JP2010264642A - Easily adhesive polyester film for forming and laminate of rubber/polyester film for forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester film for laminating rubber, wherein a laminate having high adhesion between the polyester film and rubber, excellent adhesion durability and excellent formability is obtained and to provide the laminate. <P>SOLUTION: An easily adhesive polyester film for forming is characterized in that an adhesion layer (a) containing a polyurethane resin having an unsaturated hydrocarbon bond in a molecule is laminated on at least one surface of the film which includes a copolymerized polyester constituted of one kind of monomer component (I) selected from aromatic dicarboxylic acid components, one kind of monomer component (II) selected from glycol components containing a branched aliphatic glycol and/or alicyclic glycol and at least one of monomer component different from (I) and (II) and which is oriented at least in one axial direction. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an easily-adhesive molding polyester film for bonding a resin, preferably rubber, and a rubber / film laminate using the same. More specifically, the present invention has good vacuum moldability, The present invention relates to a laminate having good elasticity and sealing properties by bonding with resin or rubber, and good adhesion and durability to resin or rubber.

  Since rubber has excellent elasticity, it is used for sealing materials and cushion materials in a wide range of industrial fields. However, since a film made of rubber is too 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 laminate (also referred to as a laminate) in which various films such as a polyester film and a film made of rubber are bonded has been proposed (see, for example, Patent Documents 1 and 2). The polyester film is excellent in heat resistance, dimensional stability and the like, and is excellent in economy, and is suitable as a base film for a laminate with the rubber. A laminated body in which a film is bonded to a rubber layer via an adhesive is disclosed. However, an epoxy resin is used as the adhesive of the laminate disclosed in the examples of the patent document, and the adhesion between the rubber layer and the adhesive interface is insufficient.

  One of the uses of the rubber / polyester film laminate is sometimes used as a constituent member of various molded products. By using a rubber / polyester film laminate 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 method of use as described above, the rubber / polyester film laminate requires high moldability and high adhesion between the rubber layer and the polyester film substrate.
Furthermore, as one of the above usage methods, there is a case where a rubber / polyester film laminate is laminated on the surface of the above molded body, and in one of the usage methods, the polyester film side is incorporated into the molded body as the outermost layer. In some cases, the surface of the polyester film is used by printing, painting, or laminating a metal thin film or metal foil by vapor deposition or laminating. 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 harsh conditions such as outdoor use, and even under such harsh conditions, it is required to maintain the adhesion between rubber and a polyester film, and therefore requires excellent adhesion durability. is there.

  In addition, the present inventors have studied the solution of the above-mentioned problems, and have already improved the above-mentioned problems by using a copolymer polyester resin having the specified composition as a raw material and specifying the stress at 100% elongation of the film. A method has been proposed (see, for example, Patent Documents 3 and 4).

  With this method, in the mold molding method with high molding pressure at the time of molding, it can greatly improve the moldability that can meet the market demand and adapt to the lowering of the molding temperature and the finished product obtained. it can. However, in the case of a molding method having a low molding pressure at the time of molding, such as a compressed air molding method or a vacuum molding method, which has become increasingly demanding in the market, it is desired to further improve the finish of the molded product.

  Moreover, as a polyester film for molding applicable to a pressure forming method or a vacuum forming method which is a molding method having a low molding pressure at the time of molding, it is composed of a biaxially stretched polyester film containing a copolymerized polyester, and the film at 25 ° C. and 100 ° C. The inventors have proposed a polyester film for molding having a specific range of stress at 100% elongation, storage elastic modulus (E ′) at 100 ° C. and 180 ° C., and thermal deformation rate at 175 ° C. (for example, Patent Document 5) reference). However, it was found that blocking and tearing are likely to occur when the film is continuously produced and wound into a roll, and then the film is unwound and processed. Therefore, there is a demand for further improving productivity and stability of quality at the time of post-processing such as vapor deposition or sputtering of metal or metal oxide on a film or printing.

JP 2001-322167 A JP 2001-330881 A JP 2001-347565 A Japanese Patent Application Laid-Open No. 2004-075713 JP-A-2005-290354

  The present invention relates to an easily-adhesive molding polyester film for laminating a flexible elastic body such as rubber, and a laminate using the same, and more specifically, it has good vacuum moldability and is bonded to a resin or rubber. It is an object of the present invention to provide a laminate having good elasticity, sealing properties, etc., and good adhesion to a flexible elastic body such as rubber and adhesion durability.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention. That is, this invention consists of the following structures.
1. One monomer component (I) selected from aromatic dicarboxylic acid components and one monomer component (II) selected from glycol components containing branched aliphatic glycols and / or alicyclic glycols, and (I), An adhesive layer (a) containing a polyurethane resin having an unsaturated hydrocarbon bond in the molecule on at least one surface of a film oriented in at least uniaxial direction containing a copolyester composed of at least one monomer component different from (II) ), An easily adhesive polyester film for molding.
2. 2. The easily adhesive molding polyester film as described in 1 above, wherein the unsaturated hydrocarbon bond is derived from a (meth) acrylate group.
3. 3. The easily adhesive molding polyester film as described in 1 or 2 above, wherein the unsaturated hydrocarbon bond concentration is contained in the molecule in the range of 50 to 2000 eq / ton.
4). The easily adhesive molding for molding according to any one of 1 to 3 above, wherein the polyurethane resin is obtained by reacting a polyester diol (A), a (meth) acrylate monomer (B), and a diisocyanate compound (C). Polyester film.
5). 5. The easy adhesion as described in any one of 1 to 4 above, wherein the polyurethane resin is further reacted with a polyol compound (D), a polyamine compound (E) and / or an amino alcohol compound (F). Polyester film for adhesive molding.
6). 6. The easy adhesion as described in any one of 1 to 5 above, wherein an anchor layer (b) made of a crosslinked polymer is provided on one side of the polyester film, and an adhesive layer (a) is further laminated thereon. Polyester film.
7). The polyester film for easy adhesion molding according to any one of 1 to 6, which satisfies the following (1) to (4):
(1) The stress at 100% elongation in the longitudinal direction and the width direction of the film is 40 to 300 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C.
(2) The thermal shrinkage in the longitudinal direction and the width direction at 150 ° C. of the film is 0.01 to 5.0%.
(3) The haze of the film is 0.1 to 3.0%.
(4) The surface roughness (Ra) of the film on at least one side is 0.005 to 0.030 μm.
(5) The plane orientation degree of the film is 0.095 or less.
8). A rubber / polyester film laminate for molding, wherein a layer (d) containing rubber as a main component is laminated on the adhesive layer (a) of the easily adhesive polyester film for molding according to any one of 1 to 7 above. .

  The adhesive layer (a) used in the present invention has an unsaturated hydrocarbon bond in the molecule of the polyurethane resin, and this adhesive layer is formed by laminating an uncrosslinked rubber layer and subsequently crosslinking the rubber layer. Crosslinking reaction proceeds at the interface between the rubber layer and the rubber layer, and a strong adhesive force is expressed. More specifically, the adhesive layer of the present invention is applied and formed on one side of a molding polyester film, and an uncrosslinked rubber layer is laminated thereon, followed by a crosslinking treatment by irradiation with active energy rays. As a result, the crosslinking of the rubber layer itself and the crosslinking reaction of the adhesive layer of the present invention and the rubber layer interface proceed simultaneously to obtain a laminate in which the rubber layer and the molding polyester film are firmly bonded.

(Raw material for polyester film)
The polyester film which is the base material of the polyester film for easy adhesion molding of the present invention is a glycol component containing one monomer component (I) selected from an aromatic dicarboxylic acid component and a branched aliphatic glycol or alicyclic glycol. 1 type monomer component (II) chosen from these, and (I) and the copolymer polyester comprised from at least 1 type of monomer component different from (II) are included.

The raw material for producing the molding polyester film is selected from one monomer component (I) selected from aromatic dicarboxylic acid components and a glycol component containing a branched aliphatic glycol and / or alicyclic glycol. Even if the copolymerized polyester is composed of at least one monomer component different from one monomer component (II) and (I), (II), it is a blend of the copolymerized polyester and the homopolyester. Alternatively, it may be a blend of the copolymerized polyester with another copolymerized polyester. A blend is more preferable than a single compound because it can suppress a decrease in melting point.
The raw material for producing the molding polyester film is preferably prepared so that the glass transition point of the molding polyester film has a melting point.

