JPH0812409B2 - 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 and color-forming property of a color developer are improved and continuous processing is performed. The present invention relates to a processing method in which the rise of fog is remarkably reduced.

(Prior Art) A color developing solution containing an aromatic primary amine color developing agent has been used for a long time in the formation of color development, and now plays a central role in the image forming method of color photography. Is playing. However, the above color developer has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developer, fog increases, sensitivity and gradation change. It is well known that desired photographic characteristics cannot be obtained due to the

Therefore, means for improving the preservability of various color developing solutions have been conventionally studied, and among them, the method of using hydroxylamine and sulfite ion in combination is the most general. However, since hydroxylamine is remarkably promoted to decompose in the presence of metal ions, and the resulting ammonia causes fog generation and changes in photographic properties, various means for concealing metal ions have been investigated.
-Hydroxy-alkylidene-diphosphonic acid (West German patent
2227639) and aromatic polyhydroxy compounds (US Patent 374
No. 6544) has a great effect and is partially used.

However, there is no protection against air oxidation even with the appropriate hidden pay means of metal ions, and in some cases even acceleration. For such air oxidation, sulfite ion has been used for a long time, but its use amount is limited due to great inhibition of color development, and it is not possible to sufficiently prevent air oxidation. When used in a system in which benzyl alcohol does not exist, or when an emulsion made of silver halide having a high chlorine content is processed, the color density is remarkably lowered.

In this sense, the amount of sulfite ion used is as small as possible, but it is preferable not to use it. However, in such a case, since the air oxidation prevention is inevitably insufficient, a new air oxidation prevention technique is being studied.

Alkanolamines described in JP-A-54-3532 and polyethyleneimines described in JP-A-56-94349 have been proposed as compounds replacing sulfite, but sufficient effects can be obtained even by using this compound. I couldn't do it.

In addition, Japanese Patent Publication No. 53-12381 discloses a technique using cyclohexanediaminetetraacetic acid. Although this compound exerts a remarkable effect in preventing air oxidation, it may adversely affect photographic characteristics and is not a preferable method.

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

(Means for Solving Problems) The above-mentioned object can be achieved by the method described below. That is, the halogen is characterized by processing with a color developing solution containing an aromatic primary amine color developing agent, a compound represented by the following general formula (I) and a compound represented by the following general formula (II). It could be achieved by a method of processing a silver halide color photographic light-sensitive material.

The silver halide color photographic light-sensitive material used in the method of the present invention uses a high silver chloride silver halide emulsion having a silver chloride content of 80 mol% or more as described later, and a specific cyan coupler is used as a halogen. It is contained in the silver halide emulsion layer.

General formula (I) M may be the same or different and represents a hydrogen atom, an alkali metal (Na, K, etc.) and an ammonium ion. n
Represents an integer of 1 to 4.

The compounds of general formula (I) are known as chelating agents, but the fact that such a chelating agent significantly prevents air oxidation when contained in a color developer is quite predictable. It happened.

 Specific examples of the compound represented by formula (I) are shown below.

The carboxylic acid may form a salt with an alkali metal atom such as sodium, lithium and potassium and ammonium.

Of the above compounds, I-1 is particularly preferable. These compounds can be purchased commercially, but Beilst
It can be synthesized based on ein, 4 (3), 1186, etc.

The amount of the compound of formula (I) added to the color developer is
It is preferably 0.05 g to 30 g, more preferably 0.1 g to 1
It is 15g.

Hereinafter, the color developer used in the present invention will be described.

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 typical examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N -(Β-hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline 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 to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developing solution.

In particular, when the color developing agent D-4 is used in the presence of the compound of the general formula (I), it is preferable in that the fog increase is small and good photographic characteristics are obtained.

Further, the compound of the present invention has particularly remarkable storage performance in a system using an aromatic primary amine color developing agent in combination with a compound which directly stabilizes the developing agent. In the color developing solution used in the present invention, the compound represented by the following general formula (II) is used together with the compound represented by the general formula (I).

General formula (II) In the formula, R ²¹ and R ^{22 each} represent an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R ²¹ and R ²² are alkyl groups or alkenyl groups, and it is more preferable that at least one of them has a substituent. R ²¹ and R ²² may be linked to form a heterocycle together with the nitrogen atom.

