JPS62103643A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration of resistance to color fading, particularly at high temp. and at high humidity by treating a photosensitive material with a color developer contg. no benzyl alcohol to develop color, treating then with a treating liquid having fixing effect contg. an iodide, treating further with a stabilizing soln. contg. no aldehyde compd. in place of washing with water in combination with above described treatment. CONSTITUTION:After image-exposing a photosensitive material having >=10mum dry film thickness in total of the thickness of a photosensitive silver halide emulsion layer and a non-photosensitive layer, the material is treated with a color developing soln. contg. no benzyl alcohol, then with a fixing soln. having fixing effect and contg. >=10<-3>mol/l iodide, then treating further with a stabilizing soln. in place of water washing having 8-50dyne/cm surface tension contg. no aldehyde compd. and drying after the treatment. The amt. of the iodide to be contained in the fixing soln. is >=10<-3>mol/l, most pref. 2X10<-3>-2X10<-2>mol/l. Among materials giving 8-50dyne/cm surface tension to the 2nd stabilizing soln., such compd. giving 15-40dyne/cm surface tension is most preferred.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a processing method for silver halide color photographic materials (hereinafter referred to as "photosensitive materials") that eliminates the washing process, and more specifically, to improve the storage durability under light irradiation at high temperature and high humidity through continuous processing. The present invention relates to a method for anhydrous washing of photosensitive materials.

[Conventional technology]

Generally, after image exposure, photosensitive materials are processed through processing steps such as color development, bleaching, fixing, stabilization, bleach-fixing, and water washing. In recent years, depletion of water resources and increased costs for washing due to rising crude oil prices have become increasingly serious problems in such treatment processes. For this reason, as a method of omitting the washing process or extremely reducing the amount of washing water, a multi-stage counter-current stabilization treatment technique such as that described in JP-A No. 57-8543 and JP-A No. 58-134636 have been proposed. A treatment technique using a water washing substitute stabilizing solution containing a bismuth complex salt as described in the publication has been proposed. However, in the process using a water washing alternative stabilizing solution, the total amount of replenishment solution to the stable tank solution is 6 times the stable tank capacity.
~ If continuous processing is carried out over a long period of time to increase the amount by more than 7 times,
It was found that color staining occurred in the processed photosensitive material, resulting in staining. It has been found that the occurrence of staining is a serious problem that deteriorates the storage durability when a dye image is stored, especially under light irradiation at high temperature and high humidity. Furthermore, it has been found that the above-mentioned staining is more likely to occur when the processing liquid having fixing ability contains iodide ions.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a processing method that prevents the deterioration of the storage stability of dye images when continuously processed using a water-washing substitute stabilizing solution, especially the deterioration of the original color property under high temperature and high humidity. .

[Structure of the invention]

As a result of intensive research, the present inventors discovered that after imagewise exposure of a photosensitive material having a total dry film thickness of a photosensitive silver halide emulsion layer and a non-photosensitive layer on one side of a support of 10 μm or more, benzyl alcohol was used. After processing with a color developing solution substantially free of iodide, processing with a fixing solution having a fixing ability containing 10-' mol/l or more of iodide, followed by a fixing solution with a surface tension of 8 to 50
It has been found that the object of the present invention can be achieved by a treatment method in which the product is treated with a water-washing substitute stabilizing solution that is dyne and does not substantially contain an aldehyde compound, and then dried. The present inventors have also found that, as a preferred embodiment of the present invention, the effects of the present invention are more pronounced when the light-sensitive material contains a sensitizing dye represented by the following general formula [I]. General formula (1) In the formula, ZI and Z are each a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzimidazole nucleus, a naphthoimidazole nucleus, a pyridine nucleus or represents an atomic group necessary to form a quinoline nucleus, RI and R7 each represent an alkyl group, an alkenyl group, or an aryl group, R3 represents a hydrogen atom, a methyl group, or an ethyl group, and X1e represents an anion. , Q is 0 or! represents. The present invention will be further explained below. In the conventional water washing process after development, bleaching, and fixing, there are many! The washing water of 'Ii removes the emulsion composition and processing solution composition (including color developing agent, benzyl alcohol, bleach, thiosulfate, etc.) from the inside of the light-sensitive material and the surface of the light-sensitive material.
Or all of those reactants, oxidizing substances, etc. were washed away. Therefore, in the treatment using a water washing substitute stabilizing solution without the water washing process, all of these components are eluted and accumulated in the stabilizing solution. In particular, when the amount of replenishment of the water washing substitute stabilizing solution is small, the accumulated concentration of the substance to be cleaned increases. Furthermore, the renewal rate of the water-washing alternative stabilizer decreases, resulting in long-term storage, and due to the coloring components of the above-mentioned substances in the washing-alternative stabilizer, the washing-alternative stabilizer is quite colored, making it difficult to wash with water. It is presumed that these coloring components are adsorbed onto the photosensitive material in the alternative stabilizing solution, or their washing out from the photosensitive material is suppressed, thereby contaminating the photosensitive material and promoting deterioration in image storage. Benzyl alcohol has generally been used as a development accelerator in color developing solutions for a long time. It is also well known that formalin, which is an aldehyde compound, is used in the final stabilizing solution for the purpose of image stability in the final step of ordinary color processing steps. However, after a photosensitive material with a dry film thickness of 10 μm or more is color-developed with a color-developing solution that does not contain benzyl alcohol, it is processed with a processing solution that has a fixing ability and contains 10-3 mol/l or more of iodide. It was surprising that the above-mentioned problems peculiar to the washing substitute stabilizing solution could be solved by combining a washing substitute stabilizing solution having a molecular weight of 8 to 50 dyne and containing no aldehyde compound. Furthermore, it has been found that the present invention is extremely effective for light-sensitive materials containing the sensitizing dye represented by the general formula [I]. In the present invention, processing with a processing solution having fixing ability after color development refers to a process using a fixing bath or a bleach-fixing bath for the purpose of fixing the light-sensitive material after processing with a normal color developer. . That is, the present invention solves the problem of using a water-washing alternative stabilizer after color development and treatment with a constant bleach bath or a bleach-fix bath. It is particularly effective for In the present invention, the iodide contained in the processing solution that improves the fixing ability (T) is one that releases iodide ions such as potassium iodide, sodium iodide, ammonium iodide, and silver iodide. There is a method of incorporating iodide into a fixing solution or a bleach-fixing solution through continuous processing, by directly adding it to the tank solution and replenisher solution, or by incorporating it into the photosensitive material. 10-
The content is preferably 10-3 to 5X 1 (I'mol/l), and most preferably 2X103 to 2x10-t mol/l. In the invention, when processing with a processing solution having fixing ability and subsequently processing with a washing substitute stabilizing solution without substantially washing with water, the fixing bath or bleach-fixing bath is directly followed by processing with the washing substitute stabilizing solution. This processing step is completely different from the conventionally known steps of washing with water and treating with a stabilizing solution after a fixing bath or bleach-fixing bath.Thus, in the present invention, Processing using a stabilizing solution instead of washing with water refers to processing for stabilization treatment that is performed immediately after processing with a processing solution that has fixing ability and does not substantially require washing with water, and the processing solution used for the stabilization processing. is referred to as a water washing substitute stabilizing solution, and the treatment tank is referred to as a stabilizing bath or a stabilizing tank. In the present invention, the effect of the present invention is greatest when the number of stabilizing tanks is 1 to 5, and particularly preferably 1 to 3. 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, and the weaker the effect of the present invention will be. Measured using the general measurement method described in "Analysis and Test Methods of Surfactants" (co-authored by Fumio Kitahara, Shigeo Hayano, and Betsu Hara, published March 1, 1982, published by Kodansha Co., Ltd.). In the present invention, the surface tension value is determined by a normal general measuring method at 20°C.The stabilizer of the present invention has a surface tension of 8 to 50 dyne/cm.