As the copolymer polyester, specifically, a copolymer polyester composed of an aromatic dicarboxylic acid component and a glycol component containing ethylene glycol and a branched aliphatic glycol or alicyclic glycol can be used.
As the aromatic dicarboxylic acid component, terephthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalenedicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably It is 75 mol% or more, particularly preferably 80 mol% or more.

Examples of branched aliphatic glycols include neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and the like.
Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.

  Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable. Furthermore, in the present invention, it is a more preferable embodiment that 1,3-propanediol or 1,4-butanediol is used as a copolymerization component in addition to the glycol component. Use of these glycols as a copolymerization component is essential for imparting moldability, and is also preferable from the viewpoint of improving transparency, heat resistance, and adhesiveness.

Examples of the catalyst used for producing the copolymer polyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, titanium / silicon multilayer oxides, and germanium compounds. . Of these, titanium compounds, antimony compounds, germanium compounds, and aluminum compounds are preferred from the viewpoint of catalytic activity.
When producing the copolymer polyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.

(Production method of polyester film)
The polyester film used as the base material for the easy-adhesive molding polyester film of the present invention is obtained by subjecting an unstretched film obtained by melting and extruding a raw material resin chip to a longitudinal direction (longitudinal direction) and a transverse method (width direction). After axial stretching, it can be produced by heat setting.

As a method for obtaining an unstretched film, a method in which the raw material pellets are sufficiently dried and then supplied to an extruder, melt-extruded into a film at about 285 ° C., and the melted film is cooled and solidified with a cooling roll is suitably employed. can do. In order to impart other functions, the polyester film for easy adhesion molding of the present invention can be made into a laminated structure by a known method using different types of polyester. The form of the laminated film is not particularly limited. For example, the laminated film has an A / B two-kind two-layer structure, a B / A / B two-kind three-layer structure, and a C / A / B three-kind three-layer structure. A known method can be applied to rapidly cool the film-like melt to an unstretched film while adhering the film-like melt to the rotary cooling drum. For example, a method using an air knife for the film-like melt or static A method of applying an electric charge can be preferably applied.
As a method for cooling the air surface of the film-like material, a known method can be applied. For example, a method of bringing the film surface into contact with a cooling liquid in the tank, a liquid evaporating with a spray nozzle on the film air surface You may use together the method of apply | coating, and the method of spraying a high-speed airflow and cooling. The unstretched film 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 film is stretched in the longitudinal direction (also referred to as the longitudinal direction) by a roll or a tenter type stretching machine, and then the width orthogonal to the first stretching direction. The method of extending | stretching to a direction can be mentioned.
The stretching temperature in the longitudinal direction is 50 to 120 ° C., and the stretching ratio in the longitudinal direction is 1.6 to 4.5 times, preferably 3.0 to 4.3 times. If the stretching temperature in the longitudinal direction is less than 50 ° 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. When the draw ratio in the longitudinal direction is less than 1.6, the flatness of the obtained film is deteriorated, which is not preferable. On the other hand, if it exceeds 4.5 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.

  In the case of stretching in the width direction, the stretching temperature needs to be 80 to 210 ° C, and 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.
Yes.
The thickness of the easily adhesive molding polyester film of the present invention is not particularly limited, but is preferably 20 to 400 μm.

  Moreover, in the polyester film for easy-adhesion molding of this invention, microparticles | fine-particles can be added as needed. Examples of the fine particles added at that time include known inorganic fine particles and organic fine particles. Furthermore, in the resin forming the film, various additives as necessary, for example, waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stabilizers, coloring pigments, An anti-coloring agent, an ultraviolet absorber and the like can be added. It is preferable to add fine particles to the polyethylene terephthalate resin in the present invention to improve the workability (slidability) of the polyethylene terephthalate resin film. Any fine particles can be selected. Examples of inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate. Examples of the organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. The average particle diameter of the fine particles can be appropriately selected as necessary within a range of 0.05 to 2.0 μm.

  In the present invention, in order to improve the adhesiveness between the rubber layer and the molding polyester film, for laminating comprising a polyurethane resin having an unsaturated hydrocarbon bond in the molecule and a solvent and / or a reactive diluent. It is necessary to provide an adhesive layer (a) containing an adhesive.

  The polyurethane resin having an unsaturated hydrocarbon bond in the molecule used as an adhesive in the present invention can be synthesized by a conventionally well-known method. For example, a method in which a compound having an unsaturated hydrocarbon group is introduced into a polyurethane resin by copolymerization, a prepolymer is synthesized by copolymerizing a compound having an unsaturated hydrocarbon group, and then the chain is extended. Examples thereof include a method of using a polyurethane resin, and a method of synthesizing a polyurethane resin and then modifying its end group with a compound having an unsaturated hydrocarbon group.

  The unsaturated hydrocarbon bond of the adhesive used in the present invention is preferably derived from an acrylate group or a methacrylate group, and the concentration thereof is desirably included in the range of 50 to 2000 eq / ton. More preferably, it is 100 to 1000 eq / ton. If it is less than 50 eq / ton, the crosslinking effect at the rubber layer interface is not sufficiently exhibited. If it exceeds 2000 eq / ton, the curing reaction shrinkage of the adhesive layer at the time of the crosslinking reaction becomes too large, and the adhesiveness with the rubber layer interface is lowered. Or the laminate may be distorted.

  The polyurethane resin used in the adhesive used in the present invention is preferably one obtained by reacting polyester diol (A), (meth) acrylate monomer (B) and diisocyanate compound (C), and if necessary, further polyol. The compound (D), polyamine compound (E) and / or amino alcohol compound (F) may also be reacted.

  Examples of the acid component of the polyester diol (A) component constituting the polyurethane resin include aromatic dibasic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxalic acid, glutaric acid, adipic acid, and azelaic acid. And aliphatic dibasic acids such as sebacic acid and dodecanoic acid, or alicyclic dibasic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. It is done. Of these dibasic acids, terephthalic acid, isophthalic acid, adipic acid, and sebacic acid are more general and preferred.

  In addition, by copolymerizing these acid components with a dibasic acid having an unsaturated hydrocarbon bond such as maleic acid, fumaric acid or itaconic acid, it is possible to expect an improvement in crosslinking reactivity by active energy rays.

Examples of the glycol component of the polyester diol (A) component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol. 1,4-butylene glycol, 2-methyl-1,3-propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2 , 4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3-hydroxypropanoate, 2- n-butyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanedi , Aliphatic diols such as 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, and 1,3-bis (Hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis (hydroxypropyl) cyclohexane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2bis (4-hydroxymethoxycyclohexyl) propane, 2,2-bis (4hydroxyethoxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 2,2- Bis (4-hydroxycyclohexyl) propane, 3 And alicyclic glycols such as (4), 8 (9) -tricyclo [5.2.1.0 ^2,6 ] decanedimethanol.
Among these glycol components, ethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, and neopentyl glycol are preferable from the viewpoint of versatility.

  The number average molecular weight of the polyester diol (A) component is desirably less than 5000, and more desirably 3000 or less. Above 5000, the copolymerization amount of the (meth) acrylate monomer (B) component introduced by copolymerization becomes relatively small, and the excellent adhesive effect with the rubber layer interface in the rubber / film laminate tends to be difficult to be expressed. It is in.

  Examples of the (meth) acrylate monomer (B) component constituting the polyurethane resin include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycerin-1,3-diacrylate, glycerin-1-acrylate-3-methacrylate, pentaerythritol. Diol compounds such as glycidyl (meth) acrylate adducts to various glycols or terminal hydroxyl groups of bisphenol A, such as monool compounds such as triacrylate, ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and the like can be used. Of these, pentaerythritol triacrylate and various glycols or glycidyl (meth) acrylate adducts to the terminal hydroxyl groups of bisphenol A are preferred in terms of the efficiency of introducing acrylate groups into the polyurethane molecule.

  Examples of the diisocyanate compound (C) component constituting the polyurethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate, 3, 3'-dimethoxy-4,4'-biphenylene diisocyanate, 2,6-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-diphenylene diisocyanate, 4,4'-diisocyanate Aromatic polyisocyanates such as diphenyl ether, 1,5-naphthalene diisocyanate, m-xylene diisocyanate, or hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diph Aliphatic and alicyclic polyisocyanates such as water additions of nylmethane diisocyanate and m-xylene diisocyanate are included, among these, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene Diisocyanate is preferred from the viewpoint of versatility.

