JPH0588824B2 - - 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 Fats such as 3,4-epoxycyclohexylmethyl-2,4-epoxycyclohexane carboxylate, or 1,6-hexanediol diglycidyl ether. cyclic and aliphatic polyepoxides, 3 monomers capable of polymerizing epoxy or silane groups, 4 ultraviolet absorbers (eg benzophenone), 5 cationic polymerization initiators 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; However, although these compositions are excellent in abrasion resistance and hardness, in order to improve adhesion to silver halide emulsions made of gelatin,
An organic functional silane compound is also used. 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 a high mixing ratio of polyglycidyl ether of aromatic polyols has excellent scratch resistance (water resistance) when immersed in water, and a silver halide emulsion with 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. In order to eliminate the above-mentioned drawbacks, the present inventors have conducted intensive research and found that in addition to the polyglycidyl ethers of aromatic polyols and alicyclic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyhydric alcohols, and It has been discovered that by adding at least one epoxy compound selected from polyglycidyl ethers of oxyalkylene glycols and urethane epoxy compounds, yellowing of the resulting protective coating layer due to sunlight can be prevented, and further Surprisingly, it has been found that the adhesion of the protective coating layer to the silver halide emulsion is 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 having a protective coating layer with excellent flexibility that does not cause cracks even when folded. A third object of the present invention is to provide a photographic material having a protective coating layer that does not yellow even when exposed to sunlight and has excellent light resistance. A fourth object of the present invention is to provide a photographic material having a protective coating layer that hardens rapidly even when exposed to low-intensity ultraviolet light. [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 layer selected from the following group (a), at least one layer selected from the group (b), ( This is achieved by a photographic material in which a composition containing at least one member selected from group c) and at least one member selected from group (d) is cured by irradiation with light in the ultraviolet region. Group (a): Polyglycidyl ethers of aromatic polyols, Group (b): Alicyclic polyepoxides, Group (c): Polyglycidyl ethers of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyoxyalkylene glycols. polyglycidyl ether and urethane epoxy compounds, group (d): cationic polymerization initiators. [Specific Structure of the Invention] The protective coating layer of the photographic material of the present invention contains an epoxy compound of group (a), an alicyclic polyepoxide of group (b), and a polybasic acid of group (c), which are detailed below. Contains at least one epoxy compound selected from polyglycidyl ethers, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, and urethane epoxy compounds, and a halogen polymerization initiator of group (d). A composition that can be cured by light in the ultraviolet region (hereinafter referred to as the ultraviolet-effect composition of the present invention) is 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. 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 epoxy 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,
Contains small amounts of 2 and/or 3. The epoxy compound used in the present invention mainly consists of diglycidyl ether of bisphenol A and is about
It has an average molecular weight of less than 400 and an epoxy equivalent weight in the range of 170-200, usually about 172-187. For specific synthesis methods of such compounds,
Handbook of Epoxy Resins 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. 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 epoxy compounds have an epoxy equivalent 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 of bisphenol F (a condensate of formaldehyde with phenol) and epichlorohydrin. This compound has an average molecular weight of 400 or less and an epoxy equivalent weight of 170-190. (D) Epoxidized resins of novolac resins and cresol novolac resins. These products are prepared by combining 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. ) to obtain a liquid or low-melting 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. Epoxyphenol novolac resins generally have the following formula:

[Chemical formula] Furthermore, compounds derived from polynuclear phenol glycidyl ether and represented by the following general formula 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 (A) above.
In the structural formulas of ~(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 the aromatic polyol which is the epoxy compound (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.
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 epoxy compounds of the above group (a) should be used alone or in combination of two or more in the composition in an amount of at least 10% by weight based on the total weight of the ultraviolet curable composition of the present invention. It is necessary to contain 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. Next, the alicyclic polyepoxide of group (b) used in the protective coating layer of the present invention will be explained. The alicyclic polyepoxide has an average of two or more epoxy groups per molecule. An example of a suitable alicyclic polyepoxide is a diepoxide of a cycloaliphatic ester of a dicarboxylic acid represented by the following general formula (). General formula ():

