JPH077199B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, the stability or color developability of a color developer is improved, and continuous processing is performed. The present invention relates to a processing method in which the rise of fog at time is remarkably reduced.

(Prior Art) A color developing solution using an aromatic primary amine color developing agent has been used for a long time in a color image forming method, and now plays a central role in a color photographic image forming method. . However, the color developer is very easily oxidized by air or metal, and when a color image is formed by the oxidized developer, fog is increased, sensitivity and gradation are changed, and desired photographic characteristics cannot be obtained. This is well known.

Therefore, means for improving the preservative property of various color developing solutions have been conventionally investigated, and among them, the method of using hydroxylamine and sulfite ion in combination is the most general. However, when hydroxylamine is decomposed, ammonia is generated, which causes fog, and sulfite ion has a drawback that it acts as a competitive compound of a developing agent and inhibits color development. Not a preservative.

In addition, various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, preservatives include JP-A Nos. 52-49828 and 59-160.
142, 56-47038, and aromatic polyhydroxy compounds described in U.S. Pat.No. 3,746,544, U.S. Pat.
Hydroxycarbonyl compounds described in 5,503 and British Patent No. 1,306,176, α-aminocarbonyl compounds described in JP-A-52-143020 and 53-89425, alkanolamines described in JP-A-54-3532, Examples thereof include the metal salts described in JP-A-57-44148 and JP-A-57-53749. Further, as the chelating agent, aminopolycarboxylic acids described in JP-B-48-30496 and JP-B-44-30232, JP-A No.
6-97347, Japanese Patent Publication No. 56-39359 and West German Patent No. 2,227,6
39, organic phosphonic acids, JP-A-52-102726,
53-42730, 54-121127, 55-126241 and 5
5-65956, and the like, phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, and JP-B-53-40.
Examples thereof include compounds described in No. 900 and the like.

(Problems to be solved by the invention) However, even if these techniques are used, the preserving performance is insufficient or the photographic characteristics are adversely affected,
No satisfactory results have been obtained.

In particular, in terms of pollution and preparation, in a color developer from which harmful benzyl alcohol is removed, it is inevitable that the color forming performance is deteriorated, but in such a system, a preservative acting as a competing compound is In order to significantly inhibit color development,
There are many things that cannot be satisfied with the technologies studied in the past.

Further, it is described in JP-A Nos. 58-95345 and 59-232342 that color fog light-sensitive materials containing a silver chlorobromide emulsion having a high chlorine content are susceptible to fog during color development. When such an emulsion is used, a preservative having low emulsion solubility and superior preservative performance is indispensable, but in this sense, no satisfactory preservative has been found. .

Therefore, the object of the present invention is, firstly, a processing method which is excellent in stability of a color developing solution, secondly, a processing method which is excellent in developability (for example, color developability), and thirdly, fogging during continuous processing. It is to provide a treatment method in which the rise is remarkably reduced.

(Means for Solving the Problems) The above-mentioned object is to provide a silver halide color photographic light-sensitive material after exposure, and at least one aromatic primary amine developing agent and a hydrazide represented by the following general formula (I). Of at least 1.5 × 10 ⁻³ mol per 1 color developing solution
It is achieved by a method of processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing 3.0 × 10 ^-1 mol.

General formula (I) in ^{R 1 -X-NHNH-R 2} ( wherein, X is -CO- and SO ₂ - .R ¹ representing a divalent group selected from a hydrogen atom, an alkyl group, an aryl group, a heterocyclic A group, an alkoxy group or an aryloxy group, R ²
Represents a hydrogen atom or an alkyl group. The substituents R ¹ and R ² may form dimers or multimers. ) The hydrazides represented by the general formula (I) will be described in detail below.

In the general formula ^{(I) R 1 -X-NHNH} -R 2 formula, X is -CO- and -SO ₂ - represents a divalent group selected from. R ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 10 carbon atoms, for example, methyl, ethyl, cyclohexyl, methoxyethyl, benzyl, t-
Butyl), a substituted or unsubstituted aryl group (preferably having a carbon number of 6 to 10, for example, phenyl group, p-tolyl group,
2-hydroxyphenyl, 2-aminophenyl), a substituted or unsubstituted heterocyclic group (preferably having 1 to 1 carbon atoms)
0, more preferably a 5- or 6-membered ring, which contains at least one of oxygen, nitrogen, sulfur and the like as a hetero atom, for example, 4-pyridyl, N-acetylpiperidine-
4-yl), a substituted or unsubstituted alkoxy group (preferably having a carbon number of 1 to 10, for example, methoxy, ethoxy, butoxy group, methoxyethoxy group, benzyloxy group, etc.), or a substituted or unsubstituted aryloxy group (preferably C 6-10, for example, phenoxy group, p-methoxyphenoxy group and the like), R ² is a hydrogen atom, or a substituted or unsubstituted alkyl group (preferably C 6-
10, for example, methyl group, ethyl group, cyclohexyl group,
Methoxyethyl group).

Substituents R ¹ and R ² may be further substituted on a halogen atom (eg, chlorine atom, bromine atom, etc.), hydroxyl group, carboxyl group, sulfo group, amino group, alkoxy group, amide group, sulfonamide group, A carbamoyl group, a sulfamoyl group, an alkyl group, an aryl group and the like are preferable, and they may be further substituted.

In the general formula (I), R ¹ is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, more preferably an aryl group or an alkoxy group. R ² is preferably a hydrogen atom. Further, X is preferably -CO-.

When the compound represented by formula (I) is a monomer, the total carbon number thereof is preferably 15 or less, more preferably 10 or less, and most preferably 7 or less.

The compound of general formula (I) may form a bis form, tris form, or polymer linked by R ¹ or R ² .

