JPH0469932B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a photographic light-sensitive material, and more specifically, an electron beam curable resin composition layer is provided on a substrate, this layer is irradiated with an electron beam to cure it, and is used as a support. The present invention relates to a method for producing a photographic material in which a photosensitive layer is provided on this support. [Prior Art and its Problems] Conventionally, there is a photosensitive material of this kind, for example, a photosensitive material for photographic paper whose support base material is paper, which is made by coating the surface of the paper base material with a polyolefin resin. , this is in order to speed up photo processing, etc.
It has been frequently used in recent years. The polyolefin resin contains an inorganic white pigment such as titanium oxide or calcium carbonate in order to improve the whiteness and hiding power of the support, and the resolution and sharpness after coating the photographic emulsion. By the way, when forming a polyolefin resin coating, it is necessary to melt the resin at a high temperature of about 280 to 340°C. It is not possible to incorporate a large amount of the above-mentioned inorganic white pigment into such a polyolefin resin melted at a high temperature, and the dispersibility is also poor under such conditions. For this reason, it was not possible to obtain sufficiently satisfactory sharpness of photographic images. Under these circumstances, attempts have been made to disperse large amounts of inorganic pigments in polyolefin resins using dispersants. For example, JP-A-51-6531, JP-A-52-35625,
No. 55-108658, No. 55-113039, No. 55-113040
No. 1, etc. disclose techniques for coating the surfaces of titanium oxide particles with various compounds. However, with these techniques, when polyolefin resin is melted at high temperatures, contamination from these additives occurs at the tie exit end of the extruder, and concave lines are formed on the surface of the molten film, which causes damage to the support. There is a problem in that surface grooves form and uneven coating of the emulsion occurs. In addition, in JP-A-57-151942, instead of the above additive (which functions as a type of dispersant),
It has been proposed to use alkyl titanates, which would improve the above problems. However, in this case, the alkyl titanate-treated pigment is added to the molten polyolefin resin.
It contains only about 20wt%, which is insufficient in terms of sharpness, and free alkyl titanates that are not bonded to pigments are likely to be generated, which thermally decomposes during melting, emitting smoke in the coating, and causing damage to the cooling roll. Problems arise such as adhesion and the inability to obtain a smooth film surface. As described above, when pigments are incorporated into conventional polyolefin resin coatings, sufficient sharpness has not yet been achieved. In order to solve the above problems, Japanese Patent Application Laid-open No. 57-27257,
No. 57-49946 proposes a photographic support having a coating layer formed by coating a paper base material with a composition that can be cured by electron beam irradiation and curing the composition by irradiating it with electron beams. ing. With such a support, the content of inorganic white pigment can be increased up to 20-70 wt%,
As a result, sharpness was significantly improved compared to polyolefin resin coating. However, when photographic materials obtained by coating a photosensitive layer on a coating layer that has been cured by electron beam irradiation are subjected to normal storage and development processing, fog increases, and this is a problem that cannot be ignored as a product. It turns out that there are cases where this happens. As an improvement method for this, Japanese Patent Application Laid-Open No. 59-124336 proposes a technique in which a blocking layer is provided between the paper of the support and the electron beam curable lacquer layer. However, this method still does not have a sufficient effect of suppressing fogging, and requires a process to further provide a blocking layer in addition to the conventional manufacturing process, which is disadvantageous in terms of manufacturing cost. The cause of fogging is not clear, but in the specification of JP-A-59-124336, page 10, lines 4 to 12, it is stated that the cause is curable or uncured low molecular weight monomers contained in the lacquer layer. It is estimated that it is one of the In order to put into practical use a photographic material using a support having an electron beam cured coating layer,
A solution to the above fogging problem is desired. [Object of the Invention] The object of the present invention is to coat at least one side of a support base material with an electron beam curable composition, cure this with an electron beam to obtain a photographic support, and coat the cured coating layer on the cured coating layer. When a photosensitive material is formed by applying a photosensitive layer, there is little increase in fog over storage, and the photographic image has excellent sharpness, surface smoothness, and adhesion between the base material and the coating layer. The object of the present invention is to provide a manufacturing method for obtaining a photosensitive material. [Structure of the Invention] In order to achieve the above object, the inventors of the present invention have conducted various studies, and have found that when curing an electron beam curable resin composition, it is better to irradiate the electron beam sufficiently so that no low molecular monomer remains. Rather, under conditions where the amount of electron beam irradiation is small, that is, when curing the electron beam curable resin composition, the electron beam is passed through an electron beam semi-transparent membrane that absorbs substantially 50 to 95% of the energy of the electron beam. The inventors have found the completely unexpected fact that fog is significantly reduced when a curable resin composition layer is irradiated and cured, and based on this fact, the above object has been achieved. In other words, the problem with the prior art described above is that the electron beam is irradiated from the electron beam curable resin composition layer side, and this electron beam irradiation absorbs substantially more than 50% and less than 95% of the energy of the irradiated electron beam. This problem can be solved by a method of transmitting electron beams through a semi-transparent membrane. When a product was manufactured using the method of the present invention, the sharpness of the photographic image, the smoothness of the surface, and the adhesion between the base material and the coating layer were not impaired. It should be noted that the method of closely adhering an electron beam transparent film on the electron beam curable composition layer during electron beam curing is disclosed in Japanese Patent Application Laid-open No.