(20°C) may be used, but in particular, the following general formula CI+ ), general formula [
II] and water-soluble f1° mechanical siloxane compounds are particularly preferably used from the viewpoint of effectiveness toward the object of the present invention. ~, hereafter, 1ゝ1, -'/ General formula CII) A O(B)m Xt In the formula, A is a monovalent organic group, for example, a group having 6 to 20 carbon atoms
, preferably an alkyl group of 6 to 12, hexyl,
Represents heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc. or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms, such as propyl, butyl, pentyl, hexyl, heptyl, octyl, Represents nonyl, decyl, undecyl, dodecyl, etc. Aryl groups include phenyl, tolyl, xylyl,
Biphenyl or naphthyl, preferably phenyl or tolyl. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions. B represents ethylene oxide or propylene oxide,
m represents an integer of 4 to 50. X is a hydrogen atom, so, y
or PO3Yt, where Y is a hydrogen atom, an alkali metal (
(Na%K or Li, etc.) or ammonium ion. General formula (111) ■, 4 R6 In the formula, R6, R1, R8 and R7 each represent a hydrogen atom, an alkyl group, or a phenyl group, but the total number of carbon atoms of %R4, R6, R6 and R7 is 3 to 3. It is 50. x3 is a halogen atom, hydroxyl group, sulfuric acid group, carbonic acid group, nitric acid group, acetic acid group,
Indicates an anion such as p-toluenesulfonic acid group. The water-soluble organic siloxane compound of the present invention can be used, for example, in JP-A-47-18333, JP-B-55-51172,
It means general water-soluble organic siloxane compounds such as those described in Japanese Patent Publication No. 51-37538, Japanese Patent Application Laid-open No. 49-62128, and US Pat. No. 3,545,970. Next, specific representative examples of the compounds represented by the general formulas (II) and (III) and water-soluble organic siloxane compounds of the present invention will be listed. Example of the compound represented by 1) 11-I C,, H, 50 (Ct) 1.0). II
H-2C,I(,70(C,3H,O), JII-3
C111100 (Ctl140)4SOJa11-4
Cl011t10(CJ40)+5POJa2 (Example of compound represented by general formula ([)) C■3 CH. CI! . 11m (Water-soluble if-functional siloxane compound) ■ N 1 (CIIJ*St OSt OStωI+
,)3C311d-IIaholl 1V-2(CIla)*Si-0-Si-0-Si(
CIIs)*CJs(()C-11,i.011 CII. N 3 (CIIs)isi O+Si O÷, 5i
(CI!3)sC,118@C! If, MCII. C.B. N4 (C1la), lsi-O5i-0-3i
(C1ls)3c3na@cln4+ osi(C11
3) sIV 5 (C113)*Si -0-3i-
0-5i(C113)-wordC3H〆OC*lI4MC11*CI. 1V 6 (CH3)-5i OSi O5
i (CB Yu) C yo H-+ 0Ctll-+11 C3■s + 0CtL +l tO-Si (CH3
)3 ■ CJs + MiQC, II4). -3i(CIlz)aIV
-10(Cl-)3Si-OSi O5i(Cn-)
sC,11,-G OC,H,-90C,■5fold (CI, CI+, 0+1.II a+b=41 Among the water-soluble organic siloxane compounds, the compound represented by the following general formula (IV) is particularly preferred. , is more preferably used in the present invention in order to achieve the desired effect of the present invention.General formula [■] In the formula, R8 is a hydrogen atom, a hydroxy group, a lower atom, or a lower alkyl group (preferably a carbon atom). represents an alkyl group having a number of 1 to 3, such as methyl, ethyl, propyl, etc.), and R8, RIG, and R in iq may be the same or different, respectively. n represents an integer of 1 to 4; , p and q represent integers from 1 to 15. In the present invention, Goret et al.
Among the things that exceed 50 dync/cm, especially 1
What gives a surface tension of 5 to 40 dyne/cm is
It is particularly preferably used from the viewpoint of the effect on the present invention. These compounds represented by the general formulas (II) and (III) and the water-soluble organic siloxane compounds may be used singly or in combination. Further, good effects can be obtained when the amount added is in the range of o, oi to 2Qg per 1Q of stabilizing liquid. In the present invention, a water-washing alternative stabilizing solution that does not substantially contain aldehyde compounds refers to a water-washing alternative stabilizing solution that is added to the final stabilizing solution in a conventional processing step that involves washing with water for the purpose of improving the storage stability of dye images.
．． It refers to a water washing alternative stabilizing solution in which the concentration of aldehyde added at 5 to 2.0 g/l is 0.1 g/12 or less. 0.
A concentration of approximately 0.02 g/l falls within the range of substantially no content, but it is particularly preferable that no content be present at all. The aldehyde used in the stabilizing bath in the conventional treatment process is exclusively formaldehyde, and other aldehydes include glutaraldehyde, chloral, mucochloric acid, sodium formaldehyde bisulfite, sodium glutaraldehyde bisbisulfite, etc., but the water washing alternative stabilizer of the present invention Liquids not only deteriorate the storage stability of dye images but also cause precipitate formation and other problems. In the sensitizing dye represented by the general formula (II) used in the present invention, the nucleus represented by Zl and Z may be substituted, and the substituent is a halogen atom (for example, chlorine).
