JPH0469896B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide photographic materials. This type of photosensitive material is used, for example, as photographic paper for producing printed images. [Prior Art] Various improvements have been made to conventional photographic paper, such as photographic paper, but there are still some problems in which the white background becomes contaminated over time and the image deteriorates. be. That is, Paraita paper was initially used as a support for photographic paper, but this paper support had many drawbacks. That is, the processing liquid that causes the paper to expand and contract permeates into the paper, and requires a long time to wash with water to remove it, requiring a ferrotype for drying, which requires a large equipment and energy burden. In order to improve these drawbacks, so-called polyolefin laminated paper, in which a resin film such as polyethylene is laminated onto a paper support, has been put into practical use. This support consists of an inner paper whose main component is natural pulp, and resin film layers laminated on the front and back sides of the inner paper. Various additives are added to the natural pulp of the inner paper to improve the performance of the paper support. In other words, JP-A No. 56-54436 describes the use of dry paper strength agents, sizing agents, fillers, wet paper strength agents, fixing agents, PH regulators, dyes, fluorescent brighteners, etc. has been done. The laminate layer on the side to which the emulsion is applied contains titanium dioxide, pigments, etc. for the purpose of improving whiteness. However, a number of problems were found with this polyolefin-in laminated paper. That is, the surface smoothness is poor. Pulp fibers grow like whiskers on the cut surface, reducing product value. Even if it is attempted to incorporate titanium dioxide into the polyolefin layer to improve whiteness and image sharpness, the limit is 20%. The processing liquid seeps into the inner paper from the cut surface of the photographic paper, causing contamination at the cut portion. When stored for a long period of time, the polyolefin layer may crack, deteriorating the photographic quality.When polyolefin is laminated to paper, its adhesive strength is weak, causing problems such as easy peeling during use. To address these problems, for example, US Patent No. 4288287, French Patent No. 1483603,
No. 51-114125, etc., and JP-A No. 51-6631, same.
53-19021, 55-108658, 56-5987, etc., and JP-A-54-147032, 55-14235, etc.
Improvement methods have been disclosed in Japanese Patent Laid-Open Nos. 54-147221, 56-109343, and JP-A-57-102622, but they were not sufficient. JP-A-57-27257, JP-A-57-30830, and JP-A-57-30830 show that many of the problems with polyolefin laminated paper mentioned above can be improved by using a support whose inner paper surface is coated with a resin that is cured by electron beam irradiation. 57−
It is disclosed in No. 49946 etc. However, when applied to a color photographic support having a resin treated by irradiation with an electron beam, the problem arises that staining occurs over time, as described above. In other words, when a color photographic emulsion is coated on a support as described above and developed, the white background of the color image obtained by the development process turns yellow when stored, which significantly impairs the image quality. It was found that this occurs. In addition, in order to avoid such discoloration over time as much as possible, the electron beam curable resin constituting the coating layer on the support is limited to one that does not easily cause discoloration.