No. 47-30730, JP-A No. 51-77800, JP-A No. 57-
No. 30576, JP-A-57-21965, JP-A-57-22204
No. 59-68240, etc.,
In either case, it is not expected that irradiation with electron beams under the conditions of the present invention would produce effects such as a significant reduction in fog. The structure of the present invention, materials used, etc. will be further explained below. The method for producing a photographic material of the present invention includes coating an electron beam curable resin composition substantially consisting of an electron beam curable compound and a pigment on at least one side of a substrate to form an electron beam curable resin composition layer. When this layer is irradiated with an electron beam, the electron beam is applied to the electron beam curable resin composition layer through an electron beam semi-transparent film that absorbs substantially 50% to 95% of the energy of the irradiated electron beam. It consists of preparing a support by irradiation and curing, and providing a photosensitive layer on this support. Next, materials that can constitute the electron beam curable composition used to obtain the silver halide photosensitive material of the present invention will be explained. In the present invention, as the electron beam curable compound for forming the coating layer on the support, any compound can be used as long as it is curable by electron beam irradiation. Examples of compounds that can be cured by electron beams that can be used in the present invention include two unsaturated double bonds in the molecular chain that do not polymerize by generating radicals or the like upon electron beam irradiation, but are cured by crosslinking. Compounds containing the above can be mentioned. Further, examples thereof include cationic polymerizable compounds (in this case used in combination with an initiator) as shown in JP-A No. 59-147018, Japanese Patent Application No. 59-32237, and the like. In this way, there are no particular restrictions on the compounds that can be cured by electron beams, but acrylate compounds (acrylate compounds having a urethane bond in the molecule,
Similarly, acrylate compounds having epoxy bonds), esters (including those having similar bonds), etc. can be employed. In addition, especially when using a paper base material as a support base material, increasing the amount of inorganic white pigment added may easily cause the cured coating layer to become brittle. It is preferable to choose. The following examples can be suitably used. (1) Acrylic compounds such as acrylic polymers (1)-1 Aromatic acrylates such as aromatic monoacrylates and aromatic diacrylates (such as those used in the examples) Aliphatic monoacrylates, aliphatic diacrylates, aliphatic Aliphatic acrylates such as triacrylates (such as those used in the examples) (1)-2 Polyester acrylates A.C.G. Juan Dostachot & A. Juan Nearbos (A.
CJ Van Dosterhout and A. van Neerbos)
Author, Double Liaison-ChiM Peint. 27 (295),
135 (1980). (1)-3 Acrylate oligomer (1)-4 Epoxy acrylate A compound disclosed in Japanese Patent Publication No. 47-13023 and Japanese Patent Publication No. 57-162713. That is, epoxy acrylates obtained by adding acrylic acid or other α, β unsaturated carboxylic acids to polyfunctional epoxy compounds. If it is commercially available, the product name
There are EA800 and EPM800 (Shin Nakamura Chemical Co., Ltd.). (1)-5 Silicon acrylate A condensate of hydroxyl or methoxy group-containing silicone and hydroxyethyl methacrylate, which is disclosed in Japanese Patent Publication No. 48-22172 and Japanese Patent Application Laid-open No. 48-39594. (1)-6 Urethane acrylate Aromatic urethane acrylate (such as those used in Examples), etc. U.S. Patent No. 3864133, U.S. Patent No. 3891523, U.S. Pat.
No. 3912516, Special Publication No. 1972-22172, Japanese Patent Publication No. 1973-
No. 39594, JP-A-49-26337, JP-A-49-
No. 35346, JP-A-49-96043, JP-A-52-
No. 31239, JP-A-54-80394, JP-A-54-
Urethane acrylate disclosed in No. 129034 and JP-A-54-127994. Specifically, urethane acrylate obtained by adding hydroxyethyl methacrylate to a polyfunctional isocyanate compound, urethane obtained by reacting a polyoxyalkylene bisphenol A derivative with a polyisocyanate and a hydroxyl group-containing acrylate. Acrylate Examples include amide urethane acrylate, which is obtained by reacting an amide-containing compound having a hydroxyl functional group, a polyisocyanate, and a hydroxyl-containing acrylate compound. Commercially available products include the trade names Uvisan 783 and Uvisan 793 (Toraythiokol Co., Ltd.). (2) Unsaturated polyester Special Publication No. 48-23654, Special Publication No. 49-23293, Special Publication No. 47103, Special Publication No. 49-44572, Japanese Patent Publication No.