  Polyol (D), polyamine compound (E), and amino alcohol compound (F) copolymerized as necessary as a constituent component of the polyurethane resin are the molecular weight of the polyurethane resin, the urethane group contained in the molecule, and the unsaturated hydrocarbon. Used to adjust the amount of groups. Some are used to impart further characteristics. For example, as the diol compound, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl -1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ', 2' -Dimethyl-3-hydroxypropanate, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2,2 -Diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 3-phenyl-1,5-pentanediol 2,5-dimethyl-3-sodium sulfo-2,5-hexanediol, and the like. Alternatively, the end group concentration of the polyurethane resin can be increased by using a triol compound such as trimethanolpropane or glycerin as a copolymerization component. Examples of the diamine compound include 1,2-propanediamine, 1,5-pentamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,2-diaminocyclobutane, 1,2-diaminocyclopentane, 1,2 -Diaminocycloheptane etc. are mentioned. The polyurethane resin is copolymerized with a diol having an NBR skeleton and other olefinic diol compounds in which an unsaturated bond is left or hydrogenated in order to impart affinity with the rubber layer component to be laminated. May be.

  It is necessary to use a solvent and / or a reactive diluent for the adhesive used in the present invention. These are also important for adjusting the viscosity to be applicable when applied to the substrate. Among these, what was used for the synthesis | combination of the said polyurethane resin can be used for a solvent as it is. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like may be mentioned alone or as a mixture. Among these, from the viewpoint of coating and drying workability, methyl ethyl ketone alone or a mixed system of toluene and methyl ethyl ketone is preferable.

  In the synthesis of the polyurethane resin, the reaction can be performed in a non-catalytic system. For example, a catalyst such as a tin-based or amine-based catalyst can also be used. From the viewpoint of reactivity, it is preferable to use a tin-based catalyst.

  In the adhesive used in the present invention, a monofunctional or polyfunctional (meth) acrylate compound that is not copolymerized in the molecule may be used as a reactive diluent for the purpose of improving the coating property. In order to increase the crosslinking reactivity with the rubber layer to be laminated, it is preferable to use a polyfunctional (meth) acrylate compound. Examples of such polyfunctional (meth) acrylate compounds are 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, glycerol dimethacrylate, glycerol triacrylate, glycerol trimethacrylate, trimethylolpropane trimethacrylate Pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, tetramethylol methane diacrylate, tetramethylol methane dimethacrylate , Tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol tetraacrylate, tetramethylol tetramethacrylate, dimer diol diacrylate, dimer diol dimethacrylate, etc., and especially three or more allylic acid esters or methacrylic acid esters. Containing compounds are preferred Arbitrariness.

  The adhesive used in the present invention includes resins other than inorganic and organic pigments, dyes, antistatic agents, leveling agents, and polyurethane resins within a range not impairing the effects of the present invention, such as polyester resins, polyamide resins, polyimide resins, Polyamideimide resin, other polyurethane resins, and the like can be appropriately blended.

  As one of the methods of using the adhesive used in the present invention, a solution in which a polyurethane resin solution is blended with a crosslinking agent or an additive is applied to an adherend, dried and then superimposed on the other adherend, and heated roll Or the method of making it pressure-bond with a heat press and performing a heat-hardening process as needed is mentioned.

  Using the adhesive used in the present invention, a laminate of rubber and polyester film can be produced. The base material is not particularly limited as long as it is plastic, but among them, one of polyethylene terephthalate, polyethylene naphthalate, and polycarbonate is preferable in view of heat resistance, dimensional stability, and strength. Further, polyethylene terephthalate exhibits the maximum adhesion of the adhesive of the present invention.

(Rubber-based layer)
In the present invention, the rubber component constituting the rubber layer is not particularly limited. For example, natural rubber (NR), silicone rubber (Q), ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), acrylic rubber (ACM), fluorine rubber (FKM), etc. Rubber or a mixture thereof may be mentioned. The rubber component is appropriately selected depending on the required characteristics according to the purpose of use.

In the present invention, it is preferable to add an adhesion improver to the rubber layer.
As the adhesion improver, it is preferable to use a compound containing a reactive group active against radical reaction. Examples of this compound include acrylic acid derivatives, methacrylic acid derivatives, and allyl derivatives. Among them, derivatives having 2 or more, particularly 3 or more unsaturated bonds are preferable. These compounds are widely used as rubber co-crosslinking agents, and examples thereof include acrylic acid esters and methacrylic acid esters of polyhydric alcohols, allyl esters of polycarboxylic acids, triallyl isocyanurate, triallyl cyanurate, and the like. .

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. Glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol acrylate, 1,4-butanediol methacrylate, 1,6-hexanediol di Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2,2′-bis (4-acryloxydiethoxyphenyl) propane, 2,2′-bi (4-Methacryloxydiethoxyphenyl) prone, glycerin dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentane Erythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylol methane diacrylate, tetramethylol methane dimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol tetraacrylate, tetramethylol tetramethacrylate, dimer diol diacyl Examples thereof include relate and dimer diol dimethacrylate, and a compound containing 3 or more allylic acid esters or methacrylic acid esters is particularly preferable. In addition, although said compound illustrated each single ester compound of acrylic acid and phthalacrylic acid, the form of 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, and pyromellitic acid tetraarylate.

Any one of the rubber layer adhesion improvers may be used alone, or two or more may be used in combination. Further, the adhesion improver used in the present invention is not limited to the above exemplary compounds.
The compounding amount of the adhesive property improving agent is 0.2 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total rubber component. On the contrary, when the amount exceeds 20 parts by mass, the effect of improving the adhesive strength reaches saturation, and the physical properties of the rubber decrease.

  Moreover, in order to accelerate | stimulate the expression of the adhesive improvement effect by an above described adhesive improvement agent, it is a preferable embodiment to mix | blend a peroxide compound with respect to a rubber layer. The correspondence further improves the delamination strength between the rubber layer and the plastic substrate.

  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. If the blending amount is less than 0.05 parts by mass, the development of the effect of improving adhesiveness is not promoted, and if it exceeds 10 parts by mass, the above-mentioned promoting effect is saturated and the physical properties of the rubber layer 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, for example, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, vinyl group, allyl group, butenyl. 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, 3 -Halogenated alkyl groups such as chloropropyl group and 3,3,3-trifluoropropyl group, etc. are mentioned, and preferred are methyl group, vinyl group, phenyl group and 3,3,3-trifluoropropyl group. 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, and in some cases a small amount The RSiO _3/2 unit and / or the R ₃ SiO _1/2 unit can be partially branched. In addition, a resinous polymer composed of R ₃ SiO _1/2 units and SiO _4/2 units can be blended as a part of the silicone rubber component. As described above, the silicone rubber component may be a mixture of two or more polymers.

In addition, the molecular structure of the uncrosslinked silicone rubber component is not particularly limited, and examples thereof include a straight chain, a partially branched linear chain, a branched chain, and a resin. A linear polymer or a mixture containing a linear polymer as a main component. 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-blocked dimethylsiloxane / methyl (3,3,3-trifluoropropyl) siloxane copolymer, both ends of molecular chain silanol group-blocked 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-group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, trimethoxysiloxy-group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, R ₃ SiO _1/2 unit and SiO _4/2 unit Organopolysiloxane copolymer, R ₂ SiO _2/2 unit and RSiO _3/2 unit organopolysiloxane copolymer, R ₃ SiO _1/2 unit, R ₂ SiO _2/2 unit and RSiO _3/2 Examples thereof include an organopolysiloxane copolymer composed of units, and a mixture of two or more of these. The viscosity of the silicone rubber component at 25 ° C. is not particularly limited, but 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 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.

Further, instead of blending uncrosslinked silicone rubber into the rubber layer, an uncrosslinked silicone rubber composition layer in which an adhesion improver is blended as an intermediate layer between the rubber layer and the polyester film is used for polyester. You may improve the delamination strength of a film and a rubber layer. In this case, the uncrosslinked silicone rubber can be the same as described above, and the adhesion improver can be the same as that blended in the rubber layer. And 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, 0.5 mass part If it is less than 30%, the adhesive strength with the substrate film becomes insufficient, and if it exceeds 30 parts by mass, the strength is saturated, which is economically disadvantageous.
The thickness of the uncrosslinked silicone rubber layer is preferably 0.0005 to 0.05 mm.

