JP2016221860A - Double-side coated film and photosensitive resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a double-side coated film which has excellent dye bleed-out prevention performance even under severe heating conditions and shows good adhesiveness to a functional layer such as a hard coat layer and an adhesive layer, antistatic property and halation prevention performance, and to provide a photosensitive resin laminate.SOLUTION: A double-side coated film has a coating layer on both surfaces of a laminate polyester film comprising at least three layers including a layer containing a dye, in which one coating layer is formed from a coating liquid containing at least two types of crosslinking agents selected from a melamine compound, an epoxy compound and an oxazoline compound, and at least one surface of the film has an average roughness (Ra) of 0.30 to 0.70 μm. A photosensitive resin laminate includes a photosensitive resin layer and a cover film successively laminated with an adhesive layer on the coating layer of the double-side coated film, the coating layer formed from a coating liquid containing at least two types of crosslinking agents.SELECTED DRAWING: None

Description

  The present invention relates to a double-sided coating film having a configuration in which coating layers are provided on both sides of a polyester film substrate containing a dye, and has the ability to prevent the dye from bleeding out from the film substrate to the film surface. And a film having good adhesion to a functional layer such as a hard coat layer and an adhesive layer, and having a good antistatic property and antihalation performance, for example, for resin layer processing, for display, etc. The present invention relates to a use that can be suitably used as a special photosensitive resin laminate.

  Polyester films have been used for various industrial applications, taking advantage of their excellent heat resistance, water resistance, chemical resistance, mechanical strength, dimensional stability, etc., but their applications are expanding and diversifying. It has also been used for applications in which a dye or pigment is added to a transparent polyester raw material to form a colored polyester film.

  For example, in the use of colored films containing dyes, such as for resin layer processing and display applications, even when a good dye such as color formulation, heat resistance and dispersibility is selected, the dye can be used under severe heating conditions. Bleeding out of the dye occurs from the film containing, and contamination of various manufacturing processes and an increase in film haze may occur, and the situation is in need of improvement.

  In order to solve the above problems, for example, Patent Documents 1 and 2 propose a coextruded laminated film composed of three or more layers containing a dye in an intermediate layer to prevent dye bleed out. However, the film described in the above patent document may still have insufficient dye bleed-out preventing performance under severe heating conditions.

  Application examples of the colored film include resin layer processing. As a specific example of the application, a dry film resist (DFR) application is exemplified. The photosensitive resin laminate used in the DFR process is generally composed of a laminate such as a base film / adhesive layer (containing a colorant) / photosensitive resin layer / cover film.

  In the DFR process, the protective film having the laminate structure is generally peeled off, the photosensitive resin layer is pressure-bonded to a copper foil substrate, a pattern mask is placed on the base film, and the photosensitive resin layer is formed from the base film side. It consists of a manufacturing process in which a circuit is formed on a substrate by exposing, peeling off and developing the base film.

  Thus, in order to draw a circuit image by exposure with ultraviolet rays or the like by placing a pattern mask on the base film, the base film needs appropriate light transmittance and smoothness. Furthermore, there is a method of selecting a colorant capable of appropriately reducing the light transmittance at a specific wavelength as an antihalation agent for preventing irregular reflection of light on the surface of the base film, so-called halation phenomenon, and adding it to the adhesive layer. It is common (for example, patent document 3).

  In addition, by using at least one surface of the colored film as a mat treatment, it is possible to reduce halation and to adjust the adhesive force and the peeling force, so that it is generally used (for example, Patent Document 4).

  On the other hand, in order to improve the adhesiveness of the adhesive layer with the photosensitive resin layer laminated thereon, it is often necessary to set the coating thickness (after drying) to be thick. Therefore, when a colorant is contained in the adhesive layer as an antihalation agent, the content of the colorant also tends to increase as the coating thickness increases. There is a concern about the transfer.

  Furthermore, when the content of the colorant in the adhesive layer is reduced in consideration of prevention of migration of the colorant, the adhesiveness is good, but the desired antihalation performance may not be obtained.

  In order to ensure the halation preventing effect uniformly in the adhesive layer, the dispersibility of the colorant and the adhesive component is required to be more uniform. Therefore, it is difficult to satisfy all of the technical problems of adhesiveness of the adhesive layer, uniformity of the antihalation effect, and prevention of migration of the antihalation agent over time at the same time.

Japanese Patent Laid-Open No. 10-157040 JP 2002-52675 A JP-A-8-87106 JP-A-6-342213

  The present invention has been made in view of the above circumstances, and its solution is to have excellent dye bleed-out prevention performance even under severe heating conditions, and functions such as a hard coat layer and an adhesive layer. An object of the present invention is to provide a double-sided coated film and a photosensitive resin laminate that have good adhesion to a layer, and good antistatic properties and antihalation performance.

  As a result of intensive studies in view of the above circumstances, the present inventors have found that the above-described problems can be easily solved by using a double-sided coating film having a specific configuration, and have completed the present invention.

  That is, the gist of the present invention is to have a coating layer on both sides of a laminated polyester film composed of at least three layers including a layer containing a dye, and one coating layer includes a melamine compound, an epoxy compound, and an oxazoline compound. It is formed from a coating liquid containing at least two kinds of crosslinking agents selected from among the above, and the average roughness (Ra) of at least one surface is 0.30 to 0.70 μm A photosensitive resin layer and a cover film are sequentially laminated via an adhesive layer on a double-sided coating film and a coating layer formed from a coating solution containing at least two types of crosslinking agents of the double-sided coating film. It exists in the photosensitive resin laminated body characterized by being formed.

  According to the double-sided coating film of the present invention, the double-sided coating has excellent anti-bleeding-out performance of the dye and good adhesion to functional layers such as a hard coat layer and an adhesive layer, and has good antistatic properties and antihalation performance. A film can be provided, and its industrial value is high.

  The polyester film constituting the double-sided coated film in the present invention is required to have at least three layers or more. As long as the gist of the present invention is not exceeded, the number of layers may be four or more, and is not particularly limited. For example, it is possible to change the raw material of the surface layer and the intermediate layer into a three-layer structure for the purpose of effectively improving various properties using a polyester film with high functionality as the surface layer raw material. In the polyester film of the present invention, the surface layer is a layer constituting two exposed surfaces, and the other layers are called intermediate layers.

  In one preferred embodiment of the present invention, the polyester film having a multilayer structure has a three-layer structure, the dye is contained only in the intermediate layer, and the surface layer is a polyester layer containing substantially no dye, A method for preventing bleed-out of the above is mentioned.

  The intrinsic viscosity of the polyester composition constituting the surface layer and the intermediate layer is usually 0.3 to 0.9 dl / g, preferably 0.4 to 0.8 dl / g, more preferably 0.5 to 0.8 dl / g. g. When the intrinsic viscosity is less than 0.3 dl / g, the heat resistance and mechanical strength of the film tend to be inferior. On the other hand, if the intrinsic viscosity exceeds 0.90 dl / g, the load becomes excessive in the extrusion process during the production of the polyester film, and as a result, the productivity may decrease.

