JPH0588822B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to photographic materials having a protective coating layer. More specifically, the present invention relates to a photographic material having a protective coating layer that has excellent adhesion to an image forming layer (gelatin/silver halide emulsion layer) and improved water resistance. [Background of the Invention] Photographic materials in which a light-sensitive emulsion such as a silver halide emulsion with gelatin as a binder is coated on a support are subjected to image formation and then subjected to various usage and climatic conditions. May be exposed. Even under these conditions, a protective coating layer is generally provided on the surface of the photographic material so as not to impair its appearance and function as a photographic material. Various types of protective coating layers for photographic materials are known. For example, a composition containing an acrylic prepolymer having an unsaturated group and a photopolymerization initiator that generates photoradicals is photographed to form a protective coating layer by irradiating the coating composition with ultraviolet rays and curing it. For example, JP-A-53-57023 and JP-A-56-56 disclose materials that are coated on the surface of a material and cured by radical polymerization.
-91233, US Pat. No. 4,333,998, and other publications. However, these known photopolymerizable compositions are not fully satisfactory in terms of adhesion to the photographic image layer of the photographic material. In addition, a composition comprising an epoxy resin and a cationic polymerization initiator such as an aromatic onium salt is coated on the photographic image layer of a photographic material and cured by cationic ring-opening polymerization to form a protective coating layer, as disclosed in the US patent.
No. 4156046, these compositions consist of: 1 Epoxy-terminated silanes such as γ-glycidoxypropyltrimethoxysilane, 2 Alicyclic rings such as 3,4-epoxycyclohexylmethyl-2,4-epoxycyclohexanecarboxylate, or 1,6-hexanediol diglycidyl ether. and aliphatic polyepoxide, 3. A monomer capable of polymerizing epoxy or silane groups, 4. Ultraviolet absorber (for example, benzophenone), 5. Cationic polymerization initiator such as triarylsulfonium hexafluorophosphate. Furthermore, U.S. Pat. No. 4,426,431 describes aliphatic or alicyclic polyfunctional compounds such as 1 1,4-butanediol diglycidyl ether or adipic acid bis(3,4-epoxy-6-methylcyclohexylmethyl). an epoxy compound; 2 a cationic polymerization initiator for initiating the polymerization of an epoxy compound, such as triphenylsulfonium hexafluoroantimonate; 3 a polymerizable acrylic compound, such as pentaerythritol triacrylate; 4, for example 4,4-bischlor. Ultraviolet curable compositions are disclosed comprising: a free radical initiator such as methylbenzophenone; 5 a polymerizable organofunctional silane such as gamma-glycidoxypropyltrimethoxysilane; Although these compositions are excellent in terms of abrasion resistance and hardness, they also contain an organic functional silane compound in order to improve adhesion to silver halide emulsions made of gelatin. Compositions containing such organofunctional silane compounds cannot be cured with low-output ultraviolet lamps, and it is necessary to use high-output lamps (200 W/cm ² ) to cure compositions containing silane compounds. Because of this, it generates a large amount of heat and generates ozone, which requires devices such as a cooling device and an exhaust fan, resulting in an increased size and cost. Also, it is not sufficient in terms of water resistance. In particular, it has been found that the protective coating layer has poor scratch resistance when immersed in water or hot water, and has drawbacks such as the photographic image layer falling off from the support. In addition, the protective coating layer formed using a composition with an increased mixing ratio of polyglycidyl ether of aromatic polyols has excellent scratch resistance (water resistance) when immersed in water, and a silver halide emulsion containing gelatin as a binder. It was found that although the adhesion to the photographic image layer was improved, the light fastness of the protective coating layer was poor and the protective coating layer yellowed when stored under exposure to sunlight. As a result of intensive research in order to eliminate the above-mentioned drawbacks, the present inventors discovered that by adding a polyglycidyl ester of a polybasic acid to the polyglycidyl ether of the aromatic polyol, yellowing of the resulting protective coating layer was prevented. Furthermore, it was surprisingly found that the adhesion to silver halide emulsions was significantly improved even after immersion in water. [Object of the Invention] Therefore, the first object of the present invention is to provide a material that has strong scratch resistance even when immersed in water, and has significantly improved adhesion to a photographic image layer formed from a silver halide emulsion made of gelatin. The object of the present invention is to provide a photographic material having a protective coating layer. A second object of the present invention is to provide a photographic material in which the light resistance