  If necessary, reinforcing fillers, pigments, dyes, antioxidants, antioxidants, mold release agents, flame retardants, thixotropic agents, filler dispersants, and the like can be blended. Moreover, a peroxide can be mix | blended as an adhesive improvement promoter for promoting the adhesive improvement effect by said adhesive improvement agent.

  The method of blending the above compounding agent with rubber is not particularly limited. For example, when preparing a rubber compound, it may be performed using a rubber kneader such as a two-roll, Banbury mixer, or dough mixer (kneader). When the rubber is dissolved in a solvent and formed into a film by the casting method, the rubber compound may be dissolved in the solvent to prepare a solution, or may be added and blended either after forming the solution.

(Rubber / polyester film laminate)
The method for producing the rubber / film laminate of the present invention is not particularly limited. For example, it is preferable that the adhesive layer (a) is provided on the surface of the plastic substrate, an uncrosslinked rubber layer is laminated, and the laminate is crosslinked. In the method, it is a more preferable embodiment that the rubber layer is blended with the above-mentioned adhesion improver.
The rubber / polyester film laminate can be produced economically by the above measures.
The method of laminating the rubber layer is arbitrary, for example, a method of forming a rubber layer by applying a solution obtained by dissolving a rubber composition in a solvent to the surface of the polyester film base material for easy adhesion having an adhesive layer and drying it, Examples of the method include a method in which an adhesive layer is provided on the surface of the plastic substrate layer and the rubber composition is extruded under high pressure to form a rubber layer, a calendar method, and the like. When liquid rubber such as liquid silicone rubber is used, it can be applied without dilution with a solvent.

  The crosslinking method in the said manufacturing method is not specifically limited. For example, thermal crosslinking may be used, and crosslinking using high-energy active rays such as electron beams and γ rays may be used. In particular, the method using actinic radiation does not require the addition of additives for radical generation such as peroxides, there is no deterioration in rubber properties due to residues of these additives, and it can be crosslinked efficiently and productivity. Is preferable.

  As a more preferred embodiment, it is preferable to manufacture by coating and drying an uncrosslinked rubber layer dissolved in a solvent on the surface of the adhesive layer (a) and subsequently crosslinking the rubber. At this time, it is expected that, along with the cross-linking of the rubber layer, interfacial cross-linking occurs between the rubber layer and the NBR structure in the adhesive layer (a), and stronger adhesiveness is expressed.

(Anchor layer)
In the present invention, it is preferable to provide the anchor layer (b) on the surface of the molding polyester film substrate before providing the adhesive layer (a). By providing the anchor layer, the adhesiveness between the rubber and the film substrate becomes better. The anchor layer is preferably formed by laminating a crosslinked polymer layer having a thickness of 0.01 to 5 μm. The thickness of the crosslinked polymer layer is more preferably 0.03 to 3 μm, and further preferably 0.05 to 1 μm. If the thickness of the crosslinked polymer layer is less than 0.01 μm, the effect of improving the adhesion between the polyester film and the rubber layer is lowered, which is not preferable. On the other hand, if it exceeds 5 μm, the effect of improving the adhesion between the polyester film substrate and the rubber layer is saturated, which is disadvantageous economically.

  The structure of the anchor layer (b) is not limited, but is preferably a polyester having a functional group such as amino group, phenol group, epoxy ring, isocyanate group, vinyl group or carboxylic acid as a crosslinking agent. It is provided by combining at least one polymer compound selected from polyurethane and acrylic acid polymers to form a crosslinked structure that is insoluble or hardly soluble in water by applying heat, electron beam, radiation, or the like. As the polymer compound, the above polymers may be used alone, or two or three different types may be used in combination. It is also possible to use a polymer having the functional group alone.

The polyester has an ester bond in the main chain or side chain, and is obtained by polycondensation of a dicarboxylic acid and a diol.
As the carboxylic acid component constituting the polyester, aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used.
As aromatic dicarboxylic acids, 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, etc. can be used. From the viewpoint of the strength and heat resistance of the laminated film, these aromatic dicarboxylic acids are preferably polyesters that occupy 30 mol% or more, more preferably 35 mol% or more, and most preferably 40 mol% or more of the total dicarboxylic acid component. It is preferable to use it.
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, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.

  As the glycol component of the polyester resin, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 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-si Rhohexanedimethanol, 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′-isopropylidene Phenol, 4,4′-isopropylidene bin diol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol and the like can be used.

  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 sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo -1,4-bis (hydroxyethoxy) benzene or the like, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof can be used, but are not limited thereto.

  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- 1,4-bis (hydroxyethoxy) benzene or the like, or an alkali metal salt, alkaline earth metal salt, or ammonium salt thereof can be used, but is not limited thereto.

  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 However, it is not limited to these.

In the present invention, for example, a modified polyester copolymer such as a block copolymer or a graft copolymer modified with acrylic, urethane, epoxy, or the like can be used.
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. When water resistance is required, a copolymer having trimellitic acid as its copolymer component can be suitably used instead of 5-sodium sulfoisophthalic acid.

Examples of the urethane resin used in the anchor layer (b) include known polyisocyanates containing a urethane component, polyols, polyurethane resins having an anionic group, and polyurethane resins based thereon.
For example, the anionic groups of the urethane resin, preferably _-SO ³ -, -COO ^- sodium salt, potassium salt, lithium salt, magnesium salt or ammonium salt is used. 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 20,000 or a prepolymer obtained by reacting a chain extender having two or more active hydrogen atoms in the molecule.

  Examples of the resin to be contained in the coating liquid other than the urethane resin include water-dispersible or water-soluble polyester copolymer resins, and water-dispersible sulfonic acid metal base-containing polyester copolymer resins are suitable.

  As a method for providing the anchor layer (b), a conventionally used method such as 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 is applied. it can. As a step of applying, any method such as a method of applying before stretching of the film, a method of applying after longitudinal stretching, and a method of applying to the film surface after the orientation treatment is possible.

  In the present invention, the surface treatment layer (c) can be provided on the opposite side of the anchor layer (b). The method of providing the surface treatment layer is the same as the method of providing the crosslinked polymer layer, the method of providing a resin layer by in-line coating or offline coating, the method of corona treatment or plasma treatment, the method of depositing a layer of metal or metal oxide, There is a method of providing by sputtering. Functions such as enabling printing on the film surface by using these methods, providing a hard coat layer to prevent scratches on the molded product surface, providing other material layers, and improving design Can be granted. Examples of other material layers include metal, plastic, paper, cloth, and spunbond.

(Technical meaning and significance of physical properties described in the present invention)
In the present invention, the stress at 100% elongation of the polyester film for molding (abbreviated as F100) is a measure closely related to the moldability of the film. The reason why F100 is closely related to the moldability of the film is, for example, when a biaxially oriented polyester film is molded using a vacuum forming method, the film locally expands to 100% or more near the corner of the mold. There is a case. In a film having a high F100, extremely high stress is partially generated in such a locally stretched portion, and it is considered that the film breaks due to the stress concentration and the formability is lowered. On the other hand, a film having an F100 that is too small has good moldability, but only a very weak tension is generated in a portion that is uniformly stretched, such as a flat portion of a mold. Cannot be stretched.

In the present invention, stress at 100% elongation at 100 ° C. (abbreviated as F100 ₁₀₀ ) is important as a physical property related to moldability corresponding to the molding temperature.
In addition, when molding using a mold having irregularities and depressions, 100% at 25 ° C. is a physical property related to the moldability when the film before molding is lightly followed by the mold before molding. The stress at elongation (F100 ₂₅ ) is important.

The polyester film for molding in the present invention preferably has a stress at 100% elongation (F100 ₂₅ ) at 25 ° C. in the longitudinal direction and the width direction of the film of 30 to 300 MPa. The lower limit is more preferably 50 MPa, particularly preferably 60 MPa. The upper limit is more preferably 250 MPa, still more preferably 200 MPa, and particularly preferably 180 MPa. When F100 ₂₅ is less than 40 MPa, when the roll film is pulled and unwound, the film is stretched or torn, resulting in poor workability. On the other hand, when F100 ₂₅ exceeds 300 MPa, the moldability becomes poor. In particular, when molding is performed using a mold having irregularities and depressions, a film before molding may be followed by lightly following those molds in advance. In such a case, it is difficult to mold the film, and the finished product may have poor design properties.