  The polyester used for the film in the present invention may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical polyester includes polyethylene terephthalate and the like. On the other hand, the dicarboxylic acid component of the copolyester includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.), etc. 1 type or 2 types or more are mentioned, As a glycol component, 1 type or 2 types or more, such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexane dimethanol, neopentyl glycol, is mentioned.

  The double-sided coated film of the present invention is required to contain a dye in the multilayer polyester film constituting the film. In the present invention, from the viewpoint of reducing the bleed out of the dye, a constitution in which the dye is contained in the intermediate layer of the multilayer polyester film is preferable.

  As a dye to be blended in the polyester layer of the film of the present invention, it is preferable to consider the heat resistance at the time of polyester production and the dispersibility in the polyester, and in terms of chemical structure, anthraquinone, phthalocyanine, perinone And dyes such as isoquinoline are preferably used.

  These dyes are generally used by appropriately selecting several types and mixing them, and the content in the raw material polyester constituting each layer is preferably in the range of 0.01 to 10% by weight. The range of 0.01 to 5% by weight is preferable. When the dye content is less than 0.01% by weight, the effect of the contained dye may not be sufficiently exerted. When the dye content exceeds 10% by weight, the dye bleeds out on the surface, process contamination and film There is concern about the deterioration of transparency.

  It is preferable to add inorganic particles, organic salt particles and crosslinked polymer particles to the polyester layer of the film of the present invention. Inorganic particles that can be used include calcium carbonate, kaolin, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, Examples thereof include lithium fluoride. On the other hand, examples of the organic salt particles include calcium oxalate, terephthalate such as calcium, barium, zinc, manganese, and magnesium. In addition, organic particles such as poly-handed trifluoroethylene, valve guanamin resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, thermosetting phenol resin may be used.

  On the other hand, the shape of the particles to be used is not particularly limited, and any of a spherical shape, a block shape, a rod shape, a flat shape, and the like may be used. Moreover, there is no restriction | limiting in particular also about the hardness, specific gravity, etc. These series of particles may be used in combination of two or more as required.

  Moreover, the average particle diameter of the particle | grains used for at least one polyester surface layer becomes like this. Preferably it is the range of 3-8 micrometers. When the average particle size of the particles blended on the rough surface side is 3 μm or less, the ability to form protrusions on the surface may be insufficient, and when it exceeds 8 μm, breakage and the like frequently occur when the film is stretched. The product may not be collected stably.

  Furthermore, the particle content in at least one polyester surface layer is usually 5% by weight or less, preferably 0.1 to 3% by weight, based on the polyester layer containing the particles. If the particle content is less than 0.1% by weight, the number of protrusions on the film is not sufficient, so the effect of reducing halation may not be sufficient, while when adding more than 5% by weight, When the film is stretched, breakage or the like frequently occurs, and the product may not be collected stably.

  The average roughness (Ra) of at least one surface of the polyester film of the present invention needs to be in the range of 0.30 to 0.70 μm. If Ra is less than 0.30 μm, it is not possible to obtain a film excellent in reducing halation when mat processing is not performed in the subsequent step. Moreover, in order to make it larger than 0.70 micrometer, it is necessary to mix | blend a large amount of coarse particles, and when extending | stretching a film, a fracture | rupture etc. occur frequently and cannot collect | collect a product stably.

  Further, in the present invention, the method of adding particles and colorants to the polyester is not particularly limited, but a method of adding to the polymerization step, a method of kneading particles or dye using an extruder to obtain a master batch, etc. Is mentioned.

  In addition, in the multilayer polyester film constituting the double-sided coated film in the present invention, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, ultraviolet absorbers and the like as necessary in addition to the above-mentioned particles. Can be added.

  In this invention, you may contain a ultraviolet absorber and a fluorescent whitening agent in the laminated polyester film which comprises a double-sided coating film as needed. An ultraviolet absorber and a fluorescent brightening agent are blended, for example, in order to reduce a specific absorption wavelength desired when patterning is performed by ultraviolet irradiation in a resin processing application. In addition, as an ultraviolet absorber contained in a polyester film, an organic type ultraviolet absorber and an inorganic type ultraviolet absorber are mentioned.

  Specific examples of the organic ultraviolet absorber include salicylic acid type, for example, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like, benzophenone type, for example, 2-hydroxy-4 -Benzyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxy Benzophenone, 2-2'-dihydroxy-4,4'-dimethoxybenzophenone and the like, benzotriazole series, for example, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (2'- Hydroxy-5'-t-octylphenyl) -benzo Triazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy- Natural products such as 3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′5′-di-t-butylphenyl) 5-chlorobenzotriazole Examples include oryzanol, shea butter, baicalin, and other biological systems such as keratinocytes, melanin, urocanic acid, and the like. These organic ultraviolet absorbers can be used alone or in combination of two or more. These organic ultraviolet absorbers can be used in combination with a hindered amine compound as an ultraviolet stabilizer.

  Specific examples of the inorganic ultraviolet absorber include titanium oxide, zinc oxide, indium oxide, tin oxide, talc, kaolin, calcium carbonate, titanium oxide composite oxide, zinc oxide composite oxide, ITO (tin doped indium oxide) ), ATO (antimony-doped tin oxide) and the like. Examples of the titanium oxide-based composite oxide include zinc oxide doped with silica and alumina. These inorganic ultraviolet absorbers can be used alone or in combination of two or more. Moreover, you may use together an organic type ultraviolet absorber and an inorganic type ultraviolet absorber.

  Specific examples of the optical brightener include benzoxazoyl derivatives, coumarin derivatives, styrene biphenyl derivatives, pyrazolone derivatives and the like. These fluorescent brighteners can be used alone or in combination of two or more. Moreover, you may use together a fluorescent whitening agent and said ultraviolet absorber.

  As a method of blending UV absorbers and fluorescent brighteners into polyester films, a method of directly adding UV absorbers and fluorescent brighteners to an extruder, or a polyester resin kneaded with UV absorbers and fluorescent brighteners in advance. The method etc. which are added to an extruder can be mentioned, Among these, any one method may be employ | adopted and two methods may be used together.

  In the double-side coated film of the present invention, the absorbance at each measurement wavelength of 360 nm, 380 nm, and 420 nm is preferably in the range of 0.3 to 1.4, and more preferably 0 in order to improve the antihalation performance. The range is from 4 to 1.0. In the case where the absorbance is less than 0.3, for example, when the photosensitive resin layer is cured by ultraviolet irradiation, there may be a problem such as curing to a region that is not originally desired to be cured at the time of patterning. Moreover, when the said light absorbency exceeds 1.4, it will be necessary to increase hardening time, for example, and productivity may deteriorate. Therefore, from the viewpoint of controlling light transmittance, in the present invention, it is preferable to contain a yellow dye in the polyester film.

  Specific examples of yellow dyes include Solvent Yellow 18, Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 22 and the like when Solvent Yellow classified by color index is taken as an example. These dyes may be used alone or in combination of two or more as required.

  In the double-side coated film of the present invention, when the photosensitive resin layer is cured by ultraviolet irradiation, a measurement wavelength of 350 nm to 450 nm is obtained in order to obtain a stable antihalation performance without being limited to a specific wavelength. The absorbance in the range is preferably in the range of 0.3 to 1.4, more preferably in the range of 0.4 to 1.0.