Compounds disclosed in No. 54-7473, etc. For products that are commercially available, the product name
There are M8030 and M8060 (both manufactured by Toagosei Chemical Industry Co., Ltd.). (3) Modified unsaturated polyester urethane modified unsaturated polyester In particular, the compound disclosed in Japanese Patent Publication No. 14667-1983. Acrylic urethane-modified unsaturated polyester In particular, the compound disclosed in Japanese Patent Publication No. 14790/1983. Liquid unsaturated polyester having an acrylic group at the end, especially the compounds disclosed in US Pat. No. 3,455,802 and US Pat. No. 3,485,732. (4) Ester oligomano acrylate such as oligoester monoacrylate, oligoester diacrylate, oligoester triacrylate, etc. Preferable examples of this compound include the following. Maronics M-102, M-150, M-152,
M-5400, M-5500, M-5700, XM-101,
XM-111, XM-113, XM-117, X215A (all trade names, manufactured by Toagosei Chemical Industry Co., Ltd.). (5) Butadiene-based polymer Urethane-ized 1,2-polybutadiene disclosed in JP-A-50-123187, JP-A-54-
Examples include modified polybutadiene, which is disclosed in No. 148094, which is obtained by adding a monoester compound to epoxidized polybutadiene and further adding an aliphatic lower carboxylic acid. In addition, the molecular chain contains hydrogenated or non-additive polybutadiene, and electron beam reactive groups (vinyl group, epoxy group, isocyanate group, etc.) or non-reactive groups (hydroxyl group, alkyl group, carboxyl group,
A compound containing a COOR group (where R is an alkyl group), etc. can be used. Examples of such compounds include NISSO PB B series, G series, C series, BI series,
GI series, CI series resins, TE resins,
Maleated PB resin, BF resin (Nippon Soda Co., Ltd.),
Poly bd series, HTP-4, HTP-9,
HTP-5MLD, HTP-9PA, R-45HT, R
-45M, R-45MA, R-45EPT, R-
Commercial products such as 45EPI and R45ACR (Idemitsu Petrochemical Co., Ltd.) are also available. (6) Electron beam curable polymers containing carbocyclic or heterocyclic bonds in their molecular chains. Electron beam curable compounds containing carbocyclic or heterocyclic bonds in the chain can be used. The ring structure of this compound is preferably a phenylene ring, a spiran ring, or a triazolone ring. Also preferred are cycloalkylene rings, bicycloalkylene rings, naphthalene rings, furan or fused furan rings, thiophene or fused thiophene rings, pyrrole or fused pyrrole rings, pyran or pyrone rings, pyridine rings, quinoline or isoquinoline rings, azole rings, and diane rings. . These compounds are, for example, NK ester EA-
800, EPM-800, A-BPE-4, BPE-200
(Shin Nakamura Chemical Co., Ltd.), Photomer4028 (Diamond
Shamrock), M210 (Toagosei Chemical Industry Co., Ltd.), R
Commercial products such as -604 (Nippon Kayaku Co., Ltd.), M315, and M325 (Toagosei Chemical Industry Co., Ltd.) are also available. The above compounds may be used alone or in combination of two or more. In addition, its number average molecular weight is preferably 500 to
It is about 20,000, more preferably about 1,000 to 10,000.In addition, for the purpose of adjusting the viscosity of the composition, curing characteristics, physical properties of the cured layer, etc., especially for the purpose of imparting flexibility,
It is preferable to use a monomer having an unsaturated bond in combination with the above compound. The mixing ratio with the monomer is arbitrary, for example 5/
It can be used in a wide range of weight ratios ranging from 95 to 90/10. Any reactive compound that can be copolymerized may be mixed as these monomers, but acrylate and methacrylate monomers are particularly preferred. Typical monomers used in combination include the following. (A) Polyester acrylate, polyester methacrylate Toagosei Chemical Industry Co., Ltd., trade name Aronix
M6100, Aronix M6200, Aronix
M6250, Aronix M6300, Aronix
M6500, Aronix M7100, Aronix
M8100. Sannopco Co., Ltd., product names Fotomer 5007, Fotomer 5018, Fotomer 4149. Nippon Kayaku Co., Ltd., product name Kayamer MANDA;
Kayaratu HX220, Kayaratu HX620. (B) Polyurethane acrylate, polyurethane methacrylate Osaka Organic Chemical Co., Ltd., trade name, Bismart 829. Toagosei Chemical Industry Co., Ltd., product name Aronix
M1200, Aronix M1100 Japan U-Pica Co., Ltd., product name AC5801 Shin-Nakamura Chemical Co., Ltd., product name NK Ester U-
108A, NK ester U4HA Toray Thiokol Co., Ltd., product name: Iupisan 893 San Nopco Co., Ltd., product names: Fotomer 5007, Fotomer 6008. (C) Epoxy acrylate, epoxy methacrylate Osaka Organic Chemical Co., Ltd., product name Viscoat 60 San Nopco Co., Ltd., product name Fotomer 3016, Fotomer 3082 Nippon U-Pica Co., Ltd., product name AC5301, AC5701,
AC5702; EX9004, EX9006. (D) Silicone acrylate A compound disclosed in Japanese Patent Publication No. 48-22172 and Japanese Patent Publication No. 48-39594, respectively. (E) Monofunctional monomer methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, n-hexyl acrylate, lauryl acrylate, and the like. Commercially available products include the product name Photomer4039 (Diamond Shamrock);