Therefore, a problem arises in that the selection range of resins is limited. [Object of the Invention] The object of the present invention is to significantly reduce yellow staining of photographic images over time even when a photographic light-sensitive material is produced using a support having a coating layer cured by electron beams. Therefore, it is possible to obtain a stable image with excellent image performance, and the electron beam curing resin to be coated on the support is not restricted and can be arbitrarily selected. An object of the present invention is to provide a method for processing photographic materials. [Structure of the Invention] The method for processing a photographic light-sensitive material of the present invention is to cure a coating layer containing at least an aromatic acrylate electron beam-curable compound by irradiating it with an electron beam, and to cure a support having the cured coating layer. A processing method for processing a silver halide photographic material having at least one silver halide emulsion layer formed thereon, wherein the photographic material is developed in a developer for 3 minutes. The water absorption rate of the coating layer cured by the electron beam during the development process is set to 15% or less by carrying out the process within a range not exceeding 15%. In another preferred embodiment of the present invention, a method is adopted in which the amount of organic solvent in the developer is 10 g or less. As described above, by reducing the water absorption rate of the coating layer during development processing, yellowing of the white background area after development is prevented, and the object of the present invention is achieved. The present invention has been made based on the following findings. That is, as a result of repeated studies on yellowing caused by the presence of white background areas in prints, it was found that such yellowing is likely to occur when the water absorption rate of the cured coating layer by the treatment liquid exceeds 5%. However, as a means to reduce the water absorption rate, the water absorption rate is sufficiently small if the treatment with the developer is carried out for no more than 3 minutes. Provides anti-yellowing effect. If it is less than 5%, the effect will be more certain. In addition, as another example of means for reducing the water absorption rate,
The amount of organic solvent in the developing solution can be 10 g or less. This is because it was found that the water absorption rate is strongly related to the amount of organic solvent (especially benzyl alcohol, which is commonly used) in the developing solution. This is because we have found that yellowing is significantly reduced. In particular, it is preferable to use 7g or less per portion. As described above, when the amount of the organic solvent (particularly benzyl alcohol) in the developing solution is 10 g or less, the yellowing prevention effect is large even if the above-mentioned water absorption rate is 15% or less. In addition, the previously mentioned publicly known document, JP-A-57-
No. 27257, No. 57-30830, No. 57-120934, No. 59
Although No. 124336 mentions water resistance, it does not mention anything about preventing yellowing, and it does not say that yellowing is related to the water absorption rate during treatment.
There is no suggestion that benzyl alcohol or a coloring agent in the processing solution is involved and that the degree of yellowing changes depending on the amount. Unexamined Japanese Patent Publication 1987
No. 49946 discloses that a support coated with a composition having an unsaturated double bond that can be polymerized by electron beam irradiation and cured was developed and no yellowing occurred. There is no suggestion that water absorption is involved in this development or that the amount of benzyl alcohol in the developer is involved. Thus, the present invention achieves the above object by using a configuration that was not considered or anticipated in the prior art. In the present invention, the electron beam curable composition for forming the coating layer on the support contains at least an aromatic acrylate electron beam curable compound. Various kinds of aromatic acrylate electron beam curing compounds can be used. for example,
Those with an ester of aromatic carboxylic acid such as fumaric acid as a backbone and acrylated ends, and those with an aromatic phenol such as bisphenol A as a backbone with acrylic chains bonded via oxide or urethane bonds as necessary. You can use whatever you have. Specifically, for example, ACJVan Dosterhout
and A. Van Neerbos, Double Liajson−Chin
The polyester acrylate oligomers described in Peint. 27 (295), 135 (1980) can be used;
Moreover, urethane acrylate obtained by reacting a polyoxyalkylene bisphenol A derivative with a polyisocyanate and a hydroxy group-containing acrylate can be used. These aromatic acrylate electron beam curing 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. Further, for the purpose of adjusting the viscosity of the composition, curing characteristics, physical properties of the cured layer, etc., it is preferable to use a monomer having an unsaturated bond in combination with the above compound. Representative examples of these monomers include the following. a) Monofunctional monomer methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, glycidyl methacrylate, n-hexyl acrylate,
lauryl acrylate etc. b) Bifunctional monomer 1,6-hexanediol diacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol, 1,4-butanediol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate,
