JPS6363043A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability and color developing power of a color developing soln. and to control the rise of fog during continuous processing by carrying out processing with a developing soln. contg. an arom. prim. amine color developing agent and a specified compd. CONSTITUTION:A silver halide color photographic sensitive material is processed with a color developing soln. contg. an arom. prim. amine color developing agent and at least one kind of compd. represented by the formula. The pref. amount of the compd. represented by the formula in the developing soln. is 0.05-30g/l, especially 0.1-15g/l. The pref. amount of the developing agent in the developing soln. is about 0.1-20g/l, especially about 0.5-10g/l. Especially when a D-4 color developing agent is used in the presence of the compd. represented by the formula, fog is hardly increased and satisfactory photographic characteristics are obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and in particular, a method for processing silver halide color photographic materials, which improves the stability and color development of a color developer, and enables continuous processing. Regarding the NYC processing method, the rise in fog is significantly reduced.

(Prior Art) Color developers containing aromatic primary amine color developing agents have been used for a long time to form color images, and currently play a central role in the image capture method of color photographs. Riwo is walking. However, the color developer mentioned above has the problem that it is very easily oxidized by air and metals, and if a color image is formed using an oxidized developer, fog increases and the density decreases, resulting in poor sensitivity and gradation. It is well known that the desired photographic characteristics cannot be obtained because of changes in the

Therefore, various means for improving the preservation properties of color developing solutions have been studied, and among them, the most common method is to use a combination of hydroxylamine and sulfite ions. However, the decomposition of hydroxylamine is significantly accelerated in the presence of metal ions, and the resulting ammonia can cause fogging and changes in photographic properties. Various studies 1fi, especially /
The use of -hydroxy-alkylidene diphosphonic acid (West German Patent No. 22 Core 63) and aromatic polyhydroxy compounds (US Pat.

However, even with the use of suitable concealment means for metal ions, there is no ability to prevent, or even accelerate, atmospheric oxidation. Sulfite ions have been used for a long time to prevent air oxidation, but their use is limited due to their strong inhibition of color development, and it is difficult to sufficiently prevent air oxidation. Furthermore, when fc is used in a system in which benzyl alcohol is not present, and fcυ is treated with an emulsion made of a halogenated polyester having a high chlorine content, the color density is significantly reduced, which is a drawback.

In this sense, the amount of sulfite ions used is as small as possible,
It is preferable not to use it. However, in these cases, air oxidation prevention is inevitably insufficient, so
New air oxidation prevention technologies are being considered.

Compounds that can replace sulfites include alkanolamines described in JP-A No. 3!32 and JP-A-KOKAI SHO! The polyethyleneimines described in No. J-1≠3 have been proposed, but
Even with the use of this compound, sufficient effects could not be obtained.

Also, Tokko Akira! ! -/231/ discloses a technique using cyclohexanediaminetetraacetic acid. Although this compound has a remarkable effect on preventing air oxidation, due to its photographic properties,
This is not a desirable method as it may have negative effects.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a processing method that is excellent in the stability and color development of a color developer. Another object is to provide a processing method in which an increase in fog during continuous processing is significantly reduced.

(Means for solving the problem) The above purpose can be achieved by the method described below. That is, Fy can be achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized by processing an aromatic primary amine color developing agent and a compound represented by the following general formula t1) in a color developer containing gold dust. , - I was able to do it.

General formula (NM may be the same or different and represents a hydrogen atom, an alkali metal (Na, etc.), and an ammonium ion.n
represents an integer between / and Hiro.

The compound of the general formula tt+ is a compound known as a chelating agent, but the fact that such a chelating agent significantly prevents air oxidation when gold dust is present in a color developer is completely unexpected. It's a matter of fact.

Specific examples of the compound of general formula (1) are shown below.

(2)-2 1-Hiro The above carboxylic acid may form a salt with an alkali metal atom such as sodium, lithium, potassium, or ammonium.

Among the above compounds, l-/ is particularly preferred. These compounds can be purchased commercially 75;
It is possible to synthesize f based on 1lstein, Hiro+31, //r4, etc.

The amount of calories added to the color developer of the compound of general formula (I) is:
Ill preferably o, ort~30? , more preferably 0. /l-/! There is t″t′.

The color developer used in the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, one representative example of which is shown below, but the invention is not limited thereto.

f)-/N,N-diethyl-p-phenylenediamine D-x 4A-[N-ethyl-N-(β-hydroxyethyl)aminecoaniline D-32-Methyl-Hiroshi-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline D-<z Hiro-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline Also, these p-phenylenediamine H forms are sulfates,
Salts such as hydrochloride, sulfite, and p-toluenesulfonate may also be used. The amount of the aromatic-grade amine developing agent used is preferably about θ, /2 to about 209-
More preferably about 0.6f! ~10y concentration.

In particular, D-Hiroshi's color developing agent is preferably used in the presence of the compound of general formula (I), since good photographic properties can be obtained with little increase in fog.

Furthermore, the compounds of the present invention have remarkable storage performance, particularly in systems using aromatic primary amine color developing agents, when used in combination with compounds that directly stabilize the developing agent. Here, water-soluble antioxidants are generally known as compounds that directly stabilize the developing agent, and include, for example, the compounds mentioned above, such as hydroxylamines.

Hydroxylamines are preferable as compounds that can be used in combination with the color developer used in the present invention, and compounds represented by the general formula rlI) are particularly preferable.

General formula (III R21N R22 H In the formula, R21 and R22 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

1 (21-R22 is preferably an alkyl group or an alkenyl group, and more preferably at least one has a substituent. Also, -R21 and R22 may be linked together to form a heterocycle with a nitrogen atom. .

Alkyl groups and alkenyl groups may be linear, monobranched or cyclic, and substituents include halogen atoms (F, C1,
B r, etc.), aryl group (phenyl group - p-chlorophenyl group nato) - alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.) - aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group - p - toluenesulfonyl group), sulfonamide group (methanesulfonamide group - inzenesulfonamide group, etc.), sulfamoyl group (diethylnulfamoyl group - unsubstituted sulfamoyl group, etc.) - carbamoyl group (m
tJl-substituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.)
- ureido group (methylureido group - phenylureido group - h, etc.) - alkoxycarbonylamino group 7 (methoxycarbonylamino group, etc.) - aryloxycarbonylamino group (C phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.) ), aryloxycarbonyl group (phenoxycarbonyl group, etc.)
.

Cyan group, hydroxy group, carbonyl group, sulfo group, nitro group-amino group (unsubstituted amino group-diethylamino group), alkylthio group (methylthio group, etc.), ruthio group (phenylthio group, etc.), and heterocycle Groups (morpholyl group-pyridyl group, etc.) can be mentioned. Here, 1(21 and R22 may be the same or different, and the substituents of R21 and R22 may also be the same or different.

Further, the number of carbon atoms in R21=R22 is preferably 7 to io.
Particularly preferred are 7 to j. Examples of the nitrogen-containing heterocycle formed by linking R21 and 1(22) include -piperidyl group-hyrolysilyl group, N-alkylpiperazyl group-morpholyl group, and indolinyl group-benztriazolyl group.

Preferred substituents for R21 and R22 are -hydroxy group,
They are an alkoxy group, a sulfonyl group, an amide group, a carboxy group-cyano group, a sulfo group-nitro group, and an amine group.

Specific examples of compounds represented by the general formula (Ill) used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

■-(1)OH C2H3-N-C2H40CH3 II-(J) OH CH3-N-C2H4QC2H5 ■,-(Gl OH nC4Hg-N-C2H40CH3 n-(j) 0H C) I30C2H4-N-C2H40CH3It-(Otsu ) OHC2H50C2H4-N-
C2H40C2H5■-17) ON CH30C2H40C2H4-N-C2H40C2H4
0CH2n-(f) 0I-(C2
H50C2H4N-C2H5 II-(5'l OH[C2H50C2H4NCH2-CH=CH2■-(Il
l OH Fuki CH3N-C2H4CONH2 ■-(/l, >OH C)T3-N-C2H4SO2C2H511-(/7)
OH C2H5SO2C2H4-N-C2I(4SO2C2H
5It-(/ri) I OH [-(J410H HOOC-CH2-N-CH2-COOH■-(27)
OH HOCH2CH2NCH2CH20H II-(3/) OH(JH ■-(3λI CH3NCH2CH25O2CH2
CH3OH I[-(33)OH CH3CH2N CH2CH3 ■-(3μ) NH2OH The compound represented by the general formula (IN) can be synthesized by the known method shown below.