Moreover, it is preferable that 100% elongation stress (F100 ₁₀₀ ) at 100 ° C. in the longitudinal direction and the width direction of the polyester film for easy adhesion molding of the present invention is 1 to 100 MPa.
The upper limit of F100 ₁₀₀ in the longitudinal direction and the width direction of the film is more preferably 90 MPa, further preferably 80 MPa, and particularly preferably 70 MPa from the viewpoint of moldability. On the other hand, the lower limit of F100 ₁₀₀ is more preferably 5 MPa, more preferably 10 MPa, and particularly preferably 20 MPa from the viewpoint of elasticity and shape stability when using a molded product.

  The heat shrinkage rate in the longitudinal direction and the width direction at 150 ° C. of the easily adhesive molding polyester film of the present invention is preferably 0.01 to 5.0%. The lower limit value of the heat shrinkage rate at 150 ° C. is preferably 0.1%, more preferably 0.5%. On the other hand, the upper limit value of the heat shrinkage rate at 150 ° C. is preferably 4.5%, more preferably 4.1%, and still more preferably 3.2%. Even when a biaxially stretched polyester film for molding having a thermal shrinkage of less than 0.01% in the longitudinal and width direction films at 150 ° C. is produced, there is no significant difference in practical effects, and productivity is improved. Since it is very low, there is no necessity to make the heat shrinkage rate at 150 ° C. less than 0.01%. On the other hand, if the thermal shrinkage rate of the film in the longitudinal direction and the width direction at 150 ° C. exceeds 5.0%, the film tends to be deformed in a post-treatment process that requires heat such as vapor deposition, sputtering, or printing, and after post-processing. The appearance and design of the film will be poor.

  Further, the haze of the easily adhesive molding polyester film of the present invention is preferably 0.1 to 3.0%. The lower limit of haze is preferably 0.3%, more preferably 0.5%. On the other hand, the upper limit of haze is preferably 2.5%, more preferably 2.0%. It is difficult to produce a film having a haze of less than 0.1% on an industrial scale with high normal productivity. On the other hand, when the haze of the film exceeds 3.0%, when the vapor deposition or sputtering surface of the metal or the printed surface or the printed surface is viewed from the back surface of the film, the metal or the printed surface looks dull, so that the design is poor. In addition, it is difficult to obtain a film having a haze of 2.0% or less by a method for forming irregularities on the film surface by incorporating particles in the film, which is generally performed for improving handling properties in the film. .

  The surface roughness (Ra) of at least one surface of the easy-adhesive polyester film of the present invention is preferably 0.005 to 0.030 μm. The lower limit value of Ra is more preferably 0.006 μm, still more preferably 0.007 μm. On the other hand, the upper limit value of Ra is more preferably 0.025 μm, still more preferably 0.015 μm. As the Ra of at least one side of the film becomes smaller, it becomes difficult to wind the film, and the frequency of occurrence of blocking or breaking of the film increases when the film once wound up in a roll shape is unwound. On the other hand, when Ra exceeds 0.03 μm, the protrusion becomes a defect in a post-processing step such as vapor deposition, sputtering or printing, and the design property is lowered.

  The degree of plane orientation (ΔP) of the easy-adhesive molding polyester film of the present invention is a physical property related to moldability, and the higher the degree of plane orientation, the more the molecular chains are arranged in the plane direction, thus lowering the moldability. To do. The degree of surface orientation of the easily adhesive molding polyester film of the present invention is preferably 0.095 or less. The upper limit of the degree of plane orientation is more preferably 0.090. Also, the smaller the degree of plane orientation, the better the moldability. On the other hand, the strength of the film is lowered, and the flatness such as thickness unevenness tends to deteriorate. Therefore, the lower limit of the degree of plane orientation is preferably 0.001, more preferably 0.01, and particularly preferably 0.04.

  In general, as a means for lowering the degree of plane orientation, a method of lowering the draw ratio and a method of increasing the blending amount of the copolymer component are known, but the former method deteriorates the thickness unevenness of the film. This is not preferable because the melting point is lowered and the heat resistance is deteriorated. In the present invention, in order to reduce the degree of plane orientation of the biaxially oriented polyester film and the thermal shrinkage at 150 ° C., it is preferable to perform heat setting at a higher temperature than usual.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, but may be implemented with appropriate modifications within a scope that can meet the gist of the present invention. These are all included in the technical scope of the present invention. The measurement and evaluation methods employed in this specification are as follows.

(1) Intrinsic viscosity of raw polyester resin for forming polyester film
0.1 g of the chip sample was precisely weighed and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 60/40 (mass ratio) and measured at 30 ° C. using an Ostwald viscometer. In addition, the measurement was performed 3 times and the average value was calculated | required.
(2) Glass transition temperature (Tg) and melting point (Tm) of polyester film for molding
DSC measurement was performed according to “Plastic transition temperature measurement method” described in JIS K7121. About 10 mg of a sample piece was sealed in an aluminum pan, melted at 300 ° C. for 3 minutes, and quenched with liquid nitrogen. A differential scanning calorimeter (manufactured by Seiko Instruments Inc., EXSTAR 6200DSC) was used as a measuring instrument, and the measurement was performed under a dry nitrogen atmosphere. After heating from room temperature at a rate of 10 ° C./min to determine the midpoint glass transition temperature, the melting peak temperature (melting point) was determined.
(3) Haze of molding film Based on JIS-K7136-2000, it measured using the haze meter (the Nippon Denshoku Industries Co., Ltd. make, 300A). In addition, the measurement was performed twice and the average value was calculated | required.
(4) Thickness of film for molding Using Millitron, a total of 15 points were measured, 5 points per sheet, and the average value was determined.
(5) 100% elongation stress and elongation at break of polyester film for molding A sample was cut with a single-blade razor into strips having a length of 180 mm and a width of 10 mm, respectively, in the longitudinal direction and the width direction of the biaxially stretched film. Next, the strip-shaped sample was pulled using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress at 100% elongation (MPa) and elongation at break (%) in each direction were determined from the obtained load-strain curve. .
The measurement was performed in an atmosphere of 25 ° C. under the conditions of an initial length of 40 mm, a distance between chucks of 100 mm, a crosshead speed of 100 mm / min, a recorder chart speed of 200 mm / min, and a load cell of 25 kgf. In addition, this measurement was performed 10 times and the average value was used.
In addition, a tensile test was performed under the same conditions as described above even in an atmosphere at 100 ° C. At this time, the sample was held for 30 seconds in an atmosphere at 100 ° C. and then measured. In addition, the measurement was performed 10 times and the average value was used.

(6) Surface roughness of molding polyester film (Ra)
Based on JIS-B0601-2001, Ra was measured with Surfcom 304B (manufactured by Tokyo Seimitsu Co., Ltd.). The measurement conditions were a cutoff of 0.08 μm, a stylus radius of 2 μm, a measurement length of 0.8 mm, and a measurement speed of 0.03 mm / second.

(7) Thermal contraction rate of polyester film for molding at 150 ° C. A strip sample having a length of 150 mm and a width of 20 mm is cut out in the longitudinal direction and the width direction of the film. Two marks are made at 100 mm intervals in the length direction of each sample, and the distance A between the two marks is measured under no load. Subsequently, one side of each strip-shaped sample is hung with a clip on a basket under no load, and placed in a gear oven under an atmosphere of 150 ° C., and time is taken. After 30 minutes, the basket is removed from the gear oven and left at room temperature for 30 minutes. Next, for each sample, the interval is read under no load. From the read intervals A and B, the thermal shrinkage rate at 150 ° C. of each sample is calculated by the following formula: Thermal shrinkage rate (%) = ((A−B) / A) × 100

(8) Plane orientation degree of molding polyester film (ΔP)
Using a sodium D line (wavelength 589 nm) as a light source and using an Abbe refractometer, the refractive index (Nz) in the longitudinal direction of the film, the refractive index (Ny) in the width direction, and the refractive index (Nz) in the thickness direction are measured. The degree of plane orientation (ΔP) was calculated from the equation.
ΔP = ((Nx + Ny) / 2) −Nz

