JPH042177B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials that does not cause edge staining of color paper and improves the stability of images after processing. [Prior Art] Generally, after exposure, silver halide photographic materials are processed through the steps of development-fixing-washing or development-bleaching-fixing-washing. Resource issues are becoming more important. For this reason, methods have been proposed to reduce the amount of washing water that is used in large quantities. For example, a West German patent has been published as a technology to reduce the amount of washing water by configuring the washing tank in multiple stages and causing the water to flow backwards.
2920222 specification and SR as technical document
Goldwasser, “Water Flow rate in immersion
−washing of motionpicture film”Jour.
SMPTE, 64, 248-253, May (1955) is known. Furthermore, a method of omitting the water washing step and performing stabilization treatment without substantially washing with water is disclosed in JP-A-57-8543.
It is described in Publications No. 58-14834, No. 58-134636, etc. On the other hand, polyethylene coated paper is mainly used as conventional color paper, but these polyethylene coated papers are impregnated with benzyl alcohol and color developing agent contained in the color developing solution, and the oxidizing agent and the color developing agent contained in the fixing solution penetrate into these polyethylene coated papers. It was found that metal ions were easily adsorbed and that it was easily contaminated during storage. In particular, when performing waterless washing treatment, the adsorbed treated material is not removed, so even if it is colorless immediately after treatment,
It was found that storage over time resulted in significant coloring and caused the problem of edge contamination. Furthermore, it has been found that yellow staining and cyan dye fading are likely to occur when images are stored. It was also found that these phenomena were significantly accelerated under high humidity. [Problems to be Solved by the Invention] The present invention has a technical object to provide a processing method for silver halide color photographic light-sensitive materials that does not cause edge staining even when subjected to waterless washing treatment or stored over time. Take it as a challenge. [Structure of the Invention] As a result of intensive research, the present inventor has developed a silver halide color photograph having at least one photosensitive silver halide emulsion layer on a support coated with a resin cured by irradiation with an electron beam. The above-mentioned technical problem (objective) is solved by subjecting a photosensitive material to imagewise exposure, color development processing, processing with a processing solution having fixing ability, and then stabilization processing without substantially undergoing a water washing step. I discovered that. Conventionally, as a support for color paper, a support having a polyolefin resin coating layer on the paper has generally been used. It has been found that color papers using these supports have the disadvantages that when the prints are stored for a long time, contamination appears on the cut surface, yellow stain occurs on the emulsion surface, and the cyan dye fades significantly. . It has been found that these phenomena appear significantly when color paper is subjected to anhydrous washing treatment. Therefore, as a result of intensive research, the present inventor has completed the present invention. That is, it was discovered that the above-mentioned problem was contamination at the interface between the polyethylene coating and the emulsion, resulting in deterioration of the image and white background. 1
The volume of the processing liquid having fixing ability brought into the foremost stabilization tank without washing the color print material having the silver halide photographic material in the layer is relative to the volume of the stabilizing liquid in the frontmost stabilization tank. 1/500
It has been found that the above can be achieved by performing a stabilization treatment using a stabilizing solution containing at least one compound selected from the following [A] to [F]. [A] Phenol compound [B] Thiazoline compound [C] Triazine compound [D] Morpholine compound [E] Imidazole compound [F] Guanidine compound. The method of applying a coating layer that can be cured by electron beam irradiation on paper and curing it by irradiating it with electron beams used in the present invention includes Japanese Patent Application Laid-open No. 57-27257;