U.S. Patent No. 3. Otsu 6/, Tata 6, 3,342゜ri 6
/ issue, same 3. λri 3,03 ≠ % special public show μ 2-ko, 79
≠ - U.S. Patent No. 3. Data/,/! r/issue, same j, 63
No. 3,769, 3. Hiroshi 67.7// issue, same 3. Gejj
, ri/No.A, 3.2♂71/, 2j, J, 217
．． /2≠No.

These compounds may form salts with various acids such as hydrochloric acid-sulfuric acid-nitric acid, phosphoric acid, ./euric acid, and acetic acid. In addition to hydroxylamines, examples of "compounds that directly stabilize the developing agent" that are preferable when used in combination with the compound of the present invention include hydrazines, hydrazides - sugars -
Examples include hydroxamic acids, α-hydroxy/ketone systems, and the like.

What is the amount of these compounds added to the color developer?

The color developer is preferably 0.077 to 20, preferably 0.7 to 109.

In addition, as other preservatives, sulfites such as potassium sulfite-sodium bisulfite, potassium N sulfite-sodium metasulfite, potassium metasulfite, and monocarbonyl sulfite adducts may be added as necessary. can do. What is the amount of O added to these color developers? ~20f/l-or less, preferably 0g~! 2/ is below, and one less is preferable if the stability of the color developer is maintained.

Other preservatives include U.S. Patent No. 3. AI! , No. 603 and the hydroquine acetones described in British Patent Nos. 1,301r and 7g;
! α-Aminocarbonyl compound described in No. 94t Koo - JP-A-37-411. /gf issue and the same! r7-! 37≠?
Various metal rings described in the issue, etc., JP-A-Shoj,! -102727
Various sugars listed in the issue - same! 9-/60/≠7 pupil α,
α'-dicarbonyl compounds - salicylic acids described in 5Q-IRO 22 - gluconic acid derivatives described in 4!7, etc. may be contained as necessary, and these preservatives are necessary. Two or more types may be used in combination depending on the situation. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developer used in the present invention is preferably 1) T
-19~7.2- More preferably ~ //, O and -
The color developer may be impregnated with other known developer component compounds.

In order to maintain the upper Mif pH, it is preferable to use various buffering agents. Buffers include carbonate, phosphate, borate-tetraborate, hydroxybenzoate, glycine salt-N,N-dimethylglycine salt, leucine salt, norleucine salt-quanine salt, 3, II- Dihydroxyphenylalanine salt, alanine salt-aminobutyrate-co-amino-methyl-7,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt-
Lysine salt and the like can be used. Especially carbonates, phosphates, tetraborate-hydroxybenzoates.

It has the advantages of being excellent in solubility, pH, and buffering capacity in the high pH range of 0 or higher, without having any negative effects on photographic performance (such as fog) when added to color developers, and being inexpensive. It is particularly preferred to use a buffer of

Specific examples of these buffers include carbonic acid, potassium carbonate, sodium bicarbonate-potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate - disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (C borax) - potassium tetraborate - Sodium hydroxybenzoate (sodium salicylate) ), potassium 0-hydroxybenzoate,!
- Sodium sulfo-2-hydroxy-7benzoate (S -
Sodium sulfosalicylate),! -Potassium sulfo-2-hydroxybenzoate (potassium j-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably -0.1 mol/l or more, particularly o, i mol/l -0,
Particular preference is given to μmol/l.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. Sho Il♂-30μ96 and No. +4<-30232, and the aminopolycarboxylic acids described in Japanese Patent Publication No. Sho J6-973≠
No. 7, Special Publication Shoj Otsu-3ri No. 3j, and West German Patent No. 2,
Organic phosphonic acids described in No. 227,639, JP-A-Shojλ
-10272, same! r3-II-2730-same!
Goo/λ//27, same rr-i, zt, 2ui and same! ! r-6! Phosphonocarboxylic acids described in SO6 etc. - Other JP-A-Sho! g-/rij♂da! No.-JF-2
Examples thereof include compounds described in Japanese Patent Publication No. 0311μ0 and Japanese Patent Publication No. 33-'AO900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid-7,3 -Diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, l 2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid -II Coleetherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine ortho Hydroxyphenylacetic acid, cophosphonobutane-7,21≠-tricarboxylic acid, /-hydroxyethylidene-/,/-diphosphonic acid, N,N'-bis(cohydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to completely sequester metal ions in the color developer. For example, / is about o, iy to ioy.

Any optional development accelerator can be added to the color developer if necessary. However, it is preferable that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and fog prevention. The term "substantially" as used herein means that the amount of developer solution contained in the developer is less than 2 ml, preferably not at all.

The compound of general formula (I) used in the present invention has a remarkable effect on the stability of color developing solutions that do not substantially contain benzyl alcohol.

Other development accelerators include Tokuko Sho 37-/i<θrza No., J7-39g7, No. 3♂-7g-Δ, and No. 4L.
Hiro-/No. 2310, same group! -TaO/DE and US Patent No. 32g/3. Thioether compounds shown in Kohiro No. 7, etc., JP-A No. 3. ! -119g No. 29 and the same! FO-/
j! ! p-phenylenediamine compound represented by It No. -% Kaisho so-/j7'7! J issue, Tokko Akira & 4t-
No. 30074, JP-A-Sho TT-IRTR Coro No. and the same!
φ-class ammonium salts represented by Co≠3≠λ, etc. - U.S. Patent No.

p-amine phenols described in ≠6λ, US Patent No. 2
．． '191f, No. 903, P3. /21. / Doko No., same μ, Ko 30, 7ri No. 6 - Doko 3, 2! ;3゜Ri/ri No., Special Publication Shogu/-//113/, U.S. Patent No. 2. ≠♂ko, j
Hiro 6, same co, 396. Deco wo issue and ro 3. jr12
, amine compounds described in No. 3μ6, etc.,
No. 1O♂za, PIII 2-2!20/, U.S. Patent No. 3. /Koza, /r3, Tokuko Shoμ/-/lhiro 37, same goo! 3gg3 and U.S. Patent No. j,! ! 2. ! 0/
Polyalkylene oxides represented by No., etc., etc./
- Phenyl-3-pyrazolidones, hydrazines - meso ion type compounds, ionic type compounds, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include: 14-<nzodoriazole-2-nitrobenzimidazole, j-nitroisoindazole, j-methylbenzotriazole,! -Nitrobenzotriazole, J-chloro-penztriazole-
! Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylbenzimidazole-2-thiazolylmethyl-benzimidazole, indazole, and hydroxyazaindolizine-adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, q, ≠′−
Diaminorco, 2'-disulfostilbene type compounds are preferred. The amount added is 0-j 9/, preferably O0/1~
119/l-.

Furthermore, various surfactants such as alkylsulfonic acids, alkylsulnic acids, aliphatic carboxylic acids, and aromatic carbonic acids may be added as necessary.

The processing temperature of the color developer of the present invention is zo-r.

OC is preferably 3o-txooc. Processing time is 2
The time is 0 seconds to j minutes, preferably 30 seconds to λ minutes.

It is preferable that the amount of replenishment is small, but per photosensitive material/m2,
! o~tooml preferably! ;0 to 300rnt. More preferably /oomt, 2ooml.

Next, the bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but especially organic complex salts of iron (mI) such as aminopolycarbonate salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. acids, complex salts with aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid-tartaric acid and malic acid; persulfates;
Hydrogen peroxide and the like are preferred.

Among these, organic complex salts of iron (■) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Examples of aminopolycarboxylic acid-aminopolyphosphonic acid, organic phosphonic acid, or salts thereof useful for forming an organic complex salt of iron (Ill) include:

Ethylenediaminetetraacetic acid ~ Diethylenetriaminepentaacetic acid - Ethylenediamine-N-(β-oxyethyl)-N,N
',N'-triacetic acid, /,3-diaminopropanetetraacetic acid- triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid-nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid- /,3-diamino-λ-propanol Tetraacetic acid, methyliminodiacetic acid - iminodiacetic acid - hydroxyliminoniacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid.

ethylenediaminenipropionacetic acid, 7z Nijirenjiryominshizuzu a- 2-phosphonodutan/,,? , 4t-triacetic acid.