Pentaerythritol diacrylate, divinylbenzene, etc. c) Monomers with trifunctional or higher functionality Trimethylolpropane triacrylate, trimethylolpropane methacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethyl acrylate of ethylenediamine, etc. In addition, flexibility and support For the purpose of improving the adhesion of the body base material, thermoplastic resins represented by the following may be mixed and used. (1) Cellulose derivatives, nitrocellulose, cellulose acetate butyrate, ethyl cellulose, butyl cellulose, etc. (2) Polyvinyl alcohol resins polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, etc. (3) Polybutadiene and butadiene copolymers polybutadiene, acrylonitrile butadiene, etc. Polymers, styrene-butadiene copolymers, etc. (4) Vinyl chloride copolymers Vinyl chloride, vinyl acetate copolymers, vinyl chloride-vinyl acetate-maleic acid copolymers, etc. (5) Polyurethane resins (6) Unsaturated , saturated polyester resins (7) polyamide resins, etc. These thermoplastic resins may or may not have acrylic modified double bonds introduced therein. When forming these electron beam curable resins as a coating layer, it is recommended to mix them so that the water absorption rate is 15% or less when immersed during development processing (for example, after processing for 20 minutes at 40°C). preferable. Water absorption rate is 5
% or less, it is most preferable and almost no yellowing occurs. In the resin layer, pigments, dyes, brighteners,
It can contain softeners, electrolytes, and other additives, and in particular, the resin layer on the emulsion layer side may contain titanium dioxide, zirconium oxide, zinc oxide, zinc sulfide, antimony oxide, barium sulfate, or carbonate for the purpose of improving photographic image quality after processing. It can contain calcium and the like, but titanium dioxide is particularly effective. The greater the amount of these white pigments added, the more sharp the photographic image can be. However, if the amount is too large, the dispersibility in the resin layer will deteriorate, so 10 to 60% by weight (per resin layer) is appropriate, and preferably 40 to 60%. This is advantageous because it means that it can be added in a much higher amount than the 10 to 20% added in conventional polyolefin coated paper. Paper can be used as a support in practicing the present invention. The paper may be made of natural pulp, synthetic pulp, or a mixture thereof. For example, any paper with good flatness, such as photographic base paper or high-quality paper produced by various methods, may be used. The thickness is about 80 to 250 μm, and the weight is 80
It is preferably about 200 g/m ² . These papers can be used with addition of paper strength enhancers, sizing agents, colorants, fluorescent whitening agents, etc., if necessary. Other films such as polyester, polystyrene, cellulose triacetate, and polycarbonate can be used instead of the above paper.
It may or may not contain a pigment. In order to form the above-mentioned coating layer on the photosensitive material used in carrying out the present invention, a coating composition can be prepared, for example, as follows. That is, the above-mentioned components are charged into a kneading machine either all at the same time or individually one after another. Various kneaders can be used to knead and disperse the coating composition. For example, kneading machines include two-roll mill, three-roll mill, pebble mill, ball mill,
Sand grinders, high speed stone mills, high speed impact mills, kneaders, homogenizers, etc. are advantageous. Moreover, as a coating method, methods such as air doctor coating, blade coating, squeeze coating, 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 electron beam accelerator used may be any of an electrocurtain system, a van de Graff type scanning system, a double canning system, etc. In addition, in terms of electron beam characteristics, in terms of penetrating power,
It is preferable to use an electron beam accelerator of 100 to 750 KV, preferably 150 to 300 KV, so that the absorbed dose is 0.5 to 20 Mrad. Note that during electron beam irradiation, N ₂ , He, CO ₂
It is desirable to irradiate in an inert gas atmosphere such as The coating layer can be smoothed to give it a mirror finish, and can also be patterned if necessary. To achieve a mirror finish, the surface to be treated can be brought into contact with a mirror roll, and an electron beam is irradiated from the back side of the roll to harden it, thereby giving the surface a mirror finish. Also,
A method may be used in which preliminary irradiation is performed in advance to partially harden the surface, and then the surface is peeled off after contacting with a mirror-finished roll, and secondary irradiation is performed to completely harden the surface. Examples of mirror-finished rolls include chlormetsuki rolls and stainless steel rolls. In addition, when molding is performed, a roll such as a stainless steel roll or a chrome-plated roll can be used instead of a mirror-finished roll, and the molding roll can be used to create a textured or fine-grained pattern by surface polishing, vapor deposition, etching, plating, etc. A roll having a desired pattern such as a surface can be used. For compositions for electron beam curing, organic solvents can, but are not necessarily, used. In this case, since the viscosity of the coating composition becomes lower, the filling properties of the inorganic white pigment are further improved, and the surface smoothness is further improved. 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 of methyl acetate, ethyl acetate, butyl acetate, and ethyl butyrate Golicol ethers such as ethylene golycol 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. Among the photographic materials to which the processing method of the present invention is applied, silver halide color photographic materials usually have three types of light-sensitive silver halide emulsion layers having different spectral sensitivities, and each emulsion layer has a yellow coupler. , magenta coupler, and cyan coupler. 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 of these yellow, magenta and cyan couplers may be used. Preferred yellow couplers include benzoylacetanilide couplers and pivaloylacetanilide couplers. A preferred magenta coupler is 1-phenyl-3-