, alkyl groups (e.g. methyl, ethyl), alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl)
, an aryl group (eg, phenyl), a cyano group, and the like. The alkyl group and alkenyl group represented by R1 and R7 preferably have 5 or less carbon atoms, and preferably R1 and R7.
, is an alkyl group. Specific compounds of the sensitizing dye represented by general formula [I] are shown below, but are not limited thereto. CI-■] [1-3] C, 11゜ Cl-5) ([-7) CI-9) (1-IQ) (1,-13) CI-14) Cl-161 (C11,) islJ+H (1-IT) (T-19) (CIl, JySOJa S030 CI-23) The amount of the sensitizing dye represented by general formula (11) to be added to the emulsion is 2X10-"- per mole of silver halide. IXIO
-''' mole range is suitable, preferably 5 x 10-
"~sx io-' moles. Many of the above-mentioned sensitizing dyes are green-sensitive or male in light-sensitive materials.
A sensitizing dye having a spectral sensitizing ability in a wavelength range called sensitization, and the light-sensitive material used in the present invention must be spectral sensitized with the above-mentioned sensitizing dye to the extent permitted by the spectral sensitizing ability. Preferably, the majority (50 mol % or more) of the sensitizing dyes in at least the green-sensitive emulsion and the blue-sensitive emulsion are the above-mentioned sensitizing dyes. It is preferable that the water washing substitute stabilizer of the present invention contains an antifungal agent. Preferably used antifungal agents include salicylic acid,
Sorbic acid, dehydroacetic acid, hydroxybenzoic acid compounds, alkylphenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, These are isoxazole compounds, propatoolamine compounds, sulfamide derivatives, and amino acid compounds. The hydroxybenzoic acid compounds include hydroxybenzoic acid and ester compounds of hydroxybenzoic acid such as butyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester, isobutyl ester, and hydroxybenzoic acid. It is a propyl ester, and more preferably a mixture of the three types of hydroxybenzoic acid esters. Alkylphenol compounds have an alkyl group with 1 carbon number
It is a compound having ~6 alkyl groups as a substituent, preferably ortho-phenylphenol and ortho-cyclohexyphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a 5-membered ring, and preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isodeazolin 3
-one, 2-year-old cutyl-4-isodeazolin-3-one,
5-chloro-2-methyl-4-isothiazolin 3-one, 2-(4-deazolyl)benzimidazole. Specifically, pyridine-based compounds include 2,6-dimethylpyridine, 2,4,6-drimethylpyridine, radium-2-
Among them, radium-2-pyridinethiol-1-oxide is preferable. Specific examples of the guanidine compound include cyclohexidine, polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred. Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate. Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetraalkylphosphonium salts are preferred, and more specific preferred compounds are tributyl-tetradecylphosphonium chloride and triphenyl-nitrophenylphosphonium chloride. It is. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridinium salts, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, laurylpyridinium chloride, etc. be. Specifically, urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-90lophenyl)urea, N-(
3-1-lifluoromethyl-4-chlorophenyl)-N
'-(4-chlorophenyl)urea, etc. Isoxazole compounds are specifically 3-hydroxy-
Examples include 5-methyl-isoxazole. Propertoolamine compounds include n-propertools and isopropertools, specifically DL-2-benzylamino-1-propertool, 3-diethylamino-
1-Propertool, 2-dimethylamino-2-methyl-
1-propatur, 3-amino-1-propatur, idopropaturamine, diisopropaturamine, N
Examples include N-dimethyl-isopronolamine. Sulfamide derivatives specifically include fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, sulfanilamide, acetosulfamine, sulfapyridine, sulfaguanidine, sulfathiazole,
Examples include sulfadiazine, sulfamethacine, sulfamethacine, sulfine oxazole, homosulfamine, sulfisomidine, sulf7guanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole, and the like. A specific example of the amino acid compound is N-lauryl-β-alanine. Among the above-mentioned antifungal agents, compounds preferably used in the present invention are pyridine compounds, guanidine compounds, and quaternary ammonium compounds. The antifungal agent is added to the washing substitute stabilizing solution in an amount of 0.002 g to 50 g, preferably 0.005 g to 10 g, per washing substitute stabilizing solution IQ. In order to more effectively achieve the present invention, I)H of the water washing substitute stabilizing solution in the present invention is preferably 3.0 to 0.0.
pI is in the range of 0, more preferably pI-15.0 to 9.
5, particularly preferably p) 16. Q~9.0
is within the range of As the pH adjusting agent that can be contained in the water washing alternative stabilizer of the present invention, any commonly known alkaline agents or acid agents can be used. The present invention is most effective when the amount of water-washing substitute stabilizing solution refilled into the stabilizing bath is small, and the replenishing amount ranges from 1 to 50 times the amount brought in from the previous bath per unit area of the photographic material to be processed. Preferably, the effect of the present invention is particularly significant in the range of 2 to 20 times. The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time. Especially +i;j tank 2
It is desirable to sequentially process with 0% to 50% additional processing time. When the method for supplying the washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multi-tank countercurrent method, it is preferable to supply it to the rear bath and overflow from the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated solution to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. Although there are various methods such as using it as a supply liquid, it may be added by any method. The bleaching solution or bleach-fixing solution used in the present invention preferably contains an organic acid ferric complex salt as a bleaching agent. Representative examples of organic acids that form organic acid ferric complex salts include the following. (1) Diethylenetriaminepentaacetic acid (Ml=393.
27) (2) Diethylenetriaminepentamethylenephosphonic acid a+i= 573.12) (3) Cyclohexanediaminotetraacetic acid (+aw= 36
4.35) (4) Cyclohexane diamine tetramethylene phosphonic acid (MW = 508.23) (5) Triethylenetetramine hexaacetic acid (MT = 364
．． 35) (6) Triethylenetetramine hexamethylenephosphonic acid (MW = 710.72) (7) Glycol ether diamine tetraacetic acid (M? = 3
80.35) (8) Glycol ether diamine tetramethylene phosphonic acid (MY = 524.23) (9) 1,2-diaminopropane tetraacetic acid (lH = 30
6.27) (10) 1.2-diaminopropane tetramethylenephosphonic acid (: MY = 450.15) (11) 1.3-diaminopropane-2-ol tetraacetic acid (MW = 322.27) (12) 1 , 3-diaminopropan-2-ol tetramethylenephosphonic acid (MW = 466.15) (13)
Edgelenediamine diorthohydroxyphenylacetic acid (M
W = 360.37) (I4) Ethylenediamine diorthohydroxyphenyl methylene phosphonic acid (MW 2432.31) (I5) Ethylene diamine tetramethylene phosphonic acid (MW = 436)
．． 13) (16) Ethylenediaminetetraacetic acid (MW = 292.2
5) (17) Nitrilotriacetic acid (Mf = 191.14)
(18) Nitrilotrimedylenephosphonic acid (MW = 2
99.05) (19) Iminoniacetic acid (MT= 133.IQ) (20
) Iminodimethylenephosphonic acid (MW=205.04
) (21) Methyliminodiacetic acid (Mf = 147.13
) (22) Methyliminodimethylenephosphonic acid (Mf=
219.07) (23) Hydroxyethyliminodiacetic acid (M'W-17
7,16) (24) Hydroxyethylimino dimethylene phosphonic acid (Mw = 249.10) (25) Ethylenediaminetetrapropionic acid (Mf =
348.35) (26) Hydroxyethylglycidine (MW=163
．． 17) (27) Nitrilotripropionic acid (M1=
233.22) C28) One type can be arbitrarily selected and used from among them, and two or more types can be used in combination as necessary.Among the organic acids forming the hexagonal acid ferric salt used in the present invention, particularly Preferred examples include the following: (1) Diethylenetriaminepentaacetic acid (MY=393.
