JPS63146043A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability and the coloring property of a color developer and to reduce the increase of fogging of the titled material at the time of continuously processing by processing the silver halide color photographic sensitive material with the color developer contg. a aromatic primary amine color developing agent and a specific hydrazide, after exposing it. CONSTITUTION:The silver halide color photographic sensitive material is processed with the color developer contg. at least one kind of the aromatic primary amine color developing agent and at least one kind of the hydrazide shown by formula I, after exposing it. In formula, X is a bivalent group selected from -CO- or -SO2- etc., R<1> is hydrogen atom, alkyl, aryl, a heterocyclic ring, alkoxy or aryloxy group, R<2> is hydrogen atom, alkyl or aryl group, R<1> and R<2> may form a dimer or a polymer more than the dimer. Thus, the stability and the coloring property of the color developer are remarkably improved. As the result, the increase of fogging and the change of gradient of the titled material are remarkably reduced, even in the method of processing, using the color developer which has lapsed time.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and particularly relates to a method for processing a silver halide color photographic light-sensitive material. The present invention relates to a processing method in which an increase in fog during continuous processing is significantly reduced.

(Prior Art) Color developers using aromatic primary amine color developing agents have long been used in color image forming methods, and currently play a central role in color photographic image forming methods. .

However, the color developer mentioned above is very easily oxidized by air and metals, and when a color image is formed using an oxidized developer, fog increases, sensitivity and gradation change, and desirable photographic characteristics cannot be obtained. This is well known.

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, when hydroxylamine is decomposed, ammonia is generated, which causes fogging, and sulfite ions act as a competitive compound for the developing agent and inhibit color development. It can hardly be called a preservative.

In order to improve the stability of color developers, various preservatives and chelating agents have been studied. For example, as a preservative, JP-A-52-49828,
Aromatic polyhydroxy compounds described in US Pat. No. 9-160142, US Pat. No. 56-47038, and US Pat. No. 3,746.544, US Pat. No. 3,615,503 and British Patent No. 1.306, 176. Hydroxycarbonyl compounds described in JP-A-52-143020 and JP-A-52-143020
Examples thereof include the α-aminocarbonyl compounds described in JP-A-89425, the alkanolamines described in JP-A-54-3532, and the metal salts described in JP-A-57-44148 and JP-A-57-53749. In addition, as a chelating agent, Japanese Patent Publication No. 48-30496 and No. 44-302
Aminopolycarboxylic acids described in No. 32, JP-A-56-9
Organic phosphonic acids described in Japanese Patent Publication No. 7347, Japanese Patent Publication No. 56-39359 and West German Patent No. 2.227.639;
-121127, 55-126241 and 55
-65956, and other phosphonocarboxylic acids described in JP-A-58' 1958.15 and JP-A-58-20
Examples thereof include compounds described in Japanese Patent Publication No. 3440 and Japanese Patent Publication No. 53-40900.

(Problems to be Solved by the Invention) However, even if these techniques are used, the preservation performance is insufficient or the photographic properties are adversely affected.
No satisfactory results have been obtained.

In particular, in color developers from which benzyl alcohol, which is harmful due to pollution and liquid preparation, has been removed, the coloring performance inevitably deteriorates, but in such systems, the preservatives that act as competing compounds are In order to significantly inhibit color development,
Many of the techniques considered in the past are unsatisfactory.

Furthermore, color photographic window light materials containing silver chlorobromide emulsions with a high chlorine content tend to cause G2 fog during color development, as disclosed in JP-A-58-95345 and JP-A-59-23234.
It is stated in No. 2. When using such emulsions, a preservative that is less soluble in the emulsion and has better preservative performance is essential, but no preservative that is satisfactory in this sense has yet been found. .

Therefore, the objects of the present invention are, firstly, a processing method with excellent color developer stability, secondly, a processing method with excellent developability (e.g., color development), and thirdly, a method that reduces fog during continuous processing. It is an object of the present invention to provide a processing method in which the increase is significantly reduced.

(Means for Solving the Problems) The above object is to develop a silver halide color photographic light-sensitive material into at least one aromatic primary amine developing agent and a hydrazide represented by the following general formula (1) after exposure. This is achieved by a method for processing a silver halide color photographic material, which is characterized by processing with a color developer containing at least one of the following.

General formula (I) R' -X-NHNH-R2 (wherein, X is 2 selected from 100- and =SO2-
Represents a valence group. R' represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group, and R2 represents a hydrogen atom, an alkyl group, or an aryl group. A dimer or more multimer may be formed by the substituents R' and R2. ) The hydrazide represented by the general formula (1) will be explained in detail in terms of yield.

General formula (1) %Formula% In the formula, X represents a divalent group selected from 100- and 13O2-. R1 is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 1 to 1 carbon atoms, for example, methyl, ethyl, cyclohexyl, methoxyethyl, benzyl, L-butyl), a substituted or unsubstituted aryl group (preferably a carbon number 6 to 10, e.g. phenyl group, p-)
(lyl group, 2-hydroxyphenyl, 2-aminophenyl), a substituted or unsubstituted heterocyclic group (preferably a carbon number of 1 to 10, more preferably a 5 to 6-membered ring, and the heteroatom includes oxygen, nitrogen, those containing at least one of sulfur, etc., e.g. 4-pyridyl, N-acetylpiperidin-4-yl), substituted or unsubstituted alkoxy groups (preferably 1 to 10 carbon atoms, e.g. methoxy, ethoxy, butoxy group, methoxyethoxy group, benzyloxy group, etc.), or a substituted or unsubstituted aryloxy group (preferably having 6 to 10 carbon atoms, such as a fenoquine group, p
-methoxyphenoxy group, etc.), and R2 represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 6 to 10 carbon atoms, for example, a methyl group, an ethyl group, a cyclohexyl group, a methoxyethyl group, etc.), or a substituted Alternatively, it represents an unsubstituted aryl group (preferably having 6 to 10 carbon atoms, for example, phenyl group, 3-hydroxyphenyl group, etc.).

Substituents R' and R2 are further substituted with halogen atoms (e.g., chlorine atom, bromine atom, etc.), hydroxyl group, carboxyl group, sulfo group, amino group, alkoxy group, amide group, sulfonamide group, carbamoyl group. A sulfamoyl group, an alkyl group, an aryl group, etc. are preferred, and they may be further substituted.

In general formula (1), R1 is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group, and more preferably an aryl group or an alkoxy group. R2 is preferably a hydrogen atom or an alkyl group, most preferably a hydrogen atom. Furthermore, X is preferably -C-.

When the compound represented by general formula (1) is a monomer, the total number of carbon atoms is preferably 15 or less, and 10
It is more preferably 7 or less, most preferably 7 or less.

The compound of general formula (1) may form a bis body, a tris body, or a polymer linked by R1 or R2.

Specific examples of the compound represented by general formula (1) are listed below, but the present invention is not limited thereto.

NH2NHCOOCzH5 NH, NHCOCH.

and 5 HO' N H2N HCO@ CHz+T-CON HN H
t(I-12) NH2NHCHO (I-16) (I-18) N Hz N HCOOCz Hs○CON HN H
z (T-19) NH2NH3O20C□II, (i+ (I-21) (CH3) 3 CCON HN HzN-26,) (CH3) :l COCN HN HzH HOOC,, CH,C00H i:l-39) < I -40> HO・111, '゛/-ゝ・CONHNH2 '5 HOCH2CH, SO□NHNH2 N a O:l S CHz CHz CON HN
i', 2H2NCONHCH2CH, So□N HN
HzCHsCONHNH+CH listrSO3NaNa
0xSCH2CHtOCNHNHz○ (CH3”r; CCN HN I(CH2CH-○1
1. Many of the compounds represented by the general formula (1) can be obtained manually as commercial products, and can also be obtained using "Organic 5 syntheses", Coa
l, Vol.

