JPS614047A - Treatment of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a dye image superior in storage stability by processing a silver halide photographic sensitive material contg. specified magenta, yellow, and cyan couplers, after imagewise exposure, in the three steps of color development, fixing, and stabilization excluding water rinsing. CONSTITUTION:The photosensitive material contains a magenta coupler represented by formula I (Ar is phenyl; Y1 is a group releasable on coupling with the oxidation product of a developing agent and forming a dye; X1 is halogen, alkyl, or the like; R1 is the substituent of the benzene ring; and n is 1 or 2), a yellow coupler of formula II (X is halogen, alkoxy, or the like; Z1 is a group releasable on coupling with the oxidation product of a developing agent, and forming a dye, and an atomic group selected among C, N, and S capable forming 5- or 6-membered ring together with N; R2 is the substituent of the benzene ring; and m is 1 or 2), and a cyan coupler of formula III (R3 is 1-4C straight or branched alkyl or -NHCOR5; R4, R5 are each an alkyl, aryl, or heterocyclic group; R6 is H or halogen; and Z2 is H or a group releasable on coupling reaction with the oxidation product of a developing agent), and after imagewise exposure, it is processed through the three steps of color development and fixing, and stabilization excluding water rinsing. A chelating agent having a stability degree of >=8 is incorporated in the stabilizing soln., and the soln. is treated to prevent mold, and an epoxy compd. is added to the fixing soln. and/or the stabilizing soln. As a result, the storage stability of a dye image can be improved without water rinsing.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials.
More specifically, dye 1 has excellent storage stability and can be stored for a long period of time after treatment without the substantial water washing process.
The present invention relates to a method for processing a silver halide color photographic material (hereinafter referred to as a "photosensitive material") that forms a pattern. [Prior art] In general, photosensitive materials undergo color development, bleaching, and
Although it is processed in the first stage of processing such as fixing, stabilization, bleach-fixing, and washing with water, in the washing process that follows the processing with a processing solution that has fixing ability, compounds that react with silver halide to form water-soluble complex salts are used. If thiosulfate, other water-soluble silver complex salts, as well as sulfites and metabisulfites as preservatives are contained or adhered to photosensitive materials and brought into the photosensitive material, and the amount of water used for washing is small, image preservation may occur. It is known to have negative effects on sexuality. Therefore, in order to eliminate such drawbacks, the current situation is to wash away the above-mentioned salts from the photosensitive material by using a large amount of running water during washing after processing with a processing liquid having fixing ability. However, in recent years, due to economic reasons such as lack of water resources, rising sewerage charges and utility costs, and pollution reasons, there has been a desire for a treatment process that reduces the amount of washing water and takes measures against pollution. Conventionally, as a countermeasure against these problems, for example, a method of arranging the washing tank in a multi-stage configuration and causing water to flow in countercurrents was proposed, as disclosed in West German Patent No. '2,920.
．． No. 222 and Nis R. Goldbasser (8,
R, Golchwasser), [Water Flow Late in Immersion Washing Op.
Motion picture a film (water Flo
w Rate In Immeralon-Wash
lng ofMotion-picture File
m) J8MPTB, vol, 54°248~
May, (1953), p. 253, etc. A processing method is also known in which a preliminary washing is provided immediately after the fixing bath to reduce the polluting components contained in and attached to the photosensitive material and enter the washing process, and also to reduce the amount of washing water. However, these technologies are not treatment methods that do not use flushing water at all, and therefore, the recent depletion of water resources and increased costs for flushing due to rising crude oil prices are becoming increasingly serious problems. On the other hand, there is a processing method in which stabilization processing is performed immediately after photographic processing without washing with water. For example, U.S. Patent No. 3,335.
Silver stabilization treatment using thiocyanate is known, as described in the specification V of No. 004 and the like. However, this method has the drawback that since the stabilizing bath contains sulfite in multiple vertical directions, the surface recognition dye formed is likely to be converted into a leuco form, which has a large effect on the deterioration of color photographic images. Furthermore, as a method of omitting the washing process and extremely reducing lockstitching by water washing, there is a multi-stage countercurrent stabilization treatment technology as described in JP-A No. 57-8543, and JP-A No. 58-Sho. As described in Publication No. 134636,
A treatment technique using a stabilizing liquid containing a sumus complex salt is known. However, in both cases, although this technology reduces the amount of replenishment of the stabilizing solution and reduces pollution, the preservation of photographic images over time is extremely insufficient, especially when displayed in a showland, etc. Alternatively, under conditions of high temperature and high humidity, yellow, magenta and cyan dyes in photographic images are significantly faded, and furthermore, staining occurs in unexposed areas. In particular, since each pigment has a different rate of fading, the color balance is visually out of whack after storage, resulting in prints that look extremely strange.
Therefore, there has been a need for a method for processing light-sensitive materials in which each dye undergoes less discoloration during storage, and even when the color fades, the rate of discoloration of each dye is almost the same, the color balance is different, and there are fewer laths and stains. [Object of the Invention] Accordingly, an object of the present invention is to provide a method for processing photosensitive materials that substantially does not use washing water, reduces energy cost, and reduces pollution load. Another object of the present invention is to provide a method for processing photosensitive materials that can form color photographic images that are stable during long-term storage without substantially using washing water. [Summary of the Invention] As a result of intensive research by the present inventor, the following general formula [I]
A magenta coupler represented by the following general formula [11], and a yellow coupler represented by the following general formula [111]
After exposing a silver halide photographic light-sensitive material containing a cyan coupler represented by 1 to 1 image, it does not include a color development process, a process of treating it with a processing solution having fixing ability, and 1 substantive washing with water. The inventors have discovered that the above object can be achieved by a treatment method having at least three steps of stabilization treatment, leading to the present invention. General formula [■] (In the formula, A r ld phenyl group flYl 1ri
XI represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent;
These are halogen atoms, alkoxy groups, and alkyl groups. R
1 digit represents a group that can be substituted on the benzene ring, n digit] or 2
represents. n is 2 and 1! R1 may be the same or different, General formula [II] (In the formula, , 5 by an atom selected from sulfur atoms.