[Chemical formula] In the above formula, R ₁ to R ₁₈ may be the same or different, and are hydrogen atoms or 1
Alkyl group of ~9 carbon atoms, preferably 1~
represents an alkyl group containing 3 carbon atoms,
Examples of alkyl groups include methyl, ethyl, n
-propyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl. R _p represents a valence bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 6 carbon atoms; such hydrocarbon groups include, for example, trimethylene, tetramethylene, , pentamethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, nonamethylene, hexadecamethylene, etc.; 1,4-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclohexylene and similar Examples include divalent cycloaliphatic groups such as cycloaliphatic groups. Particularly desirable epoxides belonging to formula () are:
In the formula, R ₁ to R ₁₈ are all hydrogen atoms, and R _p
is an alkylene having 4 to 6 carbon atoms. Specific diepoxides of cycloaliphatic esters of dicarboxylic acids include: Bis(3,4-epoxycyclohexylmethyl)oxalate, Bis(3,4-epoxycyclohexylmethyl)adipate, Bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, Bis(3,4-epoxycyclohexylmethyl) pimelate, and similar. Other suitable compounds include 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexane carboxylate, this compound is described in US Pat. No. 2,750,395. General formula ():

[C] In the above general formula (), R ¹ to R ¹⁸ can be the same or different, and these represent the general formula ()
The definitions are the same as those defined for R ₁ to R ₁₈ in . Particularly preferred compounds are those in which all of R ¹ to R ¹⁸ are hydrogen atoms. Examples of compounds belonging to general formula () include the following compounds. 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate,
3,4-Epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexylmethyl 3,4-epoxy-1-methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-6 -Methyl-3,4-epoxy-6-
Methyl-cyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5 -Methylcyclohexanecarboxylate. Other suitable compounds are diepoxides represented by the following general formula () and described, for example, in US Pat. No. 2,890,194. General formula ():

[Chemical formula] In the above formula, R ₁ ′ to R ₉ ′ and R ₁ ″ to R ₈ ″ may be the same or different, and each represents a monovalent substituent, such as a hydrogen atom, a halogen atom, i.e., chlorine, bromine, iodine, or These include each fluorine atom and a monovalent hydrocarbon group. Particularly preferred compounds are R ₁ ′ to R ₉ ′, R ₁ ″ to
A compound in which R ₈ ″ is all hydrogen. Other suitable cycloaliphatic epoxides include the following.

[ka]

[C] and similar. Among the compounds represented by the above general formulas (), () and (), preferred cycloaliphatic epoxides include the following. (1) 3,4-epoxycyclo-xylmethyl-
3,4-epoxycyclohexanecarboxylate

[Chemical formula] (2) Bis-(3,4-epoxycyclohexylmethyl)adipate

[Chemical formula] (3) Di-(3,4-epoxy-6-methylcyclohexylmethyl)adipate

[Chemical] (4) 2-(3,4-epoxycyclohexyl-5,
5-spiro-3,5-epoxy)cyclohexane-meth-dioxane

embedded image These compounds can be used alone or in combination of two or more. The cycloaliphatic polyepoxide resins of group (b) above can be mixed with small amounts of cycloaliphatic monoepoxides as shown below.

[ka] limonene monoepoxide with

[ka] norbornene monoepoxide having

4-vinylcyclohexene monoepoxide having the formula: The above alicyclic monoepoxide acts as a reactive diluent that cures into the final product, has a remarkable effect on lowering the viscosity, does not volatilize during the UV curing operation, and does not retard the curing speed. . The above-mentioned alicyclic monoepoxide can be used in an amount of 0 to 30% by weight based on the UV curable composition of the present invention. The content of the alicyclic polyepoxide of group (b) of the present invention is based on the total weight of the ultraviolet curable composition of the present invention.
About 10-80% by weight is preferred, more preferably 20-80% by weight.
Can be mixed in a range of 70% by weight. If the content of the alicyclic polyepoxide is less than 10% by weight, a sufficient degree of curing cannot be obtained, and if it is more than 80% by weight, the adhesion of the protective coating layer to the silver halide emulsion of the photographic material deteriorates. In the epoxy compounds of group (c) used in the present invention, examples of polyglycidyl esters of polybasic acids include polyglycidyl esters of polycarboxylic acids shown below, but the present invention is not limited thereto. (1) Diglycidyl phthalate (phthalic acid diglycidyl ester) (2) Diglycidyl tetrahydrophthalate (tetrahydrophthalic acid diglycidyl ester) (3) Diglycidyl hexahydrophthalate (hexahydrophthalic acid diglycidyl ester) (4) Dimethylglycidyl Phthalate (dimethylglycidyl phthalate ester) (5) Dimethylglycidyl hexahydrophthalate (dimethylglycidyl hexahydrophthalate ester) (6) Dimer acid glycidyl ester (7) Dimer acid glycidyl ester modified product (8) Aromatate diglycidyl ester ( 9) Cycloaliphate diglycidyl ester Among the above polycarboxylic acid polyglycidyl esters, the diglycidyl phthalates shown in (1), (2), and (3) are preferable, and the following (1), (2), A specific example of (3) is shown below. (1) Diglycidyl orthophthalate (Kawakaron A, Cyodyne 508)

