JP2010264644A - Easily adhesive white polyester film and rubber/white polyester film laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester film for laminating rubber lamination, wherein a laminate having high adhesion between a white polyester film and rubber and excellent adhesion durability can be obtained and to provide the laminate. <P>SOLUTION: An easily adhesive white polyester film has an adhesion layer (a) having an adhesive for lamination comprising a polyurethane resin having an unsaturated hydrocarbon bond in a molecule, a solvent and/or a reactive diluent, contained on one surface of the film which is oriented at least in one axial direction and has light transmittance of 1 to 50%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an adhesive for laminating rubber or elastomer and a white polyester film, and a laminate thereof. More specifically, the present invention is an adhesive suitable for laminating various plastic films and rubber. By using a polyamidoimide-based resin having a polyacrylonitrile butadiene structure in the molecule as an agent, the affinity with the rubber interface is improved, excellent adhesive strength and adhesion durability are exhibited, and a laminate having excellent moldability It is obtained.

  The present invention relates to an easily-adhesive white polyester film for bonding rubber and elastomer and a rubber / white polyester film laminate using the same. More specifically, the present invention relates to a laminate having good elasticity and sealing properties when bonded to rubber or elastomer, and good adhesion and durability to rubber or elastomer.

  Since rubber has excellent elasticity, it is used for sealing materials and cushion materials in a wide range of industrial fields. However, since the rubber film is flexible, it is inferior in workability when incorporated in an apparatus or a part. On the other hand, polyester films are used in a wide range of fields because they are harder than rubber, have good dimensional stability, have excellent workability when incorporated into devices and parts, and have good sliding properties. 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 in which various films such as a polyester film and a rubber film are bonded together has been proposed. (For example, see Patent Documents 1 and 2)
The polyester film is excellent in heat resistance, dimensional stability and the like, and is excellent in economic efficiency, and is suitable as a base film for a laminate with the rubber. A laminate in which a film is bonded to a rubber film 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.

  As one of the uses of the rubber laminate, it may be used as a constituent member of various molded bodies. By using a rubber laminate as the member, distortion generated during molding of the molded body can be relaxed using the elasticity of the rubber, so that, 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 usage method as described above, the rubber laminate requires high moldability and high adhesion between the rubber and the polyester film in the rubber laminate.

Further, as one of the above usage methods, a rubber laminate may be used by laminating on the surface of the molded body, and in one of the usage methods, the polyester film side is incorporated into the molded body as the outermost layer, and the polyester is used. There are cases where printing, painting, or laminating metal thin films or metal foils on the surface of the film by vapor deposition or laminating methods. By the correspondence, the effect of reducing the gas permeability of the surface of the molded body and oxygen gas, water vapor and the like can be exhibited. In this method of use, the adhesive layer at the interface between the rubber and the polyester film is eroded by the solvent used in printing, painting, laminating, etc., and the adhesiveness is lowered. In addition, the molded body may be used under 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.
Moreover, when it provided in the transparent film, it became easy to see rubber | gum from the back, and there existed a problem in the external appearance and the designability.