of the protective coating layer is significantly improved and is resistant to yellowing even when exposed to sunlight. [Structure of the Invention] The above object of the present invention is to provide a photographic material having a protective coating layer, wherein the protective coating layer comprises at least one member selected from the following group (a), at least one member selected from the group (b), and ( This is achieved by means of a photographic material in which a composition containing at least one selected from group c) is cured by irradiation with light in the ultraviolet region. Group (a): polyglycidyl ethers of aromatic polyols; Group (b): polyglycidyl esters of polybasic acids; Group (c): cationic polymerization initiators. [Specific Structure of the Invention] The protective coating layer of the photographic material of the present invention contains at least one selected from group (a), at least one selected from group (b), and at least one selected from group (c), which are detailed below. (hereinafter referred to as the ultraviolet curable composition of the present invention), which can be cured by irradiation with light in the ultraviolet region, is used. (a) used as a protective coating layer in the present invention
The polyglycidyl ethers of aromatic polyols of the group are preferably polyglycidyl ethers of aromatic polyols having an epoxy equivalent weight of 400 or less and a molecular weight of 1000 or less, which also includes polymethylglycidyl ethers. included. Specific examples of polyglycidyl ether and polymethylglycidyl ether of aromatic polyols include compounds represented by bisphenol A diglycidyl ether, and this compound is
For example, they are produced by reacting aromatic polyols with epichlorohydrin or methylepichlorohydrin. Specific examples of aromatic polyols include bisphenol F, bisphenol A, novolac resin, cresol novolac resin, resorcinol, polyparahydroxystyrene, and the like. Hereinafter, the polyglycidyl ether of aromatic polyols of group (a) of the present invention will be specifically explained. (A) Glycidyl ether of bisphenol A This compound is obtained by the reaction of epichlorohydrin (1-chloro-2,3-epoxypropane) and bisphenol A (4,4'-isopropylidene diphenol). The reaction product is a polyglycidyl ether or diglycidyl ether of bisphenol A (the glycidyl group is more formally 2,
3-epoxypropyl group) and is therefore considered to be a polyether derived from diphenyl and glycidol (2,3-epoxy-1-propanol). The structure usually given to this resinous product is as follows.

In the above formula, the glycidyl group having a non-terminal position on the polymer molecule becomes a 2-hydroxytrimethylene group -CH ₂ CH(OH)CH ₂ -. A viscous liquid having an average molecular weight of about 380 can be obtained from the above compound by reacting bisphenol A with a large amount of epichlorohydrin. The reaction product is more than 85 mol% diglycidyl ether of bisphenol A (n=0) {which is referred to as 2,2-bis[p-(2,3-epoxypropoxy}phenyl]propane}) , and n is 1, 2 and /
Or contains a small amount of 3. The compounds of group (a) used in the present invention mainly consist of diglycidyl ether of bisphenol A and have an average molecular weight of about 400 or less, and from 170 to 200, usually about
It has an epoxy equivalent weight ranging from 172 to 187. For specific synthesis methods of such compounds,
Handbook of Epoxy Resins H.Lee and K.Neville
“Synthesis of Glycidyl type Epoxy Resins” described in “Synthesis of Glycidyl type Epoxy Resins” written by M. Mcgrow-Hill Book Company, 1967.
Reference may be made in particular to the synthesis of monomeric diglycidyl ethers of bisphenol A. (B) Polyglycidyl ether compound having the following structure

[Chemical formula] In the above formula, R represents an alkylene group having 2 to 3 carbon atoms, R' and R'' each represent a hydrogen atom, a methyl group, or an ethyl group, and l and m are each larger than 1 but smaller than 3. Represents an integer. Compounds with the above structure are typically obtained by reacting epichlorohydrin with an addition polymer obtained by addition polymerizing alkylene oxide to bisphenol A. Specific examples of these compounds include bisphenol A. Ethylene oxide adduct diglycidyl ether of phenol F, propylene oxide adduct diglycidyl ether of bisphenol F, bisphenol A
ethylene oxide adduct diglycidyl ether, propylene oxide adduct diglycidyl ether of bisphenol A, and the like. These compounds have an epoxy equivalent weight of 330-360 and an average molecular weight of 450-480. (C) Glycidyl ether of bisphenol F

embedded image The above compound is obtained by a condensation reaction between bisphenol F (a condensate of formaldehyde and phenol) and epichlorohydrin. This compound has an average molecular weight of 400 or less and an epoxy equivalent weight of 170-190. (D) Epoxidized Novolac Resins and Cresol Novolac Resins These resins are prepared by mixing formaldehyde and an excess of commercial grade cresol (or phenol) using an acid catalyst according to methods well known in the phenol-formaldehyde resin industry. It is produced by carrying out a condensation reaction with a liquid or low melting point thermoplastic product. Such products are
Average molecular weight around 1000 and 160-200, often approx.