5, p1055, P, A, S, SMTTII,
'Derwat4vesof hydrazine
and other hydronitrogens
havingn-n-bonds Jp, 12
0-124. P130-131, TIIE BEN
JAMIN/CUMMINGS PUBUSHINGC
OMPANY (1983), 5tanle
y R, 5 andler Walf Karo, ro
rganic Functional Group P
reparations JVol I 5econd
It can be synthesized according to a general synthesis method such as that published in J.D. Edition, p. 457. Synthesis examples are illustrated below.

Synthesis Example 1 (Synthesis of Exemplified Compound 1-9) 32 g (1.0 mol) of anhydrous hydrazine was poured into 200 mff1 of ethanol, and 38 g (0.2 mol) of P-toluenesulfonyl chloride was gradually added dropwise thereto while stirring. . After refluxing for 30 minutes after dropping, the system was placed in ice water, the precipitated crystals were filtered off, and recrystallized from acetonitrile to obtain P-1.
-23 g of colorless crystals of luenesulfonyl hydrazide were obtained.

Melting point 107-8°C0 Synthesis Example 2 (Synthesis of Exemplified Compound 1-8) Phenylhydrazine 21. 6 g (0.2 mol) and 30 mf of triethylamine are poured into 200 ml of ethanol and 21.6 g of ethyl chloroformate are added thereto while stirring.
(0.2 mol) was gradually added dropwise.

After refluxing for 30 minutes after the dropwise addition, the system was placed in ice water, extracted with ethyl acetate, concentrated, and purified by column chromatography to obtain 31 g of N-phenyl-N'-ethoxycarbonylhydrazine as an oil.

Synthesis Example 3 (Synthesis of Exemplary Compound!-23) After dissolving 180 g of terephthalic acid monomethyl ester in 11 methanol, it was slowly added dropwise to 500 ml of 50% hydrazine hydrate at room temperature while stirring. After completion of the dropwise addition, the mixture was heated under reflux for 5 hours with stirring, and then slowly added with an aqueous hydrochloric acid solution while cooling with water to bring the pH of the solution to about 1, and white crystals were precipitated. Two glasses of water! After stirring for a while, crystals were collected by vacuum filtration. Add this to 200mj2 of water
After washing twice with water and drying, 160 g of p-carpoxyhens hydrazide was obtained.

Melting point: 235-6°C0 Synthesis Example 4 (Synthesis of Exemplified Compound (1-25)) 62 rr+/2 pivaloyl chloride was added dropwise to 156 g of hydrazine hydrate (80%) under water cooling, and the mixture was further stirred for 1 hour. 300ml of saturated saline in the reaction solution! , and ethyl acetate 50
Extracted three times at 0 mA. The organic layer was distilled off under reduced pressure and 150 m/! of 10% hydrochloric acid was added to the resulting residue. After washing with chloroform, add 40ml of 50% aqueous sodium hydroxide solution,
Extracted with ethyl acetate. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from hexane/ethyl acetate to obtain 7.2 g of the target product.

Melting point 69-70°C0 Synthesis Example 5 (Synthesis of Exemplified Compound (1-49)) To a solution of 94 g of hydrazine hydrate (80%) added to 100 mff of ethanol, 38 ml of phenyl chloroformate was added dropwise under water cooling, and further 1 Stir the plate for a while.

200 mf of saturated brine was added to the reaction solution, and the mixture was extracted three times with ethyl acetate. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. Hexane was added to the resulting residue, which was crystallized and collected by filtration. The obtained crystals were recrystallized from xane/ethyl acetate to obtain 7.1 g of the desired product. Melting point 106-107
°C0 These compounds generally represented by 2N) include hydrochloric acid, sulfuric acid,
Salts may be formed with various vinegars such as nitric acid, phosphoric acid, oxalic acid, and acetic acid.

The amount of the compound represented by the general formula (I) added to the color developer is preferably 1.5 per 11 of the color developer.
XIO-' mol to 3.0XIO-' mol, more preferably 5.0XIO-3 mol-1, OX 10-' mol.

Examples of using hydrazides in color developers include U.S. Pat. Nos. 3,141.771 and 2,772.
, No. 973, but sufficient stability cannot be obtained. However, according to the method of the present invention, the preservation property was significantly improved and the occurrence of fogging was suppressed.

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, representative examples of which are shown below, but are not limited thereto.

DIN, N-diethyl-p-phenylenediamine D-22-aminol 5-dinithylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl-N -(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-[β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D8 N,N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N- Ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The aromatic-grade amine developing agent is used in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per 1 p of developer solution.

Furthermore, in terms of the effects of the present invention, especially the stability of the developer, it is preferable that the color developer used in the present invention does not substantially contain p-amine phenol type developer.

Further, it is preferable that the color developer does not contain a coupler such as a color coupler.

The color developer used in the present invention preferably does not contain hydroxylamine. Even if it contains
It is preferable that the amount added be as small as possible.

Further, it is preferable that benzyl alcohol is substantially not contained in terms of preventing fogging. Substantially free of benzyl alcohol means that the color developer l! This means that the amount of benzyl alcohol per unit is 2m42 or less. Preferably, it does not contain any benzyl alcohol.

(Left below) In addition, as other preservatives, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, potassium metasulfite, potassium metasulfite, and carbonyl sulfite adducts may be added as necessary. can do. The amount added to these color developers is 1. Og
/j2 or less, preferably 0.5g#2 or less. When the preservative of the present invention is used in a color developer that does not contain benzyl alcohol, it is preferable that the amount of sulfite ion added be small in terms of preservability and/or photographic properties.

Other preservatives include hydroxyacetones as described in U.S. Pat.
α-aminocarbonyl compounds described in JP-A-57-44148 and JP-A-57-53749, various saccharides described in JP-A-52-102727, hydroxams described in JP-A-52-27638, etc. Acids, α, α'-dicarbonyl compounds described in No. 59-160141, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, No. 56
Examples include poly(alkylene imine)s described in No. 94349, gluconic acid derivatives described in No. 56-75647, and the like. Two or more of these preservatives may be used in combination, if necessary.

Particularly preferred is the addition of alkanolamines (triethanolamine, jetanolamine, etc.) and/or aromatic polyhydroxy compounds.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Buffers include carbonate, phosphate, borate, concave borate, hydroquine benzoate, glycine salt, N, N
-dimethylglycine salt, leucine salt, norleucine salt,
Guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. Can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even when added to color developers, they have no effect on photographic performance. It is particularly preferable to use these buffers because they have the advantages of having no adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate-11, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boron. Potassium acid, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol/or more, particularly 0.1 mol/2 to 0.1 mol/2.
Particularly preferred is 4 mol/1.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 227
, organic phosphonic acids described in No. 639, JP-A-52-10
No. 2726, No. 53-42730, No. 54-1211
No. 27, No. 55 126241 and No. 55-6595
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 1973
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, No. 58-203440, and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethylenetriaminepentaacetic acid ・ethylenediaminetetraacetic acid ・triethylenetetraminehexaacetic acid ・N, N, N-)rimethylenephosphonic acid ・ethylenediamine ~ N, N, N' , N' -tetramethylenephosphonic acid ・1, 3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthoacetic acid Hydroxyphenylacetic acid/2-phosphonobutane-1,2,4-tricarboxylic acid/l-hydroxyethylidene-1,1-diphosphonic acid/N,N'-bis(2-hydroxyhensyl)ethylenediamine-N,N'-di Acetic 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 sequester metal ions in the color developer. For example 12
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 16088, No. 37-5987, No. 3B-7826
No. 44-12380, No. 45-9019, and U.S. Patent No. 3. 813. 247, etc.; JP-A-52-49829 and JP-A-52-49829;
p-phenylenediamine compounds represented by No. 0-15554, JP-A-50-137726, and JP-B No. 44-
30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium salts represented by U.S. Pat. No. 2,610,122 and U.S. Pat. No. 4,119.
p-amine phenols described in '462, U.S. Pat.
, No. 494.903, No. 3゜128.182, No. 4.
Described in No. 23-0.796, No. 3.253,919, Japanese Patent Publication No. 11431/1973, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596.926, U.S. Patent No. 3,582,346, etc. amine compounds, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128.18
No. 3, Special Publication No. 41-11431, No. 42-23883
No. 3 and U.S. Pat. 532. Polyalkylene oxide represented by No. 501, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Optional antifoggants can be added to the color developer used according to the invention, if desired.