  Next, the example of formation of the polyester film in this invention is demonstrated. The structure of the polyester film in the present invention is one of the preferred embodiments. The film has a three-layer structure, and the dye layer is contained only in the intermediate layer and the surface layer does not contain the dye. However, the present invention is not limited to the following examples.

  The polyester used for the intermediate layer containing a predetermined amount of dye and the polyester used for the surface layer containing a predetermined amount of particles as needed are supplied to separate melt extrusion apparatuses and heated to a temperature equal to or higher than the melting point of each polymer. Melt. Next, the molten polymer is bonded and laminated in a laminar flow in an extrusion die, extruded from a slit die, rapidly cooled and solidified on a rotating cooling drum to a temperature below the glass transition temperature, and substantially amorphous. An unstretched sheet in a state is obtained. In this case, in order to improve the flatness of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum. In the present invention, an electrostatic application adhesion method and / or a liquid application adhesion method is preferably employed.

  Specifically describing the stretching conditions in the present invention, the unstretched sheet is preferably stretched 2 to 6 times at 70 to 120 ° C. in the longitudinal direction to form a uniaxially stretched film, and then at 90 to 160 degrees in the lateral direction. The film is stretched 2 to 6 times to form a biaxially stretched film, and heat treatment is performed at 150 to 250 ° C. for 1 to 600 seconds. Further, at this time, there is a method of relaxing at 15% or less in the vertical direction and / or the horizontal direction in the maximum temperature zone of the heat treatment and / or the cooling zone at the heat treatment outlet. Further, it is possible to add re-longitudinal stretching and re-lateral stretching as necessary.

  Next, formation of the coating layer which comprises the double-sided coating film in this invention is demonstrated. Regarding the coating layer, it may be provided by in-line coating, which treats the film surface during the above-mentioned polyester film forming process, or may be applied off-system on a once produced film. . More preferably, it is formed by in-line coating.

  In-line coating is a method of coating within the process of manufacturing a polyester film, and specifically, a method of coating at any stage from melt extrusion of a polyester to heat setting after stretching and winding up. Usually, it is coated on any of an unstretched sheet obtained by melting and quenching, a stretched uniaxially stretched film, a biaxially stretched film before heat setting, and a film after heat setting and before winding. Although not limited to the following, for example, in sequential biaxial stretching, a method of stretching in the transverse direction after coating a uniaxially stretched film stretched in the longitudinal direction (longitudinal direction) is particularly excellent. According to such a method, film formation and coating layer formation can be performed at the same time, so there is an advantage in manufacturing cost. In addition, in order to perform stretching after coating, the thickness of the coating layer can be changed by the stretching ratio. Compared to offline coating, thin film coating can be performed more easily.

  In the present invention, it is essential that one side of the polyester film is formed from a coating solution containing at least two kinds of crosslinking agents selected from an oxazoline compound, a melamine compound, and an epoxy compound. It is what.

  Examples of the crosslinking agent used in the present invention include oxazoline compounds, melamine compounds, and epoxy compounds. In addition, other known crosslinking agents such as an isocyanate compound, a carbodiimide compound, an aziridine compound, a silane coupling compound, and an organometallic complex are included within the range not impairing the gist of the present invention. Although it is possible to use two or more species, it is necessary to use at least two or more types of compounds selected from oxazoline compounds, melamine compounds, and epoxy compounds from the viewpoint of preventing bleeding out of the dye.

  The oxazoline compound is a compound having an oxazoline group in the molecule, and a polymer containing an oxazoline group is particularly preferable, and can be prepared by polymerization of an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Addition polymerizable oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, and the like can be mentioned, and one or a mixture of two or more thereof can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not limited as long as it is a monomer copolymerizable with an addition polymerizable oxazoline group-containing monomer. For example, alkyl (meth) acrylate (the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, (meth) acrylic acid esters such as n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene Unsaturated carboxylic acids such as sulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); Unsaturated nitriles such as acrylonitrile, methacrylonitrile; (meth) acrylamide, N-alkyl ( (Meth) acrylamide, N, N-dialkyl (meth) acrylamide, As the alkyl group, unsaturated amides such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group and cyclohexyl group); vinyl acetate Vinyl esters such as vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride And α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene, and the like, and one or more of these monomers can be used.

  The content of the oxazoline group contained in the oxazoline compound is usually 0.5 to 10 mmol / g, preferably 1 to 9 mmol / g, more preferably 3 to 8 mmol / g, and further preferably 4 to 6 mmol in terms of the amount of the oxazoline group. / G. Use in the above range is preferable for improving the coating film strength of the coating layer.

  The melamine compound is a compound having a melamine skeleton in the compound. For example, an alkylolized melamine derivative, a compound partially or completely etherified by reacting an alcohol with an alkylolated melamine derivative, and these Mixtures can be used. As alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol and the like are preferably used. Moreover, as a melamine compound, either a monomer or a multimer more than a dimer may be sufficient, or a mixture thereof may be used. Further, a product obtained by co-condensing urea or the like with a part of melamine can be used, and a catalyst can be used to increase the reactivity of the melamine compound.

  The epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include condensates of epichlorohydrin with ethylene glycol, polyethylene glycol, glycerin, polyglycerin, bisphenol A and the like hydroxyl groups and amino groups, There are polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, and the like. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, glycerol polyglycidyl ether, trimethylolpropane. Examples of the polyglycidyl ether and diepoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, poly Examples of tetramethylene glycol diglycidyl ether and monoepoxy compounds include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl amine compounds such as N, N, N ′, N′-tetraglycidyl-m-xylyl. Examples include range amine and 1,3-bis (N, N-diglycidylamino) cyclohexane.

  The isocyanate compound is a compound having an isocyanate derivative structure typified by isocyanate or blocked isocyanate. Examples of the isocyanate include aromatic isocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, and aromatic rings such as α, α, α ′, α′-tetramethylxylylene diisocyanate. Aliphatic isocyanates such as aliphatic isocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropylidene dicyclohexyl diisocyanate Ne Alicyclic isocyanates such as bets are exemplified. Further, polymers and derivatives such as burettes, isocyanurates, uretdiones, and carbodiimide modified products of these isocyanates are also included. These may be used alone or in combination. Among the above isocyanates, aliphatic isocyanates or alicyclic isocyanates are more preferable than aromatic isocyanates in order to avoid yellowing due to ultraviolet rays.

  When used in the state of blocked isocyanate, the blocking agent includes, for example, bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol, and alcohols such as propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, methanol, and ethanol. Compounds, active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, lactam compounds such as ε-caprolactam and δ-valerolactam , Amine compounds such as diphenylaniline, aniline, ethyleneimine, acetanilide, acid amide compounds of acetic acid amide, formaldehyde, acetoald Examples include oxime compounds such as oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, and these may be used alone or in combination of two or more.

  The carbodiimide compound is a compound having one or more carbodiimide or carbodiimide derivative structures in the molecule, but a polycarbodiimide compound having two or more in the molecule is more preferable for better adhesion and the like.

  The carbodiimide compound can be synthesized by a conventionally known technique, and generally a condensation reaction of a diisocyanate compound is used. The diisocyanate compound is not particularly limited, and any of aromatic and aliphatic compounds can be used. Specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, hexa Examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, and dicyclohexylmethane diisocyanate.