and so on. (F) Bifunctional monomer 1,6-hexanediol diacrylate,
1,6-hexanediol diacrylate, neopentyl glycol, 1,4-butanedio-
polyethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate,
such as divinylbenzene. (G) Trifunctional or higher functional monomer trimethylolpropane triacrylate,
trimethylolpropane trimethacrylate,
Pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethylenediamine acrylamide, etc. Furthermore, for the purpose of improving flexibility and adhesion of the support base material, thermoplastic resins represented by the following may be mixed and used. (1) Cellulose derivatives Nitrocellulose, cellulose acetate butyrate, ethylcellulose, butylcellulose, etc. (2) Polyvinyl alcohol resins Polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, etc. (3) Vinyl chloride copolymers Vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic acid copolymers, etc. (4) Polyurethane resins (5) Unsaturated and saturated polyester resins (6) Polyamide resins (7) Low molecular weight polyolefins, low molecular weight polybutadienes, etc. These thermoplastic resins may or may not have an acrylic modified double bond introduced therein. These thermoplastic resins can be used in an amount of, for example, 50 wt % or less based on the total amount of the electron beam curable compound and electron beam curable monomer of the present invention. Furthermore, a solvent can be added to the cured coating layer coating composition of the present invention, if necessary. The solvent to be used is not particularly limited and is appropriately selected in consideration of solubility, compatibility, etc. with the electron beam curable composition. Solvents that can be suitably used in preparing the composition include methanol, ethanol, isopropanol,
Alcohols such as butanol Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Esters such as methyl acetate, ethyl acetate, butyl acetate, and ethyl butyrate Glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, and dioxane Benzene, toluene, and xylene Examples include aromatic hydrocarbons such as hexane, aliphatic hydrocarbons such as heptane, and mixtures thereof. Inorganic white pigments used in the present invention include titanium oxide (anatase type, rutile type), barium sulfate,
Any of calcium carbonate, aluminum oxide, magnesium oxide, etc. can be used, but titanium oxide, barium sulfate, and calcium carbonate are preferred. Further, the surface of titanium oxide can be treated with a hydrous metal oxide such as hydrous alumina oxide, hydrous ferrite oxide, etc. to improve its dispersibility. The inorganic white pigment is the electron beam curable composition 100
It is preferably in the range of 25 to 250 parts by weight. More preferably, it is 30 to 150 parts by weight. The average particle diameter of the pigment is 0.05 to 10μ.
m is preferable, and more preferably 0.1 to 3 μm. In addition, a blue pigment, an antistatic agent, a fluorescent whitening agent, etc. may be added to the electron beam curable resin composition, if necessary. As the support base material used in the present invention, in addition to commercially available medium-quality paper and high-quality paper, paper base materials made of natural pulp, synthetic pulp, or mixtures thereof, and various types of photographic base papers can be used. Alternatively, a film may be used in which an inorganic white pigment is dispersed in a polyester or polyolefin base, if necessary. The thickness of the paper base material is 8.0 to 250 μm, and the basis weight is 60
It is preferably ~250 g/ ^m2 , more preferably 80-200 g/ ^m2 , and its surface may be smooth or rough. The surface may be subjected to various surface treatments, such as corona discharge, if necessary. The electron beam curable composition for coating in the present invention is prepared, for example, as follows. That is, the above-mentioned components to form a composition are charged into a kneading machine either all at the same time or individually one after another. In this case, various types of kneading machines can be used for kneading and dispersing the coating composition, and usable kneading machines include, for example, a two-roll mill, a three-roll mill, a pepple mill, a ball mill, a sand grinder, a high-speed stone mill, and a high-speed stone mill. There are impact mills, kneaders, homogenizers, etc. Application methods include air doctor coat, blade coat, squeeze coat,
Methods such as air knife coating, reverse roll coating, transfer roll coating, and cast coating are used. The coating thickness is preferably 1 to 100 μm, more preferably 5 to 50 μm. The coating layer of the present invention can be smoothed to have a mirror finish, and can also be patterned if necessary. The electron beam accelerator used may be, for example, an electrocurtain system, a Van de Graff type scanning system, a double scanning system, or the like. In addition, the electron beam characteristics are preferably 70 to 750 KV, more preferably 100 to 750 KV in terms of penetrating power.