Examples include anilino-5-pyrazolone 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 silver halide emulsion layer described above, the silver halide color photographic light-sensitive material according to the present invention includes a protective layer, an intermediate layer, a filter layer, and a scavenger layer in an appropriate layer order and number of layers on the support. A non-photosensitive layer such as can be provided. The silver halide contained in the silver halide emulsion layer of the photosensitive material to be processed may be any of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, chloride salt, and silver chloroiodide. It may be silver halide or a mixture thereof. These silver halides may be produced by any of the ammonia method, neutral method, acidic method, etc., and may be produced by any of the simultaneous mixing method, forward mixing method, reverse mixing method, convergence method, etc. Furthermore, silver halide grains with or without boundaries between different halogen compositions can be effectively used. The binder used in the constituent layers of photographic materials is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin, but some of this gelatin and derivative gelatin such as phthalated gelatin and phenylcarbamoyl 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 may be used in combination. . The silver halide emulsion used in the present invention includes salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum, and gold (for example, ammonium chloroparatate, potassium chloroplatinate, potassium chloroparadide, potassium chloroaurate, etc.). ), activated gelatin, sulfur sensitization with unstable sulfur compounds (e.g. sodium thiosulfate, etc.), selenium sensitization with selenium compounds, or reduction sensitization with stannous salts, polyamines, etc. and under low PAg conditions. It may also be one that has undergone chemical sensitization such as sensitization. Furthermore, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Examples of pigments include US Pat. No. 1939201, US Pat. No. 2072908,
Same No. 2739149, No. 2213995, No. 2493748, Same No.
No. 2519001, West German Patent No. 929080, British Patent No. 505979
The cyanine dyes, merocyanine dyes, or composite cyanine dyes described in No. 1, etc. 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 silver halide color photographic materials, and controlling development (for example, gradation). It can also be used for purposes such as control, etc. Furthermore, various photographic additives such as ultraviolet absorbers (e.g., benzophenone compounds and benzotriazole compounds),
Dye image stabilizers (e.g. phenolic compounds,
bisphenol-based compounds, hydroxychroman-based compounds, bisspirochroman-based compounds, hydantoin-based compounds, and dialkoxybenzene-based compounds, etc.), stain inhibitors (e.g., hydroquinone derivatives, etc.), surfactants (e.g., alkylnaphthalene sulfonic acids) soda, sodium alkylbenzenesulfonate, sodium alkylsuccinate sulfonate, polyalkylene compounds, etc.),
Water-soluble anti-irradiation dyes (e.g., azo compounds, styryl compounds, oxonol compounds, triphenylmethane compounds, etc.),
Hardeners (e.g., halogen-substituted S-triazine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers (e.g., glycerin,
Polyalkylene glycols, aqueous polymer dispersions (latexes) and solid or liquid paraffins, etc.) can be added. Each constituent layer of the silver halide color photographic light-sensitive material is coated onto the support by a commonly known coating method, such as dip coating, roller coating, bead coating, curtain flow coating, etc. ,
It may then be dried. In order to obtain a dye image by the processing method of the present invention, 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, each process may be independent, or two or more of the processes may use processing liquids that have those functions, so that only one process is required. Further, each step can be divided into two or more times as necessary. In addition to the above, various steps such as a pre-hardening bath, a neutralization bath, a first development (black and white development), an image stabilization bath, and water washing are combined as necessary during the processing steps. 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 silver halide color photographic light-sensitive material according to the present invention is particularly suitable for processing at 30°C or higher. Color developing agents used for color development include:
Includes those widely used in various color photographic processes. Particularly useful color developing agents are p-phenylenediamine compounds. For example, a compound represented by the following general formula [] can be preferably used. General formula [] In the formula, R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 5 carbon atoms.