No. 57-30830, No. 57-49946, No. 59-124336
The method described in Japanese Patent Application No. 59-32237, Japanese Patent Application No. 59-105969, etc. can be employed. When produced by the method described above, the photographic image forming layer (hereinafter simply referred to as photographic layer) is a hydrophilic colloid layer having a continuous layer of gelatin-based hydrophilic colloid, such as a gelatin silver halide emulsion layer. It is necessary to take some kind of adhesive means to firmly adhere the above-mentioned coating layer to the support having the coating layer. Typical methods for creating adhesive force between such a photographic layer and a support having the coating layer include, for example, corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment on the surface of the support. A method of surface activation treatment is known, in which a photographic layer is directly applied after this surface activation treatment,
Alternatively, there may be a method in which one or more layers of a subbing liquid having an affinity for the photographic layer are provided on the surface of the support to form a subbing layer, and then a photographic layer is coated thereon. A compound that can be cured by electron beam irradiation, particularly a known compound having an ethylenically unsaturated double bond in its molecule, is coated on a support base material, and a cured layer is formed by irradiating the electron beam. It is also possible to coat the cured layer with a photographic layer, but in this case, the means for adhering the support having the cured layer and the photographic layer is surface activation treatment such as corona discharge treatment as described above. Although it is difficult to expect sufficient adhesive strength using this method alone, it can be improved by forming a cured resin coating layer by ring-opening polymerization of epoxy. In the present invention, a resin cured by irradiation with an electron beam refers to a resin cured by irradiation with an electron beam to initiate a polymerization reaction in the presence of a polymerization initiator, or a resin cured by irradiation with an electron beam to initiate a polymerization reaction in the presence of a polymerization initiator, or a resin cured by irradiating an electron beam to initiate a polymerization reaction in the presence of a polymerization initiator. This includes both resins that have been cured. When a polymerization initiator is used, examples of compounds that initiate the polymerization reaction by electron beam irradiation include compounds having at least two epoxy groups in one molecule. That is, a compound having at least two epoxy groups in one molecule (hereinafter referred to as an epoxy compound according to the present invention) is a compound that does not undergo ring-opening polymerization even when irradiated with an electron beam, and
A polymerization reaction occurs when a substance that initiates cationic polymerization is coexisting. Examples of the epoxy compound according to the present invention include the following epoxy resins. However, the epoxy compound according to the present invention is not limited to these. (Exemplary compounds) [1] Glycidyl ether type of bisphenol A [2] Side chain diglycidyl ether type of bisphenol A [3] Di-(or tri-)glycidyl ether type of glycerin [4] Alicyclic diglycidyl ester or alicyclic di-β-methylglycidyl ester type (diglycidyl or di-β-methylglycidyl containing an alicyclic group derived from tetrahydrophthalic acid, hexahydrophthalic acid, etc. in the molecule) Compounds with an ester structure) (R is

[Formula] group or

[Formula] represents a group. ) (R ₁ is

[Formula] Group or

[Formula] represents a group. ) [5] Cyclohexene oxide type (epoxy compound containing one or two cyclohexene oxide or cyclopentene oxide groups in the molecule) [6] Novolac type epoxy resin The epoxy compounds according to the present invention as exemplified above can be obtained as commercial products as shown below. (a) Glycidyl ether type of bisphenol A, such as Epicote 827 (trade name, manufactured by Ciel Chemical Co., Ltd.);
828, 834, 836, 1001, 1004,
1007: Ciba Geigy Co., Ltd. product name Araldite