JP 2001-322167 A JP 2001-330881 A

  The present invention relates to an easily-adhesive white polyester film for laminating rubber and elastomer and a rubber / white polyester film laminate using the same. More specifically, the present invention relates to laminating rubber and elastomer. It is a problem to obtain a rubber / white polyester film laminate having good elasticity and sealing properties, and good adhesion to rubber and elastomer 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. Easy adhesion, characterized in that a polyurethane resin adhesive layer (a) having an unsaturated hydrocarbon bond in the molecule is laminated on at least one side of a white polyester film having a light transmittance of 1 to 50% oriented at least in a uniaxial direction. White polyester film.
2. 2. The easily adhesive white polyester film as described in 1 above, wherein the unsaturated hydrocarbon bond is derived from a (meth) acrylate group.
3. 3. The easily adhesive white 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 white polyester according to any one of the above 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). the 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). White polyester film.
6). An anchor layer (b) made of a crosslinked polymer is provided on one side of a white polyester film having a light transmittance of 1 to 50% oriented at least in a uniaxial direction, and an adhesive layer (a) is further laminated thereon. Said easily adhesive white polyester film in any one of said 1-5.
7). The easily adhesive white polyester film as described in any one of 1 to 6 above, which has a surface treatment layer (c) on the film surface opposite to the adhesive layer (a).
8). A rubber / white polyester film laminate, wherein a layer (d) containing rubber as a main component is laminated on the adhesive layer (a) of the film 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 polyester film, an uncrosslinked rubber layer is laminated thereon, and subsequently subjected to crosslinking treatment by irradiation with active energy rays. Thus, the crosslinking of the rubber layer itself and the crosslinking reaction of the adhesive layer and the rubber layer interface of the present invention proceed simultaneously to obtain a laminate in which the rubber layer and the polyester film are firmly bonded.

Hereinafter, embodiments of the present invention will be described in detail.
(White polyester form)
The white polyester film used as the base material of the easy-adhesion white polyester film of this invention consists of a polyester resin which has ethylene glycol and terephthalic acid as main components. Other dicarboxylic acid components and glycol components may be copolymerized as long as the object of the present invention is not impaired. Examples of the other dicarboxylic acid components include isophthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxybenzophenone, bis- (4-carboxyphenylethane), adipine Examples include acid, sebacic acid, 5-sodium sulfoisophthalic acid, cyclohexane-1,4-dicarboxylic acid, and the like. Examples of the other glycol component include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, ethylene oxide adducts such as bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, oxycarboxylic acid components such as p-oxybenzoic acid can also be used.

In order to obtain a white polyester film having a light transmittance of 50% or less, it is preferable to add an incompatible thermoplastic resin, inorganic fine particles, or crosslinked organic fine particles to the polyester resin. When an incompatible thermoplastic resin is added, a large number of cavities appear inside, the apparent density decreases, and the light transmittance decreases due to light scattering by the cavities. Examples of incompatible thermoplastic resins include polypropylene, polystyrene, polymethylpentene, polycarbonate, and cyclic olefin. Moreover, the addition amount is 5-30 mass%, Preferably it is 8-25 mass%, More preferably, it is 10-20 mass%. If it is less than 5% by mass, sufficient light scattering does not occur. If it is 30% by mass or more, breakage during film formation occurs frequently, making it difficult to produce a film. Moreover, the addition amount is 2-40 mass%, Preferably it is 4-25 mass%, More preferably, it is 5-20 mass%. If it is less than 5% by mass, sufficient light scattering does not occur. If it is 40% by mass or more, breakage during film formation occurs frequently, making it difficult to produce a film.
By adding inorganic fine particles or crosslinked organic fine particles, light scattering similarly occurs, and a white polyester film having a light transmittance of 50% or less can be produced. Examples of the fine particles include titanium dioxide, calcium carbonate, barium sulfate, silicon dioxide, crosslinked polystyrene particles, and crosslinked acrylic particles.

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

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

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

  As a method of stretching the film in the biaxial direction, the obtained unstretched sheet is stretched in the longitudinal direction by a roll or a tenter-type stretching machine, and then stretched in the width direction orthogonal to the first-stage stretching direction. A method can be mentioned. The stretching temperature in the longitudinal direction is 75 to 120 ° C., and the stretching ratio in the longitudinal direction is 2.5 to 4.5 times, preferably 3.0 to 4.3 times. If the stretching temperature in the longitudinal direction is less than 75 ° C., the film tends to break, which is not preferable. On the other hand, when the temperature exceeds 120 ° C., the thickness unevenness of the obtained film is deteriorated, which is not preferable. When the draw ratio in the longitudinal direction is less than 2.5 times, the flatness of the obtained film is deteriorated, which is not preferable. On the other hand, if it exceeds 4.6 times, the orientation in the longitudinal direction becomes strong, and the frequency of breakage increases in stretching in the transverse direction, which is not preferable.