  In the present invention, the ratio of the crosslinking agent in the coating solution is preferably 20% by weight or more, more preferably 30% by weight or more, from the viewpoint of preventing bleeding out of the dye. When the ratio of the crosslinking agent is less than 20% by weight, the bleedout prevention performance of the dye may be deteriorated.

  In the present invention, the double-sided coating film containing a dye may be required to have adhesiveness to a functional layer such as a hard coat layer or an adhesive layer depending on the intended use. Therefore, when it is necessary to achieve both the prevention of dye bleedout and the adhesion to a functional layer such as a hard coat layer, a form using two or more of the above-mentioned crosslinking agents is required. Are preferably a combination of a melamine compound and an oxazoline compound, a melamine compound and an epoxy compound, an oxazoline compound and an epoxy compound, or a combination of a melamine compound, an oxazoline compound and an epoxy compound.

  As a ratio with respect to all the non-volatile components in the coating liquid which forms the coating layer which comprises the double-sided coating film in this invention, a crosslinking agent is 20 weight% or more normally, Preferably it is the range of 40 weight% or more. If the amount is less than 20% by weight, sufficient dye bleed-out prevention performance may not be obtained. On the other hand, if the amount is more than 70% by weight, the amount of other components is small. May not be obtained.

  In the present invention, various crosslinking catalysts that promote the reaction of the crosslinking agent may be used in combination from the viewpoint of improving the bleedout prevention property of the dye.

  Examples of the melamine compound crosslinking catalyst include organic acids such as aromatic sulfonic acid compounds and phosphoric acid compounds and salts thereof, amine compounds, salts of amine compounds, imine compounds, amidine compounds, guanidine compounds, and heterocyclic rings containing N atoms. Examples thereof include metal compounds such as formula compounds, organometallic compounds, zinc stearate, zinc myristate, aluminum stearate and calcium stearate.

  Examples of cross-linking catalysts for oxazoline compounds include proton acids such as paratoluenesulfonic acid, phosphoric acid, and phosphorous acid, ammonium paratoluenesulfonate, ammonium chloride, diammonium imidodisulfonate, diammonium hydrogen phosphate, and hydrogen phosphate dihydrogen. Examples thereof include proton acid salts such as sodium, proton acid esters such as ethyl paratoluenesulfonate, dimethyl phosphite and diphenyl phosphite, and onium salts such as tetrabutylammonium tetrafluoroborate.

  Examples of epoxy compound crosslinking catalysts include piperidine, N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6, -tris (dimethylaminomethyl) phenol, and the like. Examples thereof include tertiary and secondary amine compounds, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, imidazole compounds such as epoxy-imidazole adduct, and the like.

  The cross-linking agent is used in a design to improve the performance of the coating layer by reacting in the drying process or film forming process. Therefore, it can be inferred that unreacted products of these crosslinking agents, compounds after the reaction, or a mixture thereof exist in the finished coating layer. And the analysis of the component in a coating layer can be performed by analysis, such as TOF-SIMS, ESCA, and a fluorescent X ray.

  In the present invention, the coating layer may contain one or more polymers for the purpose of improving the film forming property of the coating film, and the structure and ionicity of the polymer used are not particularly limited. Examples thereof include polyester resins, polyurethane resins, acrylic resins, vinyl resins such as polyvinyl alcohol, epoxy resins, amide resins, and the like.

  In addition, these skeleton structures may have a composite structure by copolymerization or the like, and examples of the polymer having a composite structure include acrylic resin graft polyester, acrylic resin graft polyurethane, vinyl resin graft polyester, vinyl Resin graft polyurethane etc. are mentioned.

  In the present invention, for example, when used for processing a resin layer, a coating layer containing an antistatic agent is provided on the surface of the film opposite to the film on which the resin layer is laminated for the purpose of preventing anti-peeling. preferable.

  Antistatic agents contained in the coating layer include ion conductive polymer compounds such as ammonium group-containing compounds, polyether compounds, sulfonic acid compounds, and betaine compounds, polyacetylene, polyphenylene, polyaniline, polypyrrole, polyisothianaphthene. And π-electron conjugated polymer compounds such as polythiophene. These are used to impart antistatic properties to the film. Among these, an ion conductive polymer compound is preferable, and an ammonium group-containing compound is particularly preferable. Since a coating layer formed from a coating liquid containing a π-conjugated conductive polymer such as polythiophene or polyaniline is generally strongly colored, it may not be suitable for optical applications requiring transparency. In addition, since π-conjugated conductive polymer paints are generally more expensive than ion conductive paints, ion conductive antistatic agents are preferably used from the viewpoint of manufacturing cost.

  The ammonium group-containing compound refers to a compound having an ammonium group in the molecule, and is preferably a polymer compound having an ammonium group. For example, a polymer containing a monomer having an ammonium group and an unsaturated double bond as components can be used.

  Specific examples of such a polymer include a polymer having a constituent represented by the following formula (1) or the following formula (2) as a repeating unit. These homopolymers and copolymers, and other plural components may be copolymerized. From the viewpoint of improving the compatibility with other materials and the transparency of the resulting coating film, a polymer having a constituent represented by the following formula (1) as a repeating unit is preferred. Moreover, the polymer which has the structural element shown by following formula (2) as a repeating unit from the viewpoint of the high antistatic performance obtained and heat resistance is preferable.

In the above formula (1), R ² is —O— or —NH—, R ³ is an alkylene group, or other structure capable of forming the structure of formula (1), R ¹ , R ⁴ , R ⁵ , R ⁶ Are each independently a hydrogen atom, an alkyl group, a phenyl group or the like, and these alkyl group and phenyl group may be substituted with the following groups. Substitutable groups include, for example, hydroxy group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy group, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, halogen, etc. is there.

In the above formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a phenyl group or the like, and these alkyl group and phenyl group may be substituted with the groups shown below. . Substitutable groups include, for example, hydroxyl group, amide group, ester group, alkoxy group, phenoxy group, naphthoxy group, thioalkoxy group, thiophenoxy group, cycloalkyl group, trialkylammonium alkyl group, cyano group, halogen, etc. is there. R ¹ and R ² may be chemically bonded. For example, — (CH ₂ ) _m — (m is an integer of 2 to 5), —CH (CH ₃ ) CH (CH ₃ ) —, -CH = CH-CH = CH - , - CH = CH-CH = N -, - CH = CH-N = C -, - CH 2 OCH 2 -, - (CH 2) 2 O (CH 2) 2 - Etc.

  In the case of a polymer having the structural element represented by the above formula (1) as a repeating unit, the viewpoint of improving the compatibility with other materials and improving the transparency of the resulting coating film, and further improving the releasability From the viewpoint of, it is preferable to copolymerize with other repeating units. Other repeating units include, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Can be mentioned.

  In the case of a polymer having the constituent represented by the above formula (2) as a repeating unit, it is preferably copolymerized with another repeating unit from the viewpoint of suppressing a decrease in releasability. Other repeating units include, for example, alkyl acrylates, alkyl methacrylates, and acrylamides such as n-methylol acrylamide.