Available in epoxidized form with epoxy equivalent weight ranging from 170 to 180. Novolac resins generally have the following formula:

[Chemical formula] Furthermore, compounds represented by the following resins derived from polynuclear phenol glycidyl ether are also included.

[ka] or

embedded image In the above formula, n has a value of 0.2 to 1.6. In the present invention, preferable results can be obtained by using this hydrogenated compound in addition to the polyglycidyl ether of the aromatic polyol. Examples of such hydrogenated compounds include the above (A) to
In the structural formula (D), examples include a cyclohexylene group in which each phenylene group is saturated with hydrogen, and a compound in which a portion of the phenylene group is replaced with a hydrogenated cyclohexenyl group. The epoxy equivalent of the polyglycidyl ether of aromatic polyols, which is the epoxy compound of group (a) used in the present invention, is preferably 400 or less from the viewpoint of photocurability, and particularly preferably 100 to 360. The epoxy equivalent is expressed in grams of resin containing 1 mole of epoxy groups (for example, in the case of bisphenol A-based epoxy resins, it is usually equal to 1/2 of the molecular weight). The epoxy equivalent can be determined by a known method, for example, Kline, High Polymers, Vol. 12, Analytical Chemistry of Polymers.
Chemistry of Polymers), Chapter 5 Epoxy Resins. Further, the average molecular weight is preferably as high as possible from the viewpoint of water resistance and adhesiveness, but from the viewpoint of the viscosity of the composition liquid, it is preferably 100 to 1,500. In order to particularly improve water resistance, the compounds of the above group (a) may be used alone or in combination of two or more in the composition.
It is necessary to contain at least 10% by weight based on the total weight of the ultraviolet curable composition of the present invention. More preferably 20% to 80% by weight, still more preferably 50 to 80% by weight. If it is less than 10% by weight, the scratch resistance and adhesion will not be sufficient;
Above this amount, the curability is not sufficient. Examples of polyglycidyl esters of polybasic acids of group (b) used in the present invention include polyglycidyl esters of polycarboxylic acids shown below. (1) Diglycidyl phthalate (phthalic acid diglycidyl ester) (2) Glycidyl tetrahydrophthalate (tetrahydrophthalic acid diglycidyl ester) (3) Glycidyl hexahydrophthalate (hexahydrophthalic acid diglycidyl ester) (4) Dimethylglycidyl phthalate ( Dimethylglycidyl phthalate ester) (5) Dimethylglycidyl hexahydrophthalate (dimethylglycidyl phthalate ester) (6) Dimer acid glycidyl ester (7) Dimer acid glycidyl ester modified product (8) Chromatake diglycidyl ester (9) Cycloaliphatate diglycidyl ester Among the above-mentioned polycarboxylic acid polyglycidyl esters, the diglycidyl phthalates shown in (1), (2), and (3) are preferred, and specific examples thereof are shown below. (1) Diglycidyl orthophthalate (Kawakaron A, Cyodyne 508)

[Chemical] (2) Diglycidyl tetrahydrophthalate (Kawakaron H, Araldite CY-182)

[Chemical] (3) Diglycidyl hexahydrophthalate (Kawakaron H, Epicote 190, Araldite CY-
183)

Synthesis of the diglycidyl ester of polycarboxylic acid used in the present invention is disclosed in, for example, US Pat. No. 3,053,855,
This can be done by the method described in Japanese Patent Publication No. 41-6573, Handbook of Epoxy Resins, etc.