  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.

The light transmittance of the film before laminating the rubber of the present invention is 50% or less, preferably 40% or less, more preferably 30% or less. If it exceeds 50%, the rubber in the case where the rubber is laminated becomes easy to see through the film, and the appearance is not good. The lower limit is 1%. Below that, the productivity of the film becomes poor.
Although the thickness of the white polyester film used by this invention is not specifically limited, It is preferable in it being the thickness of 20 micrometers or more and 400 micrometers or less.

Moreover, in the white polyester film used by this invention, in order to improve the handleability of a film, microparticles | fine-particles can be added. 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.

(Adhesive layer (a))

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

  The adhesive used for the adhesive layer (a) in the present invention has an unsaturated hydrocarbon bond in the molecule of the polyurethane resin. By laminating an uncrosslinked rubber layer, and subsequently crosslinking the rubber layer, The crosslinking reaction proceeds at the interface between the adhesive 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 polyester film, an uncrosslinked rubber layer is laminated thereon, and subsequently subjected to crosslinking treatment by irradiation with active energy rays. Thus, the crosslinking of the rubber layer itself and the crosslinking reaction of the adhesive layer and the rubber layer interface of the present invention proceed simultaneously to obtain a laminate in which the rubber layer and the polyester film are firmly bonded.

  The polyurethane resin having an unsaturated hydrocarbon bond in the molecule for use in the adhesive layer (a) of 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 is preferably derived from an acrylate group or a methacrylate group, and the concentration thereof is desirably contained in the molecule in the range of 50 to 2000 eq / ton, more preferably 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 present invention is preferably one obtained by reacting a polyester diol (A), a (meth) acrylate monomer (B) and a diisocyanate compound (C), and if necessary, a polyol compound (D), What reacted also including the polyamine compound (E) and / or the amino alcohol compound (F) may be used.

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. If it is 5000 or more, the copolymerization amount of the (meth) acrylate monomer (B) component introduced by copolymerization is relatively small, and the excellent adhesive effect with the rubber layer interface of the present invention tends to be hardly exhibited.

  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 for the adhesive layer (a) 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 carried out in a non-catalytic system, but 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 adhesive layer (a) in the present invention, a monofunctional or polyfunctional (meth) acrylate compound that is not copolymerized in the molecule is used as a reactive diluent for the purpose of improving the coating property. Also good. 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.

  In the adhesive used in the adhesive layer (a) in the present invention, 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 resins, other polyurethane resins, and the like can be appropriately blended.

(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 of the present invention is provided on the surface of a 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 rubber layer is formed by applying a solution obtained by dissolving the rubber composition in a solvent to the surface of an easily-adhesive white polyester film substrate having the adhesive layer (a) and drying it. Examples thereof include a method, a method in which an adhesive layer is provided on the surface of a plastic substrate layer, and a rubber composition is formed by extruding a rubber composition under high pressure, 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 produce an uncrosslinked rubber layer dissolved in a solvent on the surface of the adhesive layer of the present invention, followed by drying and subsequently crosslinking the rubber. At this time, it is expected that interfacial cross-linking occurs between the rubber layer and the NBR structure in the adhesive layer of the present invention together with the cross-linking of the rubber layer, so that stronger adhesiveness is expressed.

(Anchor layer)
In the present invention, it is preferable to provide the anchor layer (b) on the surface of the white 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.

  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) Light transmittance of polyester film It sampled every 100 m from the film roll, and calculated | required the average value of the total light transmittance by Nippon Denshoku Industries Co., Ltd. NDH-1001DP by JIS-K7105-1981.