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

(I-1) NH ₂ NHCOOC ₂ H ₅ (I-2) NH ₂ NHCOCH ₃ (I-5) NH ₂ NHSO ₂ CH ₃ (I-7) CH ₃ NHNHCOOC ₂ H ₄ OCH _{3 (I-11) NH 2 NHCOCH} 2 4 CONHNH 2 (I-15) NH ₂ NHCHO (I-18) NH ₂ NHCOOC ₂ H ₄ OCONHNH ₂ (I-19) NH ₂ NHSO ₂ OC ₃ H ₇ (i) _{(I-25) (CH 3} ) 3 CCONHNH 2 (I-44) HOCH ₂ CH ₂ SO ₂ NHNH ₂ (I-45) NaO ₃ SCH ₂ CH ₂ CONHNH ₂ (I-46) H ₂ NCONHCH ₂ CH ₂ SO ₂ NHNH ₂ (I-49) CH ₃ CONHNHCH _{2 3} SO ₃ Na Many of the compounds represented by the general formula (I) are available as commercial products, and "organic synthesis"
(Organic Syntheses), Coll.Vol.5, p1055, PASSMIT
H, `` Derwatives of hydrazine and other hydronitrog
ens having n-n-bonds "p.120-124, p130-131, THE
BENJAMIN / CUMMINGS PUBUSHING COMPANY (1983), Stan
ley R. Sandler Walf Karo, `` Organic Functional Grou
p Preparations ”Vol I, Second Edition, p457 and the like can be synthesized according to a general synthesis method. Examples of synthesis are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound (I-4)) 32 g (1.0 mol) of anhydrous hydrazine was poured into 200 ml of ethanol, and 38 g (0.2 mol) of p-toluenesulfonyl chloride was gradually added dropwise thereto with stirring. After the mixture was refluxed for 30 minutes after the dropping, the system was opened in ice water, and the precipitated crystals were separated by filtration and recrystallized from acetonitrile to obtain 23 g of colorless crystals of p-toluenesulfonyl hydrazide.

Melting point 107-8 ° C. Synthesis Example 2 (Synthesis of Exemplified Compound I-23) 180 g of terephthalic acid monomethyl ester was added to methanol 1
Dissolve it in 50 ml of hydrazine hydrate, and slowly add dropwise to it while stirring at room temperature. After completion of the dropwise addition, the mixture was heated and refluxed for 5 hours while stirring, and then an aqueous hydrochloric acid solution was slowly added under ice cooling to bring the pH of the solution up to about 1, whereby white crystals were precipitated. After adding 2 liters of water and stirring for a while, the crystals were separated by vacuum filtration. This was washed twice with 200 ml of water and then dried to obtain 160 g of p-carboxybenzhydrazide.

Melting point 235-6 [deg.] C.

Synthesis Example 3 (Synthesis of Exemplified Compound (I-25)) To 156 g of hydrazine monohydrate (80%), 62 ml of pivaloyl chloride was added dropwise under ice cooling, and the mixture was further stirred for 1 hour. 300 ml of saturated saline was added to the reaction solution, and the mixture was extracted 3 times with 500 ml of ethyl acetate. The organic layer was distilled off under reduced pressure and the resulting residue was diluted with 10% hydrochloric acid water 15
After adding 0 ml and washing with chloroform, 40 ml of 50% sodium hydroxide aqueous solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried 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 desired product.

Melting point 69-70 ° C.

Synthesis Example 4 (Synthesis of Exemplified Compound (I-53)) To a solution of 94 g of hydrazine hydrate (80%) in 100 ml of ethanol was added dropwise 38 ml of phenyl chloroformate under ice cooling, and the mixture was further stirred for 1 hour. To the reaction solution was added saturated saline (200 ml), and the mixture was extracted 3 times with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the obtained residue to crystallize and collected by filtration. The obtained crystals are hexane /
Recrystallization from ethyl acetate gave 7.1 g of the desired product. Melting point 106-1
07 ℃.

These compounds represented by the general formula (I) may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.

The amount of the compound represented by the general formula (I) added to the color developing solution is preferably 1.5 × 1 per color developing solution.
It is 0 ^-3 mol to 3.0 x 10 ^-1 mol, more preferably 5.0 x 10 ^-3 mol to 1.0 x 10 ^-1 mol.

Examples of using hydrazides in a color developing solution are described in, for example, U.S. Pat. Nos. 3,141,771 and 2,772,973, but sufficient preservability cannot be obtained. However,
According to the method of the present invention, the homeostasis was remarkably improved and the generation of fog was suppressed.

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

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- [β-hydroxyethyl) amino] aniline D-6 N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D- 9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β-
Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β-
Butoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per developer.

Further, it is preferable that the color developing solution used in the present invention does not substantially contain a p-aminophenol-based developing agent from the viewpoint of the effects of the present invention, particularly the stability of the developing solution.

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

The color developer used in the present invention preferably contains no hydroxylamine. Even if it contains
The added amount is preferably as small as possible.

Further, it is preferable that benzyl alcohol is not substantially contained from the viewpoint of preventing fog. Substantially free of benzyl alcohol means that the amount of benzyl alcohol is 2 ml or less per color developer. The case where benzyl alcohol is not contained at all is preferable.

Further, as other preservatives, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sulfite salts such as sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts can be added if necessary. . The amount added to these color developers is 2.0 g / l
The following is preferably 0.5 g / l or less. When the preservative of the present invention is used in a color developing solution in which benzyl alcohol is not present, it is preferable that the amount of sulfite ion added is small in terms of preservability and / or photographic characteristics.

As other preservatives, hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176, JP-A-5-
2-143020 and 53-89425 α-aminocarbonyl compounds, various metals described in JP-A-57-44148 and 57-53749, various sugars described in JP-A-52-102727 , 52-27638, hydroxamic acids, 59-16014
Α, α′-dicarbonyl compounds described in No. 1, 59-18058
Examples thereof include salicylic acids described in No. 8, alkanolamines described in No. 54-3532, poly (alkyleneimines) described in No. 56-94349, and gluconic acid derivatives described in No. 56-75647. Two or more kinds of these preservatives may be used in combination, if necessary.

In particular, addition of alkanolamines (triethanolamine, diethanolamine, etc.) and / or aromatic polyhydroxy compounds and / or compounds described in Japanese Patent Application No. 62-24374 is preferable.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

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

As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, 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 and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they are effective for photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being inexpensive.