! , 3-diaminopropanol-N,N,N'.

N'-tetramethylenephosphonic acid-ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid-/3-propylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid- l-Hydroxyethylidene-1,/-diphosphonic acid- You can get all the information.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron rI[I] of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, /, 3-diaminopropanetetraacetic acid, methyliminodiacetic acid
Complex salts are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferrous sulfate, ferric chloride-ferric nitrate, and ferric ammonium sulfate.

When used in the form of a complex salt, a ferric ion complex salt may be formed in a solution using ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. - One type of complex salt may be used, or two or more types of complex salts may be used, while the second type of complex salt may be used.
When forming a complex salt in a solution using an iron salt and a chelating agent, one or more types of ferrous salts may be used. Furthermore, one type or two or more types of chelating agents may be used.

In either case, the chelating agent may be used in excess of the total ferric ion complex formed.

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred - the amount added is from 0.07 to 0 mol/, preferably 0.0! ~o, to mol/l.

Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include those described in U.S. Pat. Zari 3゜♂5♂, West German Patent No. 1.2qO, 1112, West German Patent No. 20!9.91#,
JP-A No. 33-32736, No. 33-! 713/issue, same! 3-37μ/za issue-same! 3-6!732, same j3-
No. 72623-No. 33-93430, same! 3-taj Otsu 3/No., 33-io≠232, 3-/-Hiroshi≠i
μ No. 63-/4 (/4λ3 No. 63-2g & J4
Compounds having a mercapto group or a disulfide group such as those described in Research Disclosure No. 7/Kota No. C/7g (July 2013); Thiazolidine derivatives such as those described in JP-A No. 14012/1973; Tokko Akira+j
-gjtOt issue-Unexamined Japanese Patent Publication No. 1983-,! No. 0132-Same! 3
-3273! issue.

U.S. Patent No. 3,701. ．． Thiourea placed conductor as described in No. 661; West German Patent No. 1. /J7,7/! No. - Tokukai Shoj♂ -
/623! Iodide described in West German Patent No. ytt, ai
Polyethylene oxides described in No. o, U, 74♂, 4L30; -Polyamine compounds described in IIJA No.; other JP-A Showa Star 4L Coμ3q, same≠Taryo 26t1, same j3-9μ Taco No.7, same J4T
-3j727, Ro3! -26! OA and 5r-
It3≠Compounds described in No. O, iodine, bromine ions, etc. can all be mentioned. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of highly accelerated curing, and are particularly preferred in US Pat. No. 3. ♂93, RSR No., West German Patent No. 1, 20. r/- issue, Tokukai Sho! 3-9jtt3
The compound described in No. 0 is preferred.

Other 1 The bleach or bleach-fix solution used in the present invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride - ammonium chloride) or iodides. (
For example, a re/logenating agent such as -ammonium iodide) may be included. Boric acid, borax, sodium metaborate-acetic acid, sodium acetate, sodium carbonate-potassium carbonate, phosphorous acid-phosphoric acid, sodium phosphate-citric acid, as required
Inorganic or organic acids having pH buffering capacity such as sodium citrate-tartaric acid, and alkali metal or ammonium salts thereof or corrosion inhibitors such as ammonium mononitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thionanate-ammonium thiocyanate; or ethylene. Bisthioglycolic acid, 3. Otsu-jithia-/
These include water-soluble silver halide dissolving agents such as thioether compounds such as I♂-octanediol and thioureas, and these can be used alone or in combination of two or more. Also, Tokukai Akira! r-/! ! A special bleach-fixing solution consisting of a combination of the fixing agent described in No. 3jt≠ and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferred to use -thiosulfates, especially ammonium thiosulfates.

The amount of fixing agent per /l is preferably from 0.3 to 2 mol, more preferably from o, r to /, 0 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
IO is preferred, and j to ri are particularly preferred. If the pH is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the N'an dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fixing solution may contain - various other fluorescent brighteners, antifoaming agents or surfactants - organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and fixing solution in the present invention contain sulfite (for example, 11 um of sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (for example, in a few cases) as a preservative.
containing sulfite ion releasing compounds such as ammonium bisulfite (sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.); These compounds have approximately 0.0% in terms of sulfite ion.
The content is preferably from 0.02 to 0.60 mol/l, more preferably from 0.0≠ to 70 mol/l.

As a preservative, bisulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carinyl compounds, etc. may also be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, and the like may be added as necessary.

Next, the water washing step in the present invention will be explained.

Here, the "washing step" includes washing alternative treatments such as rinsing treatment and washing promotion treatment.

In the present invention, a treatment method such as a so-called 1-stabilization treatment may be used instead of the usual water-washing treatment without providing a substantial water-rinsing step.

The amount of washing water or stabilizing liquid in the present invention is difficult to specify because it varies depending on the number of baths in multistage countercurrent processing and the amount of pre-bath components brought into the photosensitive material. It is sufficient that the bleaching and fixing solution components in the bath or the bath after the bath having full fixing ability are 7×io' or less. For example, in the case of 3-tank countercurrent water washing, it is preferable to use at least about 7000 ml per m2 of photosensitive material - more preferably at least 1 jooom. In addition, in the case of water-saving treatment, it is preferable to use 00-/000 ml per m2 of photosensitive material.

The water washing treatment or stabilization treatment temperature is l! 0C~gus'
C- is more preferably ko'C to 3j0C.

In the washing process, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericidal agents and anti-inflammatory agents that prevent the growth of various types of cutilia, algae, and molds (for example, ``Journal of Antibacterial and Antifungal Agents” (J, Antibact, Antifun
g, Agents).

Vol, / /, Aj, p207-2231 / Riza3
) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts such as magnesium salts and aluminum salts, alkali metals and ammonium salts - or for preventing dry load and unevenness. Surfactants and the like can be added as necessary. Or West [Photo, Sci, Eng, Vol. 6, 34+'~J! The compounds described in Part 9 (l. 6j) etc. may be added to Part 9.

Furthermore, chelating agents, fungicides and anti-piping agents are added to the washing water,
The present invention is particularly effective when the total amount of washing water is significantly reduced by multi-stage countercurrent washing using two or more tanks. Also - instead of the normal washing process, use JP-A-7-1! It is also particularly effective when carrying out all of the multistage countercurrent stabilization treatment steps (so-called stabilization treatment) as described in No. 3. In these cases, the bleaching and fixing components in the final bath are preferably less than s x 1o-2 /
It is sufficient if it is not more than ×10−2. Also, for calcium and magnesium ions in water such as distilled water and ion-exchanged water! It is also effective to use only properly removed water to significantly reduce the amount of water used.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (for example) (
Various buffering agents (e.g. borate, metaborate-borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia-monocarboxylic acid-dicarmenic acid, polycarboxylic acid) for Typical examples include aldehydes such as (used in combination with acids, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid-aminopolycarboxylic acid-organic phosphonic acid, aminopolyphosphonic acid,
Uses various additives such as phosphonocarboxylic acids, etc.), bactericidal agents (thiazole series, inthiazole series, halogenated phenols, sulfanilamide, penztrisol, etc.), surfactants - fluorescent brighteners, and hardening agents. Alternatively, two or more of the same or different target compounds may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, and ammonium nitrous acid-ammonium thiosulfate in order to improve image storage stability.

When the amount of washing water or stabilizing liquid is significantly reduced as described above, part or all of the overflow liquid of the first washing water is allowed to flow into the bleach-fixing bath or fixing bath, which is a pre-bath, in order to reduce the amount of waste liquid. Good for the purpose of reduction.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the product-moment replenishment amount to reduce costs.

Each processing bath is equipped with a heater, temperature sensor, liquid level sensor-circulation pump, filter, various floating pigs, various squeegees, and nitrogen stirring as necessary.

Air stirring or the like may be provided.