27) (3) Cyclohexanediaminotetraacetic acid (MW=
364.35) (5) Triethylenetetraminehexaacetic acid (
MllI = 494.45) (7) Glycol ether diamine tetraacetic acid (MW = 380.35) (9) t,2-diaminopropane tetraacetic acid (Castle 1 = 30
6.27) (11) 1,3-diaminopropan-2-ol tetraacetic acid (MY = 322.27) (19) Iminoniacetic acid (MW = 133.10) (21
) Methyliminoniacetic acid (M1 = 147.13) (23
) Hydroxyedyliminoniacetic acid (M-177,16
) (28) ethylenediamine diacetic acid (MW = 176.
17) The organic acid ferric complex salt used in the present invention is a free acid (
Hydrogen salts), alkali metal salts such as sodium salts, potassium salts, and lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine, but preferably potassium salts, sodium salts, and ammonium salts are used. be exposed. These bleaching agents are used in amounts of 5 to 450 g/Q, more preferably 20 to 2509 g/Q. The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, a solution containing saliva sulfate as a preservative is applied. In addition, a bleach-fix solution consisting of a hexagonal acid iron (III) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halide such as ammonium bromide may be used. many + a
A bleach-fixing solution consisting of a composition added to an organic acid iron (
III) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used. Silver halide fixing agents contained in fixing solutions and bleach-fixing solutions include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate and sodium thiosulfate, which are used in normal fixing processes. Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium diocyanate, thioureas, and thioethers. These fixing agents are used in an amount of 59/l or more, within the range that can be dissolved, but generally 70 g to 250 y
Use with /l. The fixing solution and bleach-fixing solution include the above-mentioned fixing agent, and compounds other than the iodide of the present invention such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and acetic acid. , sodium acetate, ammonium hydroxide, and the like may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, organic chelating agents such as hydroxylamine, hydrazine, and aminopolycarboxylic acids, and stabilizers such as nitroalcohols and nitrates,
Organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained. The bleach-fix solution used in the present invention includes Japanese Patent Publication No. 46-280, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 46-556, Belgian Patent No. 770.910, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854. , JP-A No. 5441634 and No. 49
Various bleach accelerators described in Japanese Patent No. 42349 and the like can be added. The pH of the bleach-fix solution is used at 4.0 or higher, but generally it is used at a pH of 5.0 or higher and pH 9.5 or lower, preferably at a pH of ptts, o or higher and pH 8.5 or lower, and more preferably at a pH of 8.5 or higher. (is processed at a temperature of 6.5 or more and 8.5 or less. The processing temperature is 80°C or less, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank. The photosensitive material used in the method of the present invention is one in which a silver halide emulsion layer and a non-photosensitive layer (non-emulsion layer) are coated on a support. As the silver halide emulsion, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, etc. is used. These emulsion layers and non-light-sensitive layers may contain any couplers and additives known in the photographic industry, such as yellow dye-forming couplers, magenta dye-forming couplers, cyan dye-forming couplers, stable dye-forming couplers, etc. agents, sensitizing dyes, gold compounds, high-boiling organic solvents, antifoggants, dye image fading inhibitors, color stain inhibitors, optical brighteners, antistatic agents, hardeners, surfactants, plasticizers, wetting agents and an ultraviolet absorber, etc. The photosensitive material used in the method of the present invention may contain +
Each constituent layer such as an emulsion layer and a non-photosensitive layer containing various photographic additives such as those described in IRF is placed on a support that has been subjected to corona discharge treatment, flame treatment or ultraviolet irradiation treatment.
Alternatively, it can be manufactured by coating on a support via a subbing layer and an intermediate layer. Advantageously used supports include, for example, baryta paper,
Examples include polyethylene coated paper, polypropylene synthetic paper, glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polyamide films. Most of the silver halide emulsion layers and non-photosensitive layers are usually hydrophilic colloid layers containing a hydrophilic binder. This hydrophilic binder includes gelatin,
Alternatively, 14 gelatins such as acylated gelatin, guanidylated gelatin, phenylcarbamylated gelatin, phthalated gelatin, cyanoethanolated gelatin, and esterified gelatin are preferably used. Examples of hardening agents for hardening this hydrophilic colloid layer include chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
dimethylolurea, methyloldimethylhydantoin, etc.) dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-8-)lyazine, 1,3-vinylsulfonyl- active/%rogen compounds (2,4-dichloro-6-hydroxy-8-
triazines, etc.), mucohalogen acids (mucochloric acid,
mucophenoxychloric acid, etc.), etc. 111 may be used alone or in combination. Further, the present invention is particularly effective when the photosensitive material is of the so-called oil-protected type, which contains a coupler dispersed in a high-boiling organic solvent. Examples of the high-boiling organic solvent include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., especially diethyl phthalate, diethyl phthalate, di-propylphthalate,
Di-butyl phthalate, di-n-octyl phthalate,
Phthalate esters such as di-propyl phthalate, cyamyl phthalate, dinonyl phthalate, diisodecyl phthalate, phosphate esters such as tricresyl phosphate, triphenyl phosphate, tri(2-ethylhexyl) phosphate, trinonyl phosphate, dioctyl seba Kate, G (2-ethylhexyl)
Sebacic acid esters such as sebacate and diisodecyl sebacate, glycerin esters such as glycerol tripropionate and glycerol tribudylate, others, adipic acid esters, geltaric acid esters, succinic acid esters, maleic acid esters, phthalic acid esters, and citric acid. The effects of the present invention are great when using phenol derivatives such as ester, ')-tert-amylphenol, and n-octylphenol. The layer structure of the light-sensitive material used in the present invention can be a structure known for color negative films, color papers, and reversal color films, such as a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler in one of the supports. ,
A green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler and a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler (each of these color-sensitive layers may be one or two layers).
