JPH0588823B2 - - 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 1 1,4-butadiol diglycidyl ether or adipic acid bis(3,4-epoxy-
2. A cationic polymerization initiator for initiating the polymerization of epoxy compounds, such as triphenylsulfonium hexafluoroantimonate, 3. For example, pentaerythritol. polymerizable acrylic compounds such as triacrylates, 4 free radical initiators such as 4,4-bischloromethylbenzophenone, 5 polymerizable organofunctional silanes such as γ-glycidoxypropyltrimethoxysilane, etc. Ultraviolet curable compositions comprising 1) to 5) are disclosed. 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. A protective coating layer obtained from a composition containing such a silane compound is hard, easily cracks when bent, and has insufficient water resistance. It has been found that there are drawbacks such as poor scratch resistance especially when immersed in water or hot water, and the emulsion layer may fall off from the support. [Object of the Invention] Therefore, the first object of the present invention is to provide a photographic material having a protective coating layer with excellent flexibility that does not cause cracks even when folded. A second object of the present invention is to provide a photographic material having a protective coating layer that has strong scratch resistance even when immersed in water and has significantly improved adhesion to an image forming layer formed from a silver halide emulsion made of gelatin. The purpose is to provide materials. [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 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; (b) Group: polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, urethane epoxy compounds and epoxidized butadiene, Group (c): cationic polymerization initiators. [Specific Structure of the Invention] The protective coating layer of the photographic material of the present invention contains epoxy compounds of group (a), polyglycidyl ethers of polyhydric alcohols and polyoxyalkylene glycols of group (b), which are detailed below. polyglycidyl ether of
A composition containing at least one epoxy compound selected from urethane epoxy compounds and epoxidized butadiene, and a cationic polymerization initiator of group (c), which can be cured by light including the ultraviolet region (hereinafter referred to as a composition of the present invention). UV curable compositions) are used. (a) used as a protective coating layer in the present invention
The epoxy compounds of the group are preferably polyglycidyl ethers of aromatic polyols with an epoxy equivalent weight of 400 or less and a molecular weight of 1000 or less, which also includes polymethylglycidyl ether. 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. The epoxy compounds of group (a) of the present invention will be specifically explained below. (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=O) {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 epoxy compound of the above group (a) used in the present invention mainly consists of diglycidyl ether of bisphenol A,
having an average molecular weight of about 400 or less, and 170 to 200,
It typically has an epoxy equivalent weight in the range of about 172-187. For specific methods of synthesizing such epoxy compounds, see Handbook of Epoxy Resins by H. Lee and K. Neville.
“Synthesis of Glycidyl-Type Epoxy Resins” by Author, Mcgrow-Hill Book Company, 1967.
Glycidyl type Epoxy Resins”, in particular the synthesis of monomeric diglycidyl ethers of bisphenol A. (B) Epoxy compounds with 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. Epoxy compounds having 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: Ethylene oxide adduct diglycidyl ether of bisphenol F, propylene oxide adduct diglycidyl ether of bisphenol F, ethylene oxide adduct diglycidyl ether of bisphenol A, propylene oxide adduct diglycidyl ether of bisphenol A, etc. These epoxy compounds have an epoxy equivalent weight of
330-360, and the average molecular weight is 450-850. (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 these hydrogenated compounds in addition to the polyglycidyl ether of the aromatic polyols. Such hydrogenated compounds include the above-mentioned
Examples of the structural formulas (A) to (D) 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 using a known method, for example, Kline, High Polymers, Vol. 12, Analytical Chemistry of Polymers.