7R is a group representing an atomic group capable of forming a six-membered ring, and is a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. Represents a group that can be substituted on the benzene ring, mFil
or represents an integer of 2. When m is 2, R3 may be the same or different,) general formula [IIr] b! (In the formula, Rs represents a linear or branched alkyl group having 1 to 4 carbon atoms, or -NHCORo. R4 and R6
are an alkyl group and an aryl group, respectively, and the parent is a heterocyclic group. aJ is a hydrogen atom or a cup with an oxidation product of a color developing agent, ! I) 'Can be removed' during yf reaction
8 in Table 61. In a preferred embodiment of the present invention, the stabilizing solution contains a chelating agent having a chelate stability constant of 8 or more with iron (HI) ions. Further, in another preferred embodiment of the present invention, the processing liquid and/or stabilizing liquid having fixing ability contains an epoxy compound, an aziridine compound, an acryloyl compound, a vinylsulfonyl compound, a triazine compound, an inoxazolicum compound, The composition may include at least one selected from sulfonic acid ester compounds, carbodiimide compounds, maleimide compounds, and isocyanate compounds. Furthermore, as another preferred embodiment of the present invention,
The stabilizing solution may be treated with at least one of the following anti-mildew means. [Mold-proofing means] (A) Means for adding a mold-proofing agent. 03) Means for passing through a magnetic field. (q Means for irradiating ultraviolet rays. [Structures of the Invention] The present invention will be explained in more detail below. Each coupler has been studied individually to improve the storage stability of the dye-1 family. However, in the present invention, certain couplers are selected and used for each of yellow, magenta, and cyan, and storage over time is performed under surprisingly poor conditions during stabilizing solution processing without substantial water washing. The present invention was achieved by discovering that the fading of dyes over time is improved compared to using each type of coupler as a single technique, and that the color balance is not disturbed, resulting in very little visual change. The couplers represented by the general formulas [■], [II], and [1■] will be described in detail.General formula [I] Suga Ar Ar: A phenyl group, particularly preferably a substituted phenyl group. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamido group, and an acylamino group.
The phenyl group represented by the above may have two or more substituents. Specific examples of substituents are listed below. Halogen atom: chlorine, bromine, fluorine Alkyl group: Methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, 1-pentyl group, etc., but alkyl groups having 1 to 5 carbon atoms are particularly preferred . Alkoxy group: methoxy group, ethoxy group, butoxy group,
5ec-butoxy group, 1so-pentyloxy group, etc., but an alkoxy group having 1 to 5 carbon atoms is particularly preferred.Aryloxy group: phenoxy group, β-naphthoxy group, etc., but this aryl moiety further includes It may have the same substituents as those listed for the phenyl group represented by Ar. Alkoxycarbonyl group: A carbonyl group with an alkoxy group as described above, preferably one in which the alkyl moiety has 1 to 5 carbon atoms, such as a methoxycarbonyl group or a pentyloxycarbonyl group.Carbamoyl group: Carbamoyl group, dimethylcarbamoyl group Alkylcarbamoyl groups such as sulfamoyl groups: sulfamoyl groups, methylsulfamoyl groups, dimethylsulfamoyl groups, ethylsulfamoyl groups, etc. Sulfonyl groups: methanesulfonyl groups, ethanesulfonyl groups, butanesulfonyl groups, etc. Alkylsulfonyl group Sulfonamide group: Alkylsulfonamide group such as methanesulfonamide group, -toluenesulfonamide group, arylsulfonamide group, etc. Acylamino group: acetamino group, pivaloylamine group, benzamide group, etc. Particularly preferably a halogen atom, Among them, chlorine is the most preferred. Y: represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine coloring agent. Concrete [i-1IZ! For example, halogen atom, alkoxy group, aryloxy group, acyloxy group, arylthio group, alkylthio group, -NZ. -7' (Z, together with the nitrogen atom, represents an atomic group required to form a 5- to 6-negative ring with atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms6) The following are specific examples: Give an example. Halogen atoms: chlorine, bromine, fluorine alkoxy groups; ethoxy groups, benzyloxy groups, methoxyethylcarbamoylmethoxy groups, tetradecylcarbamoylmethoxy groups, etc. Aryloxy groups: phenoxy groups, 4-methoxyphenoxy groups, 4-nitrophenoxy groups, etc. 7 groups: acetoxy group, myristoyloxy group, benzoyloxy group cyclic arylthio group: 7enylthio group, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2.5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group,
Nidoxyethylthio group, phenoxyethylthio group, triazolyl group, tetrazolyl group, etc. X: represents a halogen atom, an alkoxy group, an alkyl group. Specific examples are listed below. Halogen atoms: chlorine, bromine, fluorine alkoxy groups: methoxy group, ethoxy group, butoxy group,
Alkoxy groups having 1 to 5 carbon atoms such as 5ea-butoxy group and 1so-pentyloxy group are preferred. Alkyl group: Alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, 0-7' propyl group, butyl group, t-butyl group, 1-pentyl group are preferable. Particularly preferred are halogen groups. An atom, of which chlorine is preferable. R1: represents a group that can be substituted on the benzene ring, and .n represents an integer of 1 or 2. When n is 2, R1 may be the same or different. Groups that can be substituted on the benzene ring represented by R1 include a halogen atom, R,/-, R,10-. It represents an alkyl group, an alkenyl group, or an aryl group which may have a substituent. Among these, this is preferred. Specific examples of magenta couplers are shown below.b In the above formula, R1 includes the following. M −1,-NHCOC,,H,. M-2-Nl-TCOCR C,,H,. M-11-8C, □■□ M-12-8CH, CO, C, H. M -13-8CH2COOH M -15-8CH, CONHl M -16-8CH, CH, QC, HIIM -17-