(consisting of more than one layer) is included. It is preferable to use a cyan coupler represented by the following general formula (V) or (Vl) in the photosensitive material used in the present invention. General formula (V) 0■ General formula (Vl) In the formula, Y' is -COR', -CONllCOR'z or -CON II SO□
R'2 (1'l'2 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R/
, represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, R/2 and R
', and may be combined with each other to form a 5- or 6-shell ring. ), R'1 represents a ballast group, and 2' represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent. Here, R'2 is an alkyl group, preferably having 1 to 2 carbon atoms.
0 alkyl groups (e.g. methyl, ethyl, t-butyl,
dodecyl, etc.), alkenyl group preferably having 2 to 20 carbon atoms
alkenyl groups (e.g. allyl group, heptadecenyl group, etc.), cycloalkyl groups, preferably those with 5- to 7-membered rings (
(e.g., cyclohexyl), aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), heterocyclic group, preferably a 5- to 6-shell heterocyclic ring containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms. Represents a group (eg, furyl group, chenyl group, benzothiazolyl group, etc.). R'3 represents a hydrogen atom or a group represented by R/2. R'2 and R'
3 may be bonded to each other to form a 5- to 6-membered heterocycle containing a nitrogen atom. Note that any substituent can be introduced into R/2 and R/, for example, a group having 1 to 1 carbon atoms.
10 furkyl groups (e.g. ethyl, i-propyl, i-
butyl, t-butyl, t-octyl, etc.), aryl group (
(e.g., phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g., methanesulfonamide, butanesulfonamide, p-)luenesulfonamide h! P), sulfamoyl groups (e.g. methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl,
p-) luenesulfonyl, etc.), fluorosulfonyl, carbamoyl groups (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl groups (
Examples include acetyl, benzoyl, etc.), heterocyclic groups (eg, pyridyl, pyrazolyl, etc.), alkoxy groups, aryloxy groups, and acyloxy groups. In the general formula (V) Ogori (Vl), R/1 is a compound that imparts diffusion resistance to the cyan coupler represented by the general formula [V] Ogori (VI) and the cyan dye formed from the cyan coupler. represents the pallast group required for Preferred are alkyl groups, aryl groups, and heterocyclic groups having 4 to 30 carbon atoms. Examples include straight-chain or branched alkyl groups (for example, thi-butyl, n-octyl, shi-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, penta- or hexa-ring heterocyclic groups, and the like. In the general formulas [■] and (VI), Z' represents a hydrogen atom* and a group capable of being separated during a coupling reaction with an oxidation product of a color developing agent. For example, halogen atoms (e.g. chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic groups Examples include a sulfonamide group, a sulfonamide group, and more specific examples include U.S. Pat.
No. 5, Special Publication No. 1973-36894, Japanese Patent Application Publication No. 1972-101
No. 35, No. 50-117422, No. 50-13044
No. 1, No. 51-108841, No. 50-120343
No. 52-18315, No. 53-105226,
No. 54-14736, No. 54-48237, No. 55
-32071, 55-65957, 56-19
No. 38, No. 56-12643, No. 56-27147, No. 59-146050, No. 59-166956,
No. 60-24547, No. 60-35731, No. 60
-37557, those described in each publication can be mentioned. In the present invention, among the cyan couplers represented by the general formula [■] or (Vl), the following general formula [■], [
■] or the remainder below the shea represented by (IX) [7''F, 2' General formula [■] General formula [■] l General formula (IX) In the general formula [■], R' is substituted or unsubstituted. It is a substituted 7-aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent is -502R
's, halogen atoms (e.g. fluorine, bromine, chlorine, etc.),
-Ch, -NO□, -CM, -COR', -COOI
At least one substituent selected from I'i-SO□OR'6 is included. Here, R'6 is an alkyl group, preferably having 1 to 2 carbon atoms.
0 alkyl groups (e.g., methyl, ethyl, tert-butyl, dodecyl, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (e.g., allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5~
7-shell ring group (e.g. cyclohexyl group, etc.), 7-aryl group (
For example, phenyl group, tolyl group, naphthyl group, etc.),
R'7 is a hydrogen atom or a group represented by R/6 above. A preferred compound of the phenolic cyan coupler represented by the general formula [■] is one in which R/4 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, 21-unit, -3D□R' , (R' is a furkyl group), a halogen atom, and tri7fluoromethyl. In the general formula [■] and (IXI, R6 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g., methyl, ethyl, tert-butyl, dodecyl, etc.), an alkenyl group, preferably a carbon number 2 to 20 Alkenyl group (
For example, allyl, oleyl, etc.), cycloalkyl group, preferably 5 to 7 shell ring group (for example, cyclohexyl, etc.), aryl group (for example, phenyl group, tolyl group, naphthyl group, etc.)
, heterocyclic group (preferably a 5- to 6-shell heterocyclic ring containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms,
Examples include furyl group, chenyl group, benzothiazolyl group, etc.). Said R'61R'? And R/ in general formulas [■] and [■] can further introduce an arbitrary substituent, specifically, R in general formulas [■] and (VI)
These are substituents that can be introduced into '2 or R'3. As the substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable111. In the general formulas [■], [■] and (IX), Z' and R+ have the same meanings as in the general formulas (V) and (V[], respectively.The ballast group represented by R/1 A preferable example is a group represented by the following general formula (X): General formula (X) In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, and k represents an integer of O to 4, Party indicates 0 or 1, k
If is 2 or more, two or more R/,. may be the same or different (, R/, represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group, R1° represents a -valent group, preferably hydrogen atoms, halogen atoms (e.g. chromium, bromine), alkyl groups, preferably linear or branched alkyl groups having 1 to 20 carbon atoms (e.g. methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl , 7-enethyl, etc.), aryl groups (e.g. phenyl groups), heterocyclic groups (preferably nitrogen-containing heterocyclic groups), alkoxy groups, preferably linear or branched alkoxy groups having 1 to 20 carbon atoms ( For example, methoxy, ethoxy, 1-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (e.g. phenoxy), hydroxy, acyloxy groups, preferably alkylcarbonyloxy groups, arylcarbonyloxy groups (e.g. acetoxy) group, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably a straight-chain or branched fulkyloxycarbonyl group having 1 to 20 carbon atoms, aryloxycarbonyl group, preferably phenoxycarbonyl,
Alkylthio group, preferably 1 to 20 carbon atoms, acyl group, preferably linear or branched fulkylcarbonyl group having 1 to 20 carbon atoms, 7 acylamide groups, preferably 1 carbon number
~20 straight chain or branched furkylcarboxamide, benzenecarboxamide, sulfonamide group, preferably straight chain or branched furkyl sulfonamide group or benzenesulfonamide group, carbamoyl group having 1 to 20 carbon atoms, preferably represents a straight-chain or branched fulkylamino-7carbonyl group or phenylami-7carbonyl group having 1 to 20 carbon atoms, a sulfamoyl group, preferably a straight-chain or branched fulkylamino-7sulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms. . Next, specific examples of cyan couplers represented by formula (V) or (Vl) will be shown, but the invention is not limited thereto. 1'-ゝ\, [Compound example] C4H. C2H1 C-7 C2H5 C, 11°Hz CH. C-1F C-20 C-21 Shil Olh l C-32 C-35 H C,H,. C-45 C-46 Song C2H. HC Mi Q n++ 0■ 0H H il Shimi -6roH H 0■ (C!I2hOC211s OC-76 Curved Mi HC-92 C-93 Shimi These cyan couplers are synthesized by known methods. For example, US Pat. No. 2,772,162, US Pat. No. 3,758,308, US Pat.