As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylhencytriazole, 5-nitrobenzotriazole,
Typical examples include nitrogen-containing heterocyclic compounds such as -chloro-benzotriazole, 2-thiazolyl-henzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, 5-nitroindazole, and mercaptotriazoles. .

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is O~5g/2, preferably 0.1g~
4 g/ffi.

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

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although it is preferable that the replenishment amount be small, it is 20 to 600 mA per bottle of Angry Light Material, preferably 50 to 3 oOm/! , is. More preferably 100
mf to 200mf.

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 in particular organic complex salts of iron ([1) Preferred are complex salts of polycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; and hydrogen peroxide.

Among these, organic complex salts of iron(1) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron(1) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β -oxyethyl)-N,N
', N'-triacetic acid, ■, 3-diaminopropanetetraacetic acid, acetic acid, lyethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propatol Tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyl iminodiacetic acid, dichotroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminenipropionic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane -1,2,4-triacetic acid, 1,3-diaminopropanol-N,N,N'.

N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1,-diphosphonic acid, etc. can be mentioned.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron (I [[)
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 ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid.When used in the form of a complex salt, one type of ferric ion complex salt may be formed. Alternatively, two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one type or more of ferric salts may be used. Two or more types may be used. Furthermore, one type or two or more types of chelating agents may be used.

In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex.

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/l, preferably 0.05 to 0.50 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 U.S. Pat. No. 3,893.858, West German Pat. No. 57831, same 5
No. 3-37418, No. 53-65732, No. 53-7
No. 2623, No. 53-95630, No. 53-9563
No. 1, No. 53-104232, No. 53-124424
No. 53-141623, No. 53-28426,
Research Disclosure No. 17129 (19
Compounds having a mercapto group or a disulfide group as described in JP-A No. 1978-140129;
No. 8506, JP-A-52-20832, JP-A No. 53-32
No. 735, thiourea derivatives described in US Pat. No. 3,706,561; iodides described in West German Patent No. 1,127,715, JP-A-58-16235; West German Patent No. 96
Polyethylene oxides described in Japanese Patent Publication No. 6.410 and No. 2,748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; others, Japanese Patent Publication No. 49-42434,
No. 49-59644, No. 53-94927, No. 54
-35727, 55-26506 and 58-
Examples include the compound described in No. 163940 and iodine and bromide ions. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
The compound described in No. 0 is preferred.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalogenating agent such as ammonium iodide) may be included. If necessary, one or more types of boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate 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 periosulfate or ammonium thiocyanate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate. ; Water-soluble silver halide solubilizers such as ethylene bisthioglycolic acid, thioether compounds such as 3,6-cythia-1,8-octanediol, and thioureas; one type or a mixture of two or more of these is used. can be used. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per lf is preferably 0.3 to 2 mol, more preferably 0.5 to 1. It is in the range of 0 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
10 is preferable, and 5 to 9 are particularly preferable. If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. 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, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other photobrighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds have approximately 0.0% in terms of sulfite ion.
The content is preferably 02 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/ρ.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

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

In the present invention, instead of the usual "water washing treatment", a simple treatment method may be used, such as performing only a so-called "stabilization treatment" without providing a substantial water washing step. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above. In addition, the "washing process" here includes water washing alternative processes such as rinsing process.

The amount of washing water in the present invention is difficult to specify because it varies depending on the number of baths in multistage countercurrent washing and the amount of pre-bath components brought into the photosensitive material. It is sufficient if the liquid component is 1×10 −4 mol/l or less. For example, in the case of 3-tank countercurrent water washing, the photosensitive material 1
It is preferable to use about 10,100 O or more per hole, more preferably 5,000 mf or more. Further, in the case of water-saving treatment, it is preferable to use 100 to 1000 mj2 per 1M of photosensitive material.

The water washing temperature is 15°C to 45°C1, preferably 20°C.
C to 35°C.

In the washing process, for the purpose of preventing sedimentation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, fungicides and anti-inflammatory agents that prevent the growth of various types of batateria, algae, and molds (for example, ``Journal of Antihacterial Antifungal Agency
g, ^gents), Vol, 1 1+
No, 5. Compounds described in p. 207-223 (1983) and compounds described in "Chemistry of Antibacterial and Antifogging" by Hiroshi Horiguchi, metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry loads and unevenness. A surfactant or the like may be added as necessary to prevent this.

Or West's ``Photographic Science and Engineering Magazine (Photo.

A compound described in Sci. Eng., Vol. 6, pp. 344-359 (1965) may also be added.

Furthermore, chelating agents, bactericides, and anti-piping agents are added to the washing water.
The present invention is particularly effective when the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleaching and fixing components of the final bath may be at most 5.times.10@-2 mol/l, preferably L<1.times.10@-2 mol/1 or less.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjusting the membrane pH (e.g. pH3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.) ), surfactants, fluorescent whitening agents, hardeners, and other various additives may be used, and two or more compounds for the same or different purposes may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a membrane pH 8 l adjuster for the processor in order to improve image storage stability.

When the amount of washing water is significantly reduced as described above, it is preferable for the purpose of reducing the amount of waste liquid to flow some or all of the overflow liquid of the washing water into the bleach-fixing bath or the fixing bath, which is a pre-bath.

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 standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

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.

The silver halide emulsion of the light-sensitive material used in the present invention can have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc., but when performing rapid processing or low replenishment processing For this purpose, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol % or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol % is particularly preferable. In addition, when high sensitivity is required and capri during production, storage and/or processing must be kept particularly low, silver chlorobromide emulsions containing 50 mol% or more of silver bromide or Silveride emulsions are preferred, and more preferably 70 mol% or more. If silver bromide exceeds 90 mol %, rapid processing becomes difficult, but there are ways to accelerate development, such as using a development accelerator such as a silver halide solvent, fogging agent, or developer as described below during processing. By using , it is possible to speed up the development to some extent without being limited by the content of silver bromide.
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 content is 3 mol % or less. These silver halide emulsions are preferably used mainly for color papers and the like. Color photosensitive materials for bottle shadows (negative films, reversal films, etc.) contain silver iodobromide,
Silver chloroiodobromide is preferred, where the silver iodide content is between 3 and 15
Mol% is preferred.

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 diameter 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 below 2μm
．． The diameter is preferably 1 μm or more, and particularly preferred is 1. 5
It is not more than 0.15 μm.

The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably within 15%, is used in the present invention. It is preferable to do so. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
r) crystals or those in which these coexist;
It may have a crystalline form (regu tar), or it may have a composite form of these crystalline forms. Tabular grains may also be used, and in particular, tabular grains with a length/thickness ratio of 5 or more, particularly 8 or more account for 50% of the total projected area of the grain.
An emulsion having a concentration of more than 100% 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 described in "The Chemistry and Physics of Photography" by Glafktdes, P.
e etPhysique Photography
ue, published by Paul MonLe1.