(9) Vacuum moldability of molding film After 5 mm square printing is performed on the film before rubber bonding, the film is heated with an infrared heater heated to 500 ° C. for 10 to 15 seconds, and then the mold temperature is 30. Vacuum forming was performed at ~ 100 ° C. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 40 mm, the depth was 50 mm, and all corners were curved with a diameter of 0.5 mm. .
Five molded products that were vacuum-molded under the optimum conditions were evaluated for moldability and finish, and ranked according to the following criteria. In addition, (double-circle) and (circle) were set as the pass, and x was set as the disqualification.
A: (1) The molded product is not torn,
(2) The radius of curvature of the corner is 1 mm or less, and the printing deviation is 0.1 mm or less,
(3) Further, there is no appearance defect corresponding to x. ○: (1) The molded product is not torn,
(2) The radius of curvature of the corner exceeds 1 mm and is 1.5 mm or less, or the printing deviation is 0.1.
greater than 0.2 mm and less than 0.2 mm,
(3) Further, there is no appearance defect corresponding to ×, and there is no problem in practical use. ×: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv) What to do (1) The corner radius of curvature exceeds 1.5 mm (2) The appearance is bad with large wrinkles (3) The film is whitened and the transparency is lowered (4) The printing deviation is 0.2 mm More than

(10) Print quality of polyester film for molding The film before printing was heat-treated at 90 ° C. for 30 minutes, and then four-color screen printing was performed on the surface treatment layer (c).
Furthermore, the film provided with the printing layer was dried at 80 ° C. for 30 minutes. Evaluation of printing quality was made by visually judging the printing appearance such as the following clear feeling, printing suitability, printing misalignment and the like through the film from the back side, not from the printing side. The judgment criteria were ◯ when there was no problem from all viewpoints, △ when there was a problem at least at one point, and x when there was a problem at two or more points.
a. Clear feeling: The printed design is clear without being blocked by the base film or coating layer.
To look.
b. Printability: Color unevenness and missing due to poor transfer of printing ink c. Printing misalignment: The misalignment of printing cannot be determined visually.
(11) Number average molecular weight of polyurethane resin Gel permeation chromatography (GPC) 150C manufactured by Waters Co. was used and measured at a flow rate of 1 ml / min using tetrahydrofuran as a carrier solvent. Three columns, Shodex KF-802, KF-804, and KF-806, manufactured by Showa Denko K.K., were connected as columns, and the column temperature was set to 30 ° C. A polystyrene standard was used as the molecular weight standard sample.

(12) Acid value of polyester diol After 0.2 g of resin was dissolved in 20 ml of chloroform, phenolphthalein was used as an indicator with a 0.1 N NaOH ethanol solution, and the measured value was shown as equivalent to 1 ton of resin solid content. .

(13) Composition of polyester diol The resin was dissolved in chloroform-d, and the resin composition ratio was determined by ¹ H-NMR using a nuclear magnetic resonance analyzer (NMR) “Gemini-200” manufactured by Varian.

(14) Glass transition temperature of polyurethane resin It measured on condition of the following using the dynamic viscoelasticity measuring apparatus (ITA measurement control Co., Ltd. product DVA-220).
Sample size: 4 mm (width) x 15 mm (length); Thickness: 20 μm
Measurement frequency: 110Hz
Temperature increase rate: 4 ° C./min.
The temperature at the inflection point of the temperature dependency curve of the obtained storage modulus was taken as the glass transition temperature.

(15) Interlaminar peel strength of rubber / polyester film laminate Insert a knife into the adhesive layer at the interface between the rubber layer of the rubber / plastic film laminate and the plastic film, and apply stress to the part to generate interfacial debonding. The peel strength was measured by a T-type peel method according to JIS K6854.
(16) Adhesive durability of rubber / polyester film laminate After the rubber / plastic substrate laminate was immersed 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. did.
(17) Ink adhesion strength of rubber / polyester film laminate The ink adhesion strength of rubber / polyester film laminate is UV curable ink (manufactured by Toka Dye Co., Ltd., Best Cure 161), and the coating layer surface of the film is RI tester. Irradiate 100mJ UV after printing, conform to the cross-cut evaluation described in JIS-K5400, and make 100 pieces of 1mm square with cutter blade on the film printing surface of rubber / polyester film laminate using cross cut guide Then, the adhesive strength of the grid portion was evaluated using an adhesive tape (manufactured by Nichiban Co., Ltd., cellophane tape).

The production method of the base film used in Examples 1 to 7 and Comparative Example 1 will be described below.
[Example 1]
[Adjustment of anchor layer coating solution]
Silica particles having a water-dispersed copolymer polyester resin (manufactured by Toyobo Co., Ltd., Vylonal) 3 mass%, a water-soluble urethane resin (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Elastron), and an average particle size of 0.05 μm A water / isopropyl alcohol-based coating solution containing 1% by mass with respect to the solid content was prepared.

[Manufacture of polyester film for molding]
Copolymer polyester chip having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 40 mol% of ethylene glycol units and 60 mol% of neopentyl glycol units as diol components. (A), 0.04% by mass of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle diameter (SEM method) of 1.5 μm, and a benzotriazole-based ultraviolet absorber (N) (Ciba -The chip | tip (B) of the polyethylene terephthalate (PET) which contains 0.67 mass% of specialty chemicals Co., Ltd. and tinuvin 326) was dried, respectively. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 25:75. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched film was obtained.
The obtained unstretched film was stretched 3.3 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the coating solution was applied so that the coating amount became 0.9 μm in terms of the resin solid content. The longitudinally stretched film having the coating layer was guided to a tenter while being dried, preheated at 120 ° C. for 10 seconds, and stretched 3.9 times at 110 ° C. Furthermore, the heat treatment at 235 ° C. is performed while performing the first heat treatment (hereinafter abbreviated as TS1) at 220 ° C. and the second heat treatment (hereinafter abbreviated as TS2) with a 7% relaxation treatment in the lateral direction. A biaxially stretched polyester film for molding having a thickness of 100 μm was obtained.

[Example 2]
In Example 1, a biaxially stretched polyester film for molding having a thickness of 100 μm was obtained in the same manner as in Example 1 except that both the heat setting temperatures of TS1 and TS2 were set to 235 ° C.

Example 3
In Example 1, the chip (B) was biaxially stretched with a thickness of 100 μm in the same manner as in Example 1 except that the chip (B) was changed to a polyethylene terephthalate (PET) chip (C) containing no UV absorber. A polyester film for molding was obtained.

Example 4
The following chips (D), (E), and (F) were prepared as film raw materials of Example 4.
Chip (D): 100 mol% of terephthalic acid unit as aromatic dicarboxylic acid component, 70 mol% of ethylene glycol unit and 30 mol% of neopentylglycol unit as diol components, and benzotriazole UV absorber (N) ( This is a chip of copolymer polyester containing 0.5% by mass of Tinuvin 326) manufactured by Ciba Specialty Chemicals Co., Ltd. and having an intrinsic viscosity of 0.77 dl / g.
Chip (E): Polyethylene terephthalate (PET) containing 0.67% by mass of benzotriazole ultraviolet absorber (N) (manufactured by Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) and having an intrinsic viscosity of 0.77 dl / g It is a chip.
Chip (F): Polypropylene terephthalate (PPT) containing 0.67% by mass of benzotriazole ultraviolet absorber (N) (manufactured by Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) and having an intrinsic viscosity of 0.75 dl / g It is a chip.

  After the chips were dried, chips (D), chips (E), and chips (F) were mixed so as to have a mass ratio of 50:10:40. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched film was obtained.

  The obtained unstretched film was stretched 3.5 times at 83 ° C. in the longitudinal direction between the heating roll and the cooling roll. Subsequently, the said coating liquid was apply | coated to the chill roll surface side (F surface) of a longitudinally stretched film so that the application quantity might be set to 0.9 micrometer by resin solid content thickness. The longitudinally stretched film having the coating layer was guided to a tenter while being dried, preheated at 95 ° C. for 10 seconds, and the first half of the transverse stretching was stretched 3.9 times at 80 ° C. and the latter half at 75 ° C. Further, a heat setting treatment was performed at 210 ° C. while performing a relaxation treatment of TS1 at 190 ° C. and TS2 at 7% in the transverse direction to obtain a biaxially stretched polyester film for molding having a thickness of 50 μm.

Example 5
In Example 4, a biaxially stretched polyester film having a thickness of 100 μm was obtained in the same manner as in Example 2 except that the heat setting temperature was changed to 180 ° C. for TS1 and 220 ° C. (TS2) for TS2. It was.

Example 6
The raw material composition of Example 4 was used as a core layer, and a chip in which chips (D) and chips (E) were mixed at a mass ratio of 50:50 was introduced into another extruder as a raw material for the skin layer, and melted at 280 ° C. In the same manner as in Example 2, except that the core layer raw material and skin layer / core layer / skin layer = 10/80/10 were joined by a feed block and then extruded from a T-die at 270 ° C. A biaxially stretched polyester film for molding having a thickness of 100 μm was obtained.