Using a 300KV electron beam accelerator, the absorbed dose is 0.1~
It is preferable to set it to 10 Mrad. If the voltage is 70 KV or less, the uniformity of the electron beam in the width direction of the substrate is poor during electron beam irradiation, making it difficult to obtain a uniform cured coating. In the present invention, the electron beam curable resin composition is cured by irradiating the electron beam through an electron beam semi-transparent film. The electron beam semi-transparent film may be of any material as long as it absorbs substantially 50% or more and 95% or less of the energy of the irradiated electron beam. A film-like material having sheet-like flexibility can be preferably used. Specifically, metal plates such as copper plates, aluminum plates, and steel plates, polyester films, acetic acid fiber films, fluorinated hydrocarbon (so-called Teflon) films, polyamide films, polycarbonate films, polyolefin films, polyolefin-vinyl acetate copolymer films, Examples include synthetic resin films such as polyimide films, paper sheets, synthetic paper sheets, and the like. A metal plate is more preferable in terms of resistance and shielding properties against electron beams. The electron beam semi-transparent film may be located between the electron beam irradiation window and the electron beam curable layer, but since it will be heated by the electron beam irradiation, it cannot be moved at the same speed as the substrate or independently. preferable. As necessary,
It may be cooled after electron beam irradiation. It is preferable to bring the electron beam semi-transparent film into close contact with the electron beam curable layer since this has the effect of improving the smoothness of the electron beam curable resin composition layer. The thickness of the electron beam semi-transparent film cannot be determined unconditionally because the applied voltage during electron beam irradiation and the shielding performance of the electron beam semi-transparent film vary greatly depending on the material, but it can be determined according to the formula below. It is preferable that the thickness is equal to or greater than the film thickness. H=(V-60)/D However, in the above formula, H is the thickness of the electron beam semi-transparent membrane (μ
m), V is the electron beam applied voltage (KV), and D is the electron beam semi-transparent film density (g/cm ² ). Substantially 50% or more and 95% or less of the irradiated electron beam energy is absorbed by the electron beam semi-transparent film. Here, "substantially" means that energy other than the amount of energy absorbed is consumed as energy used for curing. Preferably, it absorbs 60% or more of the irradiation energy. The specifically determined amount of absorption will, of course, vary depending on the equipment, curing composition, and other conditions. The amount of electron beam energy absorbed can be confirmed by the method described below. Commercially available electron beam-sensitive films whose coloring density changes depending on the amount of electron beam irradiation energy are available, such as FWT Radiochromic Film Detector sold by Toyo Medic Co., Ltd.
Detector), CAT film manufactured by Fuji Photo Film Co., Ltd., etc. are used to determine the energy amount of electron beam irradiation when the electron beam passes through a semi-transparent membrane and when it does not pass through. It is preferable that the electron beam energy absorption amount of the electron beam semi-transparent film determined in this manner is 50% or more of the irradiation energy. Note that when irradiating the electron beam, it is preferable to perform the irradiation in an atmosphere of an inert gas such as N ₂ , He, or CO ₂ . Further, for the purpose of improving the adhesion with the photographic constituent layers, the coating layer may be subjected to surface treatment such as corona discharge treatment, or an undercoat layer may be separately applied to the surface of the coating layer. Note that any layer configuration of the photographic emulsion layer and the photographic light-sensitive material formed on the coating layer may be used as desired. As the photographic emulsion layer, monochrome and color emulsion layers can be provided. A color photographic emulsion layer can preferably be provided in the cured coating layer of the light-sensitive material of the present invention. When the photographic material according to the present invention is applied to a color photographic material, it usually has three types of light-sensitive silver halide emulsion layers having different spectral sensitivities, and each emulsion layer has a yellow coupler, a magenta coupler, and one of the three cyan couplers
It can contain each species. In such a case, the combination of the light-sensitive silver halide emulsion layer and the coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer,
Furthermore, a yellow coupler is combined with each of the blue-sensitive silver halide emulsion layers. There are no particular restrictions on the order in which the emulsion layers are stacked. Any yellow, magenta and cyan couplers may be used as desired. Preferred yellow couplers include benzoylacetanilide couplers and pivaloylacetanilide couplers. A preferred magenta coupler is 1-phenyl-3-
Examples include anilino-5-pyrazolone couplers and pyrazoloazole couplers, such as pyrazolotriazole couplers. Preferred cyan couplers include phenolic couplers. Each of these couplers is preferably contained in the silver halide emulsion layer in an amount of about 0.05 to 1 mole per mole of silver halide. In addition to the above-mentioned silver halide emulsion layer, the color photographic light-sensitive material to which the present invention is applied includes a protective layer, an intermediate layer, a filter layer, a scavenger layer, etc. in an appropriate order and number of layers on the support. A non-photosensitive layer can be provided. The silver halide contained in the silver halide emulsion layer used may be any of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride, and silver chloroiodide. It may be present, or it may be a mixture of these. These silver halides can be prepared using the ammonia method,
It may be manufactured by any of the neutral method, acidic method, etc., and it may be manufactured by any of the simultaneous mixing method, forward mixing method, back mixing method, convergence method, etc. Furthermore, silver halide grains with or without boundaries with different halogen compositions can be effectively used. The binder that can be used in the constituent layers of the color photographic light-sensitive material to which the present invention is applied is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. Derivatives such as gelatin, albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds are used in combination. It can also be used as The silver halide emulsion used is ruthenium,
Noble metal sensitization with salts of noble metals such as rhodium, palladium, iridium, platinum, gold (e.g. ammonium chloroparadate, potassium chloroplatinate, potassium chloroparadide and potassium chloroaurate, etc.), activated gelatin, unstable sulfur compounds Sulfur sensitization with (e.g. sodium thiosulfate, etc.), selenium sensitization with selenium compounds, or stannous salts, polyamines, etc.