[ka] (2) Diglycidyl tetrahydrophthalate (Kawakaron T, 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 carried out by the method described in Japanese Patent Publication No. 41-6573, Handbook of Epoxy Resins, etc. Specifically, for example, a method of synthesizing glycidyl ester from an acid chloride and glycidol or an alkali salt of an acid and epichlorohydrin, a method of synthesizing glycidyl ester from an acid chloride and glycidol or an alkali salt of an acid and epichlorohydrin, and a method of synthesizing a glycidyl ester from an acid chloride and glycidol or an alkali salt of an acid and epichlorohydrin, and a method of synthesizing glycidyl ester from various carboxylic acids (such as acrylic acid, polyacrylic acid, stearic acid, etc.) in the presence of an excess of epichlorohydrin.
pelargonic acid, azelaic acid, sebacic acid, adipic acid, succinic acid, phthalic acid, oleic acid, linolenic acid dimer and linolenic acid trimer)
A method of synthesizing glycidyl ester using an aqueous alkali metal salt solution and quaternary ammonium halide as a catalyst, or using an alkali metal salt of bromine or iodine as a catalyst and N- as a reaction solvent.
Examples include a method using dialkylamide or disulfoxide, and a method using an alkali or tertiary amine as a catalyst. In the epoxy compounds of group (c) used in the present invention, examples of polyglycidyl ethers of polyhydric alcohols include trimethylolpropane diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, glycerin triglycidyl ether, etc. can be mentioned. Examples of the polyglycidyl ether of polyoxyalkylene glycols used in the present invention include ethylene glycol diglycidyl ether,
Diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
1,4-butanediol diglycidyl ether,
Examples include 1,6-hexanediol diglycidyl ether, polyoxytetramethylene glycol diglycidyl ether, and polybutadiene glycol diglycidyl ether. 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 (c) 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. The cationic polymerization initiator of group (d) used in the present invention is preferably an aromatic onium salt, which includes 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 detailed in Publication No. 4161478. 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 usage amount of the above cationic polymerization initiator is (a), (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 containing at least one selected from each group (c) and (d). be. 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 above (a), (b) used in the protective coating layer of the present invention,
The ultraviolet curable composition of the present invention, which contains at least one selected from each group (c) and (d), contains oils (particularly silicone oil), silicone-alkylene oxide copolymers (for example, from Union Carbide Co., Ltd.). Surfactants such as commercially available L-5410), silicone oil-containing aliphatic epoxide groups, FO-171, available from 3M Company, and FO-430, also available from 3M Company, Dainippon Co., Ltd. Fluorocarbon surfactants such as Megafac F-141 available from 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, 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 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 present invention applied on the photographic image layer of the photographic material is in the range of 2 to 30 cm ³ /m ² (coated surface) of the coating composition as a wet coverage, preferably 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 in the ultraviolet region, and examples of the irradiation light source in the ultraviolet region (hereinafter simply referred to as ultraviolet light) include sunlight, low-pressure mercury lamps, high-pressure mercury lamps, and ultraviolet rays. There are 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. 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 ultraviolet rays. When heating, the heating temperature is 30℃~80℃