Specifically, for example, a method for synthesizing glycidyl ester from an acid chloride and glycidol or an alkali salt of an acid and epichlorohydrin, a method for synthesizing glycidyl ester from an acid chloride and glycidol or an alkali salt of an acid and epichlorohydrin, and a method for synthesizing glycidyl ester from various carboxylic acids (such as acrylic acid, polyacrylic acid, stearic acid, pelargonic acid, azelaic acid, etc.) in the presence of an excess of epichlorohydrin. A method for synthesizing glycidyl ester using an aqueous alkali metal salt solution of acid, sebacic acid, adipic acid, succinic acid, phthalic acid, oleic acid, linolenic acid dimer, linolenic acid trimer, etc.) and using quaternary ammonium halide as a catalyst, or as a catalyst. Examples include a method using an alkali metal salt of bromine or iodine and N-dialkylamide or disulfoxide as a reaction solvent, and a method using an alkali or a tertiary amine as a catalyst. The polyglycidyl esters of the polybasic acids of the group (b) used in the present invention are used alone or in combination of two or more, and the weight of the polyglycidyl esters is 20 to 80% based on the total weight of the ultraviolet curable composition of the present invention. %, more preferably in the range of 20 to 70% by weight. If it is less than 20% by weight, the curability will not be sufficient, and if it is more than 80% by weight, the adhesion to the silver halide emulsion will be poor. As the cationic polymerization initiator of group (c) used in the present invention, aromatic onium salts are preferred, and include salts of Group A elements of the periodic table, such as phosphonium salts (e.g., triphenylphenacyl hexafluorophosphate). phosphonium), salts of group a elements,
For example, sulfonium salts (e.g. triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, tris(4-thiomethoxyphenyl)sulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate), and group a elements. salts, such as iodonium salts (eg diphenyliodonium chloride). The use of aromatic onium salts as cationic polymerization initiators in the polymerization of epoxy compounds is disclosed in U.S. Pat.
and No. 4161478, as detailed in each publication. Preferred cationic polymerization initiators include
Examples include sulfonium salts of group elements. Among these, triarylsulfonium hexafluoroantimonate is preferred from the viewpoint of ultraviolet curability and storage stability of the ultraviolet curable composition. The amount of the above cationic polymerization initiator used is group (a), group (b)
It is preferably 3 to 20% by weight, more preferably 5 to 12% by weight, based on the total weight of the UV-curable composition of the present invention containing the compounds of group (c). If the amount of the cationic polymerization initiator does not exceed 1% by weight based on the total weight of the ultraviolet curable composition of the present invention, the curing speed when irradiated with light containing ultraviolet rays will be extremely slow. On the other hand, even if it exceeds 20% by weight, there is no particular improvement in performance and it is not practical from an economical point of view. In the present invention, when curing the ultraviolet curable composition using a low-power lamp, the cationic polymerization initiator is
It is used in a range of ~12% by weight. At least one selected from each of the groups (a), (b) and (c) used in the protective coating layer of the present invention.
The ultraviolet curable composition of the present invention contains oils (particularly silicone oils), surfactants such as silicone-alkylene oxide copolymers (e.g. L-5410, commercially available from Union Carbide). , silicone oil-containing aliphatic epoxide groups,
FO-171 commercially available from 3M and also from 3M
Fluorocarbon surfactants such as FO-430, available from Dainippon Ink Co., Ltd., Megafac F-141, available from Dainippon Ink Co., Ltd., and the like can be included. The ultraviolet curable composition of the present invention further includes inert ingredients, such as talc, calcium carbonate, alumina, silica, mica, barium sulfate, magnesium carbonate, fillers such as glass powder, dyes, pigments, thickeners, plasticizers, etc. Wetting agents, stabilizers, leveling agents, coupling agents, tackifiers, silicone group-containing activators, fluorocarbon group-containing surfactants, and other various additives, as well as improving the fluidity of the composition during application. For this purpose, a small amount of a solvent such as acetone, methyl ethyl ketone, or methyl chloride, which hardly reacts with the cationic polymerization initiator, may be added. The ultraviolet curable composition of the present invention may further contain vinyl monomers such as styrene, paramethylstyrene, methacrylic esters, acrylic esters, cellulose, thermoplastic polyester, phenyl glycidyl ether, butyl glycidyl ester, etc. Monoepoxides such as ethers may be used within the range that does not impede the effects of the invention. In the photographic material of the present invention, the photographic image layer carrying information is formed by subjecting a black and white or color silver halide photosensitive material, various diffusion transfer type photosensitive materials, diazo photosensitive materials, electrophotographic image recording materials, etc. to predetermined processing steps. It is formed by applying The photographic image layer is a photosensitive layer or an image-receiving layer of a photosensitive material, for example, waterproof baryta paper, a white opaque resin sheet support, a support with a black and white light-shielding layer coated on the back surface thereof, or a transparent resin sheet. It can be obtained by applying a predetermined treatment to a substrate such as the following. A case in which a silver halide photosensitive emulsion layer is used as the photographic image layer will be specifically described below. As the silver halide used in the silver halide photosensitive emulsion layer, silver chloride, silver bromide, silver iodide, or a mixture thereof, silver iodobromide, can be used. In particular, several layers of color photographic emulsions made by using gelatin as a binder, dispersing silver halide grains therein, and adding necessary additives such as coloring dyes, sensitizing dyes, stabilizers, and spreading agents are spread on a transparent resin sheet. Preferably, it is coated in layers. With such a color photographic emulsion, information such as a person's face can be clearly seen in color, so it is most suitable for identifying a person. Utility Model Publication No. 46-22858 is a method for printing information on an image forming layer consisting of a silver halide photosensitive emulsion.