  Further, from the viewpoint of further improving the antistatic performance, a homopolymer having the constituent represented by the above formula (2) as a repeating unit is preferable.

X ⁻ in the above formulas (1) and (2) can be appropriately selected within a range not impairing the gist of the present invention. Examples include halogen ions, sulfonates, phosphates, nitrates, alkyl sulfonates, and carboxylates.

A polymer having a component represented by the above formula (1) is preferable because of excellent transparency of the resulting coating layer. However, in the coating stretching method, heat resistance may be inferior, and when used in the coating stretching method, X ⁻ is preferably not a halogen.

  A compound represented by the above formula (2) or other ammonium base in the polymer skeleton is excellent in heat resistance and is preferable.

  In addition, the polymer in which the constituents represented by the above formulas (1) to (2) and the polyethylene glycol-containing (meth) acrylate are copolymerized has a flexible structure, and is uniform during coating and stretching. It is preferable because an excellent coating layer can be obtained.

  Alternatively, a coating layer having excellent uniformity can also be obtained by coating a polyethylene glycol-containing (meth) acrylate polymer in a coating solution.

  Specific examples of the polyethylene glycol-containing (meth) acrylate include polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol diacrylate (the polymerization degree of polyethylene glycol units is preferably in the range of 4 to 14), and polypropylene glycol diacrylate. Acrylate, polytetramethylene glycol diacrylate, poly (ethylene glycol-tetramethylene glycol) diacrylate, poly (propylene glycol-tetramethylene glycol) diacrylate, polyethylene glycol-polypropylene glycol-polyethylene glycol diacrylate, polypropylene glycol-polybutylene glycol Monomethacrylate, methoxypolyethylene glycol Methacrylate, methoxy polyethylene glycol monoacrylate, octoxy polyethylene glycol-polypropylene glycol monomethacrylate, octoxy polyethylene glycol-polypropylene glycol monoacrylate, lauroxy polyethylene glycol monomethacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate, steer Examples include polymers starting from loxypolyethylene glycol monoacrylate, allyloxypolyethylene glycol monomethacrylate, allyloxypolyethylene glycol monoacrylate and the like.

  Moreover, the number average molecular weight of an ammonium group containing compound is 1000-500000 normally, Preferably it is 2000-350,000, More preferably, it is 5000-200000. When the molecular weight is less than 1000, the strength of the coating film may be weak or the heat resistance stability may be poor. On the other hand, when the molecular weight exceeds 500,000, the viscosity of the coating solution increases, and the handleability and applicability may deteriorate.

  The ratio of the antistatic agent is usually in the range of 10 to 70% by weight, preferably in the range of 15 to 60% by weight, more preferably in the range of 20 to 50% by weight, as a ratio to the total nonvolatile components in the coating liquid for forming the coating layer. It is. When the amount is less than 10% by weight, there is a possibility that sufficient antistatic performance may not be obtained. When the amount is more than 70% by weight, other components are small, and thus durability or transparency may not be obtained.

  In the present invention, particles may be contained in the coating layer in order to improve the slipperiness of the coating layer. Examples of the particles include inert inorganic particles such as silica, alumina, calcium carbonate, titanium dioxide, fine particles obtained from polystyrene resins, polyacrylic resins, polyvinyl resins, or organic particles represented by these crosslinked particles. .

  In the coating layer, if necessary, antifoaming agent, coating property improver, thickener, antistatic agent, mold release agent, antioxidant, ultraviolet absorber, foaming agent, colorant such as dye or pigment Etc. may be used in combination.

Further, the coating solution preferably contains water as a main medium, and may contain a small amount of an organic solvent for the purpose of improving dispersion in water or improving the film forming performance. When the organic solvent is used by being mixed with water, which is the main medium, it is desirable to use it in a range that dissolves in water.
Examples of the organic solvent include aliphatic or alicyclic alcohols such as n-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethyl alcohol and methyl alcohol, glycols such as ethylene glycol, propylene glycol and diethylene glycol, and n-butyl. Cellosolve, ethyl cellosolve, methyl cellosolve, glycol derivatives such as propylene glycol monomethyl ether, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate and amyl acetate, ketones such as methyl ethyl ketone and acetone, N-methylpyrrolidone Amides such as, but not limited to. These organic solvents may be used alone or in combination of two or more as required.

  When providing a coating layer in the double-sided coating film of this invention, the thickness (after drying) is 0.001-0.5 micrometer normally, Preferably it is 0.005-0.3 micrometer, More preferably, 0.01-0. 2 μm. When the thickness of the coating layer (after drying) exceeds 0.5 μm, the films are likely to block each other, especially when the stretched coated film is re-stretched for the purpose of increasing the strength of the film. It may become easy to stick to. If the thickness of the coating layer is less than 0.001 μm, the bleedout prevention performance of the dye may be deteriorated.

  Examples of the method for coating the polyester film with the coating solution for providing the coating layer of the present invention include, for example, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, bar coating, curtain coating, knife Conventionally known coating methods such as a coat, a transfer roll coat, a squeeze coat, an impregnation coat, a kiss coat, a spray coat, a calendar coat, and an extrusion coat can be used.

  In addition, in order to improve the applicability | paintability to the film of a coating liquid and adhesiveness, you may give a chemical process, an electrical discharge process, etc. to a film before application | coating. In addition, in order to improve the surface characteristics of the coating layer of the film of the present invention, the surface of the coating layer may be subjected to chemical treatment or discharge treatment after the coating layer is formed.

In the present invention, ΔE ^* ab is used for evaluating the bleeding out performance of the dye on the surface of the coating layer of the double-sided coating film. The value of ΔE ^* ab is determined by extracting the coated surface of the film with dimethylformamide after heating the double-coated film, and using the spectrophotometer to extract the L ^* value, a ^* value, and b ^* value of the dimethylformamide that is the extract and reference. The calculation is performed by substituting the differences ΔL ^* , Δa ^* , Δb ^* into the following formula (1).

ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² )] ^1/2 (1)
The lower the value of ΔE ^* ab, the higher the transparency of the extract, suggesting that the bleeding out of the dye to the double-coated film surface is suppressed.

In the present invention, the value of ΔE ^* ab is preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less.

  The color tone (b * value) of the double-coated film in the present invention thus obtained is preferably 30 or more. When the b * value is less than 30, the desired antihalation effect may be insufficient.

The surface specific resistance of the double-side coated film in the present invention is preferably 1 × 10 ¹¹ Ω or less. When the surface resistivity exceeds 1 × 10 ¹¹ Ω, defects such as peeling electrification may occur in the processing step using the double-side coated film.

  Next, the photosensitive resin layer laminate will be described below as an example when the double-side coated film of the present invention is applied to resin processing applications.

  In addition, when using the double-sided coating film in this invention for the resin processing use which needs hardening by ultraviolet irradiation, for example, the antihalation effect is provided as an antihalation agent by selecting suitably the dye in a double-sided coating film. It is also possible to do.

  As the photosensitive resin layer constituting the photosensitive resin laminate of the present invention, a conventional photoresist layer can be used. In general, a negative resist is generally used as the DFR photoresist layer, and is mainly composed of a thermoplastic resin and a photosensitive material which are dissolved or swelled in a developer. Only a portion exposed in the DFR process forms a circuit (image) by development, and an unexposed portion is dissolved and removed by a developer.