If the method of the present invention uses a color developer,
It can be applied to any processing step. For example, it can be applied to processing color paper, color reversal paper, color positive film, color negative film, color reversal film, etc., but application to color paper, color reversal paper, etc. is particularly preferred.

The silver halide emulsion of the light-sensitive material used in the present invention can be of any halogen composition, such as silver iodobromide-silver bromide monochlorobromide, silver chloride, etc., but in cases where rapid processing or low replenishment processing is performed. A silver chlorobromide emulsion or a silver chloride emulsion containing 20 moles or more of silver monochloride is preferred, and a silver chloride content of 10 to 10 moles is particularly preferred. In addition, when high sensitivity is required and capri during production, storage, and/or processing must be kept particularly low, silver chlorobromide emulsions containing 30 molar or more silver bromide or Silveride emulsions are preferred, and more preferably 70 molar or more. When the silver bromide concentration exceeds O molar ratio, rapid processing becomes difficult, but there are ways to accelerate development, such as using a development accelerator such as a silver halide solution, a fogging agent, or a developer as described below during processing. Development can be made somewhat faster without being limited by the silver bromide content.
It may be preferable. In either case, it is not preferable to contain a large amount of silver iodide, and it is sufficient if the silver iodide content is 3 molar or less. These silver halide emulsions are mainly colored -
A color photosensitive material for engraving, which is preferably used for pars, etc.
For negative films, reversal films, etc., silver iodobromide and silver chloroiodobromide are preferred; the silver iodide content is preferably 3 to 1j molar.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle size is taken as the particle size, and in the case of cubic particles, the particle size is taken as the particle size, and it is the average based on the projected area.

In the case of tabular grains, it is also expressed in terms of spheres. ) is 0. /μm or more is preferred, and particularly preferred is Id/,
! o below pm, and above itμm.

The particle size distribution can be narrow or wide, but
The value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is within 204r,
Particularly preferably, so-called monodisperse silver halide emulsions within ITS are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, one or more types of monodisperse silver halide emulsions with different grain sizes are used in emulsion layers having substantially the same color sensitivity (the monodispersity is defined as the above-mentioned variation). (preferably one with a certain ratio) can be mixed in a single layer or applied in multiple layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used in combination or in a stacked manner.

The shape of the silver halide grains used in the present invention is regular (cubic-octahedral, rhombidodecahedral-dodecahedral, etc.).
rrl crystals or coexistence of these crystals, and irregular rirre crystals such as spherical ones.
It may have all gular crystal forms, or it may have a composite form of these crystal forms. Tabular grains may also be used, and in particular, tabular grains with a length/thickness ratio of J or more, particularly ♂ or more, have a total projected area of ! An emulsion having a ratio of O or more may be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is -RESEARCHD
ISCLO8tJRE vol, / 70 I
tem A/ 7 At13 (1) ring 1 no 97r, /2
) can be prepared using all the methods described in . In other words, any of the acidic method, neutral method, ammonia method, etc. may be used.Also, the method for reacting the insoluble silver salt with the soluble halogen salt may be the one-sided mixing method, the simultaneous mixing method, or a combination thereof. May be used.

In the process of silver halide grain formation or physical thermal formation,
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or @ salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, salting and chemical heat deposition before being used for coating.

Known silver halide solvents C such as -Ammonia Rhodankali or U.S. Pat. λ7/, No. 157-JP-A Showa/-/λ3tO-No. JP-A Showa j3-♂,! 1. tO♂,
Tokukai Akira! 3-/G4L3/R No.-Tokkai Sho Tag-100F1F No. or Tokukai Sho J-4L-/! ! 12r, etc.) can be used in precipitation, physical thermal formation, and chemical ripening. To remove soluble silver salts from the emulsion after physical ripening, Nudel water washing,
Follow the flocculation sedimentation method or ultraconcentration method.

The silver halide emulsion used in the present invention contains active gelatin and compounds containing sulfuric acid (such as thiosulfate,
Sulfur sensitization method using reducing substances (e.g. stannous salts, amines-hydrazine derivatives, formaminesulfinic acid, 7-ranine compounds) ; Metal compounds (e.g., gold complex salts, Pt, Ir, Pd, Rh-Fe
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table, such as complex salts of metals in group 1 of the periodic table, etc., can be used alone or in combination.

The blue-sensitive, green-sensitive and red-sensitive emulsions used in the present invention are spectrally sensitized with methine dyes and other dyes so as to have color sensitivity. The dyes used include cyanine dyes, melonanine dyes-complex cyanine dyes-W total merocyanine dyes, holobolanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine-merocyanine dyes and complex merocyanine dyes. For these pigments, any of the nuclei commonly used in anine pigments can be used as the basic heterocyclic nucleus.

That is, - pyrroline nucleus - oxazoline nucleus, thiazoline nucleus, pyrrole nucleus - oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus - pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei;
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, Sunawachi, indolenine nucleus, benzindolenine nucleus, indole nucleus-benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus-naphthothiazole nucleus, benzoselenazole cedar, Benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Mero/anine dyes or complex merocyanine dyes contain pyrazoline-! as a core with a ketomethylene structure. -on nucleus-thiohydantoin nucleus, --thioxazolidine-2, kudione nucleus, thiazolidine-2,4t-dione nucleus,
Five or more member heteroarticulate coral nuclei such as rhodanine nuclei and thiobarbic acid nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is -R ear 5E
ARCHDISCLO8UREvo1. /76
Item A/ 7 O p3 (W) (/7!r, /,
2).

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits monochromatic sensitization.

These sensitizing dyes may be added at any stage during particle formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition during particle formation is effective not only to strengthen adsorption but also to control crystal shape and internal structure of particles. Furthermore, addition during chemical sensitization is effective not only to strengthen adsorption but also to control chemical sensitization sites and prevent crystal deformation. These addition methods are particularly effective in the case of emulsions containing a high silver chloride content, and it is also particularly useful to apply them to grains with a high total silver bromide or silver iodide content on the grain surface. be.

The color coupler incorporated in the light-sensitive material preferably has a pallast group or is polymerized so that it has diffusion resistance. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver per coating than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the coloring dye has appropriate diffusivity, colorless couplers, DIR couplers that release all of the development inhibitor or couplers that release the development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is - U.S. Patent No. 2. Hiro 0
No. 7,270 - No. 2. ♂7t, Oj No. 7 and Oj No. 3. -2 Otsu s, No. 306, etc. The use of m:equivalent yellow couplers is advantageous in the present invention, as described in U.S. Pat. ≠Or, l tag number - same No. 3. Hiro≠7. ri, 2
J' No. 31, No. 33,301 and No. G, O
-! .

Oxygen atom separation type yellow coupler described in No. 620 etc. or Tokko Sho! ! -10739, U.S. Patent No. ≠, 170/, 7J'2, No. 32, 0211
No., RD/10!3 (Hirotsuki, 1973) - British patent number 1
,112! , No. 020 - West German Application Publication No. 2. Ko/9. No. 77, No. 2, 26/, 36/, No. r, 329.
! ♂ No. 7 and same No. 2゜≠33. A typical example is the nitrogen atom separation type yellow coupler described in ♂72. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness.
On the other hand, α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or 7-anoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! - As for the pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye, and a representative example thereof is U.S. Pat. , same No. 2゜3
≠J, No. 703, same No. 2. I, 00, 7za♂ No. 2. ri Og, No. 573, No. 3.0 Otoko, No. 653, No. 3. /,! 2. No. 7 and No. 3 36,07
/ No. etc. Two equivalents! - As a leaving group for pyrazolone couplers, U.S. Patent No. 11,370. l
r/r, or the nitrogen atom leaving group described in US Patent No. 1I, 361. The arylthio group described in No. 7 is preferred. Further, the j-pyrazolone coupler having one ballast group described in European Patent No. 73,1.36 provides high color density.

As pyrazoloazole couplers, U.S. patent iJ,
The pyrazolobenzimidazole compounds described in JJ RI, ♂ 7, preferably the pyrazolo [yo+'C': 1[/, 1.2,
ta]) Riazoles, Research Disclosure 21I-λ0 (/Pyrazolotetrazoles and Research Disclosure 2 as described in RizalE'Al)
Examples include pyrazolopyrazoles described in Graph λ30 (year to month). Imidazo [/, z-b] pyrazoles described in European Patent No. 1/1, No. 7 Hiro/ are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness.
Pyrazolo [/] described in European Patent No. 1/R.

j-b] [/, 2. [g]Triazole 1'I is particularly preferred.