It may or may not have a substituent.
R ₂ and R ₃ represent a hydrogen atom, an alkyl group, or an aryl group. These groups may or may not have a substituent. In the case of an alkyl group, an alkyl group substituted with an aryl group is preferred. and
At least one of R ₂ and R ₃ is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or ((--CH ₂
) _q --O) _r --R ₄ is preferred. This alkyl group may further have a substituent. Note that R ₄ represents a hydrogen atom or an alkyl group.
This alkyl group is linear or branched and has 1 carbon number.
-5 alkyl groups are preferred, and q and r are 1-5
is preferred. When p-phenylenediamine derivatives are used as developing agents, they can be used in the form of organic acid or inorganic acid salts. For example, hydrochloride, sulfate, phosphate, para-toluenesulfonate, sulfite, etc. can be used. Specific examples of useful p-phenylenediamine derivatives are listed below. Of course, this is an example and is not limited to the following. As mentioned above, p-phenylenediamine derivatives can be used in the form of salts. For example, 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, 4-amino-N-(β
-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-4-amino-3-(β-methanesulfonamidoethyl)aniline sulfate, and the like. Among these exemplified compounds, N-ethyl-N-β- is more preferably used.
Methanesulfonamidoethyl-3-methyl-4-
Aminoaniline sulfate, 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, alkaline agents such as alkali metal hydroxides and carbonates or tertiary phosphates, buffers such as boric acid and acetic acid, thioethers,
-aryl-3-pyrazolidone, N-methyl-p
- Development accelerators such as aminophenol and polyalkylene glycol, organic solvents such as benzyl alcohol, ethylene glycol, diethylene glycol, methanol, and acetone, development inhibitors such as potassium bromide and nitrobenzimidazoles, sulfites, hydroxylamine, and glucose. , preservatives such as alkanolamines, water softeners such as polyphosphoric acid compounds, and nitrilotriacetic acid. [Embodiments of the Invention] Examples of the present invention will be described below. Note that the present invention is not limited to this example. (Preparation of Sample No. 1 and Sample No. 1-1) Both sides of photographic base paper weighing approximately 160 g/m ² were coated with the following composition to a thickness of 20 μ after mixing and stirring with a roll mill, and then the coating layer was coated with the following composition to a thickness of 20 μm. Each sample was irradiated with an electron beam at an accelerating voltage of 160 KV with an absorbed dose of 4 Mrad. This sample is designated as sample No. 1 (sample according to the present invention). <Composition> ●30 parts by weight of aromatic polyester acrylate <Viscoat 3700 manufactured by Osaka Organic Chemical Co., Ltd.> ●30 parts by weight of aromatic bifunctional acrylate oligomer <Photomer 4028 manufactured by Diamond Shamrock Co., Ltd.> However, (-AO)- represents alkylene oxide, which is ethylene oxide or propylene oxide. ●Trimethylolpropane triacrylate
10 parts by weight <TMPT manufactured by Shin Nakamura Chemical Co., Ltd.> Rutile titanium oxide type (surface treatment, average particle size 0.2 μm) 40 parts by weight In addition, a sample for measuring the water absorption rate of the electron beam cured coating layer was prepared as follows. . The above composition was coated on a polyethylene terephthalate base to a thickness of 20μ, and then irradiated with an electron beam at an accelerating voltage of 160 KV to an absorbed dose of 6 Mard. This sample is designated as sample No. 1-1. (Preparation of Sample No. 2 and Sample No. 2-1) Both sides of photographic base paper weighing approximately 160 g/m ² were coated with the following composition to a thickness of 20μ after mixing with a roll mill, and then the coating layer was coated with the following composition to a thickness of 20μ. Each sample was irradiated with an electron beam at an accelerating voltage of 160 KV with an absorbed dose of 4 Mrad. This sample is designated as sample No. 2 (comparative sample). <Composition> ●Aliphatic urethane acrylate 30 parts by weight <Iupitan 893 manufactured by Thiokol> ●Polypropylene glycol diacrylate
40 parts by weight <APG800 manufactured by Shin Nakamura Chemical Co., Ltd.> Titanium oxide rutin type (surface treatment, average particle size 0.2 μm) 30 parts by weight In addition, a sample for measuring the water absorption rate of the electron beam cured coating layer was prepared as follows. . The above composition was coated onto a polyethylene terephthalate base to a thickness of 20μ, and then irradiated with an electron beam at an accelerating voltage of 160 KV to an absorbed dose of 4 Mrad. This sample is designated as sample No. 2-1. (Formation and Treatment of Emulsion Layer of Samples) One side of Samples No. 1 and 2 was subjected to corona discharge treatment at 20 W/m ³ min, and then the following emulsion was coated and dried. In addition, 2.5 gelatin is applied per 1 m ² of emulsion layer.