Information can be easily carried on an image sheet by printing it using the apparatus described in the above issue and developing it with a predetermined developer. The photographic material of the present invention is subjected to a treatment to form a visible image prior to applying the UV curable composition of the present invention to the photographic image layer. This process, for example for black and white photographic materials, is generally carried out in a series of steps consisting of development, fixing and washing. Furthermore, color printing is processed through a series of steps consisting of color development, bleaching, fixing (or simultaneous bleaching-fixing), and stabilization. Furthermore, color reversal photographic materials are processed in a series of steps consisting of black and white negative development, followed by reversal exposure or fogging, color development, bleaching, fixing (or simultaneous bleach-fixing), and stabilization. The ultraviolet curable composition of the present invention can be applied to photographic materials by, for example, dipping, coating, air knife coating, roll coating, gravure coating, extrusion coating, bead coating, flow coating, use of a wire-wound coating machine, etc. I can do it. In addition, the coating described in Japanese Patent Application No. 18027-1983,
Curing equipment can also be used. Generally, the thickness of the coating protective layer of the invention applied on the photographic image layer of the photographic material ranges from 2 to 30 cm ^{3 /m 2 (coated surface) of the coating composition as a wet coverage, preferably in the range of 2 to 30 cm 3} /m ² (coated surface) of the coating composition. It is in the range of 5 to 20/cm ³ /m ² .
The coating method can be varied widely depending on the viscosity of the ultraviolet curable composition of the present invention. Generally 25~
Satisfactory coatings can easily be formed on photographic materials from coating compositions with viscosities in the range of 1000 centipoise. The ultraviolet curable composition of the present invention is cured by irradiation with light including the ultraviolet region, and the irradiation light sources including the ultraviolet region used include sunlight, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, There are metal halide lamps, xenon lamps, etc. Further, the atmosphere during irradiation with ultraviolet rays may be air or an inert gas such as nitrogen gas or carbon dioxide gas. The irradiation time for the ultraviolet curable composition of the present invention varies depending on the type of irradiation light source in the ultraviolet region, but is generally 0.5 seconds to 5 minutes, preferably 3 seconds to 2 minutes. Generally, when the irradiation time is short, a large light source with a high irradiation intensity is required, and when the irradiation time is long, a light source with a low irradiation intensity can be used, but the curing action time becomes longer, which is disadvantageous in terms of the manufacturing process. When curing the ultraviolet curable composition of the present invention, the curing time can be further shortened by heating during or before and after irradiation with light containing ultraviolet light. When heating, the heating temperature is preferably 30 to 80°C. Before irradiation with light including ultraviolet rays,
Once the ultraviolet curable composition layer of the present invention reaches this temperature, the heating time may be short or long, and after irradiation containing ultraviolet rays, the heating time is preferably 1 minute to 120 minutes. The UV-curable compositions used in the present invention have excellent wettability, spreadability (flow properties that promote flattening of defects in wet coatings), and coatability, making it easy to prepare the compositions of the present invention. can be coated onto the photographic image layer of the photographic material. They adhere firmly to the photographic image layer of the photographic material and are easily cured by convenient and readily available ultraviolet light sources to form a clear, flexible, highly scratch resistant protective coating. The UV-curable compositions of the present invention have an excellent shelf life, are free from undesirable odors, and do not exhibit undesirable chemical attack on the components of photographic materials. Another important advantage is that the resulting protective coating is resistant to contamination and damage, and is resistant to immersion in water or other solutions when used on items that are carried at all times, such as authentication identification cards such as driver's licenses, ID cards, and credit cards. It is also highly resistant. The protective coating layer formed on the photographic material of the present invention is