8CH, CH, OH M -19-8CH, CH2NH30□CH. CH. CH. C/ - Otsu - COOC,, H□ 80, C4H. General formula [II] ゝ-Z. 5 to 6 atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms
This is a group representing an atomic group capable of forming a radical, and represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine coloring agent. R2
represents a group that can be substituted on the benzene ring, and when 6m represents an integer of m by 1 or 2 and is 2, R3 may be the same or different. More specific examples of R2 include halogen atoms (eg, fluorine, chlorine, bromine, etc.), RI/RG', and the like. Cocoa, R'2, R"t y R? td same-f
ft represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group, and a peterocyclic group, each of which may have a hydrogen atom or a substituent. Preferably R'2CONH-1R/, SO, NH
-1R/, 0(41NH-), and the bow represents an alkyl group having a substituent. More preferably, it is n4coNH-, and R/. represents an alkyl group having a substituent. 14 - Specific examples of yellow couplers are shown below, but are not limited to these. C/ U -J+ - Y-4 Y-11 H l Y -15 I Y-17 Y-18 I CH. General formula CIII ] (In the formula, RIli-j represents a linear or branched argyl group having 1 to 4 carbon atoms, or -N HCOR6. R4
and R6 each represent an alkyl group, an aryl group, or a heterocyclic group, - these alkyl groups, aryl groups, and heterocyclic groups may have a substituent; R5 represents a hydrogen atom or a 710-gen atom; , Z represents a hydrogen atom or a group that can be dissociated during the coupling reaction with the oxidation product of the chromophore;
each atom of chlorine, bromine, fluorine, etc.), an acyloxy group, a carbamoyloxy group, a carbamoylmethoxy group in which an oxygen atom or a nitrogen atom is directly attached to the coupling position,
Examples include an acyloxy group, a sulfonamide group, and a succinimide group. ) Specific examples of cyan couplers are shown below, but are limited to (J II Iso CmHy C-50H OCH, C0NHCH, CH, OCH. C-60H C-70H C-80H C-90H C-100H C-1101 ( C- 120)1 In the present invention, general formulas [I], [II] and [III]
The coupler represented by can be used in combination with conventionally known couplers within the scope of the purpose of the present invention. Further, as colorless couplers that can be used in combination with the present invention, British Patent No. 861,138, British Patent No. 914,149, British Patent No. 1,
No. 109,963, No. 3,580.722, Special Publication No. 4
No. 5-14033 and Mitteilungenhausden
Forschennings Laborad IJ - Endea Agfa Level Kizusen Volume 4, pages 352-367 (19
You can choose from those listed in 1964). When the couplers according to the present invention represented by the general formulas [■], [IT] and [■''] are contained in the silver halide emulsion layer, it is usually about 0.005% per mole of silver halide.
It is used in a range of 2 mol, preferably 0.1 to 1 mol. Silver halide emulsions that can be used include silver chloride, silver bromide,
Any silver halide such as silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide may be used. In addition, as bed-standing colloids of these halogens (t), in addition to natural products obtained by re-gelatin, various synthetically obtained colloids can be used.
Conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants may also be included. Supports include Bo11 ethylene coated paper, triacetate film, polyethylene terephthalate film,
Any material such as white polyethylene terephthalate film may be used. The color developing agent contained in the color developing solution according to the present invention is a p-phenylenediamine-based color developing agent,
Preferably, it is a p-phenylenediamine-based color-forming agent having at least one group on the amino group that improves water solubility. Particularly preferred are compounds represented by the following general formula [IV]. N.H. In the formula, R2 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and R8 and Ro represent a hydrogen atom *, #'i may have a substituent It represents an alkyl group or an aryl group, and at least one of R11 and Ro is an alkyl group having a water-soluble substituent such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or ij ((CH2' q Or R
,. It is. Note that R10 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and q and r represent an integer of 1 to 5.Next, typical specific examples of the compound represented by the above general formula [■] are listed. , but is not limited to these. ■ Tsukasa IV-2 IV-3 IV-4 IV-5 IV-6 TV-7 NH. IV-8 IV-9 NH. ■-10 ■-11 ■-12 ■-13 C, H, -N % CH, CH, 0)yc, H. ■-14 NH. ■-15 ■-16 These p-phenylenediamine derivatives represented by the general formula [IV] can be used as salts of organic acids and inorganic acids, such as hydrochloride, #L salt, phosphate, p-toluene Sulfonates, sulfites, oxalates, benzenedisulfone Elf salts, etc. can be used. In addition, in the present invention, R8 and/or Ro in the compound represented by the general formula [IV] is ÷(-CH,-
) 0-)-R,, (4% r and RIo are the above q
(synonymous with r ), the desired effects of the present invention are particularly well achieved. These color-forming agents are used at a rate of about 0.1 g to about 30 g per liter of developer solution, more preferably from about 19 to about 15.9 g per liter of developer solution. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above-mentioned color development agent may be incorporated into the light-sensitive material. For example, a method of incorporating a color developing agent in the form of a metal salt as described in U.S. Pat. No. 3,719.492, and U.S. Pat. No. 3.34