The alkyl group or alkenyl group may be linear, branched or cyclic, and the substituent is a halogen atom (F, Cl, Br
Etc.), aryl groups (phenyl group, p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy groups (phenoxy group, etc.), sulfonyl groups (methanesulfonyl group, p-
Toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group,
Unsubstituted sulfamoyl group, etc., carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamido group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxy) Carbonylamino group), allyloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, Carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group), alkylthio group (methylthio group etc.), arylthio group (phenylthio group etc.), and heterocyclic group (morpholyl group, pyridyl group etc.) It can be cited. Here, R ²¹ and R ²² may be the same or different, and the substituents of R ²¹ and R ²² may be the same or different.

The carbon number of R ²¹ and R ²² is preferably from 1 to 10, particularly 1
-5 are preferable. Examples of the nitrogen-containing heterocycle formed by linking R ²¹ and R ²² include a piperidyl group, a pyrrolidylyl group,
Examples thereof include N-alkylpiperazyl group, morpholyl group, indolinyl group and benztriazolyl group.

Preferred substituents for R ²¹ and R ²² are hydroxy group, alkoxy group, sulfonyl group, amide group, carboxy group, cyano group, sulfo group, nitro group and amino group.

Specific examples of the compound represented by formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to this compound. However, II- (34) is a compound for comparison.

II- (34) NH ₂ OH The compound represented by the general formula (II) can be synthesized by the known method shown below. U.S. Patent No. 3,
No. 661,996, No. 3,362,961, No. 3,293,034, Japanese Patent Publication No. 42-
2,794, U.S. Patents 3,491,151, 3,655,764,
3,467,711, 3,455,916, 3,287,125, 3,2
87,124.

These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid. Other than hydroxylamines, "compounds that directly stabilize the developing agent" preferably used in combination with the compound of the present invention include, for example, hydrazines, hydrazides, saccharides, hydroxamic acids, α-hydroxyketones and the like. it can.

The amount of these compounds added to the color developing solution is preferably 0.1 g to 20 g, more preferably 1 g per color developing solution.
It is 0.5g-10g.

Also, as other preservatives, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite,
Sulfites such as sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. The amount added to these color developers is 0 g
It is 20 g / l or less, preferably 0 g to 5 g / l, and is preferably as small as possible so long as the stability of the color developer is maintained.

As other preservatives, hydroxyacetones described in U.S. Pat.No. 3,615,503 and British Patent 1,306,176, α-aminocarbonyl compounds described in JP-A-52-143020 and 53-89425, JP-A-57-44148 And various metals described in JP-A-57-53749, various saccharides described in JP-A-52-102727, α, α'-dicarbonyl compounds described in 59-160141, and salicylic acid described in 59-180588. , Gluconic acid derivatives described in JP-A-56-75647 and the like may be contained as necessary, and two or more kinds of these preservatives may be used in combination as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer 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. In particular, carbonates, phosphates, tetraborate and hydroxybenzoates are highly soluble and have a high pH of 9.0 or above.
It has excellent buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantage of being inexpensive. preferable.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the 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 chelates can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution or for improving the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferable, 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 Nos. 52-102726, 53-42730, 54-121127, 55-1
Examples thereof include phosphonocarboxylic acids described in JP-A Nos. 26241 and 55-659506, and other compounds described in JP-A Nos. 58-195845, 58-203440 and 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 diamine tetraacetic acid-Hydroxyethylenediamine triacetic acid-Ethylenediamine orthohydroxy acid Enylacetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 2 kinds of chelating agents as needed It may be above combination.

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 per unit.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and fog prevention. Here, “substantially” means that the amount of the developer is not more than 2 ml, preferably not contained at all.

The compound of the general formula (I) used in the present invention is remarkably effective also in the stability of a color developer containing substantially no benzyl alcohol.

Other development accelerators include JP-B-37-16088 and 37
-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat.No.3,813,247, thioether compounds represented by JP-A-52-49829 and JP-A-50-15554. P-phenylenediamine compound, JP-A-50-13772
No. 6, JP-B-44-30074, JP-A-56-156826 and JP-A-52-4
3429, quaternary ammonium salts, p-aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462, U.S. Pat.Nos. 2,494,903, 3,128,182,
4,230,796, 3,253,919, JP-B-41-11431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346.
Compounds described in Japanese Patent Publication Nos. 37-16088 and 42
-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat. No. 3,532,501 and the like, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc., if necessary. Can be added.