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

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, for example, aminopolycarboxylic acids described in JP-B-48-30496 and 44-30232, JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2,227,639. Organic phosphonic acids described, JP-A-52-102726, 53-42730, 54-121127,
Phosphonocarboxylic acids described in JP-A-55-126241 and JP-A-55-65956, and others, JP-A-58-195845 and 58-2034.
Examples thereof include compounds described in JP-B No. 40 and JP-B-53-40900. Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Diethylenetriaminepentaacetic acid-Ethylenediaminetetraacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1,3 -Diamino-2-propanoltetraacetic acid-Transcyclohexanediaminetetraacetic acid-Nitrilotripropionic acid-1,2-diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol ether diaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxyphenyl Acetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid If necessary, use two or more chelating agents in combination. Is also good.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37-16
088, 37-5987, 38-7826, 44-12380,
The thioether compounds represented by U.S. Pat. No. 45-9019 and U.S. Pat. No. 3,813,247, and JP-A-52-49829 and U.S. Pat.
No. 15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30074, JP-A-5-
Quaternary ammonium salts represented by 6-156826 and 52-43429, etc., U.S. Pat. Nos. 2,494,903 and 3,128,182
No. 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431
U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,58.
Amine compounds described in 2,346, etc., JP-B-37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41
-11431, 42-23883 and polyalkylene oxides represented by U.S. Pat.
Phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

If desired, any antifoggant can be added to the color developer used in accordance with the present invention. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-
Nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, 5-nitroindazole, mercaptotriazoles As a typical example, a nitrogen-containing heterocyclic compound such as

The color developing solution used in the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 2 minutes. The amount of replenishment is preferably as small as possible, but it is ^{20 to} 600 ml, preferably 50 to 300 ml per 1 m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 200 ml.

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

As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, any bleaching agent can be used, but especially organic complex salts of iron (III) (for example, aminopolyamines such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid). Carboxylic acids, aminopolyphosphonic acids, complex salts such as phosphonocarboxylic acids and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, malic acid; persulfates; hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. The aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β -Oxyethyl) -N, N ',
N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propanoltetraacetic acid , Methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminedipropionacetic 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'-tetramethylenephosphine Phosphate, 1-hydroxyethylidene-1,1-diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type Complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric iron salt and a chelating agent, one kind of ferric salt or You may use 2 or more types. Furthermore, one or more chelating agents may be used. Further, in any case, the chelating agent may be used in an amount more than that for forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is 0.01 to 1.0 mol / l.
It is preferably 0.05 to 0.50 mol / l.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent 1,290,8.
No. 12, No. 2,059,988, JP-A No. 53-32736, No. 53-5783
No. 1, No. 53-37418, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53-104232, No. 53
-124424, 53-141623, 53-28426, Research Disclosure No. 17129 (July 1978) and other compounds having a mercapto group or a disulfide group; JP-A-50-140129. Thiazolidine derivatives as described; JP-B-45-8506, JP-A-52-20832,
No. 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, iodide described in JP-A-58-16235; polyethylene described in West German Patents 966,410, 2,748,430. Oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434
No. 49, No. 59644, No. 53-94927, No. 54-35727,
The compounds described in JP-A-55-26506 and JP-A-58-163940, iodine, bromide ion and the like can be mentioned. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat.
Compounds described in 858, West German Patent 1,290,812 and JP-A-53-95630 are preferable.

In addition, the bleaching solution or bleach-fixing solution used in the present invention contains a bromide (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas, which may be used alone or in admixture of two or more. Can be used. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol,
More preferably, it is in the range of 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is 3 to 10
Is preferable, and 5-9 is particularly preferable. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

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

The bleach-fixing solution and fixing solution in the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, bisulfite) as preservatives. Potassium, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound. These compounds are about 0.02 ~
It is preferable to contain 0.50 mol / l, more preferably
It is 0.04 to 0.40 mol / l.

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Alternatively, a carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent, etc. may be added as required.

Next, the water washing step in the present invention will be described. In the present invention, a simple treatment method such as performing only a so-called "stabilization treatment" may be used without providing a substantial water washing step in place of the usual "water washing treatment". As described above, the “water washing treatment” in the present invention is used in a broad sense as described above. In addition, the term “rinsing treatment” as used herein includes rinsing treatment and other alternative washing treatments.

The amount of washing water in the present invention is difficult to define because it depends on the number of multi-stage countercurrent washing baths and the carry-in amount of the pre-bath component of the light-sensitive material, but in the present invention, bleaching and fixing in the final washing bath are performed. It suffices if the liquid component is 1 × 10 ⁻⁴ mol / l or less. For example, in the case of countercurrent washing with 3 tanks, it is preferable to use about 100 ml or more per 1 m ² of the light-sensitive material, and more preferably 5
It is over 000 ml. In the case of water-saving treatment, 1m of light-sensitive material
^It is recommended to use about 100 to 1000 ml per ^two .

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

In the washing process, deionized water described in Japanese Patent Application No. 61-131632 may be used for the purpose of preventing precipitation and stabilizing the washing water, or various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial And Anti-Fungal Agents "(J.Antibact.Antifung.Agents), Vol.11, No.5, p20
7 to 223 (1983) and compounds described in Hiroshi Horiguchi's "The Chemistry of Antibacterial and Antifungal Agents", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or drying load and unevenness. If necessary, a surfactant or the like for preventing the above can be added. Or West, “Photographic Science and Engineering Magazine (Phot.Sci.Eng.), Volume 6,
The compounds described on pages 344 to 359 (1965) and the like may be added.

Add chelating agents, bactericides and anti-bacterial agents to the wash water,
The present invention is particularly effective in the case where the amount of washing water is greatly reduced by multi-stage countercurrent washing with two or more tanks. It is also particularly effective when a multi-stage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the usual water washing step. In these cases, the bleaching and fixing components in the final bath are 5 × 10 ^-2 / l or less, preferably 1 × 10 ^-2
It should be less than / l.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffering agents (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monohydrate) for adjusting the membrane pH (eg pH 3 to 8). Representative examples include carboxylic acids, dicarboxylic acids, polycarboxylic acids and the like) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide,
Benzotriazole etc.), surfactant, optical brightener,
Various additives such as a hardener may be used, and two or more kinds of the same or different target compounds 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, and ammonium thiosulfate as a film pH adjusting agent for the processor in order to improve the image storability.

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

In this treatment step, a constant finish can be obtained by using a replenisher of each treatment solution to prevent the composition of the solution from changing during continuous processing. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen agitation, air agitation and the like may be provided in each treatment bath.