1967], “Photographic Emulsion Chemistry” by Duffin [G.

Written by F. Duffin, Photographic Em
Ulsion Chemistry.

Focal Press, 1966], Zelikman et al. [Photographic Emulsion Production and Coating J (V, L, Zeli
Making and C by kman etal
oating Potographic Emulsio
It can be prepared using the method described in J.D., Focal Press, 1964].

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which I'Ag in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide that has already been formed before the silver halide grain formation process is completed, into silver halide with a smaller solubility product, and Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ψ1 formation, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

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

Known silver halide solvents (e.g. ammonia, rhodankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.). It can be used for lees, physical ripening, and chemical ripening. In order to remove soluble root salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, etc. are performed.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal A noble metal sensitization method using a compound (for example, a total complex salt or a complex salt of a metal of group Ⅰ of the periodic table such as PL, Ir, Pd, Rh, Fe, etc.) can be used alone or in combination.

The blue-sensitive, green-sensitive and red-sensitive emulsions used in the present invention are spectrally enhanced by a methine dye so as to have their respective color sensitivities. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Namely, pyridine 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, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, Benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These enhancing dyes may be used alone or in combination (combinations of sensitizing dyes are often used especially for the purpose of supersensitization. A representative example is U.S. Pat.
, No. 688,545, No. 2゜977.229, No. 3,
No. 397,060, No. 3.522,052, No. 3,5
No. 27,641, No. 3,617,293, No. 3,62
No. 8.964, No. 3,666.480, No. 3. 67
2. No. 898, No. 3,679,428, No. 3. 7
03゜377, 3,7.69,301, 3,8
No. 14.609, No. 3,837,862, No. 4゜02
6.101, British Patent No. 1,344,281;
No. 507,803, Special Publication No. 43-4936, No. 53-
No. 12375, JP-A-52-110618, JP-A No. 52-
No. 109925.

Along with aggravating pigments, pigments that do not themselves have spectral aggravating effects or substances that do not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

These exacerbating 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. Also, addition during chemical sensitization not only strengthens adsorption but also controls chemical aggravation sites. This is effective in preventing deformation of II and crystals. These addition methods are particularly effective in the case of emulsions containing a high content of silver chloride, and it is also particularly useful to apply them to grains with a high content of silver bromide or silver iodide on the grain surface. be.

The color photosensitive material used in the present invention is preferably an internal color photosensitive material, that is, a color coupler is preliminarily incorporated into the photosensitive material.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the camping active position is a hydrogen atom. Couplers in which the color-forming dye has appropriate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development-promoting side 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. 2,40
No. 7,210, No. 2,875.057 and No. 3
, No. 265, 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4. 022゜6
20, etc., or Japanese Patent Publication No. 55-10739, U.S. Patent No. 4
, No. 401,752, No. 4.326.024, RD
18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application No. 2,219,917,
Same 2nd. 261. No. 361, No. 2,329,58
Typical examples include the nitrogen atom separation type yellow couplers described in No. 7 and No. 2 433.812. α-pivaloylacetanilide couplers have poor color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same No. 2゜3
No. 43.703, No. 2,600,788, No. 2,
No. 908,573, same No. 3.062. No. 653, No. 3.152,896, and No. 3.936.015. As a leaving group for diagonal 5-pyrazolone couplers, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,35
The arylthio group described in No. 1,897 is preferred.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo(5,1-c)[1,2,4] triazoles as described in U.S. Pat. No. 3,725.067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (19
Examples include the pyrazolopyrazoles described in June 1984). Imidazo(
1,2-b) Pyrazoles are preferred, as described in European Patent No. 11
Pyrazolo (1°5-b) (1,2
, 4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293 and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4.22
Typical examples include the oxygen atom elimination type divalent naphthol couplers described in No. 8,233 and No. 4,296.200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369.929 and U.S. Pat.
No. 01,171, No. 2. 772. No. 162, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus; US Pat. No. 2,772,162;
No. 758.308, No. 4,126,396, No. 4
, No. 334,011, No. 4,327゜173, West German Patent Publication No. 3,329,729, and Japanese Unexamined Patent Publication No. 1987-1
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 66956 and U.S. Pat.
．． No. 622, No. 4,333,999, No. 4,45
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in Japanese Patent Nos. 1,559 and 4,427,767.

In particular, in the treatment method of the present invention, the following general formula (C-1
) and (C-11), it is possible to obtain good photographic properties with less fog.

Such an effect is noteworthy.

General formulas (C-1) and (C-11) will be explained in detail below.

General formula (C-1) H (wherein R1+ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group.

R1□ represents an alkyl group or an aryl group. R13 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Further, RI3 may be combined with R1□ to form a ring. Z indicates a method in which separation is possible by reaction with a hydrogen atom, a halogen atom, or an oxidized product of an aromatic primary amine color developing agent. ) General formula (C~■) H (wherein, R14 represents an alkyl group, cycloalkyl group, aryl group, or heterocyclic group. R1 represents an alkyl group having 2 or more carbon atoms, R16 represents a hydrogen atom, a halogen represents an atom or an alkyl group.Z1□ 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 (C-1) and Examples of the alkyl group having 1 to 32 carbon atoms for Ro, R1□ and RI4 in the cyan coupler (C-11) include methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc. Examples of the group include phenyl group and naphthyl group, and examples of the heterocyclic group include 2-pyridyl group, 2-imidazolyl group, 2-furyl group, and 6-quinolyl group. These groups further include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g., methoxy groups, 2-methoxyethoxy groups, etc.), aryloxy groups (e.g., 2,4-di-tert-amylphenoxy groups, (2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g., 2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group) , phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl 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., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.) , aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group, etc.)', aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.),
It may be substituted with a group selected from a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like.

Further, the amino group of Ro may be substituted or unsubstituted. Here, as the substituent when substituted, the above-mentioned ones can be mentioned. Examples of the substituted amino group for R1 include anilino group and hendithiazolyl amino group.

In general formula (C-1), when R+3 is a substitutable group, it may be substituted with the optional substituent described for R11.

Examples of the optionally substituted alkyl group having at least 2 carbon atoms in RIS in the -M formula (C-■) include:
Ethyl group, propyl group, butyl group, pentadecyl i, t
Examples include ert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

In general formula (C-1) and general formula (C-11), Z
ll and ZI□ are each a hydrogen atom or a campling-off group (including a coupling-off atom).

Examples include halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.),
Alkoxy groups (e.g., ethoxy, dodecyloxy, methoxyethylrubamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, etc.)
, aryloxy groups (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy groups (e.g., acetoxy group,
(tetrazokayloxy group, benzoyloxy group, etc.)
, sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (
For example, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy group, hensyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy groups, etc.), aliphatic or aromatic groups (e.g., ethylthio groups, phenylthio groups, tetrazolylthio groups, etc.)
, an imide group (eg, succinimide group, hydantoinyl group, etc.), an aromatic ab group (eg, phenylazo group, etc.), and the like. These leaving groups may include photographically useful groups.

Preferred examples of the cyan coupler represented by the general formula (c-B or (C-11)) are as follows.

In general formula (C-L), R1+ is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, or a sulfonyl group. More preferably, it is an aryl group substituted with a group, a sulfamide group, an oxycarbonyl group, or a cyano group.

In general formula (C-1), when R13 and R1□ do not form a ring, R12 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R12 is preferably a hydrogen atom.