is preferred. 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 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, 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, 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 multilayer) 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 where the photographic image is viewed on 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 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 adheres firmly to the photographic image layer of a photographic material, is easily cured by a light source containing low-output ultraviolet rays, and is not immersed in water. It was possible to provide a photographic material having a strong scratch resistance even when the protective coating layer is not yellowed, excellent light resistance, and a protective coating layer with excellent flexibility. [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, and the following was obtained. The coating composition was applied to a coating thickness of 8 μm, and the coating composition was irradiated by passing 10 cm under a 50 W/cm ² high-pressure mercury lamp (Mini Cure Lamp 450 manufactured by Ushio Electric Co., Ltd.) at a speed of 2 m/min. After curing, photographic material samples Nos. 1 to 5 were obtained. Coating composition 1 (Sample No. 1) 1 Bisphenol A diglycidyl ether
40 parts by weight (Epotote YD-8124, manufactured by Toto Kasei Co., Ltd. Epoxy equivalent: 170-190) 2 Bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate 40 parts by weight (ERL-4299, manufactured by UCC Company, epoxy equivalent)
210) 3 Diglycidyl hexahydrophthalate
20 parts by weight (Epomic R-540 manufactured by Mitsui Petrochemicals, epoxy equivalent weight 165) 4 Triarylsulfonium hexafluorophosphate 8 parts by weight (FC-508 manufactured by 3M) 5 1 part by weight of nonionic fluorine alkyl ester (Dainippon Co., Ltd.) MegafacF-141 (manufactured by Ink Co., Ltd.) Coating composition 2 (Sample No. 2) 1 Bisphenol A diglycidyl ether
20 parts by weight (Epotote YD-8125 epoxy equivalent weight 173, manufactured by Toto Kasei Co., Ltd.) 2 10 parts by weight of novolac type epoxy resin (Epoxy equivalent weight 152, manufactured by Yuka Ciel Chemical Co., Ltd.) 3 Bis(3,4-epoxy-6-methylcyclohexylmethyl) ) Adipart 50 parts by weight (manufactured by UCC ERL-4299 epoxy equivalent
210) 4 Diglycidyl tetrahydrophthalate
20 parts by weight (Araldite CY-182 manufactured by CIBA, epoxy equivalent weight 165) 5 Triarylsulfonium hexafluoroantimony solution 8 parts by weight (UVE-1014 manufactured by GE) Coating composition 3 (Sample No. 3) 1 Bisphenol A diglycidyl ether
20 parts by weight (Epicote 834, manufactured by Yuka Ciel Chemical Co., Ltd. Epoxy equivalent: 250) 2 Hydrogenated bisphenol A diglycidyl ale
35 parts by weight (ADEKA EP-4080 epoxy equivalent, manufactured by Asahi Denka Co., Ltd.) 30 parts by weight of di-(3,4-epoxy-6-methylcyclohexylmethyl)adipate (ERL-4299, manufactured by UCC Corporation, epoxy equivalent)
210) 4 Urethane epoxy compound 15 parts by weight (Asahi Denka Co., Ltd. ADEKA EPU-11 epoxy equivalent) 5 Trianol sulfonium hexafluoroantimony solution 8 parts by weight Comparative coating composition 2 (Sample No. 4) (Japanese Patent Publication No. 58-11452) (Composition described in Example 3) 1 Vinylcyclosexene 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 Parts by weight of triarylsulfonium hexafluoroantimony solution (UVE-1014 manufactured by GE) Comparative coating composition 3 (Sample No. 5) (Similar to Example 1 of U.S. Pat. No. 4,333,998) Composition as described) 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) Example 2 A silver halide emulsion was coated on a support made of photographic base paper coated with polyethylene, and the coating composition shown below was applied to a color print that was developed.
After coating to a thickness of 10 μm, the coating composition was cured by irradiation under a high-pressure mercury lamp of 80 W/cm ² from a distance of 10 cm at a speed of 3 cm/min, and photographic material sample No. 6 was coated.
I got ~9. Coating composition 4 (Sample No. 6) 1 Bisphenol A diglycidyl ether
30 parts by weight (Epicote 834, manufactured by Yuka Schiel Chemical Co., Ltd. Epoxy equivalent: 230-250) 2 Hydrogenated bisphenol A diglycidyl ether