  Examples of the thermoplastic resin include novolak resin, resol resin, polyvinylphenol resin, polyacrylic acid resin, polyurethane resin, polyester resin, polyamide resin, and epoxy resin. Also, styrene-butadiene block copolymer resin, styrene-isoprene copolymer resin, styrene-butadiene random copolymer resin, acrylonitrile-butadiene random copolymer resin, styrene-isoprene random copolymer resin, methyl methacrylate-butadiene random copolymer resin. , Polybutadiene, polyisoprene, natural rubber and the like may be contained. As the thermoplastic resin, these may be used alone or as a mixture of two or more.

  Further, as the photosensitive material, a compound having a photopolymerizable group or a photoreactive group is used. Specific examples include ethylenically unsaturated monomers and ethylenically unsaturated prepolymers.

  Specific examples of the ethylenically unsaturated monomer include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, chlorostyrene, vinylnaphthalene, Aromatic vinyl monomers such as vinyl anthracene, divinylbenzene, and trivinylbenzene; ethylenically unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, and acrylic acid n- Amyl, isoamyl acrylate, hexyl acrylate, ethyl hexyl acrylate, octyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, Hexyl crylate, ethyl hexyl methacrylate, octyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, 1,4 -Butanediol diacrylate, 1,4-butanediol dimethacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9 -Nonanediol dimethacrylate, methoxyethylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyethylene glycol Ethylenically unsaturated carboxylic acid ester monomers such as ethyl methacrylate, methoxypropylene glycol acrylate, diethyl maleate, dimethyl itaconate, dioctyl fumarate; ethylenically unsaturated glycidyl ethers such as allyl glycidyl ether; acrylic acid, methacrylic acid Ethylenically unsaturated monocarboxylic acids such as maleic acid, fumaric acid, citraconic acid and itaconic acid; ethylenically unsaturated polycarboxylic acids such as monoethyl maleate and monomethyl itaconate; Partially esterified products: ethylene acrylate phosphate, trimethylene phosphate, propylene acrylate phosphate, tetramethylene acrylate phosphate, bisethylene acrylate phosphate, bistrimethylene acrylate phosphate, vinyl phosphate Phosphoric ester group-containing ethylenic compounds such as tetramethylene acrylate, phosphoric acid diethylene glycol acrylate, phosphoric acid triethylene glycol acrylate, phosphoric acid polyethylene glycol acrylate, phosphoric acid bisdiethylene glycol acrylate, phosphoric acid bistriethylene glycol acrylate, phosphoric acid bispolyethylene glycol acrylate, and the corresponding methacrylates Examples thereof include unsaturated monomers.

  On the other hand, as an ethylenically unsaturated prepolymer, an ethylenically unsaturated compound having a reactive group such as a carboxyl group, a hydroxyl group, or an isocyanate group is used for polyester, polyurethane, polyether, epoxy resin, acrylic resin, etc. Those having an unsaturated group introduced therein are used. Examples of such ethylenically unsaturated prepolymers include unsaturated polyesters, unsaturated polyurethanes, unsaturated polyethers, unsaturated epoxy resins, and unsaturated acrylic resins.

  The content of the photosensitive material is usually preferably 5 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin for the purpose of the present invention. In addition, the photosensitive resin layer may contain a photopolymerization initiator, a plasticizer, a storage stabilizer, a surfactant, a colorant, and the like as long as the gist of the present invention is not impaired.

  Examples of the photopolymerization initiator include α-diketones such as diacetyl and benzyl; acyloins such as benzoin and pivaloin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; anthraquinone and 1,4-naphthoquinone A polynuclear quinone; a benzophenone such as methyl-o-benzoylbenzoate; and a phenyl ketone such as 2,2-dimethoxy-2-phenylacetophenone. In general, the content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic resin and the photosensitive material.

  In order to ensure the flexibility of the resulting photosensitive resin layer, a plasticizer may be used in combination. The plasticizer is not particularly limited as long as it is uniformly compatible with other components forming the photosensitive resin layer and exhibits a plasticizing effect. Specific examples of the plasticizer include, for example, glycerin, polyethylene glycol, benzenesulfonamide, toluenesulfonamide, N-ethyltoluenesulfonamide, N-methyltoluenesulfonamide, p-hydroxylbenzoic acid ester, various olefin oligomers, vinyl oligomers. And hydrocarbon oils such as diene oligomers, naphthine oils and paraffin oils.

  Examples of the storage stabilizer include hydroquinone, pyrogallol, p-methoxyphenol, t-butylcatechol, 2,6-di-t-butyl-p-cresol, 2,2-di-t-butyl-p-cresol, and the like. Phenols; quinones such as benzoquinone, p-toluquinone and p-xyloquinone; and amines such as phenyl-α-naphthylamine.

  As the surfactant, an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant can be used. Among these, nonionic surfactants and anionic surfactants are preferable, and anionic surfactants are particularly preferable from the viewpoints of compatibility and water development effect.

  With respect to the method for producing the photosensitive resin layer, for example, each component constituting the photosensitive resin composition is dissolved in water or an organic solvent, mixed well to obtain a homogeneous solution, and then on the surface of the base film. In addition, after coating and drying by a conventional known coating method, for example, reverse coating method, gravure coating method, rod coating method, bar coating method, die coating method, etc., the thickness (after drying) is 1 to 1. A method of forming a 1000 μm photosensitive resin layer can be employed. In addition, the photosensitive resin layer can be formed on the base film by preliminarily removing the solvent of the photosensitive resin layer-forming material by hot pressing with a nip roll or the like on the base film. Furthermore, a method in which each component constituting the photosensitive resin composition is sufficiently mixed with a kneader, a Banbury mixer or the like is press-molded on a base film to form a photosensitive resin layer, and other methods such as cast molding, extrusion molding, etc. Conventionally known methods such as a method of forming a photosensitive resin layer by the method can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The physical property measurement method used in the present invention is shown below.

(1) Intrinsic viscosity (dl / g)
A mixed solvent of phenol / tetrachloroethane: 50/50 (weight ratio) was added to 1 g of polyester at a ratio of 100 ml, and the mixture was measured at 30 ° C.

(2) Average particle diameter of added particles (μm)
Using a centrifugal sedimentation type particle size distribution analyzer SA-CP3 manufactured by Shimadzu Corporation, the particle size was measured by a sedimentation method based on Stokes' resistance law. The average particle diameter was determined by using a value of 50% of integration (volume basis) in the equivalent spherical distribution of particles obtained by measurement.

(3) Method for measuring film thickness of coating layer The surface of the coating layer was dyed with RuO ₄ and embedded in an epoxy resin. Thereafter, the section prepared by ultramicrotomy stained with RuO _4, a coating layer cross-section was measured by using a TEM (Hitachi High Technologies Corporation H-7650, accelerating voltage 100 V).