Example 7
As raw materials for Example 7, the following chip (G) and chip (H) were prepared in addition to the chip (E).
Chip (G): 60 mol% of terephthalic acid unit and 40 mol% of isophthalic acid component as aromatic dicarboxylic acid components, 100 mol% of ethylene glycol units as diol components, and intrinsic viscosity of 0.71 dl / g This is a copolymer polyester chip.
Chip (H): 60 mol% of terephthalic acid unit and 40 mol% of naphthalenedicarboxylic acid component as aromatic dicarboxylic acid components, 100 mol% of ethylene glycol units as diol components, and intrinsic viscosity of 0.71 dl / g This is a copolyester chip.

  The chip (E), the copolymer polyester chip (G), and the polyethylene terephthalate chip (H) were mixed at a mass ratio of 50:25:25 and dried. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched film was obtained.

  The obtained unstretched film was stretched 3.5 times at 90 ° C. in the longitudinal direction between the heating roll and the cooling roll. Subsequently, the coating liquid of Example 1 was apply | coated to the longitudinally stretched film so that the application quantity might be set to 0.9 micrometer by the thickness of resin solid content. The longitudinally stretched film having the coating layer was guided to a tenter while being dried, preheated at 120 ° C. for 10 seconds, and the first half of the transverse stretching was stretched 3.9 times at 105 ° C. and the latter half at 100 ° C. Further, a heat setting treatment was performed at 220 ° C. while performing a relaxation treatment of 7% in the transverse direction to obtain a biaxially stretched polyester film for molding having a thickness of 100 μm.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 except that an adhesive layer was provided on the easy-adhesion surface of a transparent PET film (Toyobo Co., Ltd., Cosmo Shine A4300, 50 μm) and rubber was laminated.

  Regarding Examples 1 to 7 and Comparative Example 1, the raw material composition and polymer characteristics of the polymers used are shown in Table 1, and the production conditions and characteristics of the base film are shown in Tables 2 to 3.

The preparation method of the easily-adhesive film using the base film produced in Examples 1-7 and Comparative Example 1 is demonstrated below.
[Method for producing polyester film for easy adhesion molding]
On the obtained polyester film for molding, the resin of Synthesis Example 1 below was applied with a bar coater so that the thickness after drying was 5 μm, and an adhesive layer (a) was provided.
[Synthesis Example 1] (Synthesis of polyester diol component)
97 g of dimethyl terephthalate, 97 g of dimethyl phthalate, 73 g of neopentyl glycol, 81 g of ethylene glycol and 0.1 g of tetrabutyl titanate (TBT) as a catalyst were added to a 1 L four-necked flask equipped with a thermometer, stirring rod and Liebig condenser. The transesterification reaction was allowed to proceed at 190 to 230 ° C. for 3 hours. Subsequently, after heating up to 250 degreeC, it superposed | polymerized for 20 minutes under pressure reduction, and polyester diol a1 was obtained. The composition of the obtained polyester diol a1 was terephthalic acid / isophthalic acid // ethylene glycol / neopentyl glycol = 50/50 // 50/50 mol%, the number average molecular weight was 2000, and the acid value was 5 eq / ton. It was.
(Synthesis of polyurethane resin PU1)
100 g of the polyester diol a1, 80 g of toluene, and 80 g of methyl ethyl ketone (MEK) were charged into a 1 L four-necked flask equipped with a thermometer, a stir bar, and a condenser, and the temperature was raised to 60 ° C. and dissolved uniformly. Next, 26 g of 4,4′-diphenylmethane diisocyanate was added and reacted at the same temperature for 2 hours, then 6.5 g of NK-701A manufactured by Shin-Nakamura Chemical Co., Ltd. was added, and the reaction was continued for another 2 hours. Next, 24 g each of toluene and MEK were added for dilution, 5.2 g of trimethylolpropane was added, and the mixture was reacted at 60 ° C. for 3 hours to complete the synthesis reaction. Table 4 shows the calculated value of the unsaturated hydrocarbon bond concentration from the composition, number average molecular weight, glass transition temperature, and charged value of the obtained polyurethane resin A.

A method for producing a rubber / polyester film laminate using the easy-adhesive films produced in Examples 1 to 7 and Comparative Example 1 will be described below.
[Production of rubber / polyester film laminate]
EPDM (ethylene content 34%, “EP21” manufactured by Nippon Synthetic Rubber Co., Ltd.) as rubber, and 2-mercaptobenzimidazole zinc salt (“NOCRACK MBZ” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) as aging inhibitor A As the inhibitor B, 4,4- (α, α-dimethylbenzyl) diphenylamine (“NOCRACK CD” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) was used, respectively, and kneaded in a conventional manner with the following composition.
(Rubber compounding 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 parts by mass, 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.

  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 to degas.

  Next, the EPDM rubber solution obtained by the above dissolution and defoaming is supplied to a roll coater, applied to the polyester film adhesive layer to a thickness of 0.15 mm after drying, and then introduced into an oven. , Dried at 80 ° C., and a mat-processed film sheet (“Opylan X-60YMT4” manufactured by Mitsui Petrochemical Co., Ltd.) having a thickness of 0.035 mm made of a copolymer of poly-4-methylpentene-1 on the surface of the EPDM rubber. The matted surface is laminated so that it faces the EPDM rubber surface, and is continuously laminated using a pressure roll at a pressure of 5 kgf / cm. The resulting laminate is further continuously introduced into an electron beam irradiation device, and polyester An electron beam is irradiated from the film side with an energy of 200 KV and 3 Mrad to perform pre-crosslinking, and then the cover sheet is peeled off, and the rubber layer and the poly To obtain a laminate consisting of ester film. Then, this laminate was further introduced into an electron beam irradiation apparatus, post-crosslinking was performed by electron beam irradiation of 200 KV and 30 Mrad from the EPDM rubber layer side, and a rubber / polyester film laminate was obtained and wound into a roll. Table 5 shows evaluation results such as delamination strength and adhesion durability evaluation of the obtained rubber / polyester film laminate.

[Examples 8 to 14 and Comparative Example 2]
In the film of Example 4, the above adhesion test samples were prepared using the resins PU1 to PU7 obtained in the following Synthesis Examples 2 to 5 and Comparative Synthesis Example 1, and subjected to delamination strength and adhesion durability evaluation and the like. . The evaluation results are shown in Table 5.

[Synthesis Example 2] Synthesis of Polyurethane Resin PU2 50 g of the above polyester diol a1 and 50 g of Polylite OD-X-688 made by Dainippon Ink Co., Ltd. were placed in a 1 L four-necked flask equipped with a thermometer, a stir bar, and a condenser. 80 g and 80 g of methyl ethyl ketone were charged, heated to 60 ° C., and uniformly dissolved. Then, 26 g of 4,4′-diphenylmethane diisocyanate was added and reacted for 2 hours, then 6.5 g of NK-701A manufactured by Shin-Nakamura Chemical Co., Ltd. was added, and the reaction was continued for another 2 hours. Next, 4 g of neopentyl glycol was added and reacted at the same temperature for further 3 hours, and 23 g of MEK and toluene were added and diluted to complete the synthesis reaction. Table 4 shows the calculated value of the unsaturated hydrocarbon bond concentration from the composition, number average molecular weight, glass transition temperature, and charged value of the obtained polyurethane resin UR-2.

[Synthesis Example 3] Synthesis of polyurethane resin PU3 50 g of the above polyester diol a1, 50 g of G-3000 made by Nippon Soda Co., Ltd., 80 g of methyl ethyl ketone, 80 g of methyl ethyl ketone in a 1 L four-necked flask equipped with a thermometer, stirring rod and condenser. Was heated to 60 ° C. and dissolved uniformly. Then, 26 g of 4,4′-diphenylmethane diisocyanate was added and reacted for 2 hours, then 6.5 g of NK-701A manufactured by Shin-Nakamura Chemical Co., Ltd. was added, and the reaction was continued for another 2 hours. Next, 5 g of neopentyl glycol was added and reacted at the same temperature for 30 minutes, and 0.025 g of dibutyltin dilaurate was added. The reaction was further continued for 3 hours, and 24 g each of MEK and toluene were added and diluted to complete the synthesis reaction. Table 4 shows the calculated values of the unsaturated hydrocarbon bond concentration from the composition, number average molecular weight, glass transition temperature, and charged value of the obtained polyurethane resin UR-3.