It can be determined by the method described in Chapter 5, Epoxy Resins (Chemistry of Polymers). 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 singly 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, it is 20% to 80% by weight, and even 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. In the epoxy compounds of group (b) used in the present invention, examples of polyglycidyl ethers of polyhydric alcohols include trimethylolpropane diglycidyl ether, butanediol diglycidyl ether,
Examples include hexanediol diglycidyl ether and glycerin triglycidyl ether. Examples of the polyglycidyl ether of polyoxyalkylene glycols used in the present invention include ethylene glycol dicrycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diclycidyl ether, dipropylene glycol diglycidyl ether, polypropylene Examples include glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyoxytetramethylene glycol diglycidyl ether, polybutadiene glycol diglycidyl ether, and the like. Examples of the urethane epoxy compounds used in the present invention include aliphatic polyols such as the polyhydric alcohols and polyoxyalkylene glycols mentioned above, tolylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate. Examples include urethane epoxy compounds produced by reacting a diisocyanate compound such as isocyanate under conditions such that isocyanate groups are in excess of hydroxyl groups, and further reacting with glycidol. Examples of the epoxidized butadiene used in the present invention include compounds containing an oxirane group in the main chain of butadiene and compounds having an oxirane group at the end. The epoxy compounds of group (b) used in the present invention are:
Based on the total weight of the ultraviolet curable composition of the present invention, 20
~80% by weight is preferred, more preferably 20-70% by weight. If the content of the epoxy compound of group (b) is less than 20% by weight, a sufficient degree of curing cannot be obtained, and if it is more than 80% by weight, the adhesion of the protective layer to the silver halide emulsion of the photographic material deteriorates. 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 hexafluoronate). phosphonium), salts of group a elements, such as sulfonium salts (e.g. triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, tris(4-thiomethoxyphenyl)sulfonium hexafluorophosphate and hexafluoroantimonic acid) triphenylsulfonium), and salts of group a elements, 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 ultraviolet curable composition of the present invention, which contains at least one selected from group (c) and 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. The ultraviolet curable composition of the present invention, which is used in the protective coating layer of the present invention and contains at least one member selected from each of the groups (a), (b), and (c), may contain oils (particularly silicone oils). , surfactants such as silicone-alkylene oxide copolymers (e.g. L-5410, 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. Further, the developer curing 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 Monoepoxides such as glycidyl ether 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. Such a color photographic emulsion clearly shows information such as a person's face in color, and is therefore 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 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 according to the invention applied onto 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 from 5 to 30 cm 3 /m 2 (coated surface) of the coating composition. The range is 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. From coating compositions generally having a viscosity in the range of 25 to 1000 centipoise,
Satisfactory coatings can be easily formed on photographic materials. The ultraviolet curable composition of the present invention is cured by irradiation with light in the ultraviolet region, and the irradiation light source for light including the ultraviolet region (hereinafter also simply referred to as ultraviolet light) used includes sunlight, a low-pressure mercury lamp, and a high-pressure mercury lamp. , ultra-high pressure mercury lamps, carbon arc lamps, 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 approximately 0.5 seconds to 5 minutes, preferably 3 seconds to 2 minutes. Normally, when the irradiation time is short, a large light source with high irradiation intensity is required, and when the irradiation time is long, a light source with low irradiation intensity can be used, but the curing action time becomes longer, which is disadvantageous in terms of the manufacturing process. . During curing, the curing time can be further shortened by heating during irradiation with ultraviolet rays or before and after irradiation. When heating, the heating temperature is preferably 30 to 80°C. Before irradiation with ultraviolet rays, the heating time may be short or long as long as the ultraviolet curable composition layer of the present invention reaches this temperature, and after irradiation with light containing ultraviolet rays, the heating time may be 1 minute to 120 minutes. is preferred. 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, even when immersed in solutions such as water, when used on items that are carried at all times, such as driver's licenses, ID cards, credit cards, and other authentication identification cards. It has strong resistance. 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, and then 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 marks, 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. Furthermore, 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. Among the above-mentioned opaque pigments, titanium dioxide, barium sulfate, calcium carbonate, or barium carbonate can be used to make white opaque, and carbon black can be used to make black opaque. For other colors, the respective pigments can be selected. I can do it. 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 multilayer 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 displayed. In particular, an opaque resin sheet with hardness is preferred. 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, it is possible to provide a photographic material with excellent flexibility that does not cause cracks even when folded, and has strong scratch resistance even when immersed in water. It was possible to provide a photographic material having a protective coating layer with significantly improved adhesion to a silver halide emulsion made of gelatin. [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 consisting of white polyethylene and white opaque polyethylene terephthalate, necessary information was printed, developed, bleached, fixed, washed and dried to produce the following material. The coating composition was applied to a coating thickness of 8 μm, and irradiated for 10 seconds from a distance of 10 cm under an 80 W/cm ² high-pressure mercury lamp (Mini Cure Lamp manufactured by Ushio Electric Co., Ltd.).