The amount of gelatin coated was 1.2 g per m ² of the protective layer. Further, the silver halide in the emulsion layer was adjusted to 0.45 g/m ² in terms of silver.
Each sample thus obtained was subjected to color development processing using the processing steps and processing solutions shown below. <Emulsion> Layer 1: 2 g of gelatin, 0.042 g of blue-sensitive silver chlorobromide emulsion (silver chloride 10 mol%), 0.83 g of yellow coupler (Y-2), and 0.01 g of HQ-1 were dissolved. Blue-sensitive emulsion layer containing 0.6 g of dioctyl phthalate. Layer 2: 1.2g gelatin and 0.05g HQ-1
A first intermediate layer containing 0.2 g of dioctyl phthalate dissolved in. Layer 3: 1.9g gelatin, 0.040g green sensitive silver chlorobromide emulsion (silver chloride 50 mole %) and 0.42g magenta coupler M-2 as shown below, 0.015g HQ
A green-sensitive silver bromide emulsion layer containing 0.36 g of dioctyl phthalate dissolved in -1. Layer 4: 1.9g gelatin and 0.02g HQ-1
0.5 in which 0.7g of ultraviolet absorber UV-1 was dissolved.
A second intermediate layer containing g of dioctyl phthalate. Layer 5: 1.5 g gelatin, 0.027 g red-sensitive silver chlorobromide emulsion (50 mole % silver chloride), and 0.4 g cyan coupler C-1 below, 0.01 g HQ-1
and 0.3g of ultraviolet absorber UV-1 was dissolved.
Red-sensitive emulsion layer containing 0.35 g of dioctyl phthalate. Layer 6: Protective layer containing 1.4g gelatin. <Processing process (33℃)> Color development Process for the time listed in Table 1 Bleaching time 1 minute 30 seconds Wash with water 3 minutes drying 60-80℃ <Color developer> Pure water 800ml Ethylene glycol 15ml Benzyl alcohol 15ml (Note: , see the table below) Whitex BBcone 1g (Sumitomo Chemical Co., Ltd., fluorescent bleach) 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 water 1 and adjust the pH to 10.1 with sulfuric acid or potassium hydroxide. <Bleach-fix solution> Pure water 600ml 2-sodium ethylenediaminetetraacetate, 2H ₂ O 2.5g Ammonium sulfite (40% aqueous solution) 35ml Ammonium thiosulfate (70% aqueous solution) 150ml Ethylenediaminetetraacetate iron () ammonium 95g Aqueous ammonia (28 %) Add 25ml water to bring the total volume to 1, and adjust the pH to 6.9 with aqueous ammonia or glacial acetic acid. The samples processed by changing the amount of benzyl alcohol in the color development solution, the coloring agent, and the development time were placed in a constant temperature and humidity chamber at 70°C and 70% PH for 10 days.