[Synthesis Example 4] Synthesis of Polyurethane Resin PU4 100 g of the above polyester diol a1, 80 g of toluene, and 80 g of methyl ethyl ketone were charged into a 1 L four-necked flask equipped with a thermometer, a stirring rod, and a condenser, and the temperature was raised to 60 ° C. Dissolved in. Next, 26 g of 4,4′-diphenylmethane diisocyanate was added and reacted for 2 hours, then 2.2 g of NK-701A manufactured by Shin-Nakamura Chemical Co., Ltd. was added, and the reaction was continued for another 2 hours. Next, 40 g each of MEK and toluene were added and diluted, 31 g of A3002 manufactured by Kyoeisha Chemical Co., Ltd. was added and reacted at 60 ° C. for 3 hours under non-catalyst, and then the synthesis reaction was terminated. Table 4 shows the calculated values of the unsaturated hydrocarbon bond concentration from the composition, number average molecular weight, glass transition temperature, and charged value of the obtained polyurethane resin UR-4.

[Synthesis Example 5] Synthesis of polyurethane resin PU5 Into a 1 L four-necked flask equipped with a thermometer, a stir bar, and a condenser was charged 20 g of the above polyester diol a1, 80 g of toluene, and 90 g of methyl ethyl ketone, and the temperature was raised to 60 ° C to be uniform. Dissolved in. Next, 48 g of 4,4′-diphenylmethane diisocyanate was added and allowed to react for 2 hours, and then 56 g of MEK and toluene were added and diluted to give 120 g of A3002 manufactured by Kyoeisha Chemical Co., Ltd. and Shin Nakamura Chemical Co., Ltd. 6.5 g of NK-701A was added, and the reaction was further continued for 3 hours at 60 ° C. in the absence of a catalyst to complete the synthesis reaction. Table 4 shows the calculated values of the unsaturated hydrocarbon bond concentration from the composition, number average molecular weight, glass transition temperature, and charged value of the obtained polyurethane resin UR-5.

[Synthesis Example 6] Synthesis of polyurethane resin PU6
100 g of the polyester diol a1, 60 g of toluene, and 60 g of methyl ethyl ketone were charged into a 1 L four-necked flask equipped with a thermometer, a stir bar, and a condenser, and the temperature was raised to 60 ° C. and dissolved uniformly. Next, 13 g of 4,4′-diphenylmethane diisocyanate was added and reacted for 2 hours, 0.5 g of 2-hydroxyethyl acrylate was added and reacted for 3 hours to complete the synthesis. 24 g of toluene and 24 g of methyl ethyl ketone were added for dilution to obtain polyurethane resin UR-6. Table 4 shows the calculated values of the unsaturated hydrocarbon bond concentration from the composition, number average molecular weight, glass transition temperature, and charged value of the obtained polyurethane resin UR-6.

[Comparative Synthesis Example 1] Synthesis of polyurethane resin PU7 50 g of the above-mentioned polyester diol a1 and 50 g of Polylite OD-X-688 manufactured by Dainippon Ink Co., Ltd. were placed in a 1 L four-necked flask equipped with a thermometer, a stirring rod and a condenser. Then, 60 g of toluene and 60 g of methyl ethyl ketone were charged, heated to 60 ° C., and uniformly dissolved. Then, 12 g of 4,4′-diphenylmethane diisocyanate was added and reacted for 3 hours to complete the synthesis, and diluted by adding 24 g of toluene and 24 g of methyl ethyl ketone. Table 4 shows the composition, number average molecular weight, and glass transition temperature of the obtained polyurethane resin UR-7. The polyurethane resin UR-7 is a comparative synthesis example having no unsaturated hydrocarbon bonding group in the molecule.

以下、表中に示す略号はそれぞれ以下の化合物名を表す。
ＮＰＧ：ネオペンチルグリコール
ＴＭＰ：トリメチロールプロパン
ＭＤＩ：ジフェニルメタンジイソシアネート
ＮＫ−７０１Ａ：新中村化学（株）製 ２−ヒドロキシ−１−アクリロキシ−３−メタクリロキシプロパン、分子量：２１４、アクリレート及びメタクリレート合計濃度：０．９３ｅｑ／１００ｇ、アクリレート基濃度：２．２１ｅｑ／１００ｇ
Ａ３００２：共栄社化学（株）製 ビスフェノールＡへの２倍モル量のグリシジルアクリレート付加物、分子量：６００、アクリレート基濃度：０．３３ｅｑ／１００ｇ
ＨＥＡ：２−ヒドロキシエチルアクリレート
Ｇ−３０００：日本曹達（株）製１，２−ポリブタジエンのジオールの重合体（不飽和結合残存）、分子量：２９００
ＯＤ−Ｘ−６８８：大日本インキ（株）製アジペート系ポリエステルジオール、分子量：２０００

Hereinafter, the abbreviations shown in the tables represent the following compound names.
NPG: Neopentyl glycol TMP: Trimethylolpropane MDI: Diphenylmethane diisocyanate NK-701A: Shin-Nakamura Chemical Co., Ltd. 2-hydroxy-1-acryloxy-3-methacryloxypropane, molecular weight: 214, acrylate and methacrylate total concentration: 0 .93 eq / 100 g, acrylate group concentration: 2.21 eq / 100 g
A3002: manufactured by Kyoeisha Chemical Co., Ltd. Bisphenol A glycidyl acrylate adduct with a 2-fold molar amount, molecular weight: 600, acrylate group concentration: 0.33 eq / 100 g
HEA: 2-hydroxyethyl acrylate G-3000: 1,2-polybutadiene diol polymer manufactured by Nippon Soda Co., Ltd. (unsaturated bond remaining), molecular weight: 2900
OD-X-688: Adipate polyester diol manufactured by Dainippon Ink Co., Ltd., molecular weight: 2000

  The adhesive layer of the easy-adhesive molding polyester form of the present invention has an unsaturated hydrocarbon bond in the polyurethane resin molecule, and is applied onto an unvulcanized rubber sheet and irradiated with active energy rays. A crosslinking reaction proceeds at the interface between the polyurethane adhesive layer and the rubber layer, and as a result, excellent adhesive force is exhibited. Moreover, since the polyurethane adhesive layer and the rubber layer interface are joined by chemical bonding, excellent adhesion durability is exhibited. Therefore, a high performance rubber / polyester film laminate can be obtained.

Claims (8)

  One monomer component (I) selected from aromatic dicarboxylic acid components and one monomer component (II) selected from glycol components containing branched aliphatic glycols and / or alicyclic glycols, and (I), An adhesive layer (a) containing a polyurethane resin having an unsaturated hydrocarbon bond in the molecule on at least one surface of a film oriented in at least uniaxial direction including a copolyester composed of at least one monomer component different from (II) ), An easily adhesive polyester film for molding.   2. The polyester film for easy adhesion molding according to claim 1, wherein the unsaturated hydrocarbon bond is derived from a (meth) acrylate group.   The polyester film for easy adhesion molding according to claim 1 or 2, wherein the unsaturated hydrocarbon bond concentration is contained in the molecule in the range of 50 to 2000 eq / ton.   The easily adhesive molding according to any one of claims 1 to 3, wherein the polyurethane resin is obtained by reacting a polyester diol (A), a (meth) acrylate monomer (B) and a diisocyanate compound (C). Polyester film.   The polyurethane resin is a product obtained by further reacting with a polyol compound (D), a polyamine compound (E) and / or an amino alcohol compound (F). Polyester film for adhesive molding.   The easy adhesion according to any one of claims 1 to 5, wherein an anchor layer (b) made of a crosslinked polymer is provided on one side of the polyester film, and an adhesive layer (a) is further laminated thereon. Polyester film. The polyester film for easy adhesion molding according to any one of claims 1 to 6, which satisfies the following (1) to (4).
(1) The stress at 100% elongation in the longitudinal direction and the width direction of the film is 40 to 300 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C.
(2) The thermal shrinkage in the longitudinal direction and the width direction at 150 ° C. of the film is 0.01 to 5.0%.
(3) The haze of the film is 0.1 to 3.0%.
(4) The surface roughness (Ra) of the film on at least one side is 0.005 to 0.030 μm.
(5) The plane orientation degree of the film is 0.095 or less.   A rubber / polyester film laminate for molding, wherein a layer (d) containing rubber as a main component is laminated on the adhesive layer (a) of the easily adhesive polyester film for molding according to any one of claims 1 to 7. body.