7 uncouplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, as disclosed in US Patent No. 2. t7≠.

Naphthol couplers as described in US Pat. No. 273, preferably US Pat.

Typical examples include two-equivalent naphthol couplers of the oxygen atom separation type, which are described in PI No. 4tI4+, No. 326, PI No. ≠, 22g, 233, and No. 200, Hiromu 2000. Specific examples of phenolic couplers include U.S. Pat.
No. 2,772,162, No. 2. ♂9, it is written in Zako Otsu issue etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is an alkyl group higher than ethyl group in the meta position of the phenol nucleus described in U.S. Patent No. J, 772.002. ? "Phenolic Uncoupler with H, U.S. Pat. No. 2,77, 742, U.S. Pat. No. 3,75, 30
No. 1, No. ≠ 17.2, No. 3, No. 6, No. 3, 3317
, No. 0//, No. 327゜173, West German Patent Publication No. 3,329.727 and patent application Shoj♂-≠! t7/
2,j-diacylamino-substituted phenolic couplers described in US Patent No. 3. Hiro 4tA, 62
No. 2, No. μ, 333. Tatata issue, same number ≠, II,”/
, No. 367 and the same No.! ,! J7,7t
These include phenolic couplers that have a uK anryamino group.

In particular, in the treatment method of the present invention, the following general formula tc-1
) and (C-It), good photographic properties with less fog can be obtained.

Such an effect is noteworthy.

General formulas (U-1) and (C-111) will be explained in detail below.

General formula +c-1) H l (wherein, R31 represents an alkyl group, a /chloroalkyl group, an aryl group, an amino group, or a heterocyclic group).

R32 represents an alkyl group or an aryl group. R33 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. It may also be combined with R33 and R32 to form a ring. Zl represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ) General formula IC-1 (In the formula, R1″r represents an alkyl group, a chloroalkyl group, an aryl group, or a heterocyclic group. R35 represents an alkyl group having 2 or more carbon atoms. R36U hydrogen atom, halogen atom, or Indicates an alkyl group.Z2 (1 hydrogen atom, halogen atom, represents a group that can be separated by reaction with an oxidized product of an aromatic/classic amine color developing agent) General formula fc-11 and (C-1 ) In the cyan coupler, examples of the alkyl group having 7 to 32 carbon atoms for R31, R32 and R34 include a methyl group, a butyl group, a tridenyl group, a cyclohexyl group, an allyl group, and examples of the aryl group include , phenyl group, naphthyl group, and the like, and examples of the radical include 2-pyridyl group, 2-imidazolyl group, l-furyl group, and t-quinolyl group.

R1, R2 and R41''r, a, etc. are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group,
2-methoxymethyl group, etc.), aryloxy group (e.g., -1t-di-tert-alumiphenoxy group, 2-
Chlorophenoki 7 groups, 4 (-/Anophenoki/ groups, etc.)
, alkenyloxy groups (e.g., 2-pro is nioquine), aryl groups (e.g., acetyl, benzoyl, etc.), ester groups (e.g., butoquinocarbonyl, phenoxycarbonyl, acetoxy, benzoyl) oxy group, phenylsulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (e.g., dimethylcarbamoyl group, ethylcarbamoyl group, etc.) , sulfamoyl group (e.g., butylsulfamoyl group, etc.), imide group (e.g., saxonimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic group [7] Aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, 77 group, carboxy group, nitro group, It may be substituted with a group selected from a sulfo group, a halogen atom, etc.

When R3] is an amine group, a phenyl-substituted amine group which may have a substituent is particularly preferred.

In the general formula +C-11, when R33 is a substituent that can be substituted with #, it may be substituted with the optional substituent described for R.

Examples of the optionally substituted alkyl group having at least 2 carbon atoms in R35 in general formula (C-1) include ethyl group, propyl group, butyl group, bentadeflu group,
Examples include a tcrt-7''thyl group, a nclohexynol group, a /chlorohexylmethyl group, a phenylthiomethyl group, a dodenruoquinphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

In general formula (C-1+ and general formula +C-111, Z
and zb, respectively, a hydrogen atom or a Kampflig leaving group (excuse the coupling-off atom).

Examples include halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.),
Alcoquine group (e.g. etquine group, totinoloxy group, methquinethercarbamoylmethquine group, cal, +:
old cyprobyluoquine group, methylsulfonyl ethoxy group), aryloxy group (e.g., dichlorophenoxy group, q-methoxyphenoquine group, ≠-carboxyphenoquine group), acetoxy group (e.g., acetoxy group, tetra Tecanoyloxy group, benzoyloxy group), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutylamino group, methanesulfonyl group) (amino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloquine carbonyloxy group (e.g., phenoxycarbonyloxine group) ), aliphatic or aromatic thio groups (e.g.
Examples include ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide groups (eg, scunnimide group, hydantoinyl group, etc.), and aromatic azo groups (eg, phenylazo group, etc.). These leaving groups may include three in one groups.

Preferred examples of the cyan coupler represented by the general formula C-1) or tc-n+ are as follows.

Preferred RH aryl groups and heterocyclic groups in the general formula tc-11 include halogen atoms, alkyl groups, alkokyne groups, aryloki7 groups, acylamino groups, anlu groups, carbamoyl groups, sulfonamide groups, sulfamoyl groups,
Sulfonyl group, nulfamide group, oxocarbonyl group,
More preferably, it is an aryl group substituted with an ano group.

In the general formula (C-1+, when R33 and R32 do not form a group, R32 is preferably 1 (7) is a substituted or unsubstituted alkyl group, aryl group, particularly preferably 1L<i'j
It is an alkyl group substituted with an aryloquine, and R33 is preferably a hydrogen atom.

In the general formula [C-(11), R is preferably a substituted or unsubstituted alkyl group or an aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula tc-l, preferred Rid carbon number is 2~/
! It is a methyl group having an alkyl group and a substituent having carbon number/or more, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an arylox group, or an alkyloxy group.

In the general formula tc-11), R15 is more preferably an alkyl group having 2 to 1 carbon atoms, and 2 to q carbon atoms.
Particularly preferred is an alkyl group.

In the general formula (C-.n), preferred R3A is a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred.

In the general formulas FC-1) and fc-111, preferred Zl and Z2 are hydrogen atoms, parogen atoms,
These are an alkoke group, an arylox7 group, an alkoke group, and a sulfonamide group.

In the general formula tc-tl), a Z2H/.logen atom is more preferable, and a chlorine atom and a fluorine atom are particularly preferable.

In the general formula TC-1), Zl is more preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

Specific examples of the /uncouplers represented by the general formulas tc-1) and tc-1) are listed below, but the present invention is not limited thereto.

(U 3) 1712NS02NIl α (C-j) α (C-+1 (C-71 (C-♂) N (C-10) F F+C-//) ShikuC-/jl (C-/j) (C -/Hiroshi) ((-/j) (C-/Al ((-/♂) (L)b (C-/ri) (t)Cs H11 (C-,!(71 u (C-x/1) (C-22) FC-,!Jl (C-, z≠) , C-2s) (C-26) (C-, 27) ((knee 21) (C-λri) (C-30) α (C-J/) (C-371 (C-Jf) α (C-37) (c-po) (C-Hiroshi/ ) α (C-≠2) α (C-≠3) (C-p α (C-≠j) (c-4Ll!1) 0(-H2C)12CT(2COOtl(C-≠g) (shi-≠ri) α [C-t O) The above general formula (C Cyan couplers represented by -11 and IC-4J1 can be synthesized based on the descriptions in JP-A No. 16-16, JP-A No. 72, and the like.

The granularity can be improved by using a coupler having an appropriate coloring property and diffusivity. Such dye-diffusive couplers are described in US Pat. No. 3TL.

No. 137 and British Patent No. 2. /Ko! ,! ; Specific examples of Magenta Turnip and G are in No. 70, and European Patent Nos. 6 and 6.
No. 70 and West German Application Publication No. 3.23t! −.