(2) Apparent density of polyester film Four films were cut into 5.00 cm squares and used as samples. Four of these were stacked, and the thickness was changed with a micrometer, and arbitrary 10 locations were measured with four significant figures, and the average value of the stacked thickness was obtained. The average value was divided by 4 and rounded to 3 significant figures to obtain an average thickness per sheet (t: μm). The mass (w: g) of the four samples was measured using an automatic upper pan balance with four significant digits, and the apparent density was determined from the following equation. The apparent density was rounded to 3 significant figures.
Apparent density (g / cm ³ ) = (w × 10 ⁴ ) / (5.00 × 5.00 × t)
(3) Number average molecular weight of polyurethane resin Using water permeation gel permeation chromatography (GPC) 150C, tetrahydrofuran was measured as a carrier solvent at a flow rate of 1 ml / min. 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.

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

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

(4) Glass transition temperature of polyurethane resin It measured on the following conditions 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.

(5) Interlaminar peel strength of rubber / polyester film laminate Insert a knife into the adhesive layer between the rubber layer of the rubber / polyester film laminate and the polyester 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.

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

(8) Appearance After forming the rubber laminate, it was rated as ○ when the rubber layer was difficult to see when viewed from the film side, and × when it was clearly visible.

[Example 1]
[Adjustment of anchor layer (b) coating solution]
Water-dispersed copolyester resin (Toyobo Co., Ltd., Vylonal) 3% by mass, water-soluble urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Elastron) 6% by mass, average particle size 1.5 μm (electron microscopy) A water / isopropyl alcohol-based coating solution containing 1% by mass of silica gel fine particles)) was prepared.

[White polyester film raw material]
Anatase-type titanium dioxide particles having an average particle size of 0.3 μm and an average particle diameter of 0.32 μm obtained from a polyethylene terephthalate resin having an intrinsic viscosity of 0.62 dl / g and containing no white pigment and inorganic particles obtained by a conventional method as a film material A mixture of 0% by mass and 0.1% by mass of optical brightener (manufactured by Eastman Chemical Co., OB1) was supplied to a vent type twin screw extruder and pre-kneaded. Subsequently, this molten resin was continuously supplied to a vent type single-screw kneader, kneaded and extruded, and the obtained strand was cooled and cut to produce titanium dioxide-containing master pellets A.

  Next, a silica particle-containing polyethylene terephthalate resin pellet B having an intrinsic viscosity of 0.62 dl / g and containing 0.7% by mass of silica particles having an average particle diameter of 1.8 μm added by a conventional polymerization addition method was produced.

75% by mass of polyethylene terephthalate resin C having an intrinsic viscosity of 0.62 dl / g and containing no white pigment and inorganic particles and 25% by mass of the above-mentioned titanium dioxide-containing master pellet A are pellet-mixed and vacuum-dried at 140 ° C. for 8 hours. The film raw material (I) was obtained.
30% by mass of titanium dioxide-containing master pellets A and 70% by mass of silica particle-containing pellets B were mixed and subjected to vacuum drying at 140 ° C. for 8 hours to obtain film raw material (II).

[Preparation of white polyester film]
The film raw materials (I) and (II) were respectively supplied to different extruders, and laminated in a molten state in the order of (II) / (I) / (II) using a feed block. This molten resin was coextruded from a T-die onto a rotating cooling metal roll adjusted to 25 ° C. The discharge amount of each extruder was adjusted so that the thickness ratio of each layer was 10:80:10, and an unstretched film having a thickness of 920 μm was produced.
The obtained unstretched film was uniformly heated to 66 ° C. using a heating roll, and 3.1 between two pairs of nip rolls (low speed roll: 2 m / min, high speed roll: 6.2 m / min) having different peripheral speeds. Stretched twice. The both sides of the uniaxially stretched film thus obtained were subjected to corona discharge treatment, and the aqueous coating agent shown above was applied to both treatment surfaces by a coating method.

After that, the film end is continuously held by a clip and guided to a tenter, heated to 120 ° C. and stretched by 3.7 times, fixed in the width direction and subjected to heat treatment at 230 ° C. for 5 seconds, By relaxing 4% in the width direction at 200 ° C., a white laminated polyester film having a thickness of 50 μm having a coating layer of 0.20 g / m ^{2 on} both surfaces was obtained. On the film, an anchor layer (b) made of a crosslinked polymer was provided by coating and drying the coating solution during film formation. The resulting white polyester film had a light transmittance of 15%.