It was stored for several days and an accelerated deterioration test was conducted. In addition, another sample was irradiated for 10 days using a fade meter using a xenon arc lamp (6500W), and the contamination concentration was measured. Display the results -
Shown in 1.

[Table] The measurement of the water absorption of the cured coating film using the developing solution shown in the table (Samples 1.1 and 2-1) was carried out as follows. Peel off a single film of the cured composition in a size of 25 mm x 25 mm and leave it for 24 hours at a constant temperature and humidity of 23°C and 55%. The sample was placed in the color developing solution shown above at 40±1°C.
After immersing for 20 minutes, take it out and wipe off the water droplets adhering to the surface with paper and measure the weight (W ₀ ). Next, after drying the sample at 102 ± 2°C for 90 minutes,
The weight (W ₁ ) was measured, and the water absorption rate was determined based on the formula shown below. Water absorption rate [%] = Sample weight after immersion (W ₀ )
− Sample weight after drying (W ₁ )/Sample weight after drying (W ₁ )×
100 As is clear from Table 1, the treatments using Sample No. 2, which is a comparative sample (Processing Nos. 4 to 7), all resulted in large density changes and discoloration. Furthermore, even when using Sample No. 1, which is a sample according to the present invention, processing No. 8, in which the development processing time exceeded 3 minutes and the water absorption rate of the coating layer exceeded 15%, occurred after 10 days and after 1 month. It can be seen that the color density increases after irradiation with light from a weather meter, and yellowing occurs. In contrast, Examples of the present invention (Processing Nos. 1 to 3)
It is clear that the discoloration due to aging at each time point is small. In addition, Sample No. 3, which is a sample according to the present invention, and Samples No. 4 and 5, which are samples for comparison, are as follows.
was prepared. (Preparation of sample No. 3) In preparing sample No. 1, the absorbed dose was
Change the electron beam from 4 Mrad to 2 Mrad and irradiate the electron beam, otherwise do the same as sample No. 1.
Sample No. 3 was created. This is the sample No.
This is basically the same as 1, except that the sample was prepared with a lower irradiation dose. (Preparation of Sample No. 4) In the composition of Sample No. 1, 50 parts by weight of polypropylene glycol acrylate (APG800) used in the preparation of Sample No. 2 was added instead of 30 parts by weight of polyester acrylate (Viscoat 3700). Sample No. 4 was obtained by coating both sides of photographic base paper with the composition in the same manner as each of the samples described above. This is a comparative sample in which aliphatic acrylate was blended instead of the aromatic polyester acrylate of sample No. 1. (Preparation of Sample No. 5) A composition similar to the composition of Sample No. 4, except that polypropylene glycol diacrylate (APG800) was used instead of 30 parts by weight of polyester acrylate (Viscoat 3700), but 30 parts by weight of this was added. Prepare a sample and coat both sides of photographic paper in the same manner as each sample above.
It was set as No.5. This is a comparison sample that is the same as Sample No. 4, but with a different blending ratio of aliphatic acrylate. Each of the above samples No. 3 to 5 and the above sample No. 1
The same test as above was conducted using Display the results -
Shown in 2. In Table 2, Process No. 1 is the same as the process in Table 1 above.

〔Effect of the invention〕

As described above, according to the method for processing a silver halide photographic light-sensitive material of the present invention, even when a photographic light-sensitive material is prepared using a support having a coating layer cured by an electron beam, the photographic image becomes yellow over time. The effect is that contamination can be significantly reduced and stable images with excellent image performance can be obtained.

Claims (1)

[Claims] 1 Curing a coating layer containing at least an aromatic acrylate electron beam curing compound by irradiating with an electron beam, and forming at least one silver halide emulsion layer on a support having the cured coating layer. A processing method for processing a silver halide photographic light-sensitive material comprising 1. A method for processing a silver halide photographic light-sensitive material, characterized in that the water absorption rate of the coating layer cured by the method is set to 15% or less.