The method of the present invention is a process using a color developing solution,
It can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, color positive film, color negative film, color reversal film and the like.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride, but in the case of performing rapid processing or low replenishment processing. In particular, 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. When high sensitivity is required and fog during production, storage, and / or processing is required to be particularly low, a silver chlorobromide emulsion containing 50 mol% or more of silver bromide or an odor is used. A silver halide emulsion is preferable, and 70 mol% or more is more preferable. Silver bromide
If it is 90 mol% or more, rapid processing becomes difficult, but means for promoting development, for example, by using a means such as a silver halide solvent, a fogging agent, or a development accelerator such as a developer, which will be described later, during processing, Development can be accelerated to some extent without being limited by the content of silver bromide, which is preferable in some cases. In any case, it is not preferable to contain a large amount of silver iodide, and the amount may be 3 mol% or less. These silver halide emulsions are preferably used mainly for color paper and the like. Silver iodobromide and silver chloroiodobromide are preferable for the color light-sensitive material for photography (negative film, reversal film, etc.), and the silver iodide content is preferably 3 to 15 mol%.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. In the above case, the value is also expressed in terms of sphere. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsions used in the present invention are those described in Graphide, "Chemistry and Physics of Photography" [P. Glafkides, Chimie et Physique Photo.
graphique, Paul Montel, 1967], Duffin, "Photoemulsion Chemistry" [GF Duffin, Photograhic Emulsion Ch
emistry, Focal Press, 1966], "Production and coating of photographic emulsions" by Zelikman et al. [VL Zelikman et al, Making.
and Coating Potographic Emulsion, published by Focal Press, 196
4 years] and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method, which includes a step of converting already formed silver halide into a silver halide having a smaller solubility product until the completion of the silver halide grain formation step, and a halogenated 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 ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, rodancali or U.S. Pat. No. 3,271,157, JP-A-51-12360).
JP-A-53-82408, JP-A-53-144319, JP-A-5
4-100717 or thioethers and thione compounds described in JP-A No. 54-155828, etc. are precipitated, physically aged,
It can be used in chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, a Nudel water washing, a flocculation sedimentation method, an ultrafiltration method or the like is used.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanines); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); metals A noble metal sensitization method using a compound (for example, a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, Pd, Rh, and Fe, in addition to a gold complex salt) can be used alone or in combination.

Each of the blue-sensitive, green-sensitive and red-sensitive emulsions used in the present invention is spectrally sensitized with a methine dye or the like so as to have color sensitivity. 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 normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes.
That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, benzimidazole A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine nucleus-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or may be used in combination, and are often used for the purpose of combination of sensitizing dyes and particularly supersensitization. A typical example is U.S. Patent 2,
688,545, 2,977,229, 3,397,060, 3,522,0
52, 3,527,641, 3,617,293, 3,628,964
No., No. 3,666,480, No. 3,672,898, No. 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, Japanese Patent Publication No. 43-4936, No. 53-12375, Japanese Patent Laid-Open No.
Nos. 52-110618 and 52-109925.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion.

These sensitizing dyes may be added during grain formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition at the time of grain formation is effective not only for enhancing adsorption but also for controlling the crystal shape and the grain internal structure. Further, addition during chemical sensitization is effective not only for enhancing adsorption but also for controlling chemical sensitization sites and preventing crystal deformation. In the case of an emulsion containing a high content of silver chloride, these addition methods are particularly effective, and it is particularly useful to apply them to grains having a high silver bromide or silver iodide content on the grain surface. is there.

The color light-sensitive material used in the present invention is preferably an internal color light-sensitive material, that is, one in which a color coupler is previously incorporated in the light-sensitive material.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9.
No. 28, No. 3,933,501 and No. 4,022,620, etc., an oxygen atom-releasing yellow coupler or Japanese Examined Patent Publication No. 55-10739, U.S. Patent Nos. 4,401,752, and 4,326,02.
4, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based 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 color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, and 2,5-diacylamino-substituted phenol couplers described in JP-A-59-166956 and US Patent No. 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

Particularly, in the treatment method of the present invention, the following general formula (C-
By using at least one of the cyan couplers represented by I) and (C-II), good fog can be obtained with less fog. Such an effect is remarkable.

The general formulas (C-I) and (C-II) are described in detail below.

General formula (C-I) (In the formula, R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ₁₂ represents an alkyl group or an aryl group. R ₁₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. And R ₁₃
May combine with R ₁₂ to form a ring. Z ₁₁ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent. ) General formula (C-II) (In the formula, R ₁₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₁₅ represents an alkyl group having 2 or more carbon atoms. R ₁₆ represents a hydrogen atom, a halogen atom or an alkyl group. Z ₁₂ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent.) Cyan couplers represented by the general formulas (C-I) and (C-II) In R ₁₁ , R ₁₂ and R ₁₄ as the alkyl group having 1 to 32 carbon atoms, for example, a methyl group, a butyl group, a tridecyl group,
Examples thereof include a cyclohexyl group and an allyl group, examples of the aryl group include a phenyl group and naphthyl group, and examples of the hetero group include a 2-pyridyl group, a 2-imidazolyl group, a 2-furyl group, and 6-quinolyl group. Groups and the like. These groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group, 2
-Methoxyethoxy group, etc.), aryloxy group (eg, 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (eg, 2-propenyloxy group) Etc.), acyl group (eg, acetyl group, benzoyl group, etc.), ester group (eg, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group ( For example, acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (eg, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, butylsulfamoyl group), imide group ( For example, succinimide Group, hydantoinyl group, etc.), ureido group (eg, phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group ( For example, it may be substituted with a group selected from an ethylthio group, a phenylthio group, etc.), 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 R ₁₁ may be substituted or unsubstituted. Here, examples of the substituent in the case of being substituted include those mentioned above. Examples of the substituted amino group for R ₁₁ include an anilino group and a benzothiazolylamino group.

In the general formula (CI), when R ₁₃ is a substitutable substituent, it may be substituted with the optionally substituted substituent described for R ₁₁ .

The carbon number of R _{15 in} the general formula (C-II) is at least 2
As the alkyl group which may be substituted, for example, ethyl group, propyl group, butyl group, pentadecyl group, tert
-Butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group and the like can be mentioned.