In general formula (C-II), R14 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-n), the preferred bond has 2 to 1 carbon atoms.
5 alkyl group and a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-I[), RIS is more preferably an alkyl group having 2 to 15 carbon atoms, and RIS is an alkyl group having 2 to 4 carbon atoms.
Particularly preferred is an alkyl group.

In the -S formula (C-II), R16 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred.

In the general formulas (C-[) and (C-11'), Zll and Z12 are each preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group.

In the -i formula (C-11), ZI□ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In general formula (C-1), Zll is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

Specific examples of the cyan couplers represented by the general formulas (c-B and (C-11)) are listed below, but the present invention is not limited thereto.

(C-1) 0H
(C-2) 0
f-1 (C-4)
OH(C-5)
OH″C1゜1 (C-6) 0
H(C-7) ○H(C
-8) OH (C~13)
0H (C-14)
0H(C-1
5) 0H(C
-16)
01lOC,H.

(C-18) H (L)CJ++ (L)C3H11 (C-22) Shit (C-23) death! (C-24> (1) CsH.

(C-26) H (t)CsH+t (C-27) H (L)CsH+t (C-23) H (L)C,H,.

(C2g) 1l (C-30)? H (C-32) H (C-33) H -OCH□ (C-34) i1 (t)CaH1w (C-351 OH (t)CsHu (t)CsH++ (C-38) Shi2 (C-39 ) Shi2 (C-40) (C-, H) (C-42) ShiZ (C-431 (C-44) (C-45) Shit (C-46) (C-47) (C- 49) ○H shi2 (C-50) ?H These couplers represented by the general formulas (C-I) and ((, -If) are described in Japanese Patent Application Laid-Open No. 166956/1983 and Japanese Patent Publication No. 1983/1983.
-11572.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570; , 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4. No. 080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. 173 and U.S. Pat. No. 4,36
7.282.

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

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 1
Has a high boiling point of 75'C or higher? After dissolving either solvent 9 or a so-called auxiliary solvent with a low boiling point alone or in a mixture of the two, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling point organic solvents are described in, for example, US Pat. No. 2,322.027.

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

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (to 2-ethyl xyl benzoate,
dodecylhenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecaneamide, N-tetradecylbiolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4 - gee tert - amilfe, '- le nato),
Aliphatic carboxylic acid esters (dioctyl azelate,
glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (
N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of the process, effects, and latex for impregnation of the Latin lath dispersion process include U.S. Pat. It is described in.

The standard amount of color couplers used is in the range of 0.001 to 1 mole per mole of photosensitive halogen, preferably 0.01 to 0 for yellow couplers.
．． 5 mole, 0.003 to 0 for magenta coupler
．． 3 mol, and 0.002 to 0.3 mol for cyan couplers.

The photosensitive material used in the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, etc. 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 hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylenedioxybenzene. Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Also (bissalicylaldoximate)
Metal complexes such as nickel complexes and (bis-N, N-dialkyldithiocarbamate) nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268.593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the substitution of spiroindanes as described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of the cyan image, particularly the light fastness, it is preferable to use a hensitriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably 1X10-' mol/rri to 2X10'' mol/rrr, especially 5X10-
It is set in the range of 'mol/rd to 1.5 x 10-3 mol/rd.

In the light-sensitive material layer structure of ordinary color paper, one of the layers on both sides adjacent to the cyan coupler-containing red malignant emulsion layer,
Preferably, both layers contain an ultraviolet absorber.

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

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be selected arbitrarily as needed. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, or 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, a filter layer, an antihalation layer, and a 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, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
A variety of synthetic hydrophilic polymeric substances are used, such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. be able to. The use of acrylic acid modified polyvinyl alcohol in the protective layer is particularly useful, and even more so when rapidly processed with silver chloride emulsions.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, Japa.
Enzyme-treated gelatin such as that described in No. I6.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products 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, developing agents 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. Representative examples of these additives are described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979).

These additives are very important in rapid printing, rapid processing, and furthermore in relation to the compounds of general formula [I] of the present invention. In addition, especially when the halogen composition of the emulsion used contains a high content of silver chloride, the combined use of mercaptoazole, mercaptothiadiazole, and mercaptobenzazole compounds is useful in the present invention in terms of color development and fogging. be.

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 clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium, zinc oxide, calcium carbonate, and calcium sulfate, 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, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

(Example) The invention will be illustrated below with examples.

Example 1 Table A was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was created. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) 19.1g and color image stabilizer (b)
) 4.4g, ethyl acetate 27.2ml and solvent (c) 7
．． 9 mf was added and dissolved, and this solution was emulsified and dispersed in 185 mf of a 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, a blue-sensitive sensitizing dye shown below was added to a silver chlorobromide emulsion (containing 1 mol % of silver bromide, 70 g/kg of Ag) at a rate of 5.0 x 10-
90g of a blue-sensitive emulsion was prepared by adding 'mol. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table A to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution.

The gelatin hardening agent for each layer is 1-oxy=3.5-
Dichloro-5-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (halogenated!! 4.0X10-' mole added per mole of silver halide) SO: +llN (CzHs) 3 (7.0X10-' mole added per mole of silver halide)
Red-sensitive emulsion layer The following dyes were used as anti-irradiation dyes in each emulsion layer.

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

(a) Yellow coupler C5I H3 (C)? Solvent (d) Color mixing inhibitor H (fJ Color image stabilizer (→ 2:1 mixture of solvents (weight ratio) (h) 1:5:3 mixture of ultraviolet absorbers (molar ratio) (i) Color mixing inhibitor 0 ■ (j) Solvent (iso CJI + 90 +T-P = 0(k
) 1:1 mixture (molar ratio) of cyan coupler (+) 1:3:3 mixture (molar ratio) of color image stabilizer ＼ C mountain (1) The following treatment steps were changed.

Approximately 1LL Melon color development
Bleach-fixing at 35°C for 45 seconds Rinse 1 at 35°C for 20 seconds Rinse 2 at 35°C for 20 seconds Rinse 3 at 35°C for 20 seconds Dry at 35°C for 60 seconds Rinse at 80°C for 60 seconds Rinse was carried out in 3-tank countercurrent water washing from Rinse 3 to Rinse 1. The processing solutions used are as follows.

Left standing 2 Developer additives See Table 1 Benzyl alcohol See Table 1 Diethylene glycol See Table 1 Sodium sulfite
0.2g potassium carbonate
30g EDTA2Na Ig sodium chloride), 5g color developing agent (see table 1) 0.012 mol brightener (
4,4'-diaminostilhene series) Add 3.0 g water
1000m lP H10,05 Deep page fixed liquid E D T A Fe (m) N H4,2Hz
0 60 gE DTA ・2 Na ・2 H
zo 4g ammonium 1000sulfate (70%)
120mj2 sodium sulfite
Add 16g glacial acetic acid and 7g water and looom lpH5
,5 Yu2iryugan formalin (37%) O,1m Q
l-hydroxyethylidene-1,1-diphosphonic acid (60%) 1.6mj bismuth dichloride 0.35g aqueous ammonia (26%) 2.5mff1 nitrilotriacetic acid/3Na 1. ogEDTA
・48 0.5g Sodium sulfite 1.0 g5-chloro-2
-Methyl-4-50mg isothiaprin-3-one Add 1000ml color developer solution for each composition, immediately after preparation (fresh solution) and after preparation and leave at 40'C for 14 days (aged solution). ) were used.

Table 1 shows the photographic properties of the obtained fresh solution and aged solution.

Photographic properties were expressed in two points: Dmin at magenta density and gradation.

Dmin represents the minimum density, and the gradation is expressed as a change in density from a point representing a density of 0.5 to a density point on the high exposure side of 0.3 in logE.