(4) Average roughness (Ra)
Using a surface roughness measuring machine (SE-3500) manufactured by Kosaka Laboratory Ltd., it was determined as follows according to JIS-B-0601-2001. That is, a portion having a reference length L (2.5 mm) is extracted from the film cross-sectional curve in the direction of the average line, and the roughness curve y = f When represented by (x), the value given by the following equation is represented by [nm]. Arithmetic average roughness Ra was obtained by calculating 10 roughness curves from the surface of the sample film, and expressing the arithmetic average roughness of the extracted portions determined from these roughness curves. The tip radius of the stylus was 2 μm, the load was 30 mg, and the cutoff value was 0.08 mm.

Ra = (1 / L) ∫ L 0 | f (x) | dx

(5) Evaluation of color of double-sided coated film (b *)
The color tone reflection method b * value was measured with a spectrocolorimeter “CM-3730d” (manufactured by Konica Minolta Co., Ltd.) using the double-sided coated films prepared in Examples and Comparative Examples. In the measurement, a C light source was used as the light source.

(6) Dye bleed-out prevention performance evaluation (ΔE ^* ab value evaluation)
The double-sided coated films prepared in Examples and Comparative Examples are heated in an oven at 180 degrees for 10 minutes. Thereafter, the heat-treated film is folded so that the surface of the coating layer is inside the box, and a box shape having a length of 20 cm, a width of 12.5 cm, and a height of 5 cm is formed. Next, 10 mL of dimethylformamide was put in contact with the bottom surface (250 cm ² ) of the box prepared by the above method and allowed to stand for 3 minutes. Placed in a 45 mm quartz liquid cell, the liquid cell was installed in a spectrophotometer “UV-3100PC” manufactured by Shimadzu Corporation so that the optical path length was 12.5 mm, and the transmittance was measured. The L ^* value, a ^* value, and b ^* value at the time of visual field and standard D65 light source were obtained.
Similarly, the L ^* value, a ^* value, and b ^* value of the reference dimethylformamide are obtained, and the differences ΔL ^* , Δa ^* , and Δb ^* are substituted into the above-described formula (1), and the reference dimethylformamide is calculated. ΔE ^* ab value was calculated and evaluated according to the following criteria.
<Criteria>
A: ΔE ^* ab value is 10 or less (practical level)
×: ΔE ^* ab value is 11 or more (a level that may cause a problem in practical use)

(7) Adhesive evaluation method (practical property substitution evaluation)
Apply a mixed coating solution of 74 parts by weight of Kayanova FOP-1100 (manufactured by Nippon Kayaku Co., Ltd.) and 86 parts by weight of methyl ethyl ketone to the coating film forming surface of the polyester film so that the dry film thickness is 2 μm. After drying at 70 ° C. for 1 minute to remove the solvent, it was cured by irradiation with ultraviolet rays at 60 mJ / cm ² to form a hard coat layer. A 10 × 10 cross cut is applied to the obtained film, and a 18 mm wide tape (Cello Tape (registered trademark) CT-18 manufactured by Nichiban Co., Ltd.) is applied to the film, and the film is sharply peeled at a 180 ° peeling angle. The peeled surface after peeling was observed and evaluated according to the following criteria.
<Criteria>
○: The area peeled between the coating layer and the hard coat layer is less than 20% Δ: The area peeled between the coating layer and the hard coat layer is 20% or more and less than 50% ×: Between the coating layer and the hard coat layer The peeled area is less than 50%

(8) Evaluation method of antistatic property Using a high resistance measuring instrument: HP4339B and measuring electrode: HP16008B manufactured by Nippon Hewlett-Packard Co., Ltd., conditioning the sample for 30 minutes in a measurement atmosphere of 23 ° C. and 50% RH, then the surface The resistance value was measured.
<Criteria>
○: 1 × 10 ¹¹ Ω or less (practical level)
×: Exceeds 1 × 10 ¹¹ Ω (level that may cause problems in practice)

(9) Evaluation of antihalation performance of double-sided coated film (practical property substitution evaluation)
Asahi Kasei Co., Ltd. photosensitive resin “APR series G-31” is provided on the easily adhesive polyester film of the present invention so as to have a thickness (3 mm) after drying, and then a negative film is placed on the photosensitive resin plate. The sample after curing with a UV lamp (TL100W / 10R manufactured by PHILIPS) and removing the negative film was washed with a developer (FDO-S2 manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the photosensitive resin in the uncured part was removed. Washed away. This sample was visually confirmed, and the focus status was judged according to the following criteria.
○: Practically good level △: Slightly out of focus, but practically no problem level ×: Level out of focus and may cause problems in practice

(10) Comprehensive evaluation Using the double-sided coated films obtained in Examples and Comparative Examples, the following judgments were made for each item of dye bleed-out property, adhesiveness, antistatic property, antihalation performance and film productivity. Judgment was made based on the criteria.
(Criteria)
○: All items of dye bleeding prevention performance, adhesiveness, antistatic property, and antihalation performance are judged as ◯ or △. (Practical, no problem level)
X: At least one of the dye bleed-out prevention performance, adhesiveness, antistatic property, and antihalation performance is poor in productivity due to frequent breakage during x judgment or film stretching. (Practical level that may cause problems)

The composition component which comprises the coating layer used by the Example and the comparative example is as showing below.
In addition, the weight% used in Examples and Comparative Examples means weight% in nonvolatile content.

[Compositional components constituting the coating layer]
(A) Crosslinking agent (A-1): Hexamethoxymethylol melamine (A-2): Acrylic polymer having oxazoline group and polyalkylene oxide chain (Oxazoline group amount = 4.5 mmol / g, manufactured by Nippon Shokubai Co., Ltd.)
(A-3): Polyglycerol polyglycidyl ether.

(B) Binder resin (B-1): Acrylic resin (B-2) having a glass transition temperature (Tg) of 50 ° C. copolymerized with alkyl acrylate and alkyl methacrylate, and having a saponification degree of 88% Polyvinyl alcohol (B-3) polyester resin having a polymerization degree of 500:
Water dispersion of polyester resin copolymerized with the following composition: Monomer composition: (acid component) terephthalic acid / isophthalic acid / 5-sodium sulfoisophthalic acid // (diol component) ethylene glycol / 1,4-butanediol / diethylene glycol = 56/40/4 // 70/20/10 (mol%)

(B-4) Urethane resin having a carbon-carbon double bond: hydroxyethyl acrylate unit: dicyclohexylmethane diisocyanate unit: hexamethylene diisocyanate trimer unit: caprolactone unit: ethylene glycol unit: dimethylolpropanoic acid unit = 18: 12 : The urethane resin whose weight of the carbon-carbon double bond part formed from 22: 26: 18: 4 (mol%) is 2.0 wt%

(B-5) Urethane resin having no carbon-carbon double bond portion:
80 parts by weight of polycarbonate polyol consisting of 1,6-hexanediol and diethyl carbonate having a number average molecular weight of 2000, 4 parts by weight of polyethylene glycol having a number average molecular weight of 400, 12 parts by weight of methylenebis (4-cyclohexylisocyanate), dimethylolbutanoic acid 4 Water dispersion obtained by neutralizing urethane resin consisting of parts by weight with triethylamine

(C) Antistatic agent Diallyldimethylammonium chloride, N-methylolacrylamide, and NNdimethylacrylamide were copolymerized at a weight ratio of 90/5/5, and the number average quantity was 20000, and the main chain was cationic. Cationic group-containing resin having

(D) Particles Silica particles (average particle size: 70 nm)

≪Production of polyester (A) ≫
100% by weight of dimethyl terephthalate and 60% by weight of ethylene glycol are used as starting materials, 0.09% by weight of magnesium acetate tetrahydrate as a catalyst is placed in a reactor, the reaction start temperature is set to 150 ° C., and the methanol is gradually distilled off. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially completed. To this reaction mixture, 0.04% by weight of ethyl acid phosphate and 0.04% by weight of antimony trioxide were added, and a polycondensation reaction was carried out for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After 4 hours from the start of the reaction, the reaction was stopped and the polymer was discharged under nitrogen pressure. The intrinsic viscosity of the obtained polyester (A) was 0.65 dl / g.