2. Ft59 and Research Disclosure (R
e5earch Disclosure) 1976
A method for incorporating color-producing herbal medicine into sick salt as shown in Jfi 151.59, JP-A-58-
65429 and No. 58-24137, etc., or the method of incorporating a pigment precursor as a precursor as shown in U.S. Pat. No. 342,597. In this case, it is also possible to process the light-sensitive material with an alkali solution (activator solution) instead of a color developing solution, and bleach-fixing is carried out immediately after processing with the alkaline solution. The color developing solution according to the present invention contains an alkaline agent commonly used in a developer, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites may be added. etc. may be included. Furthermore, various antifoaming agents and surfactants, as well as organic compounds such as methanol, dimethylformamide, dimethyl sulfoxide, etc., can be appropriately contained. In addition, p) of the color rendering liquid according to the present invention is usually 7 or more, preferably about 9 to 13. In addition, the color rendering liquid used in the present invention may optionally contain an antioxidant. , hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, pyrogallol-1,
3-dimethyl ether and the like may also be contained. Further, in the developer according to the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid a,
Organic phosphonic acids such as 1-hydroxamic acid lidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid)
Among them, aminopolyphosphonic acids such as ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or glyconic acid, polyphosphoric acids such as 2-phosphonobutane 1.2°4-tricarboxylic acid and hexametaphosphoric acid, etc. are used. In the present invention, the color development solution is usually treated with a processing solution that has a fixing ability, but the processing solution that has a fixing ability may be a bleach-fix solution that is a combination of a bleaching solution and a fixing solution. . When the processing liquid having the fixing ability is a fixing liquid, a bleaching process is rarely performed. A metal complex salt of an organic acid is used as a bleaching agent in the bleach solution or bleach-fix solution used in the bleaching process. At the same time, it has the effect of coloring the uncolored parts of the coloring agent, and its structure is one in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form these metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts, or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid 1'ff [3] Ethylenediamine-N-(β-oxyethyl)-N,N'
, N'-) diacetic acid [4] globylenediaminetetraacetic acid [5] nido-110triacetic acid [6] cyclohexanediaminetetraacetic acid [7] methyliminodiacetic acid, [8] &″″°°″″″7″ Iy:
Y? ``'Acid'l (or tartaric acid)

[9] Glycol ether diamine tetraacetic acid [10]
Disodium ethylenediaminetetraacetate [11] Ethylenediaminetetraacetic acid tetra(tri+ methylammonium) salt [12] Ethylenediaminetetraacetic acid tetrasodium salt [13] Diethylenetriaminepentaacetic acid pentasodium salt [14] Ethylenediamine-N-(β-oxyethyl)
-N,N'',N'-Sodium triacetate salt [15] Sodium propylene diamine tetraacetate salt [16] Sodium nitrilotriacetate salt [17] Sodium cyclohexane diamine tetraacetate The bleaching solution used is an organic acid such as those mentioned above. as a bleaching agent, and may also contain various additives.Additives include, in particular, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, bromide, etc. It is desirable to contain rehalogenating agents such as ammonium, metal salts, and chelating agents.Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions can be added as appropriate. Furthermore, the fixer and bleach-fixer contain sulfites such as ammonium frt, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite, and boric acid. , borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, ammonium hydroxide, and other pH buffering agents, either alone or in combination. be able to. When carrying out the process of the present invention while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired.
or a suitable oxidizing agent, such as hydrogen peroxide, bromate,
A persulfate salt or the like may be added as appropriate. In the present invention, the stabilizing liquid is a processing liquid that is after the processing liquid that has fixing ability, and the replenishment amount is 53 per 100 d of light-sensitive material.
ml or less of a processing solution and has the function of improving the storage stability of pigmented paintings by processing with the processing solution. If this condition is satisfied, simple water can also be used as a stabilizing liquid in the present invention. In the present invention, the pH of the stabilizing solution is preferably in the range of 2.0 to 10, and it is particularly preferable to adjust the pH to 3.9 to 8.7 from the viewpoint of image preservation stability. The replenishment amount of the stabilizing solution in the continuous processing of the present invention is extremely effective when it is 30 ml or less per 100 ml of photosensitive material to be processed, preferably 15 ml or less, and more preferably 10 ml or less.
The maximum effect is achieved when the number is 4 or less. The chelating agent preferably used in the stabilizer of the present invention has a chelate stability constant of 8 or more with iron (lTr) ions. In the present invention, the chelate stability constant refers to the stability of a complex formed by a metal ion and a chelate in a solution, and means a constant defined as the reciprocal of the dissociation constant of the complex.L, G, 5illen. , A.E. Martel+, '5tabilit
y Con5tants ofMetallon Co
mplexes #, The Chemical
5ocietyL"andon (1964), S.
Chaberek, A. B. Martell, I.