In the general formula (CI) and general formula (C-II), Z ₁₁
And Z ₁₂ each represent a hydrogen atom or a coupling-off group (including a coupling-off atom; the same applies hereinafter), and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkoxy. Group (for example, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group,
Methylsulfonylethoxy group etc.), aryloxy group (eg 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy group etc.) ), Sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyl An oxy group (for example, an ethoxycarbonyloxy group, a benzyloxycarbonyloxy group, etc.), an aryloxycarbonyloxy group (for example, a phenoxycarbonyloxy group), an aliphatic or aromatic thio group ( In example, an ethylthio group, a phenylthio group, etc. tetrazolylthio group), an imido group (e.g.,
Succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.) and the like. These leaving groups may include groups useful for photography.

Preferred examples of the cyan coupler represented by the general formula (C-I) or (C-II) are as follows.

In formula (C-I), preferred R ₁₁ is an aryl group,
A heterocyclic group, 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, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group are more preferable.

In the general formula (CI), when R ₁₃ and R ₁₂ do not form a ring, R ₁₂ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. , R ₁₃ is preferably a hydrogen atom.

In formula (C-II), R ₁₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In formula (C-II), preferred R ₁₅ has 2 to ₁₅ carbon atoms.
Is an 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 formula (C-II), R ₁₅ is more preferably an alkyl group having 2 to ₁₅ carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₁₆ in the general formula (C-II) is a hydrogen atom or a halogen atom, with a chlorine atom and a fluorine atom being particularly preferred.

Preferred Z in the general formulas (C-I) and (C-II)
₁₁ and Z ₁₂ are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group, respectively.

In formula (C-II), Z ₁₂ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In formula (CI), Z ₁₁ 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-I) and (C-II) are shown below, but the present invention is not limited thereto.

The couplers represented by the general formulas (C-I) and (C-II) can be synthesized based on JP-A-59-166956 and JP-B-49-11572.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into a light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 17
After being dissolved in either a single solution of a high boiling organic solvent having a boiling point of 5 ° C or higher and a so-called auxiliary solvent having a low boiling point, or a mixed solution of both, finely dispersed in an aqueous medium such as water or a gelatin aqueous solution in the presence of a surfactant. . Examples of high boiling organic solvents are described in US Pat. No. 2,322,027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water, ultrafiltration or the like before being used for coating.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethyl-hexylbenzoate) , Dodecyl benzoate, 2-ethylhexyl-p-
Hydroxybenzoate etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol etc.), aliphatic carboxylic acid esters ( Dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivative (N,
N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. 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,
Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-
Examples include ethoxyethyl acetate and dimethylformamide.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The light-sensitive material used in the present invention is used as an antifoggant or a color mixing inhibitor, such as hydroquinone derivative, aminophenol derivative, amines, gallic acid derivative, catechol derivative, ascorbic acid derivative, colorless coupler, sulfonamidephenol derivative, etc. May be included.

A known anti-fading agent can be used in the light-sensitive material used in the present invention. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Typical examples thereof include ethers or ester derivatives in which the phenolic hydroxyl groups of these compounds, aminophenols, hindered amines and these compounds are silylated or alkylated. Also (bissalicylaldoximate)
A metal complex represented by a nickel complex and a (bis-N, N-dialkyldithiocarbamate) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol substructures in the same molecule, as described in US Pat. No. 4,268,593, give good results. In order to prevent deterioration of the magenta dye image, especially deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results.

In order to improve the storability of cyan images, particularly the light fastness, it is preferable to use a benzotriazole-based ultraviolet absorber in combination. This UV absorber may be coemulsified with a cyan coupler.

The coating amount of the ultraviolet absorber may be an amount sufficient to impart light stability to the cyan dye image, but if used in an excessively large amount, it may cause yellowing in the unexposed portion (white background portion) of the color photographic light-sensitive material. Therefore, it is usually preferably 1 × 10 ⁻⁴ mol / m ^2.
To 2 × 10 ⁻³ mol / m ² , especially 5 × 10 ⁻⁴ mol / m ^{2 to} 1.5 × 10
It is set in the range of ^-3 mol / m ² .

In a light-sensitive material layer structure of a normal color paper, either one layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer,
An ultraviolet absorber is preferably contained in both layers.
When the ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with the color mixing inhibitor. When the ultraviolet absorber is added to the protective layer, another protective layer may be coated as the outermost layer. The protective layer may contain a matting agent having an arbitrary particle size.

In the light-sensitive 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 prevention of irradiation or halation. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green light and red light are particularly preferable.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, stilbene-based, triazine-based,
A whitening agent such as an oxazole type or a coumarin type may be included. Water-soluble ones may be used, and water-insoluble whitening agents may be used in the form of dispersion.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural photographic materials are usually a red-sensitive emulsion layer, a green-sensitive emulsion layer, a
And at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

The light-sensitive material used in the present invention is preferably provided with an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer and a back layer in addition to the silver halide emulsion 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 and starch derivatives;
Various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. are used. be able to. The use of acrylic acid modified polyvinyl alcohol in the protective layer is particularly useful, and more useful for rapid processing with silver chloride emulsions.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan., No.16, p.30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

In the light-sensitive material used in the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developing agents or precursors thereof, development accelerators or precursors thereof as described above, lubricants and mordants are further added. , Matting agents, antistatic agents, plasticizers,
Alternatively, various additives useful for photographic light-sensitive materials may be added. Representative examples of these additives are Research Disclosure 17643 (December 1978) and 18716.
(November 1979).

These additives are very important in rapid printing, rapid processing, and further in relation to the compound of the general formula [I] of the present invention. Further, particularly when the halogen composition of the emulsion to be used contains a high content of silver chloride, it is useful in the present invention in combination with a mercaptoazole-based, mercaptothiadiazole-based, and mercaptobenzazole-based compound in color formation and fog generation. is there.

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support has an oxidation property on the support. Examples include those coated with a hydrophobic resin containing a light reflecting substance such as titanium, zinc oxide, calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as 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) Hereinafter, the present invention will be illustrated by examples.