[Preparation of easy-adhesive white polyester film]
On the anchor layer (b) of the obtained white polyester film, an adhesive layer (a) made of polyurethane resin PU1 of Synthesis Example 1 below was applied by bar coating so that the thickness after drying was 5 μm. .

[Synthesis Example 1]
(Synthesis of polyester diol component) 97 g of dimethyl terephthalate, 97 g of dimethyl isophthalate, 73 g of neopentyl glycol, 81 g of ethylene glycol and tetrabutyl titanate as a catalyst in a 1 L four-necked flask equipped with a thermometer, a stirring rod and a Liebig condenser. 0.1 g of (TBT) was charged, and the transesterification reaction was allowed to proceed at 190 ° C. 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 1 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-1.

(Manufacture of layers mainly made of rubber)
EPDM (ethylene content 34%, “EP21” manufactured by Nippon Synthetic Rubber Co., Ltd.) as rubber and zinc salt of 2-mercaptobenzimidazole (“NOCRACK MBZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.) as anti-aging agent A In addition, 4,4- (α, α-dimethylbenzyl) diphenylamine (“NOCRACK CD” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) was used as the anti-aging agent B, respectively, and kneaded by a conventional method with the following composition.

[Composition composition]
EPDM: 100.0 parts by mass, polyethylene glycol (molecular weight 4000): 2.5 parts by mass, stearic acid: 0.5 parts by mass, anti-aging agent A: 1.5 parts by mass, anti-aging agent B: 0.7 parts by mass Parts, 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.

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

  Next, the EPDM rubber solution obtained by the above dissolution and defoaming 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 made of a copolymer of poly-4-methylpentene-1 on the surface of the EPDM rubber (“Opyran X-60YMT4” manufactured by Mitsui Petrochemical Co., Ltd.) ) So that the matted surface faces the EPDM rubber surface, and is continuously laminated using a pressure roll at a pressure of 5 kgf / cm, and the resulting laminate is further continuously introduced into the electron beam irradiation apparatus. The polyester film is irradiated with an electron beam at an energy of 200 KV and 3 Mrad to perform pre-crosslinking, and then the cover sheet is peeled off, and EPDM To obtain a laminate consisting of beam layer and the polyester 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 / white polyester film laminate was obtained and wound into a roll. Table 2 shows the evaluation results such as the delamination strength and adhesion durability evaluation of the obtained rubber / white polyester film laminate.

[Examples 2 to 6 and Comparative Example 1]
The samples for adhesion test were prepared using the polyurethane resins PU1 to PU7 obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 and were subjected to delamination strength and adhesion durability evaluation. The results are shown in Table 2.
[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 1 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 1 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-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 1 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-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 1 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-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 1 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 1 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.

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

Example 7
In Example 1, an easy-adhesive white polyester film and a rubber / white polyester film laminate were obtained in the same manner except that the stretching temperature of the film was 110 ° C. for longitudinal stretching, 120 ° C. for lateral stretching, and 180 ° C. for heat setting. .

Example 8
An easy-adhesive white film and a rubber / white film laminate were obtained by the method of Example 1 except that the film was obtained by the following method.
(Adjustment of cavity forming agent)
As a raw material, 20 mass% of a polystyrene resin having a melt flow rate of 1.7, 20 mass% of a polypropylene resin having a melt flow rate of 1.7, and 60 mass% of a polymethylpentene resin having a melt flow rate of 8 are pellet-mixed, and a twin screw extruder. The mixture was sufficiently kneaded to prepare cavity forming agent pellets.