Samples Nos. 1 to 3 were obtained. Coating composition 1 (Sample No. 1) 1 Bisphenol A diglycidyl ether
30 parts by weight (Epicote 828 epoxy equivalent weight 185, manufactured by Yuka Schiel Chemical Co., Ltd.) 2 Hydrogenated bisphenol A diglycidyl ether
55 parts by weight (Adeka Resin EP-4080, manufactured by Asahi Denka Co., Ltd. Epoxy equivalent: 245) 3. 15 parts by weight of urethanized epoxy compound (EPU-7, manufactured by Asahi Denka Co., Ltd. Epoxy equivalent weight)
345) 4 Triarylsulfonium hexafluoroantimony solution 8 parts by weight (GE Corporation UVE-1014) Coating composition 2 (Sample No. 2) 1 Bisphenol A diglycidyl ale
60 parts by weight (Epotote YD-8124, manufactured by Toto Kasei Co., Ltd. Epoxy equivalent: 175) 2 Epoxidized butadiene 15 parts by weight (polybd R-45EPT, manufactured by Idemitsu Petrochemical Co., Ltd.) 3 1,6-hexanediol diglycidyl ether 35 parts by weight 4 Triaryl Sulfonium hexafluoroantimony solution 8 parts by weight (GE Co., Ltd. UVE-1014 Comparative coating composition 1 (Sample No. 3) 1 γ-glycidoxypropyltrimethoxysilane 60 parts by weight (Shin-Etsu Chemical Co., Ltd. KBM403) 2 1,4 -Butanediol diglycidyl ether 20 parts by weight (CIBA RD-2 epoxy equivalent 125~
143) 3 3,4-epoxy-6methylcyclohexylmethyl-3,4-cyclohexanecarboxylate 20 parts by weight (ERL-4221 manufactured by UCC) 4 Triphenylsulfonium hexachloroantimony solution 7 parts by weight (UVE-1014 manufactured by GE) A sample coated with the comparative coating composition and irradiated with ultraviolet rays was heated at 90° C. for 1 hour. Example 2 A silver halide color emulsion was coated on a support made of photographic base paper coated with polyethylene, and the following coating composition was applied to a color print that was developed.
It was applied to a coating thickness of 12 μm and cured by passing through a 10 cm ² area under a high-pressure mercury lamp of 80 W/cm ² at a speed of 3 m/min to obtain photographic material samples Nos. 4 to 10. Coating composition 3 (Sample No. 4) 1 Bisphenol A diglycidyl ether
20 parts by weight (Adeka Resin EP-4100 epoxy equivalent weight 180, manufactured by Asahi Denka Co., Ltd.) 2 10 parts by weight of novolac type epoxy resin (Epicoat 152 epoxy equivalent weight manufactured by Yuka Shell Chemical Co., Ltd.) 3 Hydrogenated bisphenol A diglycidyl ether
50 parts by weight (Santoto ST-3000, manufactured by Toto Kasei Co., Ltd. Epoxy equivalent: 235) 4. 20 parts by weight of urethanized epoxy compound (Adekarezin EPU-11, manufactured by Asahi Denka Co., Ltd., epoxy equivalent: 250) 5. Triarylsulfonium hexafluoroantimony solution 8 parts by weight. 6. Ionic type fluorine alkyl activator 2 parts by weight (Megafac F-141 manufactured by Dainippon Ink Co., Ltd.) Coating composition 4 (Sample No. 5) 1 Bisphenol A diglycidyl ether
20 parts by weight (Epotote YD-7126, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 180) 2. 20 parts by weight of side chain bisphenol A diglycidyl ether (manufactured by Asahi Denka Co., Ltd., Adekalezin EP-4080, epoxy equivalent: 345) 3. 1,6 hexanediol diglycidyl Ether 40 parts by weight 4 Urethane epoxy compound 20 parts by weight (Adeka Resin EPU-11, manufactured by Asahi Denka Co., Ltd. Epoxy equivalent: 250) 5 Triarylsulfonium hexafluoroantimony solution 8 parts by weight (UVE-1014, manufactured by GE) Comparative coating composition 2 ( Sample No. 6) (Composition described in Japanese Patent Publication No. 58-11452, Example 3) 1 Vinyl cyclosexene dioxide 53 parts by weight (ERL-4206 manufactured by UCC) 2 Bis(3,4-epoxy-6- Methylcyclohexylmethyl)-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. .7) (Composition described in U.S. Pat. No. 4,333,998, Example 1) 1 Pentaerythritol acrylate