Example 1 Table A on a paper support laminated on both sides with polyethylene
A multi-layer color photographic paper having the layer constitution shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer Yellow coupler (a) 19.1 g and color image stabilizer (b) 4.4
To g, 27.2 ml of ethyl acetate and 7.9 ml of the solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1 mol% of silver bromide and 70 g of Ag / kg) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 5.0 × 10 ⁻⁴ mol. The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table A was obtained, and the coating solution for the first layer was prepared.

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

As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

The following dyes were used as the anti-irradiation dye in each emulsion layer.

Structural formulas of compounds such as couplers used in this example are as follows.

(J) Solvent (iso C ₉ H ₁₉ O ₃ P = O The obtained color photographic paper was processed in the following processing steps in which the composition of the color developing solution was changed. Processing process Temperature Time Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Rinse 1 35 ℃ 20 seconds Rinse 2 35 ℃ 20 seconds Rinse 3 35 ℃ 20 seconds Dry 80 ℃ 60 seconds Rinse 3 to rinse 1 tank It was washed with countercurrent water. The treatment liquids used are as follows. Color developer additive See Table 1 Benzyl alcohol See Table 1 Diethylene glycol See Table 1 Sodium sulfite 0.2g Potassium carbonate 30g EDTA ・ 2Na 1g Sodium chloride 1.5g Color developing agent (See Table 1) 0.012 mol Whitening agent ( 4,4'-diaminostilbene type) 3.0 g water to make 1000 ml pH 10.05 bleach-fixing solution _{EDTAFe (III) NH 4 · 2H} 2 O 60g EDTA · 2Na · 2H 2 O 4g ammonium thiosulfate (70%) 120 ml sodium sulfite 16g Glacial acetic acid 7 g Water was added 1000 ml pH 5.5 Rinsing solution Formalin (37%) 0.1 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 1.6 ml Bismuth chloride 0.35 g Ammonia (26%) 2.5 ml Nitrilotriacetic acid / 3Na 1.0 g EDTA / 4H 0.5 g Sodium sulfite 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 50 mg Water was added. As the 1000 ml color developing solution, two kinds of each composition were used immediately after preparation (fresh solution) and after standing for 14 days at 40 ° C. after preparation (solution after aging).

Table 1 shows the photographic characteristics of the obtained fresh liquid and aged liquid.

The photographic property is represented by two points, that is, Dmin at magenta density and gradation.

Dmin represents the minimum density, and gradation represents the density change from the point where the density is 0.5 to the density point on the high exposure side of 0.3 at log E.

As is clear from Table 1, when hydroxylamine is added, the fog in the aged liquid is high and the gradation change is large.

On the other hand, when the treatment liquid of the present invention is used, fog is small and gradation change is small even with the aged liquid. Further, this effect is particularly remarkable in a system containing no benzyl alcohol.

Example 2 In Example 1, the bromine ion content of the green-sensitive layer emulsion was adjusted to 80%.
The change in photographic property with the passage of time was evaluated in the same manner as in Example 1 with mol% being set, and in the constitution of the present invention, good results were obtained with little increase in fog.

Example 3 As described in Table B, the first layer (lowermost layer) to the seventh layer (uppermost layer) were applied to double-sided polyethylene laminated paper that had been subjected to corona discharge machining to prepare a sample.

The coating liquid for the first layer was prepared as follows. Yellow coupler 200g, anti-fading agent 93.3g, high boiling point solvent (p) 10g and (q) 5g, ethyl acetate 6 as an auxiliary solvent
The mixture containing 00 ml was heated and dissolved at 60 ° C, and then alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont)
Was mixed with 3300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution of and was emulsified using a colloid mill to prepare a coupler dispersion. From this dispersion, ethyl acetate was distilled off under reduced pressure, and a sensitizing dye for a blue-sensitive emulsion layer and 1400 g of an emulsion containing 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole (96.7 as Ag). g, including 170 g of gelatin), and 2600 g of 10% gelatin aqueous solution were further added to prepare a coating solution. The coating solutions for the second to seventh layers were prepared according to the first layer.

The following substances were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer; Anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide Green sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3 ' -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9,9 '
-(2,2-Dimethyl-1,3-propano) thiadicarbocyanine iodide The following substances were used as stabilizers for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-1,
3,4-Triazole The following substances were used as anti-irradiation dyes.

4- (3-carboxy-5-hydroxy-4- (3-
(3-carboxy-5-oxo-1- (4-sulfonatophenyl) -2pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl) benzenesulfonate-di-potassium salt N, N '-( 4,8-dihydroxy-9,10-dioxo-3,7-
Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt 1,2-bis (vinylsulfonyl) ethane was used as a hardener.

The couplers used are as follows.

The cyan coupler was modified 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-butyl) Phenyl) benzotriazole Solvent (p): Di (2-ethylhexyl) phthalate Solvent (q): Dibutylphthalate Anti-fading agent (r): 2,5-di-tert-amylphenyl-3,5-di-tert-butyl Hydroxybenzoate anti-fading agent (s): 2,5-di-tert-octylhydroquinone Anti-fading agent (t): 1,4-di-tert-amyl-2,5-dioctyloxybenzene Anti-fading agent (u): 2,2'-Methylenebis- (4-methyl-6-tert-butylphenol) The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps: Processing step time Temperature color development 3 Minutes 30 seconds 3 3 ℃ Bleach-fix 1 minute 30 seconds 33 ℃ Rinse (3 tanks 2 minutes 30 ℃ Cascade dry 1 minute 80 ℃ The processing solution used is as follows: Color developer water 800ml Triethanolamine 10ml 5,6-dihydroxy Sodium 1,2,4-benzenetrisulfonate 300 mg N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 0.1 g Nitrilo-N, N, N-trimethylenephosphonic acid (40 %) 1.0
g Potassium bromide 0.6g Additives Table 2 Sodium sulfite Table 2 Potassium carbonate 30g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 5.5g Fluorescent brightener (4,4'-diaminostilbene 1.0g Water was added 1000ml KOH pH 10.10 Bleach-fix solution Ammonium thiosulfate (70%) 150ml Sulfurous acid Sodium 15g Ethylenediamineiron (III) ammonium 60g Ethylenediaminetetraacetic acid 10g Optical brightener (4,4'-diaminostilbene type) 1.0g 2-Mercapto-5-amino-3,4-thiadiazole 1.0
g Add water and 1000 ml with ammonia water pH 7.0 rinse solution 5-chloro-2-methyl-4-isothiazolin-3-one 40 mg 2-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-trimethylenephosphonic acid (40%) 1.0
g 1-hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.5g Optical brightener (4,4'-diaminostilbene type) 1.0g Ammonia water (26%) 2.0ml Add water to 1000ml KOH pH7.5 Color developer solution for each composition Two types were used immediately after the solution (fresh solution) and after one month of aging at 38 ° C. after preparation (aged solution).