It is advantageous to carry out this process, if appropriate, before cutting the photographic material to its final dimensions. For example, it can be processed to form a photographic image to form a visible image, dried, coated with an ultraviolet curable composition, then irradiated and cut to specific dimensions. Alternatively, the material may be cut into a specific size in advance, subjected to a predetermined development treatment to form a visible image, dried, coated with an ultraviolet curable composition, and then irradiated. The ultraviolet curable compositions described herein adhere strongly to the photographic image layer of photographic materials, making them useful in applying protective overcoats to image-bearing surfaces or in treating scratches, wear and other defects. be. The present invention is useful for obtaining adhesion with gelatin/photographic silver halide emulsion layers or protective gelatin layers commonly used in photographic image layers of photographic materials. Irradiation to cure the UV curable compositions of the present invention into a transparent, flexible, scratch-resistant crosslinked polymer layer is not suitable for photographic image layers (monolayers) even for color photographic materials where the image is a dye-based image. or multiple layers) without any significant detrimental effect on the material. The ultraviolet curable composition of the present invention can achieve its intended purpose by applying it to the surface of a photographic image layer and curing the coating solution with light containing ultraviolet light. Further, in order to further improve the durability of information and prevent discoloration of images, ultraviolet absorbers or antioxidants can be added to these compositions. Examples of the support used in the photographic material of the present invention include paper, synthetic resin sheets, etc. Synthetic resin sheets are particularly preferred due to their appropriate hardness and ease of handling, and polyethylene terephthalate, polycarbonate, cellulose triacetate, polyvinyl chloride, etc. , polyethylene, polystyrene, or polyamide, and synthetic resin sheets containing pigments in these synthetic resins are suitable. When using a transparent synthetic resin sheet among these supports, it is free to embossing, coloring, etc. on the transparent resin sheet on the side on which the photographic image is viewed over the entire surface of the card or according to a predetermined pattern. Alternatively, another image may be applied by printing or the like to the resin sheet on the opposite side to the photographic image. In addition, the opaque resin sheet placed on the back side of the photographic layer may be entirely opaque, or may be white, black, or
Alternatively, it may be a layered structure in which layers containing opacifying pigments of other colors are laminated to a predetermined thickness and in a predetermined order, and hard ones are particularly preferred. The pigments for making white opaque include titanium dioxide, barium sulfate, calcium carbonate, barium carbonate, etc. for making white opaque, carbon black etc. for making black opaque, and for other colors, select the respective pigment. be able to. The content of the opacifying pigment varies depending on the type of base resin to be mixed, film forming conditions, properties of the mixed pigment, and particle size, but is preferably 5 to 30 wt%. It should be noted that embossing, coloring, or a layered structure applied to the transparent resin sheet on the surface of the opaque resin sheet can also be used as a means for preventing counterfeiting and tampering of the card and as a means for distinguishing the card. Further, the surface of the opaque resin sheet to be bonded to the back side may be processed to include supplementary information by printing, handwriting, etc. A preferred embodiment is an authentication identification card, in which case the card has the protective coating layer of the present invention, so that it has a certain degree of hardness against external physical pressure and is not damaged by bending or the like when carried. It is particularly preferable to use an opaque resin sheet with hardness. In a transparent resin sheet carrying a developed photographic image layer (the combination of the photographic image layer and the sheet is referred to as an image sheet), the image sheet is a commercially available photographic light-sensitive material having a transparent support that is subjected to a prescribed development process. Alternatively, a photosensitive layer specially prepared for cards may be coated on a transparent resin sheet and developed. [Specific Effects of the Invention] As explained above, according to the present