CY252, CY250, GY260, GY280,
6071, 6084, 6097: Dow Chemical Co., Ltd. product name DER330, 6097
331, 337, 661, 664: Dainippon Ink & Chemicals Co., Ltd. product names Epicron 800, 1010, 1000, 3010 (b) Bisphenol A side chain diglycidyl ether type For example, Asahi Denka Trade name of Kogyo Co., Ltd. Adeka Resin EP-4000 (c) Di-(or tri-)glycidyl ether type of glycerin For example, trade name of Ciel Kagaku Co., Ltd. Epicote
812 (d) Alicyclic diglycidyl ester or alicyclic di-β-methylglycidyl ester type For example, Ciba Geigy Co., Ltd.'s trade name Araldite CY-183, Araldite CY-182 Ciba Geigy Co., Ltd.'s trade name Epicote E −190,
E-871 Showa Denko Co., Ltd. product name S-500,
Same S-508, Same S-509, Same S-601X, Same S-
603X, S-607X, S-609X, S-729,
Same S-540, Same S-550 Dainippon Ink & Chemicals Co., Ltd. product name Epicron 200, Same 400 (e) Cyclohexene oxide type For example, UCC product name ERL-4221, Same 400 (e)
4289, 4206, 4234, 4205 Ciba Geigy product name CY-179, CY
-178, CY-180, CY-175 Chitsuso Co., Ltd. product name CX-221, CX-289,
CX-206, CX-301, CX-313 (f) Novolak type epoxy resin For example, the product names Epicote 152 and 154 manufactured by Ciel Chemical Co., Ltd.; the product name DEN-431 manufactured by Dow Chemical Co., Ltd. ,same
438, 439: Ciba Geigy Co., Ltd. product name EPN-1138,
ECN-1235: Trade name of Dainippon Ink Chemical Co., Ltd. Epicron N
-740, N-680, N-695, N-565, N-577 The epoxy compound according to the present invention preferably has a molecular weight of 10,000 or less, more preferably a molecular weight in the range of 100 to 3,000. be. The polymerization initiator according to the present invention is not particularly limited, but preferable examples include onium salts that release a Lewis acid capable of initiating polymerization upon electron beam irradiation, and such onium salts have the following general formula [1 ] can be shown. General formula [1] R ¹ _a R ² _b R ³ _c R ⁴ _d Z] ^+m [MXm+n] ^-m In the formula, R ¹ , R ² , R ³ and R ⁴ are organic compounds which may be the same or different. represents a group, a, b, c and d each represent an integer of 0 to 3, a+b+c+
The sum of d is equal to the valence of Z. Z is N≡N, S, Se, Te, P, As, Sb, Bi,
represents a halogen atom (for example, an atom such as iodine, chlorine, or bromine), and M is a metal or metalloid that is the central atom of the halide complex;
Sn, Bi, Al, Ga, In, Ti, Zn, Sc, V, Cr,
Represents Mn, Co, etc. X represents a halogen atom, m represents the net charge in the halide complex ion, and n represents the number of halogen atoms in the halide ion. Examples of complex anions represented by [MXm+n) ^-m in the above general formula [1] include BF ₄ ^- ,
PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- , FeCl ₄ ^2- , SnCl ₆ ^2- ,
Examples include SbCl ₆ ^2- , BiCl ₅ ^2- , and the like. Among the compounds represented by the above general formula [1], diazonium compounds do not necessarily have good storage stability and have a short pot life, so they must be made into a two-part formulation. As a result, bubbles and pinholes are likely to occur in the coating film, and the cured layer may become discolored. Therefore, in the present invention, it has excellent storage stability,
Compounds other than diazonium compounds are preferred because they are suitable for one-component formulation and there is no concern about the generation of nitrogen gas. The onium-based polymerization initiator represented by the general formula [1] is known per se, and for example, when Z is N≡N
The diazonium compound that is the base is covered by U.S. Patent No.
It is described in No. 3708296, No. 3794576, No. 3949143, etc. Other onium-based polymerization initiators are described in Belgian Patent No. 828841, Belgian Patent No. 828669, French Patent No. 2270269, and the like. The above-mentioned diazonium compounds are described in the above-mentioned US patent No.
3708296, the method described in 3949143, and the method described in AL Mayoock et al., J. Organic Chemistry, 35.
Volume, No. 8, p. 2532 (1970), I. Goerdeler;
Methoden der Organischen Chemie, 11/12,
pp. 591-640 (1958), K. Sasse; Ibid. 12/1,
pp. 79-112 (1963), M. Drexler et al., JACS,
It can be synthesized by the method described in Vol. 75, p. 2705 (1953). The amount of the polymerization initiator according to the present invention to be used may be determined depending on the curing speed and the applied curing method.