No. 333 describes specific examples of yellow, magenta or uncoupler.

Dimers or higher polymers may be formed in the dye-forming couplers and the above-mentioned special couplers. Typical examples of polymerized dye-forming couplers include U.S. Patent No. J, 4t3/
, No. 120 and <z, oro.

It is fully described in the 2/1 issue. Specific examples of polymerized macentor couplers include British Patent No. 2,102,173 and US Patent No. e, j A7. ．． It is described in 2♂λ issue.

In order to satisfy the characteristics required for the photosensitive material, two or more types of couplers used in the present invention can be used in combination in the same layer of the photosensitive layer, or the same compound can be used in two or more different layers. It can also be introduced into

The coupler used in the present invention can be introduced into the photosensitive material by an oil-in-water dispersion method. With the oil-in-water dispersion method, the boiling point is /
After dissolving either a high boiling point organic solvent of yt'C or higher and a low boiling point so-called auxiliary solvent, either alone or in a mixture of both, it is dissolved in an aqueous medium such as a water strainer or an aqueous gelatin solution in the presence of a surfactant. finely dispersed. Examples of high boiling point organic solvents are described in US Pat. No. J, 3.22.027 and others.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use for coating.

Specific examples of high boiling point organic solvents include phthalate esters (cyphthyl phthalate, dicyclohexyl phthalate,
Gee! = ethylhexyl phthalate, tesyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, etc.)
-Ethylhexyldiphenylphosphate, trineclohex/luposphate, tri-λ-ethylhexifluphosphate, tridodecylphosphate, tryptoquine ethylphosphate, )IJ dichlorolopylphosphate, di-2-ethylhexylphenylphosponate, etc.)
, benzoic acid esters (λ-ethylhexyl phthalate, dodecyl benzoate, -1'r-tylhexyl p
-Hydroquine benzoate, etc.), amides (diethyldodecaneamide, N-tetradeneruvirolidone, etc.),
Alcohols, phenols (isostearyl alcohol, di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl acelate, glycerol tributyrate, inostearyl lactate, trioctyl ntrate, etc.) ), aniline derivative + N, N-dibutyl-2-putquine-j-1er
t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.)
Examples include. In addition, as an auxiliary solvent, the boiling point is approximately 3
00C or more, preferably about /600C above jOoCJ-L
The following solvents can be used, typical examples of which include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, nclohexanone, λ-nitoxy/ethyl acetate, dimethylformamide, and the like.

Latex Dispersion Process, Effects and Specific Examples of Latex for Impregnation U.S. Patent No./Tata.

No. 363, West German patent application (OLSI No. 2, 314/
.

λ7≠ No. and No. 2. jψ), No. 230, etc.

The standard usage amount of color couplers is in the range of 0.00 to 1 mole per mole of photosensitive halide, preferably yellow couplers.
5 mol, magenta coupler 0.003 to 0.3
Mol, also cyan coupler io, 002 to 0.3
It is a mole.

Hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, etc. may be added to the light-sensitive material used in the present invention as color fogging inhibitors or color mixing inhibitors. May contain.

Known anti-fading agents can be used in the photosensitive material used in the present invention. Organic antifading agents include hydro, quinone, O-hydroxychromans, r-hydroquine coumarans, spirochromans, p-alfuki/phenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylene. Typical examples include dioquine benzenes, aminephenols, hindered amines, and ether or shikke ester derivatives in which the phenolic hydroxyl group of each of these compounds is amrylated or alkylated. Further, metal complexes represented by (bissalicylaldoximate) nickel complex and (bis-i'J, N-; alkyl, ; thiocarbamate) nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
U.S. Pat. No. 1, 241. As described in Juri No. 3,
Good results are obtained for compounds that share the partial structures of hindered amine and hindered phenol in the same molecule. In addition, in order to prevent deterioration of magenta dye images, especially deterioration caused by light, JP-A Shoj Otsu-/! 76≠spiroindans described in No. q, 2 and 7 described in JP-A Shojj-♂ Riza No. 3j
- Hydroquinone diether is also 1. <Nimonoether-substituted chromans give favorable results.

In order to improve the retention properties of the 777 image, particularly the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This ultraviolet absorber may be co-emulsified with a cyan coupler.

The coating amount of the ultraviolet absorber may be sufficient to impart photostability to the anchromatic print image; however, if too large a quantity is used, it may cause yellowing of the unexposed areas (white background areas) of the color photographic light-sensitive material. Because there is, it is usually good!
X 70 4 mol/m2~-! X10-3 mol/m2,
In particular, it is set in the range of 3 x 10' mol/m2 to j x 10-3 mol/m2.

In the usual color -·ξ- layer structure of a light-sensitive material, one ultraviolet absorber is contained in either layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material used in the present invention may contain a water-soluble dye entirely in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation. Oxonol-based, anthraquinone-based or azo-based dyes are preferred. Oxonol dyes that absorb green and red light are particularly preferred.

In the photographic emulsion layer or U and other hydrophilic colloid layers of the light-sensitive material used in the present invention, stilbene-based, triazine-based,
It may also contain a brightening agent such as an oxazole type or a coumarin type. Water-soluble ones may be used - or water-insoluble brighteners may be used in the form of dispersions.

The present invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on a support; multilayer natural color photographic materials usually have a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on the support. Each layer has at least one emulsion layer, and the order of these layers can be selected as desired. Further, each of the above-mentioned emulsion layers may be made up of one or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

In addition to the silver halide emulsion layer, the light-sensitive material used in the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer-filter layer, and an antihalation layer-back layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material used in the present invention, it is advantageous to use gelatin, although other hydrophilic colloids can also be used.

For example, gelatin derivatives - graft polymers of gelatin and other polymers, albumin - proteins such as casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulone esters, sugar derivatives such as alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial aceter A + poly-N-vinylpyrrolidone, polyacrylic acid-polymethacrylic acid- In the protective layer of acrylic acid-modified polyvinyl alcohol, a variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyacrylamide, polyvinyl alcohol, polyvinylpyranol, etc. The use of gelatin is particularly useful, and it is even more useful to rapidly process it with a silver

Japan...! Enzyme-treated gelatin as described in /Otsu, page 30 (/ri4&) may be used - hydrolysates and enzymatic decomposition products of gelatin may also be used.

In addition to the above-mentioned additives, the photosensitive material used in the present invention further contains various stabilizers, anti-staining agents-developers or their precursors, development accelerators or their precursors as described above,
Lubricants, mordants, matting agents.

Antistatic agents-plasticizers and other various additives useful for photographic materials may be added. A typical example of these additives is Research Disclosure/7tlt3C.
July 7, 7979) and July 17, 7979
January).

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer completely clear. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium, zinc oxide, carbonate, carunium sulfate, etc., and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. . For example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, and a reflective layer were all provided together. Alternatively, a transparent support 1 in which a reflective substance is used together, such as a glass plate - a polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

[Example-1] Process g (sample grave/~-〇) with the following prescription as a color developer. 4 were made.

Compound (A) shown in Table 1 below in the amount shown in Table 1 below Compound J shown in Table 1 below (B) Amount shown in cylinder 1fi below Sodium sulfite 06-? Potassium carbonate! Of ethylenediaminetetraacetic acid sodium acetate /? Sodium chloride /,! ? ≠-Amino 3-
Methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-p-phenylenediamine sulfate!, θ2 brightener (Hiro, Hiro I-diaminostilbene series)" Add 3.0f water / 000 Go pH 10.01 Tatami Tepa Geigy UVITEX-CK A sample of the color developer prepared in this way (Mul-co 0) was placed in a test tube with an opening ratio (opening area/sample area) of 0.01c1g@
Insert each one so that it looks like this! ! I left it in the IC for a week. After μ weeks had elapsed, the reduction due to evaporation was corrected with distilled water, and the residual rate of the aromatic primary amine color developing agent was measured and calculated using liquid chromatography.

As is clear from Table 1, when using hydroxylamine and diethylhydroxylamine alone (sample A/, J)
However, by adding compounds such as triethanolamine, polyethyleneimine, sodium sulfite, or fluorohexanediaminetetraacetic acid, the residual rate of the developing agent described above can be improved, but it cannot be said to be sufficient (Sample & 3, μ,',').