Organic 8equestering Agen
ts # The chelating agent, which is generally known from Wiley (1959) and others, and which has an iron (l) ion tonochelate stability constant of 8 or more, includes polyuym salts,
Aminopolycarboxylate, oxycarboxylate, polyhydroxy compound, organic phosphate, condensed phosphate, etc. are used, but aminopolygalponate and organic phosphate are especially used in the present invention. Good results can be obtained if Specific examples of chelating agents include, but are not limited to, the following. H2O, P -C-PO, H7 H (3) CH Hatake H'00C-C-PO, H2 H One or more chelating agents may be used in combination, and the amount added is 0.05 g per stabilizer IIl. It can be used in the range of 1 to 40.9, preferably in the range of 1 to 20.9. Among these chelating agents, 1-hydroxyethylidene-1,1-diphosphonic acid is particularly preferably used. Next, it is preferable that the stabilizing liquid used in the present invention contains a metal salt. Such metal salts include Ba, C
a, Ce, Co, In, La, Mn,
Ni, pb. 8n, Zn, Tl, Zr, Mg, AI
, Sr, etc., and these can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, or water-soluble chelating agents. The metal salt is 1 x 10°4~lXl0-1 per 11 stabilizers.
It can be added in a molar range, preferably 4
10-' to 2 X 10-" moles, more preferably 8
X can be added in a range of 10-4 to 1×to-g mol. Particularly desirable compounds for addition to the stabilizers of the present invention include ammonium compounds. These are supplied by the ammonium salts of inorganic compounds in various foods, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammoelum chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. ammonium chloride, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, a
'tR ammonium, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium alarintricarboxylate, ammonium benzioate, ammonium carbamic acid, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, Ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium fudthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, salutyl Ammonium acid, ammonium conotarate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2
．． 4.6-dolinitrophenolammonium and the like. The amount of these ammonium compounds added is 1 for the stabilizer! (It can be used in the range of 1,05 to 10,011 F, preferably in the range of ld of 0.1 to 20 F. Details of the addition technology of these ammonium compounds are disclosed in Japanese Patent Application No. 58-F filed by the present applicant). You can refer to the contents of No. 8693. In addition to the above, the stabilizer of the present invention also includes organic acid salts (citric acid, acetic acid, cono-phosphoric acid, oxalic acid, benzoic acid, etc.), p[-] regulators (sulfites, phosphates, borates, etc.). , hydrochloric acid, sulfuric acid, etc.)
Alternatively, fluorescent brighteners, surfactants, formalin, polyvinylpyrrolidone (PVPK-15, -1
7) etc. can be contained. Processing with a processing solution having a fixing ability of the present invention without substantially subsequent washing with water means - Directly applying the stabilizing treatment of the present invention after bath development, bleach-fixing, bleach-fixing, or mechanism fixing. Basically, washing with water is not performed, but - bath development, bleach-fixing, bleach-fixing, or a short silver recovery bath, rinsing, etc. for silver recovery between the fixing bath and the stabilizing bath. This means that it may be provided. However, it is preferable not to provide any processing bath that increases the fixing ability between the stabilization processing steps using the stabilizing solution. The treatment temperature during the stabilization treatment is preferably in the range of 15 to 60°C, preferably 20 to 33°C. In addition, the shorter the treatment time, the better from the viewpoint of rapid processing, but it is usually 20 seconds to 10 minutes, most preferably 30 seconds to 5 minutes, and in the case of multiple tank stabilization treatment, the first stage tank should be used in a shorter time. It is preferable that the processing time in the downstream tank is long. Especially the front tank 2
It is preferable to sequentially process the processing time in increments of 0 to 50 times. In addition, it is preferable that the stabilization treatment step be carried out in a multi-stage tank, and the replenisher is replenished from the last stage tank, and a backflow method is used in which it sequentially overflows into the previous stage tank, but of course a single tank may be used. The method of bringing the stabilizing solution of the present invention into contact with the photosensitive material is preferably to immerse the photosensitive material in the solution in the same way as a general processing solution.
It may be applied to the emulsion surface of the photosensitive material, the surface of the transport leader, and the transport belt using a sponge, synthetic fiber cloth, or the like, or it may be sprayed from a spray stop. Next, epoxy compounds, azi-11dine compounds, acryloyl compounds, vinylsulfonyl compounds, triazine compounds, isoxazolium compounds, sulfonic acid ester compounds, which are used in the processing liquid and/or stabilizing liquid having fixing ability of the present invention, Carbodiimide compounds, maleimide compounds, and isocyanate compounds are shown below. It is a compound having CH, -CH- in the epoxy compound, specifically 2.2'-Bls(p-glycldoxy)-ben
zeneL2-Bib(2', 3'-epoxyp
ropoxy) ethane propylene ox
ide etc. N-ethyl-N'-ethylene urea
p-phenylene bis [old-(1-azl)
[ridinyl)phosphonate ] N-pentadecyl-N-ethylene
Examples include urea and the like. It is a compound having Aku-110 mo-C0-NH- or CH,=CH-C0-0-, and specifically VCFimucochlori
c amidebydroxy mucochlor
l:c acid3-bromo-2-phenoxy
-malealdehydric acid and the like. VCeH,=CH in vinylsulfonyl compound dissolution compound
-80,-, specifically CH,=CH30,CH,-80,-CH:=CH
. (Thria,)7 as a compound Ha2. 2,4-dichloro-6-hydroxy-1, hydroxytriazine compounds, alkoxy compounds, etc.