Chemical sensitization such as reduction sensitization under PAg conditions can be performed. Further, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired sensitizing wavelength range. Preferred sensitizing dyes that can be used at this time include, for example, US Pat.
No. 2739149, No. 2213995, No. 2493748,
No. 2519001, West German Patent No. 929080, British Patent
Cyanine dyes, merocyanine dyes, or composite cyanine dyes described in No. 505979 and the like can be used alone or in combination of two or more. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fog, preventing deterioration of photographic performance during storage of color photographic materials, and adjusting development (for example, gradation control, etc.) It can also be used for this purpose. Furthermore, the constituent layers of the color photographic light-sensitive material to which the present invention is applied may contain various photographic additives, such as ultraviolet absorbers (e.g., benzophenone compounds and benzotriazole compounds), dye image stabilizers (e.g., phenol compounds), etc. , bisphenol compounds, hydroxychroman compounds,
bisspirochroman compounds, hydantoin compounds, dialkoxybenzene compounds, etc.),
Stain inhibitors (for example, hydroquinone derivatives, etc.), surfactants (for example, sodium alkylnaphthalene sulfonates, sodium alkylbenzenesulfonates, sodium alkylsuccinate sulfonates, and polyalkylene compounds, etc.), water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, oxonol compounds, triphenylmethane compounds, etc.), hardeners (e.g., halogen-substituted S-triazine compounds, activated vinyl compounds, ethyleneimino compounds, epoxy compounds, and water-soluble (eg, glycerin, polyalkylene glycols, aqueous polymer dispersion [latex], solid or liquid paraffin, etc.) can be added. In the present invention, in order to coat each constituent layer of a color photographic light-sensitive material on a support of a light-sensitive material,
Various coating methods can be used, such as dip coating, roller coating, bead coating, curtain flow coating, and the like. After application, drying is performed. In order to obtain a dye image using a color photographic light-sensitive material, after imagewise exposure, a color development process is performed if necessary. The processing steps basically include color development and bleach-fixing steps.
In this case, even if each process is independent, two of them
In some cases, more than one process can be performed in one process using a processing liquid that has these functions.