However, as is clear from sample &7~/J',
It can be seen that by using the compound represented by the general formula (1), the residual rate of the developing agent is significantly improved and the storage stability of the color developer is improved.

Disaster A [Example-2] A multilayer color photographic paper was prepared by coating each layer of the composition shown in Table B below on a paper support laminated on both sides with polyethylene. The coating solution for each layer was prepared as follows. The structural formulas of the coupler, color image stabilizer, etc. used in the coating solution will be described later.

-A cleft yellow coupler (a)/ri,/'? of the first layer coating solution? and color image stabilizer (
b) Ethyl acetate 27.2d and solvent (c
) 7.

This solution was emulsified and dispersed in an aqueous IO% gelatin solution containing 70 sodium tidodecylbenzenesulfonate (RYTT). On the other hand, the following blue-sensitive sensitizing dye was added to a silver chlorobromide emulsion (silver bromide/mo1%, containing Ag 70 f/kl) per mo1 of silver chlorobromide! , 0x10 mol was added to form a back-end emulsion and prepared as 0fvI4#. The emulsified dispersion and the emulsion are mixed and dissolved, the gelatin concentration is adjusted to have the composition shown in Table B, and the first
A layer coating solution was prepared. The second to seventh layer coating solutions were also prepared using the components shown in Table B in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is /-oxy-3,!
-dichloro5-) riazine sodium salt was used.

The following spectral sensitizers were used in the emulsions of each layer.

(b) Spectral sensitizer for the back-sensitive emulsion layer (adding 7X10 moles per mole of silver halide) (B) Spectral sensitizer for the green-sensitive emulsion layer (adding X10 mole per mole of silver halide) (c) Spectral sensitizer for red-sensitive emulsion layer (addition of 10 moles of CoX per mole of silver halide) The following dyes were used as anti-irradiation dyes in each emulsion layer.

The structural formulas of the friend compounds used in this example, such as the dye in the emulsion of the green-sensitive layer and the dye coupler in the emulsion of the red-sensitive layer, are as follows.

(a) Yellow coupler α 13 6) Color image stabilizer (C) Bath medium (d) Color mixture inhibitor H (C) Magenta coupler (g) Solvent =:l mixture (weight ratio) (Synopsis Ultraviolet absorber C4H ,(t) C)120H2+,;IJOc8H1□/:! ”,l
Mixture (mole ratio) H O) Solvent (iso c7n,, (t) GoP 0 (k) Cyan coupler C' (Kl) α (K2) /:l Mixture (mole ratio) C4H, (t) of /', 3', 3 inclusions (molar ratio) (m) Solvent The multilayer color photographic paper prepared as described above was subjected to wedge exposure and then processed in the following processing steps.

(Processing process) (Temperature) (Time) Color development jj”c 4A3 seconds bleach fixing
! ! 'Cut stable for seconds / jj'c Stable for 0 seconds 3! Stable for 0 seconds j jj'c Stable for 0 seconds
Drying 7o' to ro'c to second stability was set to 3 tanks countercurrent from stable 3 crabs to stable 1. The formulation of each treatment solution used is as follows.

Sodium sulfite 0.2? Potassium carbonate 30? Nitonrotriacetic acid l? Sodium chloride
1. ! 1 Color developing agent shown in the following No. 1 O, O/mol
Brightener (≠, μ'-diaminostilbene type) 3. Add water of 10ooml pH10,
or Bleach-fix solution EDTA Fe (In) NH4・-2H20A
O? EDTA-j Na-J H204'S' Ammonium thiosulfate (70%) / Sodium thiosulfite /6? add water
1000mlpH! , 1 Stabilized formalin (37) 0. /xd
/-Hydroxyethylidene-/.

/-Diphosphonic acid (O%) /, 6 Bismuth chloride O.J. Aqueous ammonia (26%) Ko,! d Nitrilotriacetic acid/JN
a7, □yEDTA
o,z? sodium sulfite
1. Of! -chloro-1-methyl-≠- inthiazolin-3-one! O ■ Add water 1000.1 Meanwhile, take a portion of the above color developer to a bee force of /l and open rate is 3!0C
After leaving it for one day, the sample was treated with the above-mentioned treatment process using this aging solution.

The next treatment using the color developer solution (aged solution) left for 21 days was called an aged solution test, and the treatment using the color developer solution (fresh solution) before being left was called a fresh solution test.

The photographic properties obtained from the fresh liquid test and aged liquid test are shown in Table 1.

Photographic properties were expressed in terms of Dmin at magenta density and gradation points.

Dmin represents the minimum density, and since the gradation affects the density o and r, 1 ogE is 0. ! It is expressed as the density change up to the density point on the high exposure side.

From the results in Table 2, it can be seen that experiment A/-≠ becomes Dmin over time.
In contrast, in Jikkenya t~/r, changes in Dmln and gradation were small even after aging, indicating that the stability of photographic properties was significantly improved. Another experiment! Among the ~r, experiment sr had the smallest change in Dmin and gradation, and among the color developing agents, the compound @
is found to be the most preferable.

Color developing agent ① shows the following compounds.

■ Appetizer compounds (a), Φ), (C), (ψ are the same as mine [
Example 3 Color photographic paper was prepared in the same manner as in Example 1, except that the bromide ion content of the green-sensitive layer emulsion was rOmo 1%, and after wedge-shaped exposure, changes in photographic properties with the liquid over time were examined to prevent fogging. When evaluated in terms of occurrence, the developer of the comparative example showed a large increase in fog over time, whereas the developer of the present invention showed little increase in fog over time and maintained good photographic properties.

[Example 4] After forming a wedge of color photographic paper prepared in the same manner as in Example 4, it was subjected to a running process (until three times the tank capacity was replenished with various color developers in the following processing steps). Continuous processing) tests were conducted.

(Processing process) (Temperature) (Time) (Replenishment amount) Color development 33-'C4L7 seconds / &
OtJ/m2 Bleach-fixing 3r'c at seconds /
00 ml/m 2 rinse■ JO"CJ (7 seconds rinse■ J(ll'c 10 seconds rinse■ J
(7”C20 seconds 00ytl/m2 drying 4
00 to 7 o@c io seconds The rinsing process is as follows: 3-tank countercurrent system from Rinse ① The formulations of each processing solution used are as follows.

Additives C and Dy shown in Table 3 below, whitening agent (≠ 4t/-diaminostilbene type) shown in Table 3! ,Of ≠,oi
EDTA i,o? T,z? Potassium carbonate 30.0? 30. Of Sodium Chloride 1. Dai o, it daamino-3-methyl-N-ethyl-N- (β-(methanesulfonamido)ethyl 1- p-7 22-diamine sulfate J', 0? 7.Of
Benzyl alcohol Quantity as stated in Table 3 Diethylene glycol Quantity as stated in Table 3 /, -One part Roxybechizene -J 4cj- Trisulfonic acid 300m9 300m9
Add water 1000rrtl 100
0ynlpHio,io io,z.

E DTA Fe (l[) NH4・-2H20A
O? EDTA-J Na-J H20” ammonium thiosulfate (70%) / 20wl sodium sulfite / 62 glacial acetic acid
Add water to 7
1000go pHr, z Add water 1000ffi1p
H7,.

The processing was carried out in the above processing steps using the above processing solution, and the B, G, and R concentrations (stain) of the unexposed areas at the start of the running process and at the end of the running process were measured using a Fuji self-recording densitometer. Furthermore, after the sample @ro@c<z~1ORH) at the end of the running process was left for one period, the B, G, and R densities of the unexposed areas were measured again.

The results of the changes in photographic properties obtained are shown in Table 3.

From the results of the third experiment, the stain increases significantly as a result of the running treatment in the experiments 〇/and -, whereas in the experiments 〇3~
It can be seen that at /3, the increase in sting is extremely small. Also, looking at the changes over time after the treatment was completed, Experimental Mu3~/3
it,, the increase in stain is very small compared to experiment AI,-.