It is preferably used in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the resin component of the composition layer according to the present invention. When a polymerization initiator is not used, the resin that can be polymerized by electron beam irradiation is, for example, a compound having a double bond in the molecule, preferably a compound having a plurality of double bonds in the molecule, more preferably a compound having a double bond in the molecule. Examples include compounds containing an acryloyl group, a methacryloyl group, an acrylamide group, an allyl group, a vinyl ether group, a vinyl thioether group, and unsaturated polyesters. Particularly preferably A.Vrancken
Unsaturated polyester, unsaturated acrylic, and unsaturated polycarbonate cited in Fatipec Congress 1119 (1972), with a molecular weight of approximately 1000~
20000. The photosensitive material according to the present invention can contain an inorganic white pigment. As the inorganic white pigment, those commonly used in the photographic paper field can be used, such as titanium oxide (anatase type, rutile type), barium sulfate, calcium carbonate, aluminum oxide, magnesium oxide, etc. However, titanium oxide, barium sulfate, and calcium carbonate are particularly suitable. Further, the surface of titanium oxide may be partially coated with a hydrous metal oxide compound, for example, a metal oxide such as hydrous alumina oxide or hydrous ferrite oxide. However, it is not limited to these as long as it is an inorganic white pigment. The amount of the inorganic white pigment is preferably in the range of 20 to 200 parts by weight based on 100 parts by weight of the electron beam curable compound. In addition, the average particle diameter of the pigment is preferably 0.1 to 10 μm. The layer of the composition (hereinafter referred to as the composition according to the present invention) containing a resin polymerizable by electron beams according to the present invention, a polymerization initiator used as necessary, and an inorganic white pigment is simply formed on a support. It may be coated as one constituent layer or may be coated as a plurality of constituent layers. Examples of the support used in the present invention include paper made of natural pulp, synthetic pulp, or a mixture thereof. Known paper strength enhancers, sizing agents, inorganic pigments, colorants, optical brighteners, etc. may be added to these papers as desired. In addition to the above, synthetic papers such as polypropylene and polyester, and film bases such as polyethylene terephthalate can also be used as the support according to the present invention, and furthermore, composite materials can be formed by laminating the paper surface. Supports can also be used. A coating layer (hereinafter referred to as
The coating layer (referred to as the coating layer according to the present invention) can be smoothed to have a mirror finish, and can also be patterned if necessary. To achieve a mirror finish, the treated surface is brought into contact with a mirror roll, and an electron beam is irradiated from the back side of the roll to harden it, resulting in a mirror finish. Alternatively, a method may be used in which preliminary irradiation is performed in advance to partially harden the surface, the surface is peeled off after contact with a mirror-finished roll, and secondary irradiation is performed to completely harden the surface. Examples of mirror-finished rolls include chrome plated rolls and stainless steel rolls. In addition, when applying a pattern, the surface polishing roll can be used instead of a mirror-finish roll such as a stainless steel roll or a chrome plated roll.
It is possible to use a roll that has been patterned with textures, fine grains, etc. by a vapor deposition method, an etching method, a plating method, or the like. Mirror finishing and molding may be performed after applying the composition and removing part or all of the organic solvent, or may be performed after molding and removing the organic solvent. In the present invention, the electron beam accelerator used for electron irradiation may be any one of an electrocurtain system, a van de graph scanning system, a double scanning system, and the like. 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,
Irradiation may be performed in an atmosphere of an inert gas such as CO ₂ . The coating layer according to the present invention exhibits good adhesion to the photographic layer as it is, but even better adhesion can be achieved by subjecting the coating layer to surface activation treatment such as corona discharge treatment or glow discharge treatment. Furthermore, the same adhesive effect as described above can be obtained by simple undercoat processing using gelatin or the like. In the present invention, at least one of the coating layers according to the present invention is present on the surface of the support having a layer on which a photographic image is formed (for example, a silver halide emulsion layer, an image-receiving layer in a dye diffusion method, etc.). Further, the coating layer according to the present invention is preferably provided on both sides of the support from the viewpoint of waterproofing. Also, if there is no layer on one side of the support on which a photographic image is formed,
In this respect, this type of coating layer can also be a coating layer having a structure in which the inorganic white pigment is removed from the coating layer according to the present invention. The support according to the invention preferably has at least one barrier layer disposed between the base paper and the resin cured by electron beam, and these supports are described in JP-A-59-124336. It is described in detail. Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye. In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used as the couplers.
These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers. The yellow couplers include conventionally used closed ketone methylene compounds, active point -o-aryl substituted couplers called so-called 2-equivalent type couplers, active point -o-acyl substituted couplers, and active point hydantoin compound substituted couplers. , active point urazole compound substituted couplers, active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -o-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. can. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 3408194, No. 3551155, No. 3582322, No. 3582322, No. 3551155, No. 3582322, No.