No. 1124.396, 3. zzzz; No. 176, British Patent No. 975, No. 773, No. 8,011,693, No. 8
, No. 011,894, JP-A-47-21139, No. 5
No. 0-112038, No. 55-163537, No. 56
-29235, 55-99341, 56-11
No. 6030, No. 52-69329, No. 56-5594
No. 5, No. 56-80045, No. 50-134644, as well as British Patent No. 1,011,940, US Patent No. 3,
No. 446,622, No. 3,996,253, Japanese Unexamined Patent Publication No. 1973
No. 6-65134, No. 57-04543, No. 57-2
No. 04544, No. 5 Fu No. 204545, Patent Application No. 1983-
No. 131312, No. 56-131313, No. 56-1
No. 31314, No. 5B-131309, No. 56-13
No. 1311, No. 57-149791, No. 56-130
No. 459, JP-A-59-146050, JP-A No. 16695
No. 6, No. 80-24547, No. 60-35731,
It can be synthesized by the synthesis method described in No. 60-37557 and the like. In the present invention, the cyan coupler represented by the general formula [V) or [7] may include:
It can be used in combination with conventionally known cyan couplers. Further, cyan couplers of general formulas (V) and (VI) can also be used together. When the cyan coupler according to the present invention represented by general formula (V) or (Vl) is contained in a silver halide emulsion layer, it is usually about 0.005 to 2 mol per mol of silver halide,
It is preferably used in a range of 0.01 to 1 mol. The water washing alternative stabilizer in the present invention has the following general formula (XI)
It is preferable to contain a chelating agent represented by ~[X■]. General formula (XI) MLIl+”110310 General formula [■) Mn+2PnLn++ General formula ()it
) Δ'-I'll -Zl -R2-C00I
I General Formula (XIVI In the formula, E is a substituted or unsubstituted fullkylene group, cycloalkylene group, 7z nylene i, -R2OR2, -R?-
OR'OR'- or -R7ZIR represents Fu, Z is >
N-R'-A' or >N-A', R1-R7 each represents a substituted or unsubstituted fullkylene group, A'-A' each represents a hydrogen atom, -OH, -CoOM or -PO, M2 represents a hydrogen atom or an alkali metal atom, m represents an integer of 3 to 6, and n represents an integer of 2 to 20. General formula (X V ) R'N (CH2PO, M□)
In formula 2, R8 is a lower alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing hexacyclic group (1○H1-OR as an e substituent).
or -COOM), and M represents a hydrogen atom or an alkali metal atom. General formula (XVI) lI RIG R11 In the formula, Rs ~ R
"represents a hydrogen atom, -OH, lower fulkyl (unsubstituted or as a substituent -OH. -COOM or 1!-PO, M2), B co-B'+! each represents a hydrogen atom, -OH , -Co. M, -PO, M2 or -NJ, where J is a hydrogen atom,
It represents a lower furkyl group, -C2H, OH or -PO3M2, M represents a hydrogen atom or an alkali metal atom, and nl and 1 each represent 0 or 1. General formula [X■] N R"-0-P-OR+" In the formula, R12 and R1' are each a hydrogen atom, an alkali metal atom, an alkyl group of 01 to CI□, a fulkenyl group or a cyclic alkyl group of 01 to CI2 , M is the general formula (XV
I agree with I). General formula (XVI
1□ dialkyl amide 7 groups, ami 7 groups %01-2, allyloxy group, C6-2. represents 7 arylamide groups and an amyloxy group, and Q1 to Q3 are respectively -〇H, C, ~24
Fulkyre group, aralkyloxy group, amyloxy group,
-〇M', (M' represents a cation), an ami7 group, a morpholif group, a cyclic amino group, an alkyl7mi7 group, a dialkylamino group, a 7lylami7 group, or an alkyloxy group. General formula (XIX) I General formula (XX) In the formula, RI5. R18, R+? and R1'' each represent a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted 7enyl group.R3%?R2'
lR” and 1/R22 each have a hydrogen atom or 1 carbon atom
- represents an alkyl group of 18. General Formula [XXI] In the formula, R22 and R24 represent a hydrogen atom, a halogen atom, or a sulfonic acid group. General formula (XXII) In the formula, R2S and R2m are each a hydrogen atom, a phosphoric acid group, h
Rubonic acid group, -CHzCOOH*-CH, PO, H. or a salt thereof, Xl represents a hydroxyl group or a salt thereof, W, Z2 and Yl are each a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a salt thereof, represents an alkoxy group or an alkyl group, 112 represents 0 or 1, n2 represents an integer of 1 to 4, p represents an integer of 0 to 3, and q represents an integer of θ to 2. The chelating agents represented by the general formulas (XI) to (XXI[) [exemplary chelating agents] (1) Na=P-0,t (2) Na
3P30g (3) II, P, 0?