In the present invention, any antifoggant can be added if necessary. 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 and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightening agent, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

Further, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 40 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 2 minutes. The replenishment amount is preferably smaller, but is preferably ^{20 to} 600 ml, and more preferably 50 to 300 ml, per 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 in particular, organic complex salts of iron (III) (for example, aminoamines such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid). Polycarboxylic acids, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferable.

Among these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Examples of aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include 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 Acetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapyropionic acid, ethylenediaminedipropionacetic acid, phenyldiaminetetraacetic acid, 2-phosphonobutane-1 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, 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 kind of complex salt may be used, or two or more kinds of complex salt may be used, while a ferric salt and a chelating agent are used to form a complex salt in a solution. In that case, one type or two or more types of ferric salts may be used. Further, one or more chelating agents may be used. In any case, the chelating agent may be used in excess of the amount of 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 No. 1,29.
No. 0,812, 2,059,988, JP-A-53-32736, 53-578
No. 31, No. 53-37418, No. 53-65732, No. 53-72623, No.
53-95630, 53-95631, 53-104232, 53-1244
No. 24, No. 53-141623, No. 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 in JP-B-45-8506, JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
West German Patent 1,127,715 and iodides described in JP-A-58-16235; polyethylene oxides described in West German Patents 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Showa 49-42434 and 49-59644
No. 53-94927, No. 53-35727, No. 55-26506 and No. 58-163940, and iodine, bromine ion and the like. Among them, a compound having a mercapto group or a disulphide group is preferable from the viewpoint of large accelerated curing, and particularly, U.S. Patent No. 3,893,858 and West German Patent No. 1,2.
Compounds described in JP-A-90,812 and JP-A-53-95630 are preferred.

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. If necessary, one or more of pH buffering agents such as 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 and their alkali metal or ammonium salts, or ammonium nitrate,
A corrosion inhibitor such as guanidine can be added.

The bleach-fixing solution or the fixing solution used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-1,8
A thioether compound such as octanediol and a water-soluble silver halide solubilizer such as thioureas, and these may be used alone or in admixture of two or more. 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, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is from 3 to
10 is preferable, and 5 to 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. Conversely, if the pH is higher than this, desilvering will be delayed and stain will easily 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.

The bleach-fixing solution or the fixing solution according to the present invention may be a sulfite (for example, sodium sulfite, potassium sulfite,
Ammonium bisulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) And the like. These compounds are converted to sulfite ions by about 0.02
The content is preferably 0.5 to 0.50 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, a carbonyl bisulfite addition product, a carbonyl compound, or the like may be added.

Further, a buffer, a fluorescent brightener, a chelating agent, a fungicide and the like may be added as required.

Next, the water washing step in the present invention will be described. Here, the “rinsing process” includes rinsing treatment, rinsing acceleration treatment, and other alternative rinsing treatments.

In the present invention, it is possible to use a treatment method in which a so-called "stabilization treatment" is performed without providing a substantial water washing step instead of the usual "water washing treatment".

The amount of the rinsing water or the stabilizing solution in the present invention is difficult to define because it depends on the number of baths for multi-stage countercurrent processing and the amount of the pre-bath component of the light-sensitive material brought in, but in the present invention, The bleaching or fixing solution component in the final bath or a bath after the bath having fixing ability may be 1 × 10 ^-4 or less. For example, in the case of washing with countercurrent flow in 3 tanks, about 1000 ml per 1 m ² of light-sensitive material
It is preferably used above, more preferably 5000 ml or more. In the case of water-saving processing, 100 to 1m ² of light-sensitive material
It is recommended to use 1000 ml.

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

In the washing step, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial・ Anti-Fungal Agents "(J.Antibact.Antifung.Agents), Vol.11, No.2
07-223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts typified by magnesium salts and aluminum salts, alkali metal and aluminum salts, or drying load and unevenness. If necessary, a surfactant or the like for preventing the above can be added. Or West, “Photographic Science Science”
The compounds described in And Engineering magazine (Phot.Sic.Eng.), 6, pages 344 to 359 (1965) and the like may be added.