No. 3725072, No. 3891445, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1977-
No. 10783, JP-A-47-26133, JP-A No. 48-73147,
No. 51-102636, No. 50-6341, No. 50-123342
No. 50-130442, No. 51-21827, No. 50-
No. 87650, No. 52-82424, No. 52-115219, No. 58
Examples include those described in No.-95346. Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patent Nos. 2600788, 2983608,
No. 3062653, No. 3127269, No. 3311476, No.
No. 3419391, No. 3519429, No. 3558319, No. 3519391, No. 3519429, No. 3558319, No.
No. 3582322, No. 3615506, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417945, OLS No. 2418959,
No. 2424467, Special Publication No. 6031, No. 40-6031, No. 51-
No. 20826, No. 52-58922, No. 49-129538, No. 49
−74027, No. 50-159336, No. 52-42121, No.
No. 49-74028, No. 50-60233, No. 51-26541,
Examples include those described in Japanese Patent Application No. 53-55122 and Japanese Patent Application No. 55-110943. Furthermore, useful cyan couplers used in the present invention include, for example, phenolic and naphthol couplers. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patent Nos. 2,369,929, 2,434,272, and
No. 2474293, No. 2521908, No. 2895826, No.
No. 3034892, No. 3311476, No. 3458315, No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 4004929, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146827,
Examples include those described in No. 52-69624, No. 52-90932, No. 58-95346, and the like. In order to incorporate these couplers into the silver halide emulsion according to the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution; if they are oil-soluble, they may be added, for example, as described in US Pat. No. 2322027, No. 2801170, No. 2801170, No.
2801171, 2272191, and 2304940, the coupler is dissolved in a high boiling point solvent and, if necessary, a low boiling point solvent, and dispersed in fine particles to remove the halogen. It is preferable to add it to a silveride emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. It is also possible to use a mixture of two or more couplers. Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to an organic acid amide along with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. , carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate,
Di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate,
N,N-di-ethyl-caprylamidobutyl,
N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl- G
High boiling point solvents such as o-chlorophenyl phosphate or fluorine paraffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol,
Dissolved in low boiling point solvents such as diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids. and/or mixed with an aqueous solution containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc. It is emulsified and dispersed and added to the silver halide emulsion. Alternatively, the above couplers may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538 and JP-A-51-59943.
54-32552 and Research Disclosure, August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3
-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like. The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as those published in Research Disclosure Magazine.
Antifoggants, stabilizers, as described in No. 17643;
Ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. The silver halide color photographic light-sensitive material is subjected to imagewise exposure, color development processing, processing with a processing solution having fixing ability according to the present invention, and then stabilization processing. Typical processing liquids having fixing ability include fixing liquids and bleach-fixing liquids. When using a fixer, color development processing and
During processing of the fixer, processing with a bleaching solution is performed. In the present invention, the stabilization treatment refers to a treatment for stabilization that is performed immediately after treatment with a treatment liquid having fixing ability and does not substantially require washing with water, and the treatment liquid used for the stabilization treatment. is called a stabilizing liquid, and the processing tank is called a stabilizing bath or stabilizing tank. In the present invention, the stabilization treatment is performed in one or more tanks, preferably 1 to 3 tanks, and preferably 9 tanks or less at most. That is, if the amount of replenisher is the same, the more tanks there are, the lower the concentration of dirt components in the final stabilizing bath will be. However, if there are many tanks, the total amount of tank liquid increases, so the renewal rate of the tank liquid by the replenisher decreases, and the residence time of the stable liquid increases. Such an extension of the residence time of the bath liquid is undesirable because it deteriorates the storage performance of the liquid and promotes the formation of precipitation. Hereinafter, all the processing liquids used in the processing steps following the processing having fixing ability will be referred to as stabilizing solutions, and the step following the processing step having fixing ability will be referred to as the stabilizing treatment step. In the present invention, the stabilization treatment is performed substantially without a water washing step, which means that the volume of the processing solution (fixer or bleach-fix solution) having a fixing ability brought into the tank at the