*D-I D-2 As is clear from Table 1, when hydroxylamine was added, the fog in the solution over time was high and the gradation change was large.

On the other hand, it can be seen that when the treatment liquid of the present invention was used, there was little fogging and the change in gradation was small even with the aged liquid. Furthermore, this effect is particularly pronounced in systems that do not contain benzyl alcohol.

Example 2 In Example 1, the bromide ion content of the green-sensitive layer emulsion was changed to 8.
When the change in photographic properties of the solution over time was evaluated in the same manner as in Example 1 using 0 mol %, good results were obtained with the configuration of the present invention, with little increase in fog.

Example 3 A corona discharge machined double-sided polyethylene laminate was coated with layers 1 (bottom layer) through 7 (bottom layer) as described in Table B.
(top layer) was applied to prepare a sample.

The coating liquid for the first layer was prepared as follows. After heating and dissolving a mixture of 200 g of yellow coupler, 93°3 g of antifading agent, 5 g of high boiling point solvents (p) Log and (q), and 600 mf of ethyl acetate as an auxiliary solvent at 60°C, alkanol B (alkylnaphthalene sulfonate) was added. 5% aqueous gelatin solution containing 330 mff1 of 5% aqueous solution (manufactured by DuPont) (I3300mf!) and emulsified using a colloid mill to prepare a coupler dispersion. From this dispersion, ethyl acetate was distilled under reduced pressure, and a mulching dye for a blue emulsion layer and l-methyl-2- Mercapto-5-
1,400 g of emulsion containing acetylamino-1,3,4-) lyazole (96.7 g as Ag, 170 g of gelatin)
g), and then add 260 g of 10% aqueous gelatin solution.
A coating solution was prepared by adding 0 g of the above solution. The coating liquids for the second to seventh layers were prepared in the same manner as for the first layer.

(Margin below) Table B The following sensitizing dyes were used in each emulsion layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'-, methyl-3,3'-disulfopropylselenacyanine hydrooxide; green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3;3'-Disulfoethyloxacarpocyanine hydroxide red-sensitive emulsion layer: 3.3'-diethyl-5-methoxy9.9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine Iodide and the following were used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-1-riazole and the following were used as anti-irradiation dyes.

4-(3-carboxy-5-hydroki)-4-(1-(
3-carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl)-, nzenesulfonatophenyl potassium salt N, N' ( 4,8-dihydroxy-
9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt and 1,2-bis(vinylsulfonyl)ethane was used as a hardening agent. .

The couplers used are as follows.

yellow coupler CI2゜ magenta coupler l The cyan coupler was changed as shown in Table 2.

The compounds used in this example are as follows.

UV absorber (n): 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole UV absorber (O): 2-(2-hydroxy-3,5-di-tert-butylphenyl ) Henzytriazole solvent (p) Nidi(2-ethylhexyl) phthalate solvent (q) Nidibutyl phthalate antifading agent (r): 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxyhenzo Ethic color mixture prevention diarrhea (
2.2″- methylenebis-(4-methyl-6tert-
Butylphenol The multilayer color photographic paper obtained above was exposed to a wedge-shaped light and then processed in the following processing steps.

"1": Cheng Samurai - Plate Warm color development 3 minutes 30 seconds at 33°C Bleach fixing 1 minute 30 seconds at 33°C Rinse (3 tanks 2 minutes 30°C cascade) Drying 1 minute Processing at 80"C The liquid is as follows.

Left puni liquid water 800
n/2 triethanolamine 1
0m15.6-cyhydroxy-1.2.4-Hensentrisulfonate sodium 300mgN,
N'-bis(2-hydroxybenzyl)ethylenediamine-N.

N'-Diacetic acid 0.1g Nitrilo-N, N, N-trimethylenephosphonic acid (40%)
1.0g potassium bromide
0.6g additive
Table 2 Sodium sulfite
Table 2 Potassium carbonate 30
gN-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 565g Fluorescent brightener (4,4'-diaminostilbene type 1.0g Add water at 1000mf KOH)
pi-110, 10-reduction fixer ammonium thiosulfate (70%) 150mρ
Sodium sulfite 15g Ethylenediamine iron (111) ammonium 60g Ethylenediaminetetraacetic acid 10g Fluorescent brightener (
4,4'-diaminostilbene type) 1.0g2-
Mercapto-5-amino-3,4-thiadiazole 1.0g Add water and add 1000ml of ammonia water pH 7,012 5~Chloro-2-methyl-4-inthiazolin-3-one 40mg2-methyl-4- Isothiazolin-3-one 10 mg 2-Octyl-4-isothiazolin-3-one 10 mg Bismuth chloride (40%) 0.5 g Nitrilo-N,N,N-trimethylene-phosphonic acid (40%) 1.0 g 1-
Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g Fluorescent brightener (4,4'-diaminostilbene type) 1.0g Aqueous ammonia (26%) 2.0mff1
Add water to 1000mρKO
For each composition, pH 7.5 color developer was tested immediately after preparation (fresh solution) and 2 months after preparation at 38'C (aged solution).
type was used.

The Dmin and gradation of cyan were determined for the fresh solution and the aged solution, and the differences between the results obtained for the aged solution and the fresh solution are shown in Table 2.

*: Cyan coupler A CI! .

Cyan Coupler B IJ As is clear from Table 2, when treated with the treatment liquid of the present invention, there was little increase in fog and little change in gradation even when the aged liquid was used.

Moreover, this effect is more remarkable when the sulfite ion concentration in the treatment liquid is lower.

On the other hand, when processing with a processing liquid to which hydroxylamine is added, there is a large increase in fog and a large change in gradation as the color developer ages.

Further, when a photosensitive material containing a cyan coupler represented by general formula (C-1) or (C-11) is processed with the processing liquid of the present invention, -C formula (C-I) and (CII
It can be seen that there is less increase in fog and less change in gradation due to aging of the color developer than in the case of processing photosensitive materials containing cyan couplers other than ). Moreover, this effect is more remarkable when the sulfite ion concentration in the treatment liquid is lower.

Example 4 Using the color photographic paper obtained in Example 1, a running test was carried out in the following processing steps until the color developer was replenished to three times the daily capacity (60).

However, the composition of the color developer was changed as shown in Table 3.

Processing temperature Temperature 1 time Far-temperature 1 color development 35°C 45 seconds 160tn 1/rr
f Bleach fixing 35°C 4.5 seconds 100ml
/% Rinse■ 30"C20 seconds -Rinse■
30"C20 seconds - rinse■ 30°
C20 seconds 200m 1/r+ (drying 60~7
The 30 second rinsing at 0°C was performed using a 3-tank countercurrent flow system from Rinse ■ to Rinse ■.

The composition of each treatment liquid used is as follows.

Zhen I II Image Solution Matagigorikai Inhibition X Solution Triethanolamine 8.0g 10
．． 0g Additive See Table 3 Fluorescent brightener (4,4'-diaminostilhene type) 3.0g 4
．． 0g ethylenediaminetetraacetic acid 1.0g
1.5g Kyu/Egan Tsukokai Potassium Carbonate 30.0g
30.0 g sodium chloride 1
．． 4g 0.1g4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-aniline sulfate 5.0g 7.0
g Benzyl alcohol See Table 3 Diethylene glycol See Table 3 5-Methyl-7=hydroquine 3,,1-triazaindolizine 30 mg
-Add water 1000m It
loooom! p H10, 1010, 50 I Tsukasa fixed precept] j Relago L5 Captive Department ↓l Shi P Mi DTA F
e(III) NH4・2Hz0 60 gED
TA ・2 Na ・2 Hzo 4
gSodium 1,000 sulfate (70%) 120m
f Sodium sulfite: Add 16 g of glacial acetic acid, 7 g of water, and rinse (1000 m)2 pH5,5 Rinse/+(Tank... and (0? is town)LE D T
A.2 Add 0.4g of Na.2HzO water.
1000rn! pt+
7.0 Processed using the above processing method, the B (blue), G (green), and R (red) densities of the unexposed areas at the time of Running Star 1 and at the end of running were determined.
Measured using a Fuji self-recording densitometer. Furthermore, after the sample at the end of the run was left at 60° C. and 170% RH for two months, the B, f:, and R concentrations of the unexposed area were measured again.