≪Production of polyester (B) ≫
In the production of the polyester (A), a polyester (B) containing 10% by weight of organic particles of an alkyl methacrylate-styrene copolymer having an average particle size of 4.5 μm was obtained. The intrinsic viscosity of the obtained polyester was 0.60 dl / g.

≪Production of polyester (C) ≫
In the production of the polyester (A), a polyester (C) containing 0.05% by weight of organic particles of an alkyl methacrylate-styrene copolymer having an average particle size of 1.9 μm was obtained. The intrinsic viscosity of the obtained polyester was 0.65 dl / g.

≪Production of polyester (D) ≫
After drying 100% by weight of the polyester (B), 0.3% by weight of “Solvent Yellow 19” according to the color index classification was melt-kneaded with an extruder to obtain a polyester (D). The intrinsic viscosity of the obtained polyester (D) was 0.61 dl / g.

≪Manufacture of polyester E≫
When the polyester (A) was produced, 4,4′-bis (2-benzoxazolyl) stilbene was added as a fluorescent brightening agent to a concentration of 1.5% to prepare a polyester (D). . The intrinsic viscosity of the obtained polyester (E) was 0.65 dl / g.

Example 1:
The raw material in which the polyester (A) and the polyester (B) are mixed at a ratio of 70% and 30% is used as the raw material for the A layer, and the polyesters (A), (D), and (E) are respectively 59.4% and 40%. % And 0.6% of the raw material mixed as a raw material for the B layer, the raw material for the A layer and the B layer are melt-extruded by separate melt extruders (A / B / A), and the thickness composition ratio is An amorphous sheet of two kinds and three layers laminated with A / B / A = 5/115/5 was obtained. Subsequently, the sheet was coextruded on a cooled casting drum and solidified by cooling to obtain a non-oriented sheet. Next, the film was stretched 3.0 times in the longitudinal direction at 90 ° C., and then the coating liquid shown in Table 1 below was applied to both sides of the longitudinally stretched film, led to a tenter, passed through a preheating step in the tenter, and then lateralized at 130 ° C. The film is stretched 4.0 times in the direction, heat-treated at 230 ° C. for 10 seconds, and wound up with a film-forming machine to have a coating layer having a coating layer thickness (after drying) of 0.05 μm and having a thickness of 125 μm A double-sided coated film was obtained.

<Formation of adhesive layer>
A coating solution composed of the following adhesive layer composition is applied onto the easy-adhesion layer of the obtained double-sided coating film, heat treated at 120 ° C. for 3 minutes, and then an adhesive layer having a coating amount (after drying) of 5 g / m ² is obtained. It was.

(Adhesive layer composition)
・ Vinyl chloride resin (Sekisui E-C100 manufactured by Sekisui Chemical Co., Ltd.) 10 parts by weight ・ Nitrile rubber (Nipol1052J manufactured by Nippon Zeon Co., Ltd.) 7 parts by weight ・ Methyl ethyl ketone 50 parts by weight ・ Toluene 50 parts by weight

<< Formation of photosensitive resin layer laminate >>
Next, a photosensitive resin (APR series G-31: manufactured by Asahi Kasei E-Materials Co., Ltd.) was applied on the adhesive layer so as to have a thickness (after drying) of 3 mm. Then, a 30 μm thick polyethylene film (GF series GF-3: manufactured by Tamapoly Co., Ltd.) is pressure-bonded with 2 kg as a cover film on the surface of the photosensitive resin layer, (antistatic layer side) double-side coated film (easy adhesion layer side) / A laminate having a configuration of adhesive layer / photosensitive resin layer / cover film was obtained. Further, using a 2 kw high-pressure mercury lamp, the surface of the laminate was set for 2 minutes on each side, the distance from the light source to the laminate surface was set to 40 cm, and ultraviolet exposure was performed to cure the photosensitive resin layer.

Examples 2-10:
In Example 1, a double-sided coated film and a photosensitive resin laminate were obtained in the same manner as in Example 1 except that the coating solution was changed to the coating composition shown in Table 1, Table 2, and Table 3 below.

Examples 11-14:
In Example 1, a double-sided coated film and a photosensitive resin laminate were obtained in the same manner as in Example 1 except that the raw material for the B layer was changed to the raw material structure shown in Table 3 below.

Example 15:
In Example 1, except that a film having a thickness of 188 μm having a thickness composition ratio of A / B / A = 3/182/3 was obtained in the same manner as in Example 1, a double-side coated film and a photosensitive resin laminate were obtained. Obtained.

Example 16:
In Example 1, a double-sided coated film and a photosensitive resin laminate were obtained in the same manner as in Example 1 except that the raw material for layer A was changed to the raw material structure shown in Table 3 below.

Comparative Examples 1-6:
In Example 1, a double-sided coated film and a photosensitive resin laminate were obtained in the same manner as in Example 1 except that the coating solution was changed to the coating composition shown in Table 1, Table 4, and Table 5 below.

Comparative Examples 7 to 10:
In Example 1, a double-sided coated film and a photosensitive resin laminate were obtained in the same manner as in Example 1 except that the raw material for the B layer was changed to the raw material structure shown in Table 5. Although the performances of the film of Comparative Example 10 were good, breakage occurred frequently when the film was stretched, resulting in poor productivity.

The double-sided coated film of the present invention has good dye bleedout prevention performance, and good adhesion to functional layers such as a hard coat layer and an adhesive layer, and antistatic properties and antihalation performance are good. For example, it can be suitably used for various applications such as resin processing and display.

Claims (4)

At least two layers having a coating layer on both sides of a laminated polyester film composed of at least three layers including a layer containing a dye, wherein one coating layer is selected from a melamine compound, an epoxy compound, and an oxazoline compound A double-sided coating film, which is formed from a coating solution containing at least one kind of crosslinking agent, and has an average roughness (Ra) of at least one surface of 0.30 to 0.70 μm. The double-sided coated film according to claim 1, wherein the absorbance at each measurement wavelength of 360 nm, 380 nm, and 420 nm is in the range of 0.3 to 1.4. The double-sided coated film according to claim 1 or 2, wherein the absorbance in the measurement wavelength range of 350 nm to 450 nm is in the range of 0.3 to 1.4. The photosensitive resin layer and the cover film are formed on the coating layer formed from the coating solution containing at least two kinds of crosslinking agents of the double-sided coating film according to any one of claims 1 to 3 through an adhesive layer. A photosensitive resin laminate characterized by being sequentially laminated.