forefront of the stabilization treatment is This refers to a case where the volume is 1/500 or more, preferably 1/250 or more of the volume of the stabilizing liquid in the tank. If the concentration of the fixer or bleach-fixer in the first tank of the stabilization treatment does not become less than 1/500, a very short rinsing treatment using a single tank or multiple tank countercurrent method, auxiliary water washing, and washing acceleration bath are performed. Processing such as the following may also be performed. In particular, it is preferable that the concentration of the bleaching solution and bleach-fixing solution in the stabilizing solution is 500 ppm or more. In the present invention, the pH of the stabilizer is preferably in the range of 2.0 to 10, and it is particularly preferable to adjust the pH to 3.0 to 9.0 from the viewpoint of stability in image storage. The stabilizer used in the present invention includes, for example, chelating agents (polyphosphate, aminopolycarboxylate, phosphonocarboxylate, aminophosphonate, etc.), organic acid salts, etc., in order to improve the stability of image storage. (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), PH regulators (sulfites, phosphates, borates, hydrochloric acid, sulfuric acid, etc.), fungicides (phenol derivatives, catechol derivatives, imidazole derivatives) , triazole derivatives, thiabendazole derivatives,
Organic halogen compounds, other fungicides known as slime control agents in the paper-pulp industry), optical brighteners, surfactants, preservatives, organic sulfur compounds, onium salts, formalin, etc. can. Preferred chelating agents include polyphosphates,
Aminopolycarboxylate, oxycarboxylate,
Although polyhydroxy compounds, organic phosphates, etc. are used, particularly good results can be obtained when aminopolycarboxylic acid salts and organic phosphates are used in the present invention. Specific examples of chelating agents include, but are not limited to, those listed below. The amount of chelating agent added is 0.05g per stabilizer.
Can be used in the range of 40g, preferably
It ranges from 0.1 to 20g. Next, it is preferable that the stabilizing liquid used in the present invention contains a metal salt. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb,
Examples include metal salts such as Sn, Zn, Ti, Zr, Mg, Al, and Sr, and these include inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, and acetates, or water-soluble chelates. Can be supplied as an agent. The metal salt can be added in an amount of 1 x 10 ^-4 to 1 x 10 ^-1 mol per stabilizing solution, preferably 4 x 10 ^-4 to 2 x
It can be added in an amount of 10 ^-2 mol, more preferably 8 x 10 ^-4 to 1 x 10 ^-2 mol. Things added to the stabilizer of the present invention include optical brighteners other than the above-mentioned compounds, organic sulfur compounds, onium salts, hardeners, and polyvinylpyrrolidone (PVP K-15, Rubiscoll K-17).
etc.) can be mentioned. Specific compounds of the above [A] to [F] include:
Examples include, but are not limited to, the following: [Exemplary compounds] (1): Sodium octophenylphenol (2): 2-octyl-4-isothiazoline (3): Benzisothiazolin-3-one (4): 2-methyl-4-isothiazolin-3-one ( 5): 5-chloro-2-methyl-4-isothiazolin-3-one (6): 2-thiomethyl-4-ethylamino-6-
(1,2-dimethylpropylamino)-s-triazine (7): Hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine (8): 4-(2-nitrobutyl)morpholine (9 ): 4-(3-nitrobutyl)morpholine (10): 2-(4-thiazolyl)benzimidazole (11): Dodecylguanidine hydrochloride The compounds of [A] to [F] above are 0.001 to 50 g per stabilizer solution. It can be used in a range of 0.01 to 20 g, and good results can be obtained preferably by adding 0.01 to 20 g. For the stabilization of the present invention, the above compounds [A] to [F]
However, it is preferable to contain other soluble iron complex ions. As a specific compound of soluble iron salt, ferric chloride
Inorganic ferric salts such as iron, ferric sulfate, ferric nitrate, ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous salts, ferric acetate, ferric citrate, etc. There are carboxylic acid iron salts and various iron complex salts, and examples of compounds that form complex salts with these iron ions include compounds represented by the following general formulas [] to [XII]. General formula [ ] MmPmO ₃ m M; hydrogen, alkali metal, ammonium. m: an integer from 3 to 6. General formula [] Mn+ ₂ PnO ₃ n+ ₁ n; an integer from 2 to 20. General formula [] B-A ₁ -Z-A ₂ -C General formula []

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Example 1 The following composition liquid was mixed in a ball mill on one side of a high-quality paper having a basis weight of 100 g/m ² and having a surface size obtained from anionic starch and NaCl, the inside of which was sized with alkali ketene dimer and polyamide epichlorohydrin resin. After being dispersed, it was coated to a thickness of 20 μm, and then irradiated with an electron beam at a dose of 200 kV and 5 Mrad in a nitrogen gas atmosphere using an electron beam accelerator. (Composition liquid) 3,4-epoxycyclohexylmethyl-3,
4-Epoxycyclohexylcarboxylate (manufactured by Ciba Geigy, Araldite CY-179)
62 parts by weight 4,4-dimethyldiphenyliodonium hexafluoroarsenate 3 parts by weight Titanium dioxide (particle size 0.3 μm) 35 parts by weight Apply the above composition liquid on the opposite side of the cured coating layer.