Further, the present invention is particularly effective in the case of adding a chelating agent, a bactericidal agent and an antibacterial agent to the washing water to greatly reduce the amount of washing water by multi-stage countercurrent washing with two or more tanks. Further, it is also particularly effective when a multistage 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 should be 5 × 10 ^-2 or less, preferably 1 × 10 ^-2.
The following is acceptable. Further, a method of significantly reducing the amount of water by using only water such as distilled water or ion-exchanged water from which calcium ions and magnesium ions in the water are significantly removed is also effective.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (eg pH 3 ~
8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. Are used in combination) and aldehydes such as formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzo) Various additives such as triazole), surfactants, fluorescent brighteners, and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster for the processor,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve the image storability.

When the amount of wash water or stabilizing solution as described above is significantly reduced, a part or all of the overflow solution of wash water may flow into the bleach-fixing bath or fixing bath which is the pre-bath. It is preferable for the purpose of reduction.

In this treatment step, a constant finish can be obtained by using a replenisher of each treatment solution in the continuous treatment to prevent the composition of the solution from varying. 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 can be applied to any processing step using a color developer. 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, but it is particularly preferably applied to color paper and color reversal paper.

The silver halide emulsion of the light-sensitive material used in the present invention is a silver chlorobromide emulsion or a silver chloride emulsion containing 80 mol% or more of silver chloride. 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 chloroiodobromide is preferred for color photographic materials for photographing (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 average grain size (in the case of spherical grains or grains close to spheres, the grain size in the case of cubic grains and the edge length). Also in the case of particles, the particle size is expressed in terms of sphere.) 2 μm or less is preferably 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. 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%,
It is particularly preferred to use a so-called monodisperse silver halide emulsion within 15% in the present invention. 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 an emulsion layer having substantially the same color sensitivity (the monodispersity is defined as (Preferably those having a variation rate) can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The silver halide grains used in the present invention have a regular shape such as a cube, an octahedron, a rhodohedron and a tetradecahedron.
It may be a compound having different crystal forms or a coexisting form thereof, may have an irregular crystal form such as a sphere, 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 emulsion used in the present invention is RESEARCH DISCLOSURE.
It can be prepared using the method described in vol.170 Item No.17643 (I) (1978.12). That is, any of the acidic method, the neutral method, the ammonia method and the like may be used, and the method of reacting the insoluble silver salt and the soluble halogen salt may be any of the one-sided mixing method, the simultaneous mixing method and a combination thereof. good.

Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt, iron complex salt and the like may coexist in the process of silver halide grain formation or physical thermal formation.

The silver halide emulsion is generally used for coating after physical grain formation, desalting and chemical grain formation 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-54-
The thioethers and thione compounds described in JP-A No. 100717 or JP-A No. 54-155828 can be used for precipitation, physical thermal synthesis and chemical thermal synthesis. In order to remove the soluble silver salt from the emulsion after physical thermal accelerating, Nudel washing, flocculation precipitation method or ultrafiltration method is used.

The silver halide emulsion used in the present invention is a compound containing sulfuric acid capable of reacting with active gelatin or silver (for example, thiosulfates, thioureas, mercapto compounds, rhodanins).
Sulfur sensitization method using a reducing substance (for example, stannous salt,
Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; metal compounds (eg, gold complex salts, and metals of Group VIII of the periodic table such as PT, Ir, Pd, Rh, Fe) Noble metal sensitization method using a 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 cyanine 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,
Pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and aromatic hydrocarbon rings are fused to these nuclei A nucleus, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like 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-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. A typical example is RESEAR
CH DISCLOSURE vol.176 Item No.17643 (IV) Item (1978.
12).

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained 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 coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator.