3,5-triazinesodium 5alt 2,4-dichloro-6-carboxy me
thoxy-L3.55-5odlu 5alt hexahydro-1,3,5-tris-(2-h
ydroxyethyl)-8-trlaZine and the like. An isoxazolium compound is a compound having 2-methyl-1soxazolium p-to
Examples include luenesultonate and the like. X Ruho7 acid! It is a compound that has a sulfonic acid ester moiety, specifically 1-meth
yl 5ulfoxy-2,3-epoxyprOpa
Neglycidyl ellilsulfonate
etc. -7'J=(:
=N-, specifically hydroxyethylalylcarvldiim
ldel+3-di-1sopropyl-carbo
Examples include dl 1m1de. Maleimide compounds include compounds having a maleimide bond, specifically N,N'-trlmethylene bismal
eimideL9- divlnyl-2+C8,10
-tetra oxasplr. [5,5] undecane etc. are mentioned. Isocyanate compounds include compounds having an isocyanate group, specifically polylsopropenyl 1 socyanat
e braulfit adduct thylene
l5ocyanate and the like. Among these compounds used in the present invention, preferred are halogen triazine compounds, hydroxytriazine compounds, alkoxytriazine compounds, vinyl sulfone compounds, and epoxy compounds, and more preferred are halogen triazine compounds, Hydroxytriazine compounds, alkoxytriazine compounds,
Vinyl sulfone compounds are preferred, and halogen triazine compounds are particularly preferred. The amount of the above compound added to the processing liquid and/or stabilizing liquid having fixing ability is 0.1 g to 50 g per liter of the stabilizing liquid.
．． F, preferably in the range of 0.5 fI to 20.9. Other specific examples of the triazine compounds of the present invention are described in JP-A-58-132743, and "l'he Theory nf the Photo" by R. H. James.
graphic Process' (4th edition) 77~
Examples include those described on page 87. The protective agents preferably used in the present invention include hydroxybenzoic acid ester compounds, alkylphenol compounds, thiazole compounds, pyridine compounds, guar-didine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds,
These are urea compounds, inxa-open sol compounds, globanolamine compounds, and amino acid compounds. The hydroxybenzoic acid ester compounds include methyl ester, ethyl ester, furoyl ester, butyl ester, etc. of hydroxybenzoic acid, but preferably n-butyl ester, isobutyl ester, and furoyl ester of hydroxybenzoic acid. A more preferred mixture is a mixture of the three hydroxybenzoic acid esters mentioned above. In the alkylphenol compound, the alkyl group is C1-6
A compound having an alkyl group as a substituent, preferably ortho-phenylphenol or ortho-cyclohexyphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1.2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-one. It, Al II y
3-off, 5-2°. -2-methyl-4-isothiazolin 3-one, 2-14-thiazolylnobenzimidazole. Examples of pyridine-based compounds include 2,6-diumethylpyridine, 2,4,6-dimethylpyridine, and radium-
There are 2-pyridinethiol-1-oxide and the like, but medium-2-pyridinethiol-1-oxide is preferred. Specific examples of the guanidine-based compound include cyclohexidine, polyhexamethylene biguanidine hydrochloride, and dodecylguanidine sulfate, with dodecylguanidine and its salts being preferred. Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole car/(mate).Specific examples of morpholine compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole car/(mate). , 4-(3-nitrobutyl)morpholine, etc. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetraalkylphosphonium salts are preferred, and more specifically preferred compounds are tetraalkylphosphonium salts. Quaternary ammonium compounds such as n-butyl-tetradecylphosphonium chlorite and triphenyl-nitrophenylphosphonium chloride include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridinium salts. There are dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, etc. Urea compounds include [1N-(3,4-dichlorophenyl)-N'-C4-chlorophenyl)urea, N-(3
-)lifluoromethyl-4-chlorophenyl)-N'
-(4-"lorophenyl)urea, etc. Specific examples of inxazole-based compounds include [6-13-hydroxy-5-methyl-isoxazole, etc.] Glopanolamine-based compounds include n-propanols and inpropanols. Specifically, DL-2-benzylamino-1-cropanol, 3-diethylamino-
1-Clopanol, 2-dimethylamino-2-methyl-
1-Clopanol, 3-Amino-1-Clopanol, Idopropaturamine, Diisopropaturamine, N
Examples include N-dimethyl-isocropanolamine. A specific example of the amino acid compound is N-lauryl-β-alanine. Among the above antifungal agents, compounds preferably used in the present invention include thiazole compounds, pyridine compounds,
These are guanidine compounds and quaternary ammonium compounds. Furthermore, thiazole compounds are particularly preferred. If the amount of antifungal agent added to the stabilizer is less than 0.002 II per liter of stabilizer, the desired effect of the present invention will not be achieved.
Moreover, if it is more than 50g, it is not preferable in terms of cost, and the storage stability of the pigment painting is adversely deteriorated.
Used in the range of 9 to 50 g, preferably 1-jO, 005
It is used in the range of 11 to ioy. In the present invention, passing the stabilizing liquid through a magnetic field means passing the stabilizing liquid through the magnetic field generated between the positive and negative poles of the magnetic field, and the photosensitive material may or may not pass through the magnetic field. The magnetic field used in the present invention is obtained by using a permanent magnet made of ferromagnetic materials such as iron, cobalt, and nickel.