53.4 parts by weight (Viscoat 300 manufactured by Osaka Organic Chemical Industry Co., Ltd.) 2 γ-methacryloxypropyltrimethoxysilane 12.3 parts by weight (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) 3 p-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 14.0 parts by weight (KBM303 manufactured by Shin-Etsu Chemical Co., Ltd.) 4 1,4-butanediol diglycidyl ether 11.0 parts by weight 5 4,4'-bis-chloromethylbenzophenol 4.3 parts by weight 6 Triarylsulfonium hexafluoroantimony solution 5 parts by weight (manufactured by GE) UVE-1014) Comparative coating composition 4 (Sample No. 8) 1 Bisphenol A diglycidyl ether
70 parts by weight (manufactured by Yuka Ciel Chemical Co., Ltd. Epicote 828 epoxy equivalent weight 184-194) 2 3,4-Epoxycyclohexyl methyl-
3,4-Epoxycyclohexanecarboxylate 30 parts by weight (manufactured by UCC ERL-4221 Epoxy equivalent 131
~145) 3 Triarylsulfonium hexafluoroantimony solution 6 parts by weight (GE Corporation UVE-1014) Comparative coating composition 5 (Sample No. 9) 1 Urethane epoxy compound 100 parts by weight (Asahi Denka EPU-7 epoxy equivalent weight
345) 2 Triarylsulfonium hexafluoroantimony solution 8 parts by weight (GE Corporation UVE-1014) Comparative coating composition 6 (Sample No. 10) 1 Bisphenol A diglycidyl ether
45 parts by weight (Epicote 828, manufactured by Yuka Schiel Chemical Co., Ltd. Epoxy equivalent: 185) 2 Hydrogenated bisphenol A diglycidyl ether
55 parts by weight (Adeka Resin EP-4080 manufactured by Asahi Denka Co., Ltd.)
Epoxy equivalent: 245) 3 Triarylsulfonium hexafluoroantimony solution 8 parts by weight (GE Corporation UVE-1014) Samples Nos. 1 to 10 obtained above were evaluated by the method shown below. The results are shown in Table 1 below. 1 Curability After the coating composition was irradiated with ultraviolet rays, the stickiness of the surface was examined by touching with a finger. 〇... Not sticky at all △... Slightly sticky feeling ×... Sticky because it does not harden. 2 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…No surface change at all △…Slight scratches on the surface that did not reach the photographic image layer×…Scratch that reached the image layer and peeled off the image layer 3. Adhesion to the photographic image layer ( 1) Cellotape (manufactured by Nichiban Co., Ltd.) was firmly attached 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 (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. 〇…No peeling at all △…Half of the area of the adhesive cellophane tape peeled off (peeling occurred between the photographic image layer and the protective coating layer) ×…Most of the area of the adhesive cellophane tape peeled off (separated between the photographic image layer and the protective coating layer) 4. Flexibility A photographic material having a cured protective coating layer was bent by 180° with the protective coating layer inside to examine the occurrence of cracks. 〇…No crack occurred △…Crack occurred ×…Crack occurred with a crackling sound

[Table] *Evaluation methods for (1), (2), and (3) are based on the adhesive evaluation method described above.
As is clear from Table 1, the comparative sample (No.
3, 6 to 10), the photographic samples (Nos. 1, 2, 4, 5) having a protective coating layer formed by the ultraviolet curable composition of the present invention had better adhesion to the photographic image layer;
It can be seen that water resistance (nail scratch resistance) and flexibility are all good.

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 ethers of aromatic polyols, Group (b): Polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, urethane epoxy compounds and epoxidized butadiene, Group (c) : Cationic polymerization initiator.