Further, each step can be divided into two or more times as necessary. In addition to the above, during the processing steps, various steps such as a pre-hardening bath, a neutralization bath, a first development (black development), an image stabilization bath, and water washing may be combined as necessary. The processing temperature is set within a preferable range depending on the photosensitive material and processing prescription. Generally, the temperature is 20 to 60°C, but the above-mentioned color photographic materials are particularly suitable for processing at 30°C or higher. Color developing agents used for color development include:
A variety of those widely used in various color photographic processes are included. Particularly useful color developing agents are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(-N
-ethyl-N-dodecylamino)-toluene, N
-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline sulfate, 4-amino-3-methyl-N,N-diethylaniline sulfate, N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate Salt, 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-4-amino-3-(β-methanesulfonamidoethyl)
Examples include aniline sulfate. Among these exemplified compounds, those more preferably used include N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate and 4-amino-3-methyl-N,N-
diethylaniline hydrochloride, and 4-amino-N
-(β-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N
-diethyl-4-amino-3-(β-methanesulfonamidoethyl)aniline sulfate. Various additives can be added to the color developing solution as necessary. For example, alkali metal hydroxides and carbonates, alkaline agents such as tertiary phosphates, buffers such as boric acid and acetic acid, thioethers, 1-aryl-3-pyrazolidones, N-methyl-p-aminophenols, Development accelerators such as polyalkylene glycol, organic solvents such as benzyl alcohol, ethylene glycol, diethylene glycol, methanol, acetone, potassium bromide,
These include development inhibitors such as nitrobenzimidazoles, preservatives such as sulfites, hydroxylamine, glucose, and alkanolamines, and water softeners such as polyphosphoric acid compounds and nitrilotriacetic acid. [Examples of the Invention] The present invention will be described in more detail below with reference to Examples. It should be noted that, as a matter of course, the present invention is not limited to the following examples. The materials were blended as shown in Compositions 1 and 2 below and kneaded in a ball mill for 20 minutes to uniformly disperse them to obtain two types of compositions. and compositions 1 and 2
Each was coated on one side of paper with a basis weight of about 160 g/m ² using a reverse coater to form a thick film of 25 μm to form an electron beam curable resin composition layer. (Composition 1) Epoxy acrylate (NK Ester EA800 manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts by weight Polybutadiene TEA1000 manufactured by Nippon Soda Co., Ltd. 15 parts by weight Triethylene glycol diacrylate 20 parts by weight Titanium dioxide (anatase type average particle size 0.20 μm)
45 parts by weight (composition 2) NK ester manufactured by Shin Nakamura Chemical Co., Ltd., ABPE-4
30 parts by weight Polybutadiene manufactured by Idemitsu Petrochemical Co., Ltd., R45ACR
15 parts by weight NK ester manufactured by Shin-Nakamura Chemical Co., Ltd., APG200 15 parts by weight Titanium dioxide (rutile type, average particle size 0.25 μm)
40 parts by weight Next, as shown in FIG. 1, the composition 1 or 2 was applied onto paper 1 to form an electron beam curable resin composition layer 2. While conveying the paper 1 with the electron beam curable resin composition layer 2 at a line speed of 10 m/min, the accelerator 4 of the electron beam irradiation device 3 was operated from the electron beam curable resin composition layer 2 side. As shown in Examples 1 to 7 and Comparative Examples 1 to 5 in the table, 200 kV,
10mA, 180kV, 8mA or 180kV, 1mA
The electron beam curable resin composition layer 2 was irradiated with an electron beam at an intensity of . In addition, when irradiating the electron beam, as shown in FIG. 1, between the electron beam irradiation window 5 and the electron beam curable resin composition layer 2, a Polyethylene terephthalate stretched film with a thickness of 75 μm and 175 μm, with a thickness of 30 μm,
One type of 40 μm stainless steel plate was placed as the electron beam semi-transparent membrane 6. When the electron beam semi-transparent film 6 is not brought into contact with the electron beam curable resin composition layer 2, the electron beam semi-transparent film 6 is conveyed at a line speed of 5 m/min, and the electron beam curable resin composition layer 2 and In the case of close contact, the close contact was made immediately before electron beam irradiation, and the film was peeled off from the cured resin layer after electron beam irradiation. Next, an electron beam curable resin composition layer was formed on the opposite side of the paper in the same manner as above, and this was irradiated with an electron beam in the same manner as above to form a cured resin layer. Seven types of samples shown and Comparative Example 2
One type of comparative sample was prepared as shown below. In addition, for comparison, Comparative Examples 1, 3, and
As shown in 4 and 5, four types of comparative samples were prepared in the same manner as above except that the electron beam semi-transparent membrane was not used. There will be a total of nine types of comparison samples. In addition, the irradiation electron beam energy of Examples 1, 3, 6, and 7 and Comparative Examples 2 and 8 in the table was measured using an FWT radiochromic film detector sold by Toyo Medec Co., Ltd., and the results are shown in Figures 2 and 3. We obtained the results shown in the figure.

【table】

[Color developer]

Pure water 800ml Ethylene glycol 15ml Benzyl alcohol 15ml Whitex B Bcone (manufactured by Sumitomo Chemical Co., Ltd.)
Fluorescent bleach) 1g Hydroxylamine sulfate 3g 3-Methyl-4-amino-N-ethyl-N-(β
-methanesulfonamidoethyl)aniline sulfate
4.5g Potassium carbonate (anhydrous) 30g Potassium sulfite (anhydrous) 2.0g Potassium bromide 0.65g 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 2ml Add water to make 1, and dilute with sulfuric acid or potassium hydroxide. Adjust to PH=10.1. [Bleach-fix solution] Pure water 600ml Ethylenediaminetetraacetic acid-2-sodium.
2H ₂ O 25g Ammonium sulfite (40% aqueous solution) 35ml Ammonium thiosulfate (70% aqueous solution) 150ml Ammonium ethylenediamine iron tetraacetate 95g Aqueous ammonia (28%) 25ml Add water to make 1, and dilute with aqueous ammonia or glacial acetic acid. Adjust to PH=6.9. Next, an adhesion test and fog density measurement were performed as follows. (Adhesion test) Adhesive tape is attached to the developed sample and rapidly peeled off. At that time, it is evaluated whether peeling occurs between the paper and the electron beam cured layer. (Measurement of fog density) The developed sample was measured using a Sakura color densitometer PDA.