Alternatively, it can be obtained by passing a direct current through a coil or the like, but there is no particular limitation, and any means capable of forming a magnetic field can be used. In addition, the magnetic field may be formed by using one magnet to form lines of magnetic force, or by arranging two magnets (positive and negative poles) facing each other to form lines of magnetic force between the same pair of magnets. . The method of passing the stabilizing liquid used in the present invention through a magnetic field is to move (including rotation) a permanent magnet that is placed inside and/or outside the stabilizing liquid using a permanent magnet that forms a magnetic field, or There are methods such as moving the stabilizing solution by stirring or circulating the stabilizing solution. A particularly desirable method is to fix a permanent magnet to a part or all of the inside or outside of a circulatory system pipe and circulate the stabilizing liquid.If a permanent magnet is fixed to each pipe individually, the pipe itself It may be a permanent magnet, or the permanent magnet may be attached to the entire pipe.In the case of an automatic phenomenon machine, the purpose can be achieved by installing a permanent magnet etc. in the stabilizing bath, but the above-mentioned It is preferable to install it in the circulation system of the stabilizing bath (not limited to the circulation pipe, but also including tanks and other parts in the middle).Also, if the stabilization process is a multi-stage stabilizing bath, the stabilizing solution in all the stabilizing baths should be Although it is most preferable to pass the stabilizer through a magnetic field, it is also preferable to pass the stabilizer solution of a stable bath other than the one closest to the processing liquid having fixing ability through the magnetic field. A greaseproof lining containing a material capable of generating magnetic lines of force may be provided, and the lining may be applied to the circulatory system.In this way, the stabilizing liquid can be passed through the magnetic field in steps 1 to 1.The present invention The method of irradiating the stabilizer with ultraviolet rays is carried out using a commercially available ultraviolet lamp or ultraviolet irradiation device, and preferably the output of the ultraviolet lamp is 5 W to s.
oow (tube output) is preferable, but is not limited to this. In a preferred embodiment of the present invention, the wavelength of the ultraviolet light is in the range of 220 nm to 35 Q nm. Furthermore, as an irradiation method, 1-
There is a method of direct irradiation, and the photosensitive material to be processed may be irradiated with the ultraviolet rays. In the processing of the present invention, silver may be recovered by various methods from processing solutions containing soluble silver salts such as fixing solutions and bleach-fixing solutions as well as stabilizing solutions. For example, the electrolysis method (French Painting Patent No. 2. 299.667), precipitation method (% described in Japanese Patent Application No. 1983-73037, German Patent No. 2.331)
．． 220 specification), ion exchange method (Japanese Patent Application Laid-open No. 1982-
17114 Publication Correspondent, German Nationality Permit No. 2. F) 48.23
7 Specification i), and metal substitution method (British Patent No. 1)
, 353, 805) etc. can be effectively used. Furthermore, when recovering silver, the soluble silver salt may be used to collect the overflow solution of the processing solution and recover silver using the method described above, and the remaining solution may be disposed of as waste solution, or a regenerating agent may be added and used as a replenisher or tank processing solution. May be used. It is particularly preferred to mix the stabilizer with the fixer or bleach-fixer before silver recovery. It is also possible to use a treatment in which the strained stabilizer of the present invention is brought into contact with an ion exchange resin, an electrodialysis treatment (see Japanese Patent Application No. 59-96352), a reverse osmosis treatment (see Japanese Patent Application No. 59-96352), etc. . The light-sensitive material to which the present invention can be applied may be any light-sensitive material such as color paper, reversal color paper, color positive film, color reversal film, direct positive paper, and light-sensitive material for diffusion photography. [Example 1] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

[Color developer replenisher]

Benzyl alcohol 20.0rnl! Ethylene glycol 20b10ml Potassium sulfite 3.0II Carbonic power 11
Um 30, oI! Hydroxylamine atM salt 4.01 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Monoaniline sulfate 7.5g Fluorescent brightener (4,4'-cya7fu) minostilbendisulfonic acid derivative) ], 5. ! 71
-Hydroxyethylidene-1,1'-diphosphonic acid (60qb aqueous solution) 1.0 g Hydroxyethyliminodiacetic acid 2.5I magnesium chloride 6 water 4 0.7 g 1.2-dihydroxybenzene-3,5-disulfonic acid 0.2 g of disodium salt was added to bring the solution to 1.0 g, and the pH was adjusted to 10.70 with potassium hydroxide. [Floating fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 10011tl
Ammonium sulfite (40% solution) 27.5mg
Add water to bring the pH to 11, add potassium carbonate to pH 7,
10vcXflEt, *. [Bleach-fixing brightener A] Ferric ammonium ethylenediaminetetraate 2 liters 260.9 Potassium carbonate
42F ethylenediaminetetraacetic acid 3. Add 0.9 water to bring the total volume to 1 liter. The pI of this aqueous solution is 6.7 and 0.1. [Bleach-fix replenisher B] Ammonium thiosulfate (70% solution) 500 ml
Ammonium sulfite (40% solution) 250 ml
Ethylenediaminetetraacetic acid 17g Glacial acetic acid 65ml
Add water to make total loss 1 point...toe. The pH of this aqueous solution was 5.3±0.1. [Stabilizing solution and stable replenishing solution] 1-Hydroxyethylidene 1.1-diphosphonic acid (60% aqueous solution) Add 2.5 F water to bring the total volume to 1 liter, and adjust the pH to 7.0 using potassium hydroxide. Table 1: Comparison coupler (1) Yellow (2) Comparison coupler (2) Magenta (3) Cyan Comparative coupler (3) Cyan Each sample that has been color developed in this way was heated at 60°C and 80% RH. The sample was left under a xenon light source (70,000 lux) for 10 days, and the rate of discoloration of the 1.0 wet area of each sample before and after storage was measured using a densitometer. In addition, the stain after storage was visually judged. The results are shown in Table-(2). Table-2 In the table, △,
Medium plug degree, X indicates inferior. The results show that when the three types of foggers according to the present invention are used in greasy sweating, the fading rate of each pigment is surprisingly better than when not used in combination, and since the fading rate is almost constant, the visual acuity is It turns out that it looks neutral gray. Furthermore, staining in unexposed areas is also good. However, materials other than those of the present invention do not have a neutral gray color because the color balance is out of order, and the stain cannot be said to be good.