After coating to a thickness of 20 μm and curing by electron beam irradiation in the same manner as above, a silver chlorobromide gelatin emulsion containing a coupler and a protective layer are coated on the surface of the first coating layer and dried to form a silver halide color. Created photographic materials. The coated sample obtained here is referred to as sample (1). Next, 100 g of basis weight was sized as described above.
After mixing and dispersing the following composition liquid on one side of ^m2 high-quality paper using a ball mill, apply it to a thickness of 20 μm,
Next, an electron beam was irradiated using an electron beam accelerator at a dose of 200 kV and 5 Mrad. (Composition liquid) Bisphenol A diglycidyl ether polymer (Epicote 828 manufactured by Schiel) 57 parts by weight p-methoxybenzenediazonium hexafluorophosphate 3 parts by weight Titanium dioxide (particle size 0.3 μm) 40 parts by weight Cured coating layer Apply the above composition solution to the opposite side.
After coating to a thickness of 20 μm and curing by electron beam irradiation in the same manner as above, a silver chlorobromide gelatin emulsion containing a coupler and a protective layer are coated on the surface of the first coating layer and dried to form a silver halide color. Created photographic materials. The coated sample obtained here is referred to as sample (2). Furthermore, the basis weight 100g/m ² was sized as described above.
After mixing and dispersing the following composition liquid on high-quality paper using a ball mill, it was coated to a thickness of 30 μm, and then heated under a nitrogen gas atmosphere using an electron beam accelerator.
Electron beam irradiation was performed at a dose of 200 kV and 5 Mrad. (Composition liquid) Polyester acrylate (molecular weight approximately 1000, 4 double bonds in molecule) 25 parts by weight hexanediol diacrylate 25 parts by weight trimethylolpropane triacrylate
15 parts by weight Titanium dioxide (particle size 0.3 μm) 35 parts by weight Apply the above composition liquid on the opposite side of the cured coating layer.
After coating to a thickness of 30 μm and curing by electron beam irradiation in the same manner as above, a silver chlorobromide gelatin emulsion containing a coupler and a protective layer are coated on the surface of the first coating layer and dried to form a silver halide color. A photosensitive material was created. The coated sample obtained here is designated as sample (3). Furthermore, as a comparative sample, a high quality paper which had been subjected to the same size treatment as above was coated on both sides with about 12 g/m ² of a polyethylene mixture by extrusion coating. This polyethylene mixture contains 10 parts by weight of titanium dioxide. This sample was used as a comparative sample. After exposing the above sample to light using a conventional method, the following treatment was performed. As a comparison treatment, a water washing treatment was performed instead of the stabilization treatment. The water washing process was carried out at a flow rate of 5 times per minute. Processing process Processing temperature (°C) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 Bleach-fixing 37.8 1 minute 30 seconds 3 Stable 30-34 2 minutes 10 seconds 4 Drying Color developer, bleach-fix solution and stabilizer are as follows I used the one from [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxyamine sulfate 2.2g Potassium bromide 1.2g Diethylenetriaminepentaacetic acid 2.0g Sodium hydroxide 3.4g N-ethylene-N-β-hydroxyethyl-3
-Methyl-4-aminoaniline hydrochloride 4.6g Water was added to make 1, and the pH was adjusted to 10.05 with sodium hydroxide. [Bleach-fix solution] Ethylenediaminetetraacetic acid iron() ammonium
50g diethylenetriaminepentaacetic acid 10g ammonium thiosulfate (70% solution) 200ml ammonium sulfite (40% solution) 10ml Add water to bring the total volume to 1, and dilute with ammonium water.