[Example-5] As described in Table CK, #1 (lowest layer) to #7 layers (
A photographic paper sample was prepared by first applying the top layer). The coating solution for each layer was prepared as follows. Details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. In other words, Yellow Coupler 200? , anti-fading agent,
J fJ high boiling point solvent (p)IO? and solvent (q)! f
After adding 600 ml of ethyl acetate as an auxiliary solvent and dissolving it in to''c by heating, Alkanol B (trade name;
Alkylnaphthalene sulfonates, DuPont regulations ) of!
Contains 330 grams of aqueous solution! Chizelatin water @liquid J, 30
Please be sure to mix it with 0. This liquid was then emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the f-sensitive emulsion layer and /-methyl-2-mercapto-! -acetylamino/
, 3. Hiro - Emulsion with triazole/ , 4AOOY
(As kg?≦,7ri,contains gelatin 770f?)
A coating solution was prepared by adding a 70% aqueous gelatin solution and toor.

The second to seventh layers were prepared according to the composition of the first layer (g) according to the composition of Roasted C(7).

However, No. Photographic paper was prepared using each of the seven cyan couplers shown in the table below.

n-1(no-hydroxy-3,!-di-tcrt-amylphenyl)penzotriazole o2-(j-hydroxy-3,!-di-teyt-butylphenyl)benzotriazole p di(+2-ethylhexyl)phthalate q dibutyl Phthalate r! -G-tert-amyl phenyl-3°! −
Di-tcrt-7” hydroxybenzoate S 2.!-Di-tcrt-octylhydroquinone t / France-di-tert-amyl-,2!-dioctyloxybenzene u, 2.-I-methylenebis(≠-methyl-6-te
(rt-butylphenol) Also, be sure to use the following as a sensitizing dye for the emulsion in each layer.

Sensitizing dye of emulsion in blue-sensitive layer; anhydro-3-methoxy-
! '-Methyl-J, J'- Sensitizing dye of disulfobrovir selenocyanine hydroxide green-sensitive layer emulsion; anthrotherethyl-! ,
j'-diphenyl-3,31-disulfoethyloxacarbocyanine hydroxide sensitizing dye of red-sensitive layer emulsion, J, 3/-diethyl-methoxytheta, r'-(2,2 partially methyl-/, 3 -propano) theadicarbocyanine iodide and as a stabilizer for each emulsion/-methyl-comelkabutoner acetelamino/, 3. II-) Riazole was used.

Also, be sure to use the following as an irradiation prevention dye.

≠-(3-carboxy-!-hydrokycu-(J-
(j-carboxy-!-okine-/-(4t-sulfonatophenyl)-1-pyrazoIJ y -41-ylidene)-7-propenyl)-/-pyrazolyl)benzenesulfonate-di-potassium salt N;N/ -(≠, l-dihydroxy-2./Q-dioquine-3,7-cissulfonatoanthracene-/,!-diyl)bis(aminemethanesulfonate)-tetrasodium salt Also as a hardening agent/, -bis (vinylsulfonyl)ethane was used.

The couplers used are as follows.

Yellow Coupler 1'1 Magenta Coupler - The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

(Processing process) (Time) (Temperature) Color development 3 minutes 30 seconds 33°C bleach fixing 7 minutes 30 seconds 33@C rinse (3 tank cascade) 2 minutes 3o”c drying
The treatment solution formulation used for 7 minutes to @c is as follows.

water too
Sodium sulfite (N, N) as described in the following No. Hirooi
/-bis(,2-hydroxybenzyl)ethylenediamine-N,N/-diacetic acid 0.7? Nitrilo
N,N,N-trimethylenephosphonic acid (μ0chi) /, 0? Potassium bromide 7.02 Additives shown in Table μ below C1 D Potassium carbonate listed in No. ≠ Batter 30? N-ethyl-N-(
β-methanesulfonamidoethyl)-3 monomethyl-μm aminoaniline sulfate! l! ? Fluorescent brightener (≠, 4t/-diaminostilbene type) /, or add water at 1000rd KOH
pH/o, /0 bleach-fix with ammonium thiosulfate (70%)/zo
Sodium sulfite l! ? E
DTA-F e (III) ・N) (a ・2H
2040S'EDTA
/ o f fluorescent brightener (4L, Hiro l-diaminostilbene type) /, or-1 mercapto! -Amino- Add water / 000ml ammonia water to pH 7.

Rinse liquid! -Chloro-methyl-≠- inthiazolin-3-one ≠01n9 co-methyl-≠-isothiazolin-3-one 101η co-octyl-μm isothiazolin-3-one 10~Bismuth chloride (≠0%) o, renitrilo-N
, N, N-) lytyrenephosphonic acid (≠0%) i, or/-hydroxyethylidene-7°/-diphosphonic acid (60%) 2.61 Fluorescent brightener (≠, μ'-diaminostilbene type ) i, or add water at 1000m100O
pH 7,z In the above treatment, a portion of the fresh solution and color developer was added to pH 2.
The Dmin and gradation of cyan were measured using the aged solution after being left for 7 days.

The increase in Dmin and gradation of the aged solution relative to the fresh solution is shown in the fourth column.

Compare the 4th with the experimental point / ~ 3 from the results in the table, and experiment Aμ ~
/l, even if you use a developer that has been left for one day, the Dmi
It can be seen that the changes in n and gradation are small, and the photographic properties are extremely stabilized. In particular, as a cyan coupler “C”
-rJ or “C-3rJ+ (Experiment A B,
7.10. //.

/J, /j) and when the sulfite concentration in the developer is small (
Experimental point/'0. It can be seen that the retention of the developer is higher than that of //, /3, and /, and that the photographic properties are more stable.

Cyan couplers A) and B) in Table μ are as follows.

A) α B) α Patent applicant Zashi Photographic Film Co., Ltd. Procedural Amendment 1986-72-Monday fda 1, Indication of the case 1986 Patent Application No. 207-4 2, Title of Invention No. Processing Method for Silver Fide Color Photographic Light-sensitive Materials 3, Relationship with the Case of the Person Making the Amendment Patent Applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the Amendment In the “Claims” column of the specification, “Invention [Detailed explanation of] Column 5, the statement in the "Claims" section of the description of the contents of the amendment is amended as shown in the attached sheet.

The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) No.? Page/6th line "Methoxyethyl" Correct it to "(β-methanesulfonamidoethyl)".

2) Second page/7th line "p-7 22 diamine" "Aniline" and correct it.

3) No. 1 O Hiro page line 79 "Nitonrotriacetic acid" "Nitrilotriacetic acid" and correct it.

4) 1st//page 17th line "p-phenylenediamine" "Aniline" and correct it.

5) At the end of the 12th page O, it says, ``Example was treated in the same manner as Example ≠ except that ionized water (calcium and magnesium each less than jppm) was used as the rinse solution of Example μ, and the results were obtained in the present invention. Favorable results were obtained.''

Attachment 2, Claims (1) A silver halide color photographic light-sensitive material is prepared in a color developer containing an aromatic primary amine color developing agent and at least a compound represented by the following general formula (1). 1. A method for processing a silver halide color photographic material, the method comprising: processing a silver halide color photographic material;

General formula (I) (wherein M may be the same or different and represents a hydrogen atom, an alkali metal, and an ammonium ion; n is /~
represents an integer of (2) The method for processing a silver halide color photographic material according to claim 1, wherein the color developer contains substantially no benzyl alcohol.

(3) The aromatic primary amine color developing agent is
Silver halide color photographic photosensitive material according to claim 2, characterized by amino-3-methyl-N-ethyl-N- (which is a β-(methanesulfonamido)ethyl-to-aniline compound). How materials are processed.

Claims (3)

[Claims] (1) A silver halide color photographic light-sensitive material is processed with a color developer containing an aromatic primary amine color developing agent and at least one compound represented by the following general formula (I). A method for processing silver halide color photographic materials. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, M may be the same or different and represents a hydrogen atom, an alkali metal, and an ammonium ion. n is 1 to
Represents an integer of 4. ) (2) The method for processing a silver halide color photographic material according to claim 1, wherein the color developer does not substantially contain benzyl alcohol. (3) The aromatic primary amine color developing agent is 4-
The silver halide color according to claim 2, which is an amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine compound). Method of processing photographic materials.