[Example 11jIJ2] 1-Hydroxyethylidene 1 in the stabilizing solution of Example 1 above
．． When the same treatment as in Example 1 was carried out using a stabilizing solution adjusted to pH 7 except for 1-diphosphonic acid (chelate stability constant 33 relative to Fe') and glycine (chelate stability constant less than 6), the stain became slightly worse. However, this only damages the commercial value.1, Cuff, 92. . . , □YoA U#(m)<Off. [Example 3] Add 1.5F of 2,4-suchloro-6-hydroxy-1,3,5-) riazine sodium salt to the stabilizing solution of Example 1.
When the same experiment as in Example 1 was carried out by adding /II tutle, the fading rate of the dye was improved by 2 to 3% without disturbing the color balance.

[Example 4] Two stabilizing solutions of Example 1 were prepared, and 0.05 g/liter of 2-(4-thiazolyl)benzimidazole and 0.4 N/II of 2-methyl-4-thiazolin 3-one were added. When the same experiment as in Example 1 was carried out by adding each of these, the fading rate of the dye was further improved by 1 to 3 degrees without disturbing the color balance.

[Example 5] A magnetic water activator (11/2 unit, manufactured by Algarid, Australia) having a permanent magnet was installed in the circulation system of the stabilizing liquid tank of Example 1, and an experiment similar to that of Example 1 was conducted. I did it. As a result, the same results as in Example 4 were obtained. Agent Patent Attorney No 1) Written amendment to step-parent proceedings 1, Indication of the case Patent Application No. 125586 of 1981 2, Name of the invention Method for processing silver halide photographic light-sensitive materials 3, Person making the amendment Relationship with the case Patent Applicant Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent: 191 Address: 1-5 Sakura-cho, Hino-shi, Tokyo Date of amendment order: September 5, 1980 (Date of dispatch: September 257, 1980)
iξh6, Specification subject to amendment 7, Contents of amendment As shown in the engraving and attachment of Mei 11A"4 originally attached to the application (no change in content) Procedural amendment 1: May 30, 1985 Commissioner of the Patent Office Shiga Manabu [Body 1]
, Indication of the case 1982 Patent Application No. 1.25586 2 Name of the invention Processing method for silver halide photographic light-sensitive materials 3 Person making the amendment Relationship to the case Patent applicant address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo Konishiroku Photo Industry Co., Ltd., No. 26-2, 1 Sakura-cho, Hino-shi, Tokyo 191 Japan (Telephone: 0425-83-15)
21) Patent Department 4, date of amendment order 5, "Detailed Description of the Invention" column 6 of the specification subject to amendment, content of amendment 1) Add the following compound on page 39 of the specification. "C-13 Procedural Amendment September 17, 1985 Michibu Uga, Commissioner of the Patent Office, 1982 Patent Application No. 125586 2 Title of Invention Method for Processing Silver Halide Photographic Light-Sensitive Materials 3 Person who makes corrections Relationship to the case Patent applicant address: Konishiroku Photo Industry Co., Ltd., 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo, Sakura-cho, Hino-shi, Tokyo (Telephone: 0425-83-152)
1) Patent Part 4, Date of official order 5, "Detailed explanation of the invention" column 6 of the specification to be amended, Contents of the amendment 1) "Detailed explanation of the invention" column of the specification I would like to correct it as follows: 2) Insert the following compound next to page 39. 1”IT-1 (n) C4 〇 -15 H C,,H.

Claims (4)

[Claims] (1) A magenta coupler represented by the following general formula [I], a yellow coupler represented by the following general formula [II],
and after imagewise exposure of a silver halide photographic material containing a cyan coupler represented by the following general formula [III],
Processing of a silver halide photographic light-sensitive material characterized by having at least three steps: a color development process, a process with a processing solution having fixing ability, and a stabilization process that does not include a substantial water washing process. Method. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ar is a phenyl group. Represents a group that leaves. ) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the formula, X_2 represents a halogen atom, an alkoxy group, an alkyl group. A group representing the atomic group required to form a 5- to 6-membered ring with atoms selected from sulfur atoms, and forms a dye by coupling with an oxidized product of an aromatic primary amine color developing agent. Represents a group that sometimes leaves. R_2 represents a group that can be substituted on the benzene ring, m represents an integer of 1 or 2. When m is 2, R_2 may be the same or different.) General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5 represents a linear or branched alkyl group having 1 to 4 carbon atoms, or -NHCOR_6. R_4 and R_6 each represent an alkyl group, an aryl group, or Represents a heterocyclic group. R_3 represents a hydrogen atom or a halogen atom, and Z_2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidation product of a color developing agent.) (2) A method for processing a silver halide photographic material according to claim 1, wherein the stabilizing solution contains a chelating agent having a chelate stability constant of 8 or more with iron (III) ions. . (3) The processing liquid and/or stabilizing liquid having fixing ability contains an epoxy compound, an aziridine compound, an acryloyl compound,
Claim 1 or 2 contains at least one selected from vinylsulfonyl compounds, triazine compounds, isoxazolium compounds, sulfonic acid ester compounds, carbodiimide compounds, maleimide compounds, and isocyanate compounds. A method for processing a silver halide photographic material as described in . (4) Processing of the silver halide photographic light-sensitive material according to claim 1, 2, or 3, characterized in that the stabilizing solution is treated with at least one of the following anti-mildew means: Method. [Mold-proofing means] (A) Means of adding a mold-proofing agent. (B) Means for passing through a magnetic field. (C) Means for irradiating ultraviolet rays.