The Dmin and gradation of cyan in the fresh liquid and the aged liquid were determined, and the difference between the results obtained with the aged liquid and the fresh liquid is shown in Table 2.

As is clear from Table 2, when the treatment liquid of the present invention is used, the fog increase is small and the gradation change is small even when the aged liquid is used. Further, this effect is more remarkable when the concentration of sulfite ion in the treatment liquid is low.

On the other hand, in the case of processing with a processing solution to which hydroxylamine is added, there is a large increase in fog with the passage of time of the color developing solution and a large change in gradation.

When a light-sensitive material containing a cyan coupler represented by the general formula (C-I) or (C-II) is processed with the processing solution of the present invention, the general formulas (C-I) and (C-II) are used. )
It can be seen that, compared with the case of processing a light-sensitive material containing a cyan coupler other than the above, the increase in fog with time of the color developing solution is small and the gradation change is small. Further, this effect is more remarkable when the concentration of sulfite ion in the treatment liquid is low.

Example 4 Using the color photographic paper obtained in Example 1, a running test was conducted until the tank capacity (60 l) of the color developing solution was replenished by 3 times in the following processing steps.

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

The rinse was a tank countercurrent system from rinse to rinse.

The composition of each treatment liquid used is as follows.

Bleach-fixing solution (same as tank solution and replenisher) EDTAFe (III) NH ₄・ 2H ₂ O 60g EDTA ・ 2Na ・ 2H ₂ O 4g Sodium thiosulfate (70%) 120ml Sodium sulfite 16g Glacial acetic acid 7 g pH 5.5 Rinse solution (same as tank solution and replenisher solution) EDTA ・ 2Na ・ 2H ₂ O 0.4g Water is added 1000ml pH 7.0 Treated by the above treatment method, and B of the unexposed area at the start of running and at the end of running The (blue), G (green), and R (red) densities were measured with a Fuji type self-recording densitometer. Furthermore, the sample at the end of running is 60 ℃
After leaving it under 70% RH for 2 months, B of the unexposed area again
The G and R concentrations were measured.

The results obtained are shown in Table 3.

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

This effect is particularly remarkable when running in the treatment liquid containing no benzyl alcohol.

Example 5 A color photographic paper was produced in the same manner as in Example 1 except that the spectral sensitizer in each emulsion layer was changed as follows in the production of the color photographic paper in Example 1.

The obtained color photographic paper was imagewise exposed, and a running treatment (continuous treatment) test was conducted in the same treatment process as in Example 4 until the tank was replenished with the same various color developing solutions in an amount three times the tank volume. went. However, triethanolamine and 5-methyl-7-hydroxy-3,4-triazaindolizine were not added in the color developer composition of Example 4, but instead 1,2-dihydroxybenzene-3,
A tank solution of 4,6-trisulfonic acid and a replenisher of 300 mg were added. The rinse liquid was changed to the following aqueous water. Aqueous water (tank liquid and replenisher are the same) Tap water is H type strong acid cation exchange resin (Mitsubishi Kasei Co., Ltd.)
Manufactured by Diaion SK-1B and OH type strongly basic anion exchange resin (Same as Diaion SA-10A). 20 mg / l sodium isocyanurate was added.

Calcium ion 1.1 mg / l Magnesium ion 0.5 mg / l pH 6.9 After continuous treatment, the same evaluation as in Example 4 was performed, and similar results were obtained.

Example 6 On a paper support laminated on both sides with polyethylene, a multilayer photographic paper having the following layer constitution was produced. The coating liquid was prepared as follows.

(Preparation of coating liquid for the first layer) Yellow couplers (ExY-1) and (ExY-2) 1 each
0.2g, 9.1g and 4.4g of color image stabilizer (Cpd-1) to 27.2cc of ethyl acetate and 7.7cc (8.0cc of high boiling solvent (Solv-1))
g) was added and dissolved, and this solution was added with 185 cc of 10% gelatin aqueous solution containing 10 cc of sodium dodecylbenzenesulfonate 8 cc.
Emulsified and dispersed. This emulsified dispersion and emulsions EM1 and EM2 were mixed and dissolved, and the gelatin concentration was adjusted so as to have the following composition to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-oxy-3,5-dichloro-s as a gelatin hardening agent for each layer
-Triazine sodium salt was used.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluing dye] First layer (blue sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM1) 0.13 Monodisperse silver chlorobromide emulsion (EM2) spectrally sensitized with sensitizing 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) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-3) 0.08 Third layer (green sensitive layer) Sensitizing dye ( Monodisperse silver chlorobromide emulsion (EM3) 0.05 spectrally sensitized with ExS-2,3) 0.05 Monodisperse silver chlorobromide emulsion (EM4) 0.11 spectrally sensitized with sensitizing dye (ExS-2,3) Gelatin 1.80 Magenta coupler (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.20 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-6) 0.03 Solvent (S olv-2) 0.12 Solvent (Solv-3) 0.25 Fourth layer (UV absorbing layer) Gelatin 1.60 UV absorber [Cpd-7 / Cpd-8 / Cpd-9 = 3/2/6: weight ratio) 0.70 Color mixing prevention Agent (Cpd-10) 0.05 Solvent (Solv-4) 0.27 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EM5) 0.07 enhanced spectrally sensitized with sensitizing dye (ExS-4,5) Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with dye (ExS-4,5) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 0.32 Color image stabilizer (Cpd-8 / Cpd-9 / Cpd (-12 = 3/4/2: weight ratio)
0.17 Dispersing polymer (Cpd-11) 0.28 Solvent (Solv-2) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.54 UV absorber [Cpd-7 / Cpd-9 / Cpd-12 = 1/5/3: Weight Ratio) 0.21 Solvent (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 At this time, as an irradiation prevention dye,
(Cpd-13, Cpd-14) were used.

