) made of a crosslinked polymer is provided on one side of a polyester film oriented in at least a uniaxial direction, and an adhesive layer (a) containing a polyamidoimide resin having a polyacrylonitrile butadiene structure in the molecule is formed thereon. The easily adhesive polyester film according to claim 1, wherein the easily adhesive polyester film is formed.   The easily-adhesive polyester film according to any one of claims 1 to 3, wherein a surface treatment layer (c) is formed on the opposite side of the b layer.   The easily adhesive polyester film according to any one of claims 1 to 4, wherein the easily adhesive polyester film is a rubber easily adhesive polyester film.   A laminate comprising rubber and an easily adhesive polyester film according to any one of claims 1 to 5 bonded together through an adhesive layer (a).