(Preparation of fine particle-containing master pellets)
As a raw material, 50% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.64 mixed with 50% by mass of anatase-type titanium dioxide having an average particle size of 0.3 μm (electron microscopic method) is supplied to a vent type twin screw extruder and premixed. After kneading, the molten polymer was continuously supplied to a vent type uniaxial kneader and kneaded to prepare fine particle (titanium oxide) -containing master pellets.
Next, 10% by mass of the cavity forming agent obtained by the above method, 5% by mass of fine pellets (titanium oxide) -containing master pellets and 85% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.62 are mixed with pellets and vacuum dried. It was set as the raw material of the film which comprises A layer.
On the other hand, 30% by mass of polyethylene terephthalate resin having an intrinsic viscosity of 0.62 and 70% by mass of the above-described fine particle (titanium oxide) -containing master pellets were mixed in a pellet and vacuum-dried to obtain a film material constituting the B layer.

  Subsequently, the raw material of the film which comprises said each layer was each supplied to the separate extruder, and B layer was joined to the single side | surface of A layer in the molten state using the feed block. At this time, the discharge amount ratio of the A layer and the B layer was controlled to 93 to 7 volume ratio using a gear pump. Next, the sheet was extruded onto a cooling drum adjusted to 30 ° C. using a T die to produce an unstretched sheet having a thickness of about 600 μm. At this time, extrusion was performed so that the B layer side was a non-drum surface and the A layer side was a drum surface.

(Production of biaxially stretched film)
The obtained unstretched sheet is uniformly heated to 65 ° C. using a heating roll, and the speed is regulated (2 m / min) by sandwiching a film between a metal roll whose temperature is controlled to 65 ° C. and a rubber roll whose temperature is not controlled. The film was stretched 3.4 times with a high speed roll (6.8 m / min). The obtained longitudinally uniaxially stretched film is guided to a tenter, heated to 140 ° C. and transversely stretched 3.7 times, fixed in width and subjected to heat treatment at 220 ° C. for 5 seconds, and further at 220 ° C. in the width direction. % Cavity relaxation white polyester film having a thickness of 50 μm was obtained. The resulting film had a light transmittance of 17% and an apparent density of 1.13 g / cm ³ .

[Comparative Example 2]
A film and a rubber laminate were obtained in the same manner as in Example 1 except that the base polyester film was a transparent polyester film (Cosmo Shine A4300, thickness 50 μm) manufactured by Toyobo. The light transmittance was 90%.

  The adhesive 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, whereby the polyurethane adhesive layer and the rubber layer As a result, an excellent adhesive force is exhibited. In addition, since the interface between the polyurethane adhesive layer and the rubber layer is bonded by chemical bonding, excellent adhesion durability is exhibited. The resulting rubber / white polyester film laminate has both the flexibility of rubber and the toughness of white polyester film, so it can be used as a sealing material, cushioning material, surface tactile improvement material such as electronic / electrical products and automobile interior parts. It can be used for molded products and is useful.

Claims (8)

  Easy adhesion, characterized in that a polyurethane resin adhesive layer (a) having an unsaturated hydrocarbon bond in the molecule is laminated on at least one side of a white polyester film having a light transmittance of 1 to 50% oriented at least in a uniaxial direction. White polyester film.   The easily adhesive white polyester film according to claim 1, wherein the unsaturated hydrocarbon bond is derived from a (meth) acrylate group.   3. The easily adhesive white polyester film according to claim 1, wherein an unsaturated hydrocarbon bond concentration is contained in the molecule in a range of 50 to 2000 eq / ton.   The easily adhesive white 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). Adhesive white polyester film.   An anchor layer (b) made of a crosslinked polymer is provided on one side of a white polyester film having a light transmittance of 1 to 50% oriented at least in a uniaxial direction, and an adhesive layer (a) is further laminated thereon. The easily adhesive white polyester film according to any one of claims 1 to 5.   The easily adhesive white polyester film according to any one of claims 1 to 6, further comprising a surface treatment layer (c) on a film surface opposite to the adhesive layer (a).   A rubber / white polyester film laminate in which a layer (d) containing rubber as a main component is laminated on the adhesive layer (a) of the film according to claim 1.