invention, the material adheres firmly to the photographic image layer of the photographic material, is easily cured by a light source containing low-output ultraviolet rays, and is resistant to immersion in water. However, it was possible to provide a photographic material having a protective coating layer that has strong scratch resistance and does not yellow. [Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited to these. Example 1 After coating a color silver halide photosensitive layer on a support made of a composite material made of white polyethylene and white opaque polyethylene terephthalate, necessary information was printed, development, bleaching, fixing, washing and drying were carried out, and the following coating was carried out. Apply the composition with a coating amount of 8 μm,
Photographic material samples Nos. 1 to 3 were obtained by irradiating and curing for 10 seconds from a distance of 10 cm under a high-pressure mercury lamp of 120 W/cm ² . Coating composition 1 (Sample No. 1) (1) Bisphenol A diglycidyl ether
35 parts by weight (Epicote 828 epoxy equivalent weight 185, manufactured by Yuka Ciel Chemical Co., Ltd.) (2) Diglycidyl hexahydrophthalate
50 parts by weight (Araldite CY-183, manufactured by CIBA, epoxy equivalent: 175) (3) 15 parts by weight, diglycidyl orthophthalate (Syodyne 508, manufactured by Showa Denko, epoxy equivalent: 195) (4) Triarylsulfonium hexafluoroantimony solution, 8 parts by weight ( UVE-1014 manufactured by GE) (5) 1 part by weight of nonionic fluorine alkyl activator (Megafac F-141 manufactured by Dainippon Ink) Coating composition 2 (Sample No. 2) (1) Bisphenol A diglycidyl ether
40 parts by weight (Epotote YD-8124 manufactured by Toto Kagaku Co., Ltd. Epoxy equivalent weight 170-175) (2) Diglycidyl hexahydrophthalate
25 parts by weight (Epicote 190, manufactured by Yuka Shell Chemical Co., Ltd. Epoxy equivalent: 160-170) (3) Hydrogenated bisphenol A diglycidyl ether
35 parts by weight Adeka Resin EP-4080 epoxy equivalent (manufactured by Asahi Denka) (4) Triarylsulfonium hexafluoroantimony solution 8 parts by weight UVE-1014 (manufactured by GE) Comparative coating composition 1 (Sample No. 3) JP-A-1973- Composition described in Example 2 of No. 121100) (1) 60 parts by weight of γ-glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) (2) 20 parts by weight of 1,4-butanediol diglycidyl ether ( RD-2 manufactured by CIBA) (3) 20 parts by weight of bis(3,4-epoxy-6methylcyclohexylmethyl-3.4-cyclohexanecarboxylate) (ERL-4221 manufactured by UCC) (4) Parts by weight of triphenylsulfonium hexachloroantimony solution The comparative coating composition was applied to a coating thickness of 8 μm.
The sample was irradiated with ultraviolet light for 10 seconds from a distance of 10 cm under a 120 W/cm ² high-pressure mercury lamp and heated at 90° C. for 1 hour. Example 2 Silver halide emulsion was coated on a support made of photographic base paper coated with polyethylene, and the following coating composition was coated on a developed color print to a thickness of about 12 μm, and the coating composition was applied at 80 W/cm ² Photographic material samples Nos. 4 to 8 were obtained by passing the sample under a high-pressure mercury lamp having an output of 3 m/〓 at a speed of 3 m/〓. Coating composition 3 (Sample No. 4) (1) Bisphenol A diglycidyl ether
20 parts by weight (Epicoat 834, manufactured by Yuka Schiel Chemical Co., Ltd. Epoxy equivalent: 230 to 250) (2) 10 parts by weight of novolac-type epoxy resin (Epicoat 152, manufactured by Yuka Schiel Chemical Co., Ltd., epoxy equivalent: 172 to 179) (3) Diglycidyl tetrahydrophthalate
30 parts by weight (Araldite CY-182 manufactured by CIBA, epoxy equivalent 151-167) (4) Hydrogenated bisphenol A diglycidyl ether
40 parts by weight (Santoto ST-3000 manufactured by Toto Kasei Co., Ltd. Epoxy equivalent weight 235) (5) Triarylsulfonium hexafluoroantimony solution 8 parts by weight (UVE-1014 manufactured by GE) Comparative coating composition 2 (Sample No. 5) (Special (1) 53 parts by weight of vinylcyclosexene dioxide (ERL-4206 manufactured by UCC) (2) Bis(3,4-epoxy-6-methylcyclohexyl) Methyl)-3,4-cyclohexanecarboxylate 48 parts by weight (ERL-4221 manufactured by UCC) (3) Triarylsulfonium hexafluoroantimony solution 6 parts by weight (UVE-1014 manufactured by GE) Comparative coating composition 3 (Sample No. .6) (Composition described in Example 1 of U.S. Pat. No. 4,333,998) (1) Pentaerythritol acrylate
534 parts by weight (Viscoat 300 manufactured by Osaka Organic Chemical Industry Co., Ltd.) (2) 12.3 parts by weight of γ-methacryloxide propyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) (3) p-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane 14.0 parts by weight (KBM303 manufactured by Shin-Etsu Chemical) (4) 1,4-butanediol diglycidyl ether 11.0 parts by weight (5) 4,4'-bis-chloromethylbenzophenol 4.3 parts by weight (6) Triarylsulfonium hexa Fluoroantimony solution 5 parts by weight (UVE-1014 manufactured by GE) Comparative coating composition 4 (Sample No. 7) (1) Bisphenol A diglycidyl ether