(,4) II 9 P 30 ,. (5) Na6P40+:+ (15) (HOC2H,)2NCH2COOIl
CII2COONa PO,II IIPO311
2PO3H2 CH3C-COONa CH-COO
HPO3Na2 CH2PO3H2
++00CCH2CC0OHCHi CP(hH2P
O312PO3H2 CH2po3H2PO3If2 (37) (38') C12COO[I CH2C0OH
■ PO3H2CH2C00H PO3H. OH PO,H2 CH2CH2C0OH PO3H□ CH2COOH (59) OH H2O5P CPO3+12 △ c, nsH O HOCH2CH(OH) -CH2O-P-(ONa)
2HOCH2CH20-P-(Oll)2HOCH2C
H-0-P-(ONm)2■ OH20H HOCH2C-CH2-0-P-α■)2) 10-CH
2-CHCH2-0P-(OH)2OH Na HOOC-CHCH20P (OH)2FI2 C00 to C00HH2N
CH2CH20P-(OH)2H2N-COOP
(OK)2 H3CCOOP (OH)2 OH3 CH30P OCH2Cl CHi0K
OH C2H50P OC2+'+5 ■ OH OH OHOH l 01(0H ((CH3)2N)2- P OP (N(CH3
)2) 2SO2 meter C00C
H3CH2COOHC112Cool CH2COOHI C112COOIICH2PO
INa2 CH2C0OH In the present invention, the general formula CXI), CXll)
. (It is effective to use a chelating agent represented by XVI or (XVr). Particularly preferred is the chelating agent shown by the chelating agent XVI or (XVr)) *
'l (1), (3), (5), (31), (44),
(46), (48), (81). The method is to use a chelating agent shown in (82). Two or more of these chelating agents can also be used in combination. The above general formula (Xr) to (XXII) used in the present invention
A chelating agent indicated by either of these is a stable alternative to washing with water! L
It can be added in the range of 1X10-' mol-1 mol per Ω, preferably in the range of 2X10-' to 1X10-' mol, more preferably 5X10-' mol.
In the light-sensitive material used in the present invention, the effect of the present invention is exhibited when the total dry film thickness of the photosensitive silver halide emulsion layer on one surface of the support is 10 us or more. and is preferably 30 μm or less,
In particular, the effect of the present invention is particularly remarkable when the surface is in the range of 15 to 25μ. If the total dry film thickness is less than 10 microns, the effect of the present invention on improving contamination will be small. Aromatic primary amine color developing agents are used for color development in the present invention, and the developing agents include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. These compounds also generally have a color developer IQ of about o, Ig~
A concentration of about 30 g is used, preferably from about tg to about 1.5 g for color developer 1a. Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
These include hydroxytoluene, 2-7-7-3-hydroxytoluene, 2-hydroxy-3-7-1,4-methylbenzene, and the like. Particularly useful aromatic primary amine color developers are N, N'
It is a -dialkyl-1)-phenylenenoamine compound, and the furkyl group and phenyl group may be substituted with any substituent. Among them, an example of a particularly useful compound is N-N'-diethyl-p-phenylenediamine m
acid salt, N-methyl-p-phenylenediamine hydrochloride, N
, N-dimethyl-9-phenylenediamine hydrochloride, 2-
7 minnow 5-(N-ethyl-N-dodecylamino)-)
toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7minoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline 4-
7mi/-3-methyl-N,N'-noethyl 7niline, 4
-Ami/-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate. In the present invention, the color developing solution that does not substantially contain benol alcohol is a normal color developing solution with a concentration of 10 to 20 a/m.
! /1The concentration of benzyl alcohol contained is 1ml/1
The concentration is less than 1, and there is hardly any. Of course, 0.
A concentration of approximately 5 Tml/ffi falls within the range of substantially no benol alcohol, but it is particularly preferable that no benol alcohol be contained at all. In addition to the above-mentioned aromatic primary amine color developer, the color developer contains various components normally added to color developers, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate; pH value of a color developing solution using an aromatic primary amine color developing agent as a color developing agent which may optionally contain a metal thiocyanate, an alkali metal phenol, a water softener, a thickening agent, etc. is usually 7 or more, most commonly about 10 to about 13. The soluble silver complexes contained in the washing substitute stabilizer and bleach-fix solution used in the treatment method of the present invention may be recovered by known methods, such as electrolysis (French Patent No. 2,299,6
67), precipitation method (described in JP-A No. 52-73037, German Patent No. 2,331,220), ion exchange method (described in JP-A-51-17114, German Patent No. 2,548,2)
No. 37) and metal substitution method (British Patent No. 1,353,8)
05) can be effectively used. Margin below, 121 The processing method of the present invention is advantageously applied to the processing of color negative film, reversal color film, color negative paper, color positive paper and reversal color paper. In addition, the following (1) is a treatment step in which the present invention is particularly effective.
and (2). (1) Color development - bleach fixing - water washing alternative stabilization treatment (2)
Color development - bleaching constant fixing - washing alternative stabilization treatment [Examples] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and on top of this, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive halide emulsion layer. A light-sensitive material was prepared by coating a silver emulsion layer with a total silver density of 7 hg per 100 cm. , α-(4-nitrophenoxy)-α- as a yellow coupler in the Schif-sensitive silver halide emulsion layer.