The results obtained are shown in Table 3.

From Table 3, when hydroxylamine is added,
While the increase in capri after running is large, when the treatment liquid of the present invention is used, the increase in capri after running is small, and at the same time, the increase in stain over time after treatment is also suppressed.

This effect is particularly noticeable when running with processing solutions that do not contain benzyl alcohol.

Example 5 A color photographic paper was produced in the same manner as in Example 1 except that the spectral enhancer in each emulsion layer was changed as described below.

(a) Spectral enhancer for blue-sensitive emulsion layer 5ChHN(CzHs) + (7XIO-' mole added per mole of silver halide) (B) Spectral enhancer for green-sensitive emulsion layer (halogen (4XIO-' per mole of silver halide added) molar addition) (
C) Spectral sensitizer for red-sensitive emulsion layer (halogen (2XIO-' mol added per 1 mol of tJIij) The obtained color photographic paper was imagewise exposed, and in the same process as in Example 4, the same various Running process for color developer until replenishing 3 times the tank capacity (
Continuous processing) tests were conducted. However, in the color developer composition of Example 4, triethanolamine and 5-methyl-7-hydroxy-3,4-'ll turizaindolizine were not added, and instead, 1,2-dihydroxyhenzeindolizine was added. 300 mg of 3.4.6-dolisulfonic acid was added to both the tank solution and the replenisher solution. The rinsing liquid was changed to the following rinsing water.

Rinsing water (same for tank night and refill night) and tap water with H-type strong acid cation exchange resin (manufactured by Mitsubishi Kasei ■, Diaion 5)
Water was passed through a hotbed column filled with K-IB and an OH type strong basic anion exchange resin (Diaion 5A-1OA) to obtain the following water quality, and then sodium dichloride isocyanurate 20% was added as a disinfectant. mg/Q was added.

Calcium ion 1.1mg//! Magnesium ion 0.5mg/j2pH6.9 After continuous treatment, the same evaluation as in Example 4 was performed, and the same results were obtained.

Example 6 A multilayer photographic paper having the layer structure shown below was prepared on the north side of a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

(Preparation of first layer coating solution) Yellow coupler (ExY-1) and (ExY-2)
10.2g, 9.1g and color image stabilizer (Cpd-
1) 27°2 cc of ethyl acetate and a high boiling point solvent (So 1v-1) to 4.4 g 7. 7 cc (8.0 g) was added and dissolved, and this solution was added to 10% gelatin water containing 8cc of 10% sodium dodecylhenzenesulfonate. 8 liquid 1
It was emulsified and dispersed in 8'5 cc. This emulsified dispersion and emulsion E
A first layer coating solution was prepared by mixing and dissolving MI and 2M2 and adjusting the gelatin concentration to have the following composition. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is 1-oxy-3
, 5-dichloro-s-triazine sodium salt was used.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/bo). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye] First layer (blue-sensitive layer) Monodisperse paper spectrally sensitized with a sensitizing dye (ExS-1) Silver chlorobromide emulsion (EMI) 0.13 Monodisperse silver chlorobromide emulsion (2M2) spectrally sensitized with an enhancing dye (ExS-1) 0.13 Gelatin 1.86 Yellow coupler (ExYC-1) 0. 44 Yellow coupler (ExYC-2) '0.39 Color image stabilizer (
Cpd-1) o, 19) Container
(Solv-1) 0. 35 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-3) 0.08 Fifth layer (green sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (ExS-2, 3) Silver chlorobromide emulsion (2M3) Monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with 0.05 multiplying dye (ExS-2,3) 0.11 Gelatin 1.80 Mazenk coupler (ExM- 1) 0.39 color image stabilizer (C
pd-4) 0.20 color image stabilizer (Cpd
-5) 0.02 color image stabilizer (Cpd-6
) 0.03 Solvent (Solv-
2) 0. 127 capacity medium (S
olv-3) 0. 25 Fourth layer (
Ultraviolet absorbing layer) Gelatin 1.60 Ultraviolet absorber CCp d-7/Cp d-8/Cpd-9=3
/2/6: Weight ratio > 0.70 Color mixing inhibitor (Cpd-10) 0.05) Volume
Medium (Solv-4) 0.27 Fifth layer (red sensitive layer) Monodispersed silver chlorobromide emulsion (EM5) spectrally enhanced with sensitizing dye (ExS-4,5) 0.07 sensitizing dye ( Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with ExS-4, 5) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 0.32 Color image stabilizer (
Cp d-8/Cp d-9/Cp d-12=3/
4/2: Weight ratio) 0.17 Dispersion polymer (Cpd i 1) 0.2
81 medium (Sal v-2)
0. 20 Sixth layer (ultraviolet absorption layer) Gelatin 0.54 Ultraviolet absorber (Cpd-77 Cpd-9/Cpd-12 = 115/3: weight ratio) 0.21-8
Medium (Solv-2)
0. 08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 In addition, at this time, as an irradiation prevention dye, (Cpd -1
3, Cpd-14) was used.

Further, in each layer, Alkanol
cx F-120 (manufactured by Dainippon Ink Co., Ltd.) was used.

As a stabilizer for silver halide, (cpa-15,16
) was used.

Details of the emulsion used are as follows.

EMI 1.0 80 0.08EM2
0.75 80 0.07EM3 0.5
83 0.09EM4 0.4 83 0.
1OEM5 0.5 73 0.09EM6
0.4 73 0.10 The structural formula of the compound used is as follows.

EχY-1 xY-2 Same as Snake xY-1. however Call+7(t) xC-1 xS-1 SO□HN(CtHl)□ xS-2 ExS-3 ExS-4 pd-1 pd-2 -f-CHZ--CH)r " S OlK pd-3 pd-4 pd-5 C2H.

pd-6 C5tlz(t) pd-7 where R=-C/! Ca HQ 1't) Cpd-9 "C, HqOon Cpd-10 Same as Cpd-3. However, R=CaH1t(t)Cpd
-11 →CHz CH)T-(n = 100~1000
)C0NHC,Hq(t) Cpd-12 1: Same as pd-7.

However, R=Cj2 CHz CH2COOCs H1q Solv-1 Nidibutyl phthalate Sol~=-2: l-Liclesyl phosphate 5ol
v-3 nitrioctyl phosphate 5olv-4:) linonyl phosphate pd-13 HO011 th It
CH2G Hz where n=2 Cpd-14 Same as Cpd13. However, n = 1 pa-ts H Cpd-13 After imagewise exposing the above sample, the composition of the color developer was changed as shown in Table 5, and in each substitution process, 2 of the tank capacity of the color developer was Continuous treatment was carried out until double replenishment.

Processing process Warm 1st Special' Can Mitsuru ■2 Color development 38'C 1 minute 40 seconds 290mf
1'! ! Bleach fixing 33°C 60 seconds 150m
l 9 eWash ■ 30~34°C 20 seconds -4i! .

Wash with water ■ 30-34'C 20 seconds -412° Wash with water ■ 3
0 to 34°C 20 seconds 10E 4ffi drying 70
~80 DEG C. for 50 seconds * 1 rl of photosensitive material (3 tank countercurrent method was used for water washing ①-②) The composition of each processing solution is as follows.