Further, in each layer, an emulsifying dispersant and an alkanol XC (Dupont), sodium alkylbenzenesulfonate, succinate and Magefacx F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-15,16) was used as a stabilizer for silver halide.

Details of the emulsion used are as follows.

The structural formulas of the compounds used are as follows.

Cpd-10 Same as Cpd-3. However, R = C ₈ H ₁₇ (t) Solv-1: Dibutyl phthalate Solv-2: Tricresyl phosphate Solv-3: Trioctyl phosphate Solv-4: Trinonyl phosphate Cpd-14 Same as Cpd-13. However, n = 1 After the above sample was imagewise exposed, the composition of the color developing solution was changed as shown in Table 5 and continuous processing was carried out until each tank was filled with twice the tank capacity of the color developing solution in each processing step.

The composition of each treatment liquid is as follows.

The changes in the measured values of Dmin after the treatment and Dmin after the treatment and 60 minutes at 60 ° C./70% RH for 2 months are shown in Table 5 as in Example 4 in the above running.

According to the present invention (Nos. 47 to 53), not only Dmin immediately after the treatment but also the increase in stain with time is small.

Example 7 On a paper support laminated on both sides with polyethylene, a multilayer photographic paper having the following layer constitution was produced. The coating liquid was prepared as follows.

(Preparation of coating solution for the first layer) 29.1 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling solvent (Solv-1) were added to 19.1 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1). Add and dissolve, and add this solution to 1
10% containing 8% sodium dodecylbenzene sulfonate 10
% Gelatin aqueous solution was emulsified and dispersed in 185 cc. This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted so that the following composition was obtained to prepare a coating solution for the first layer.
The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

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

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on first layer contains white pigment (TiO2) and bluing dye] First layer (blue sensitive layer) Monodisperse salt spectrally sensitized with sensitizing dye (ExS-1) Silver bromide emulsion (EM7) 0.15 Monodispersed silver chlorobromide emulsion (EM8) 0.15 Gelatin spectrally sensitized with sensitizing dye (ExS-1) 1.86 Yellow 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 inhibitor (Cpd-3) 0.08 Third layer (green sensitive layer) Spectral sensitization with sensitizing dye (ExS-2,3) Monodispersed silver chlorobromide emulsion (EM9) 0.12 Monodisperse silver chlorobromide emulsion (EM10) spectrally sensitized with sensitizing dye (ExS-2,3) 0.24 Gelatin 1.24 Magenta coupler (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.25 Color image stabilizer (Cpd-5) 0.12 Solvent (Solv-2) 0.25 Fourth layer (UV absorbing layer) Gelatin 1.60 UV absorbing Agent [Cpd-6 / Cpd-7 / Cpd8 = 3/2/6: by weight) 0.
70 Color mixing inhibitor (Cpd-9) 0.05 Solvent (Solv-3) 0.42 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion spectrally sensitized with a sensitizing dye (ExS-4,5) (EM11 ) 0.07 Monodisperse silver chlorobromide emulsion (EM12) spectrally sensitized with sensitizing dye (ExS-4,5) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 1.46 Cyan coupler (ExC-2) 1.84 Color image stability Agent (Cpd-7 / Cpd-8 / Cpd-10 = 3/4/2: weight ratio)
0.17 Dispersing polymer (Cpd-11) 0.14 Solvent (Solv-1) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.54 UV absorber (Cpd-6 / Cpd-8 / Cpd-10 = 1/5/3: weight Ratio) 0.21 Solvent (Solv-4) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%) 0.17 Liquid paraffin 0.03 At this time, as an irradiation prevention dye,
(Cpd-12, Cpd-13) was used.

Further, for each layer, an emulsifying dispersant and an alkanol XC (Dupont), sodium alkylbenzenesulfonate, succinate and Magefacx F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-14,15) was used as a stabilizer for silver halide.

Details of the emulsion used are as follows.

The structural formulas of the compounds used are as follows.

Cpd-13 Same as Cpd-12. However, R = H, n = 1 Solv-1 dibutyl phthalate Solv-2 trioctyl phosphate Solv-3 trinonyl phosphate Solv-4 tricresyl phosphate All the gelatin used was alkali-processed gelatin with an isoelectric point of 5.0.

When the light-sensitive material thus obtained is processed in the same manner as in Example 4, the excellent effects of the present invention can be obtained.

Example 8 In place of the additives I-I used in Nos. 23 and 27 of Example 2, I-11, I-19, I-32, I-34, I-, respectively.
When the same test as in Example 2 was conducted except that 41, I-44 and I-48 were used in the same moles, the same favorable photographic properties were obtained.

(Effects of the Invention) The present invention significantly improves the stability or color developability of a color developing solution, and as a result, even in a processing method using the color developing solution after a lapse of time, an increase in fog and a change in gradation are significantly suppressed. An image having excellent photographic characteristics was obtained.

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

Further, such an effect of the present invention was more remarkable when the concentration of sulfite ion in the treatment liquid was low. Furthermore, the effect of the present invention was remarkable when a light-sensitive material containing a specific cyan coupler was processed.

Further, even in the continuous processing, the increase in fog was remarkably reduced, and the stability of the obtained image with time was excellent.

Front page continued (72) Inventor Hideaki Naruse, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Inventor Takatoshi Ishikawa, 210, Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Fujimoto, Fujimoto Central 210, Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Inventor, Mr. Ando, 210, Nakanuma, Minami Ashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (56) Reference JP-A-57-150845 (JP, A) JP 60-221751 (JP, A)

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material is exposed with at least one of aromatic primary amine color developing agents.
And at least one hydrazide represented by the following general formula (I) per color developing solution at 1.5 × 10 ⁻³
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing a mole of 3.0 × 10 ^-1 mole. General formula (I) in ^{R 1 -X-NHNH-R 2} ( wherein, X is -CO- and -SO ₂ - .R ¹ representing a divalent group selected from a hydrogen atom, an alkyl group, an aryl group, a hetero Represents a ring group, an alkoxy group or an aryloxy group,
R ² represents a hydrogen atom or an alkyl group. The substituents R ¹ and R ² may form dimers or multimers. ) 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color developer contains substantially no benzyl alcohol.