30 parts by weight (Epicoat 828 epoxy equivalent, manufactured by Yuka Schiel Chemical Co., Ltd. 185) (2) 40 parts by weight of novolac type epoxy resin (Epicoat 152 epoxy equivalent, manufactured by Yuka Schiel Chemical Co., Ltd.) (3) Bis(3,4-epoxycyclohexyl) Methyl-3,4-epoxycyclohexanecarboxylate 30 parts by weight ERL-4221 manufactured by UCC, epoxy equivalent 140) (4) Triaryphorsulfonium hexafluoroantimony solution 8 parts by weight Comparative coating composition 5 (Sample No. 8) (1 ) Bisphenol A diglycidyl ether
10 parts by weight (Epicote 828 epoxy equivalent weight 185, manufactured by Yuka Ciel Chemical Co., Ltd.) (2) 50 parts by weight of 3,4-epoxy-6-methylcyclohexyl methyl adipate (ERL-4299, manufactured by UCC) (3) 1,4- Butanediol diglycidyl ether 40 parts by weight (RD-2 manufactured by CIBA) (4) Triarylsulfonium hexafluoroantimony solution 6 parts by weight Samples Nos. 1 to 8 obtained above were evaluated by the method shown below. The results are shown in Table 1 below. 1. Water resistance The photographic material with the cured protective coating layer was immersed in tap water at 20°C day and night. Immediately after taking out the water-soaked sample from the water, it was scratched with a fingernail and its surface was observed. 〇...Those with no surface change at all △...Those with slight scratches on the surface but not reaching the photographic image layer ×...Those with scratches reaching the photographic image layer and peeling off of the photographic image layer from the support 2 Adhesion with the photographic image layer Properties (1) Cellotape (manufactured by Nichiban Co., Ltd.) was strongly applied to the surface of the cured protective coating layer, and the cellotape was rapidly peeled off from the surface, and the state of peeling was observed. (2) The protective coating layer was scratched at an angle of 90° C. using a cutter, and the adhesion to the photographic image layer was examined using the same method as in section (1). (3) Photographic material with hardened protective coating layer at 20℃
Adhesion to the photographic image layer was examined in the same manner as in (1) by immersing the sample in tap water for one day and night. (4) Photographic material with hardened protective coating layer at 20℃
Adhesion to the photographic image layer was examined using the same method as described in (2) by immersing the sample in tap water for one day and night. 〇…No peeling at all △…Half of the area of the adhesive cellophane tape peeled off (separated between the photographic image layer and the protective coating layer) ×…Most of the area of the adhesive cellophane peeled off (separated between the photographic image layer and the protective coating layer) (3) Light resistance test method A photographic material with a hardened protective coating layer was irradiated with a weather meter for 150 hours, and the whiteness was measured using a double beam color meter manufactured by Tokyo Denshoku Co., Ltd. The increase in b value in Hunter's display before and after irradiation was measured. As for the increase in b value, if it is 3 or more, yellowing will be strong and there is a problem in practical use, if it is 1.5 to 3, it can be put into practical use, and if it is 1.5
Anything less than that is considered very good.

[Table] *Evaluation methods for (1), (2), (3), and (4) are based on the adhesive evaluation method described above.
As is clear from Table 1, the samples (Nos. 1, 2, 4) protectively coated with the composition of the present invention are different from the samples (Nos. 3, 5, 6, 7, 8) obtained from the comparative composition. ), the protective coating layer does not yellow and has excellent light resistance and water resistance (nail scratch resistance).Furthermore, the adhesiveness between the protective coating layer and the photographic image layer is good even after immersion in water. It can be seen that it is giving

Claims (1)

[Scope of Claims] 1. In a photographic material having a protective coating layer, the protective coating layer comprises at least one member selected from the following group (a).
A photographic material characterized in that it is obtained by curing a composition containing at least one member selected from group (b) and at least one member selected from group (c) by irradiation with light including an ultraviolet region. : Group (a): Polyglycidyl ether of aromatic polyols, Group (b): Polyglycidyl ester of polybasic acid, Group (c): Cationic polymerization initiator.