Left Puni developer Mata 2 evening precepts catcher's armpit water
800m12 1300mf Biethylenetriaminepentaacetic acid 1.0g1. Og nitrilotriacetic acid 2. O,g 2.0g1-Hydroquinethythelene-1,1-diphosphonic acid 2. 0g 2. 0g potassium bromide 0.5g -potassium carbonate
30g 30gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5. 5g 7. 5g Additive (Table 5) 5 Xl0-”moI!, 7 XI
O-2mof fluorescent brightener (Wll rTEX4 manufactured by Sumitomo Chemical) 1.5g 2.0g 1-lyethylenediamine (1,4-diazabicyclo(2,2,2) octane 5.0g 5.0g Add water 1000100O1000m100O
(25°C) 10.20 10.060M Watarudansui also/Hitotsu--Shujukai Issui
400mf 400mff1 Ammonium thiosulfate (70%) 200m42 300mj
2Sodium sulfite 20g 40gIron (In) ammonium ethylenediaminetetraacetate 60g 40gDisodium ethylenediaminetetraacetate 5g 10gAdd water 10100O! , 1000m4pH(2
5°C) 6.70 6.30 Processed in an unexposed state during the above running, and measured changes in Dmin after processing and Drnin after 2 months at 60'C/70%RH in the same manner as in Example 4. It is shown in Table 5.

According to the present invention (Nα47-53), Dmi immediately after treatment
Not only n, but also the increase in stain over time is small.

Example 7 A multilayer photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

(Preparation of first layer coating solution) 27.2 c of ethyl acetate was added to 19.1 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1).
c and high boiling point solvent (Solv-1) 7.7cc (8
, 0g) and dissolve it. 10% gelatin water containing 8 cc of 10% dodecylbenzenesulfonium at night?
The mixture was emulsified and dispersed in 185cc for 7 days. This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution.

Coating solutions for the second to seventh layer phases were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, (1)-oxy-3,5-dichloroS-triazine sodium salt was used.

Moreover, (Cpd-1) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/bo). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye] First layer (blue-sensitive layer) Monodisperse salt odor spectrally sensitized with an aggravating dye (ExS-1) Silver emulsion (2M7) 0.15 Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with an enhancing dye (ExS-1) 0.15 Gelatin 1.86 Ilo-coupler (ExY-1) 0. 82 color image stabilizer (Cpd
-2) 0.19 solvent (Solv-
1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cp d-3) 0. 08 Third layer (green-sensitive layer) Monodisperse silver chlorobromide emulsion (EM9) spectrally sensitized with 0.12 sensitizing dye (ExS-2, 3) Spectral sensitization with 0.12 sensitizing dye (ExS-2, 3) Sensitized monodisperse silver chlorobromide emulsion (EMIO) 0.24 Gelatin 1.24 Magenta coupler (ExM-1) 0.39 Color image stabilizer (CM-4
) 0.25 color image stabilizer (Cp d-5)
0. 12 Solvent (Solv-2) 0.2
5 Fourth layer (ultraviolet absorbing layer) Gelatin 1.60 Ultraviolet absorber (Cpd-67 cpd-7/Cpd-8 = 3/2/6: weight ratio) 0.70 Color mixing prevention agent (Cpd-9) 0. 05) Container (Solv-3) 0. 42 Fifth N (red sensitive layer) Monodisperse silver chlorobromide emulsion (EMI l) spectrally sensitized with sensitizing dye (ExS-4,5) Spectral sensitized with 0.07 enhancing dye (ExS-4,5) Sensitized monodisperse silver chlorobromide emulsion (EMI2) 0.16 gelatin 0.92 cyan coupler (
ExC-1) 1.46 cyan coupler (Ex
C-2) 1.84 Color image stabilizer (Cpd-7/Cpd-8/Cpd-10 = 3/4/2: weight ratio) 0.17 Dispersion polymer (Cpd-11) 0.14 Solvent (So
lv-1) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.54 Ultraviolet absorber (Cpd-6/Cp d-8/Cp d-10 = 115/3: weight ratio) 0.21 Solvent (
Solv-4) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Also, at this time, for preventing irradiation As dyes, (Cpd-12, Cpd
-13) was used.

Further, in each layer, Alkanol
cxF-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-14,15) was used as a silver halide stabilizer.

Details of the emulsion used are as follows.

EM7 Cube 1.1 1.0 0.10E
M8 Cube 0.8 1.0 0.10EM
9 Cube 0.45 1.5 0.09EMI
O cube 0.34 1.5 0.09EMII
Cube 0.45 1.5 0.09EM12
Cube 0.34 1.6 0.10 The structural formula of the compound used is as follows.

xY-1 xM-1 x ExC-1 Cz H5 ExC2 “YenxS-1 5OiHN(CzHs)i xS-2 xS-3 xS-4 Ct Hs CZ Hs
ExS-5 cpa-t +CH, -CH)i- "SO, K p d-2 cpa-3 cpa-4 cpa-5 0HCH.

□.

ゝC4H9(t) cpa-7 cpa-3 Same as cp d-6.

\C,HQ(t) Pd-9 C)12cll□C00C,11,7 pd-11 1+CHZ CH)i-(r+=100~1000
)C0NHC4Hq(U cpa-12 1i SO,K SO□K (where,
R=C, H7, n=2) Cpd-13 Same as Cpd-12. However, R=H, n=Ipd-14 H Cpd-15 Solv-1 dibutyl phthalate 5olv-2) lyoctyl phosphate 5olv-3)
Linonyl phosphate 5olv-4) Liclesyl phosphate All gelatin used was alkali-treated gelatin with an isoelectric point of 5.0.

When the photosensitive material thus obtained was processed in the same manner as in Example 4, excellent effects were obtained in accordance with the present invention C.

Example 8 Additive 1 used in Example 2 No. 23 and 27
-1 instead of ■-11, l-19, ■-32, respectively.
A test was conducted in the same manner as in Example 2, except that the same moles of ■-34, l-41, ■-44, and ■-48 were used, and similarly favorable photographic properties were obtained in all cases.

(Effects of the Invention) The present invention significantly improves the stability or color development of color developers, and as a result, increases in fog and gradation changes are significantly suppressed even in processing methods using color developers after aging. images with excellent photographic properties were obtained.

Such effects of the present invention were particularly remarkable in color developing solutions that do not substantially contain benzyl alcohol, which has a high pollution load.

Furthermore, the effects of the present invention were more pronounced when the sulfite ion concentration in the treatment liquid was lower. Furthermore, the effects of the present invention were remarkable when processing light-sensitive materials containing specific cyan couplers.

Furthermore, even in continuous processing, the increase in fog was significantly reduced, and the obtained images had excellent stability over time.

(3 others) Cough

Claims (2)

[Claims] (1) After exposure, a silver halide color photographic light-sensitive material is treated with a color developer containing at least one aromatic primary amine developing agent and at least one hydrazide represented by the following general formula (I). 1. A method for processing a silver halide color photographic material, the method comprising: processing a silver halide color photographic material; General formula (I) R^1-X-NHNH-R^2 (wherein, X represents a divalent group selected from -CO- and -SO_2-. R^1 is a hydrogen atom, an alkyl group, an aryl group , represents a heterocyclic group, an alkoxy group, or an aryloxy group, and R^2 represents a hydrogen atom, an alkyl group, or an aryl group.The substituents R^1 and R^2 form a dimer or more multimer. ) (2) Claim (1) characterized in that the color developer does not substantially contain benzyl alcohol.
A method for processing a silver halide color photographic material as described in .