Vivalyl 5-[γ-(2,4-di-t-aminophenoxy)butyramide]-2-chloroacetanilide was used as a magenta coupler in the green-sensitive silver halide emulsion layer. chlorophenyl) -3-
((α-(2,4-di-monoamylphenoxy)acetamide]benzamide)-3-pyrazolone and l -(
2,4,6-trichlorophenyl)-3-((α-(2
,4-di-t-amylphenoxy)acetamide]benzamide)-4-(4-methoxyphenylazo)-5-
Pyrazolone was used, C-59 was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and additives such as a sensitizing dye, a hardening agent, and a spreading agent were added to each emulsion layer. However, the exemplified compound (1-16) was used as a sensitizing dye in the blue-sensitive silver halide emulsion layer. The dry film thickness of the color negative film thus obtained was 23 μm. Experiment 1 After exposing the photosensitive material described above in a conventional manner, an experiment was conducted using the following processing steps and processing solution. Processing process Processing temperature ('C) Processing time! Color development 37.8 3 minutes 15 seconds 2 Bleach fixing 37.8 6 minutes 30 seconds 3 Water
Washing 30-40 3 minutes 15 seconds 4 Stable 30-34
1 minute 37 seconds 5 dry Color developing tank solution> Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.2g Potassium bromide 1.2g Diethylenetriaminepentaacetic acid 2.0g Sodium hydroxide 3.4g N-ethyl-
N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.6g Add water to make IQ, pH 10.06 with potassium hydroxide
Adjusted to. Color development replenisher> Potassium carbonate 30 g Sacrificial sodium sulfate 2.0 g Human [J
Xylamine sulfate 2.2g Potassium bromide 1.2g Diethylenetriaminepentaacetic acid 2.0g Sodium hydroxide
3.4g N-monoethyl-N-β-hydroxyethyl-3-methyl-4-aminoamyline sulfate 5.2g Add water to make IQ, and add potassium hydroxide to pH 10.35
Adjusted to. <Bleach-fix tank solution and replenisher> Ethylenediaminetetraacetic acid ferric complex salt 0.31 mol Nitrilotriacetic acid 5.0 g Ammonium sulfite 15 g Ammonium diosulfate 150 g Add water to make IN, and adjust to pH 7 with aqueous ammonia (28% solution) , adjusted to 0. <Stable tank liquid and replenishment liquid> Water was added to prepare summer e. Fill an automatic processor with the above color developer tank solution, bleach-fix tank solution, washing water, and stabilization tank solution, and replenish the above color developer replenisher, bleach-fix replenisher, and stability tank every 3 minutes while processing the color negative film. Continuous processing was performed while replenishing the liquid through a metering cup. The replenishment amount was 1475 mff per color negative film im", 1475 mff as the replenishment amount to the color developing tank, 9261 as the replenishment amount to the bleach-fixing tank, and 926 + a12 of the stabilizing replenisher as the replenishment amount to the stabilization treatment bath.Water washing in the water washing process The amount of water was 3ON per 11ffi.Experiment-2 to Experiment-8 Using the above color negative film, an experiment was conducted using the following steps and processing solution.Processing process Processing temperature ('C) Processing time 1 Color development 37.8 3 minutes 15 seconds 2 bleach fixing 37.8 6 minutes 30 seconds 3 washing alternative stabilization 80~34 4 minutes 52 seconds 4ψ°drying Note that the washing alternative stabilization process is divided into tanks 1 to 3 in the direction of flow of the photosensitive material. A multi-tank countercurrent system was adopted in which the stabilizing tank was refilled from the final tank, the overflow from the final tank was allowed to flow into the tank at the +iij stage, and this overflow liquid was also flowed into the tank at the previous stage. Both the bleach-fix solution and the bleach-fix solution were the same as those in Experiment 1, and the water-washing alternative stabilizing solution was prepared by adding the compounds shown in Table 1 to the following formulation, and the same continuous treatment as in Experiment 1 was carried out. The amount of replenishment of the water washing alternative stabilizing solution was the same as that of the stabilizing solution in Experiment = 1.
-Methyl-4-isothiazolin-3-one
Q, 02g 2-Methyl-4-isodeazolin-3-one 0.02g Ethylene glycol 1.0g 2-octyl-4-isothiazolin-3-one 0.01g Add water to make 14, add sulfuric acid and potassium hydroxide to pH 7,
Adjust to 5. \, -shi/ Experiments 9 and 10 A light-sensitive material was prepared by removing the sensitizing dye from the blue-sensitive silver halide emulsion layer of the above color negative film, and experiments similar to Experiments 2 and 8 were conducted using this material. went. Experiment 11 In Experiment 8, a similar experiment was conducted using a color developer tank solution and a color developer replenisher to which benzyl alcohol was added at 10 mQ/l. Experiment-12 to Experiment-20 After the continuous processing of Experiment-8, instead of the bleach-fix solution in which iodide ions eluted from the light-sensitive material had accumulated, a bleach-fix replenisher was added to the color developing tank wL100+1L/Q and silver bromide 10
An experiment was conducted using a model continuous processing bleach-fix solution in which potassium iodide was added in varying amounts as shown in Table 1 to a model continuous processing solution to which 11 g/11 of potassium iodide was added. The surface tensions of the stabilizing solution and the washing substitute stabilizing solution used in the experiment were measured by a conventional method and are shown in Table 1. In addition, the cyan image portion of the sample obtained in each experiment was subjected to a double-light test using a xenon arc lamp for 200 hours at 40°C and 80% RH, and the density of the dye image was measured using an optical densitometer before and after the double-light test. (PD^-65, manufactured by Konishiroku Photo Industry Co., Ltd.) under red light to determine the rate of discoloration. These results are shown in Table-1. Note that the iodide concentration in the bleach-fixing tank solution after continuous processing used in Experiments 1 to 11 is shown as KI in Table 1. Ion chromatography was used to measure the concentration. As is clear from the results in the margin table below, normal running water washing in Experiment 1 (comparison) was stable, whereas Experiment 2 and 1/3 (comparison)
In this case, the light resistance of the cyan dye under high humidity conditions deteriorates. On the other hand, in Experiments 4 to 8 (all according to the present invention), the light resistance under high humidity was equal to or higher than that in Experiment 1, and it can be seen that they are extremely preferable. Furthermore, Experiments 2, 8, 9 (all comparative) and 10 (invention) show that the effects of the invention are more pronounced when the sensitizing dye represented by general formula [I] is contained. ing. Furthermore, from the results of Experiments 12 and 13 (both compared) and 14 to 20 (all of the present invention), the present invention shows that the iodide concentration contained in the bleach-fix solution is 0.00.
It is effective when it is 1 mol/l or more, and 0.002 to 0
．． It turns out that it is particularly effective when it is in the range of 0.02 mol/l. Example 2 In the preparation of the light-sensitive material of Example 1, 1-hydroxy-N-[α-(2,4-t-amylphenoxy)butyl 3 was used instead of cyan coupler C-59 in the red-sensitive silver halide emulsion layer. A photosensitive material was prepared in the same manner except that -2-su7tamide was used. Experiments 1, 2 and 8 were repeated using this color negative film. As a result, the cyan dye fading rate was 42% in Experiment 1, 48% in Experiment 2, and 38% in Experiment 8, all of which were significantly lower than the results in Example 1. This is Example 1
This shows that the cyan coupler represented by the general formula (V) or (Vl) used in Example 1 enhances the effects of the present invention.

Claims (2)

[Claims] (1) After imagewise exposure of a silver halide color photographic light-sensitive material having a total dry film thickness of a photosensitive silver halide emulsion layer and a non-photosensitive layer on one side of the support of 10 μm or more, it contains substantially benzyl alcohol. After processing with a color developing solution that does not have a surface tension of 8 to 50, it is processed with a processing solution that has a fixing ability containing 10^-^3 mol/l or more of iodide, and then
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a water-washing substitute stabilizing solution that has a pH of 1.5 dyne/cm and does not substantially contain an aldehyde compound, and then drying the material. (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material contains a sensitizing dye represented by the following general formula [I]. Processing method. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z_1 and Z_2 are respectively benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, Represents an atomic group necessary to form a benzimidazole nucleus, naphthoimidazole nucleus, pyridine nucleus, or quinoline nucleus, R_1 and R_2 each represent an alkyl group, an alkenyl group, or an aryl group, and R_3 is a hydrogen atom, a methyl group, or an ethyl group. represents a group, X_1 represents an anion, l
represents 0 or 1. ]