Adjusted to PH6.8. [Stabilizer] 2-methyl-4-isothiazolin-3-one
0.004g 2-Methyl-5-chloro-4-isothiazolin-3-one 0.02g 1-hydroxyethylidene-1,1-diphosphonic acid 0.01g 2-octyl-4-isothiazolin-3-one
0.03g Magnesium chloride 0.17g Bismuth chloride 0.14g Polyvinylpyrrolidone 0.1g Nitrilotriacetic acid 3g Ammonium hydroxide (28% aqueous solution) 3g Water was added to bring the total volume to 1, and the pH was adjusted to 7.1 with acetic acid and potassium hydroxide. Fill an automatic developing machine with the above color developing solution, bleach-fixing solution, and stabilizing solution, and while processing the photoprinted color paper, add the above-mentioned color developing solution, bleach-fixing solution, and stabilizer every 3 minutes. A running test was conducted while replenishing a predetermined amount of stabilizing solution. The amount of replenishment was 2.0 ml per 100 cm ² of color paper to the color development tank, 2.5 ml of bleach-fix solution to the bleach-fix tank, and 2.8 ml of stabilizing solution to the stabilizing tank. The stabilization tanks of the automatic processor are the first to third tanks in the direction of the flow of the photosensitive material, and the final tank is replenished, and the overflow from the final tank is allowed to flow into the previous tank. This overflow liquid was further flowed into the preceding tank, and a multi-tank countercurrent system was adopted in which it overflowed from the foremost tank. Continuous processing was performed until the total replenishment amount of the stabilizing solution became five times the total capacity of the first to third stabilizing tanks. Take a 1m sample after continuous treatment, 80%RH, 60℃
After storage for 2 weeks, it was rolled up and the stain concentration at the edges was measured. For comparison, a sample at the start of the run was used and saved. Furthermore, the unexposed area of the image area and the white exposed area (maximum density area) were similarly stored for two weeks under the conditions of 80% RH and 60°C. The concentration change after storage was compared with the initial concentration. The results are shown in Table-1.

[Table] As is clear from the results in Table 1, when the samples of the present invention were subjected to waterless washing, they were significantly superior to the comparative samples in terms of edge stains, stains in image areas, and dye density. In addition to this example, the results of processing in which the stabilizing solution treatment was replaced with the water washing treatment are also shown in Table 1. Example 2 An experiment was conducted in the same manner as in Example 1, except that the bleaching agent in the bleach-fix solution was replaced with the one shown below. (Bleach) (1) Ferric ammonium diethylenetriaminepentaacetate 80g/ (2) Ferric ammonium cyclohexanediaminepentaacetate 80g/ (3) Ferric ammonium triethylenetetraminehexaacetate 90g/ As a result, the same as Example 1 These results confirmed the effectiveness of the present invention. Example 3 A sample according to the present invention was treated in the same manner as in Example 1 except that the titanium oxide used in the support was replaced with barium sulfate, but substantially the same results as in Example 1 were obtained. Example 4 In place of Example 1, the bleach-fixing solution was used separately for bleaching and fixing. The time was 1 minute and 30 seconds for each, the treatment temperature was 33℃, and the treatment liquid was Sakura Color.
A CNK-4 processing agent was used. The rest was the same as in Example 1. The results obtained were substantially the same as in Example 1.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support coated with a resin cured by irradiation with an electron beam, after imagewise exposure. After color development processing and treatment with a processing liquid having fixing ability, the volume of the processing liquid having fixing ability that is brought into the frontmost tank of stabilization processing without substantially going through a water washing step is the stability of the first tank of stabilization processing. A silver halide color photograph characterized by performing stabilization treatment with a stabilizing solution that is 1/500 or more of the volume of the solution and contains at least one compound selected from [A] to [F] below. How to process photosensitive materials. [A] Phenol compound [B] Thiazoline compound [C] Triazine compound [D] Morpholine compound [E] Imidazole compound [F] Guanidine compound.