Fog density was measured using Model -60 (manufactured by Konishiroku Photo Industry Co., Ltd.). As mentioned above, the electron beam energy amount of the example was measured using the FWT radiochromic film detector sold by Toyo Medic Co., Ltd. The results are shown in Figs. 2 and 3, and the conditions for the measurement results are as follows. It is as follows. When irradiating an electron beam at 200 kV 10 mA and not passing it through an electron beam semi-transparent membrane When irradiating an electron beam at 200 kV 10 mA and passing it through a 75 μm polyethylene terephthalate film When irradiating an electron beam at 200 kV 10 mA and passing it through a 100 μm polyethylene terephthalate film When the electron beam is irradiated at 200 kV 10 mA and passes through a 175 μm polyethylene terephthalate film When the electron beam is irradiated at 180 kV 8 mA and does not pass through an electron beam semi-transparent membrane When the electron beam is irradiated at 180 kV 8 mA and a 30 μm stainless steel plate is passed through When the electron beam is irradiated at 180 kV 8 mA and passes through a 40 μm stainless steel plate When the electron beam is irradiated at 180 kV 1 mA and does not pass through the electron beam semi-transparent membrane The electrons of the electron beam semi-transparent membrane determined from this figure The shielding effects of linear energy were as follows. 〃Efficacy 47% 〃Efficacy 60% 〃Efficacy 82% 〃Efficacy 90% Shielding effect 95% Also, as a separate case of comparison, when an electron beam is irradiated at 150kV 10mA and the electron beam does not pass through a semi-transparent membrane, the electron beam is irradiated at 150kV 10mA. When an electron beam is irradiated and passed through a 175 μm polyethylene terephthalate film When an electron beam is irradiated at 150 kV 10 mA and passed through a 50 μm polyethylene terephthalate film When an electron beam is irradiated at 150 kV 1 mA and it does not pass through an electron beam semi-transparent membrane I went. The electron beam energy shielding effects in each case were as follows. Shielding effect: 99% Shielding effect: 42% The measurement results of adhesion and fog are shown in the table. From the table, it can be seen that Examples 1, 2, 3, and 4 according to the present invention have no problems with adhesion and have significantly improved fogging over time compared to Comparative Examples 1 and 2, which are outside the scope of the present invention. Ta. Furthermore, in Comparative Example 2, where the electron beam shielding effect was 47%, the effect was insufficient. Furthermore, Examples 5, 6, and 7 according to the present invention are Comparative Examples 3 to 3 outside the scope of the present invention.
It was also found that there was no problem with adhesion and fogging over time was significantly improved compared to Sample No. 9. In particular, in Comparative Example 5, curing was performed by reducing the electron beam irradiation current in order to reduce fog, but the adhesive property was poor and the objective could not be achieved. It was also found that there is no difference in effect whether the electron beam semi-transparent film is adhered to the electron beam curable resin composition layer or not in contact with it. [Effects of the Invention] As described above, according to the present invention, a photograph can be produced which has little increase in fog over time of storage, and has excellent sharpness of photographic images, surface smoothness, and adhesion between the base material and the coating layer. Photosensitive materials can be manufactured.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the state in which an electron beam curable resin composition layer provided on paper is irradiated with an electron beam from an electron beam irradiation device, and Figures 2 and 3 are diagrams showing the electron beam curable resin composition layer provided on paper. It is a figure which shows several examples of the measurement result of the electron energy irradiated to the material layer. 1...paper, 2...electron beam curable resin composition layer,
3... Electron beam irradiation device, 4... Accelerator, 5... Electron beam irradiation window, 6... Electron beam semi-transparent membrane.

Claims (1)

[Scope of Claims] 1. An electron beam curable resin composition consisting essentially of an electron beam curable compound and a pigment is coated on at least one side of a substrate to obtain an electron beam curable resin composition layer, and this layer In a method for producing a photographic material, which comprises forming a support as a cured resin layer by irradiating an electron beam, and providing a photosensitive layer on this support, the electron beam curable resin composition layer is irradiated with an electron beam. When forming a cured resin layer, an electron beam is irradiated from the side of the electron beam curable resin composition layer, and this electron beam irradiation substantially reduces the energy of the irradiated electron beam by 50% or more and 95%.
A method for producing a photographic material, characterized in that the process is carried out through an electron beam semi-transparent film that absorbs the following: 2. The method for producing a photographic material according to claim 1, wherein the electron beam semi-transparent film is not in close contact with the electron beam curable resin composition layer. 3. The method for producing a photographic material according to claim 1, wherein the electron beam semi-transparent film is in close contact with the electron beam curable resin composition layer.