30 parts by weight (Santoto ST3000, manufactured by Toho Kasei Co., Ltd. Epoxy equivalent: 235) 3 Bis(3,4-epoxy-6-methylcyclohexylmethyl) 3,4-cyclohexanecarboxylate 20 parts by weight (ERL-4221, manufactured by UCC Corporation, epoxy equivalent)
140) 4 Diglycidyl hexahydrophthalate
20 parts by weight (Epicoat 190, manufactured by Yuka Ciel Chemical Co., Ltd. Epoxy equivalent: 160-170) 5 Triarylsulfonium hexafluoroantimony solution 6 parts by weight 6 Silicone activator 2 parts by weight (L-5410, manufactured by UCC) Coating composition 5 ( Sample No. 7) 1 Bisphenol A diglycidyl ether
30 parts by weight (Epicote 832, manufactured by Yuka Ciel Chemical Co., Ltd. Epoxy equivalent: 190) 2 Diglycidyl hexahydrophthalate
25 parts by weight (Epicote 190, manufactured by Yuka Ciel Chemical Co., Ltd. Epoxy equivalent: 170) 3 Bis-(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate 35 parts by weight (ERL-4299, manufactured by UCC Company, epoxy equivalent)
210) 4 Epoxidized butadiene 10 parts by weight (manufactured by Idemitsu Petrochemical Co., Ltd. polybd R-45-
EPT) 5 Triarylsulfonium hexafluoroantimony solution 8 parts by weight (UVE-1014 manufactured by GE) 6 Silicone activator 2 parts by weight (L-5410 manufactured by UCC) Coating composition 6 (Sample No. 8) 1 Bisphenol A diglycidyl ether
30 parts by weight (Epicote 832, manufactured by Yuka Ciel Chemical Co., Ltd. Epoxy equivalent: 190) 2 Bis-(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate 40 parts by weight (ERL-4299, manufactured by UCC Company, epoxy equivalent)
210) 3 1,4-butadiol diglycidyl ether
20 parts by weight (CIBA RD-2 Epoxy equivalent: 125~
143) 4 Diglycidyl hexahydrophthalate
20 parts by weight (Epicote 190, manufactured by Yuka Ciel Chemical Co., Ltd. Epoxy equivalent: 170) 5 Triarylsulfonium hexafluoroantimony solution 8 parts by weight Comparative coating composition 3 (Sample No. 9) 1 γ-Glycidoxypropyltrimethoxysilane 60 parts by weight parts (KBM403, manufactured by Shin-Etsu Chemical) 2 20 parts by weight of 1,4-butanediol diglycidyl ether (RD-2, manufactured by CIBA) 3 20 parts by weight of 3,4-epoxy-6methylcyclohexylmethyl 3,4-cyclohexanecarboxylate (ERL-4221 manufactured by UCC) 4 8 parts by weight of triarylsulfonium hexafluorophosphate solution (FC-508 manufactured by 3M) Samples Nos. 1 to 9 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. (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 was peeled off (peeling occurred between the photographic image layer and the protective coating layer) ×…Most of the area of the adhesive cellophane tape was peeled off (peeling 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 cracks △...Cracks occurred ×...Cracks occurred with a cracking sound 5 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 beam color meter, and 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 will be a problem in practical use, if it is 1.5 to 3, it can be put to practical use, and if it is less than 1.5, it is considered to be very good.

【table】

[Table] *Evaluation methods in (1), (2), (3), and (4) are based on the adhesive evaluation method described above.
As is clear from Table 1, the samples (Nos. 1 to 3 and 6 to 8) coated with the composition of the present invention were
Samples obtained from comparative coating compositions (No. 4, 5,
9), the protective coating layer has excellent curability and water resistance (nail scratch resistance), and the adhesion between the protective coating layer and the photographic image layer shows good results even after being immersed in water. It can be seen that it has excellent flexibility and no cracks occur.

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 composition containing at least one selected from group (b), at least one selected from group (c), and at least one selected from group (d) is cured by irradiation with light including an ultraviolet region. A photographic material characterized by being Group (a): Polyglycidyl ethers of aromatic polyols, Group (b): Alicyclic polyepoxides, Group (c): Polyglycidyl ethers of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyoxyalkylene glycols. polyglycidyl ether and urethane epoxy compounds, group (d): cationic polymerization initiators.