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. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a 2-equivalent yellow coupler is preferable, and U.S. Pat. Nos. 3,408,194 and 3,44 are used.
No. 7,928, Nos. 3,933,501 and 4,022,620, etc., described in, for example, an oxygen atom-elimination type yellow coupler or JP-B No. 55-10739, U.S. Pat.No. 4,401,752, and No. 4,3
26,024, RD18053 (April 1979), UK Patent 1,425,0
No. 20, West German Application Publication No. 2,219,917, No. 2,261,361,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A-2,329,587 and JP-A-2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring 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, a nitrogen atom leaving group described in US Pat. No. 4,310,619 and an arylthio group described in US Pat. No. 4,351,897 are preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As the pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984) Pyrazolotetrazoles and Research Disclosure 24)
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of less yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 119,8
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferable.

Examples of cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,80.
1,171, 2,772,162, 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 having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol couplers and U.S. Pat.No. 3,446,622.
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like.

In the processing method of the present invention, by using at least one kind of cyan couplers represented by the following general formulas (C-I) and (C-II), it is possible to obtain good photographic properties 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 ³¹ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ³² represents an alkyl group or an aryl group. R ³³ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Group, and R
³³ may combine with R ³² to form a ring. Z ¹ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidant of an aromatic primary amine type color developing agent. ) General formula (C-II) (In the formula, R ³⁴ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ³⁵ represents an alkyl group having 2 or more carbon atoms. R ³⁶ represents a hydrogen atom, a halogen atom or an alkyl group. Z ² 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 (CI) and (C-II) In R ³¹ , R ³² and R ³⁴ , examples of the alkyl group having 1 to ³² carbon atoms include a methyl group, a butyl group, a tridecyl group, a cyclohexyl group and an allyl group, and examples of the aryl group include a phenyl group, Examples thereof include a naphthyl group, and the heterocyclic group includes, for example, a 2-pyridyl group,
A 2-imidazolyl group, a 2-furyl group, a 6-quinolyl group and the like can be mentioned.

R ₁ , R ₂ and R ₄ are each 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-aluminenoxy 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 (Eg, acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (eg, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, butylsulfamoyl group), imide Groups, (for example, 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, 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 may be substituted.

When R ³¹ is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferable.

In the general formula (C-I), when R ³³ is a substitutable substituent, it may be substituted with the optionally substituted substituent described for R ³¹ .

Examples of the optionally substituted alkyl group having at least 2 carbon atoms of R ^{35 in} the general formula (C-II) include, for example, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, Examples thereof include a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group and a methoxymethyl group.

Z in the general formula (C-I) and the general formula (C-II)
¹ and Z ² each represent a hydrogen atom or a coupling-off group (including a coupling-off atom; the same applies hereinafter), examples of which include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), 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) Group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group) Groups), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio groups For example, ethylthio group, phenylthio group, etc. tetrazolylthio group), an imido group (e.g.,
A succinimide group, a hydantoinyl group, etc.) and an aromatic azo group (eg, a phenylazo group). These leaving groups may include photographically useful groups.

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

Preferred R ³¹ in the general formula (CI) is an aryl group or a heterocyclic group, which is 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, An aryl group substituted with a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group is more preferable.

In the general formula (C-I), when R ³³ and R ³² do not form a group, R ³² is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. , R ³³ is preferably a hydrogen atom.

In formula (C-II), R ³⁴ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

Preferred R ³⁵ in the general formula (C-II) has 2 to 2 carbon atoms.
A methyl group having 15 alkyl groups and 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 ³⁶ in the general formula (C-II) is a hydrogen atom,
Halogen atom and chlorine atom and fluorine atom are particularly preferable.

Preferred Z ¹ and Z ² in the general formulas (C-I) and (C-II) 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 ² is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In formula (CI), Z ¹ 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 cyan couplers represented by the above general formulas (C-I) and (C-II) are disclosed in JP-A-59-166956 and JP-B-49-1157.
It can be synthesized based on the description of No. 2 and the like.

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.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 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 two or more layers in which the same compound is different. 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
After being dissolved in either a single liquid of a high boiling point organic solvent having a boiling point of 175 ° C or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid 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 a phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing or ultrafiltration before use 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.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl). Phosphate,
2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid Esters (2-ethylhexylbenzoate, dodecylbenzoate, 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 acetate, 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. The auxiliary solvent has a boiling point of about 30 ° C or higher,
Preferably, an organic solvent having a temperature of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

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 photosensitive silver halide,
Preferably from 0.001 to 0.5 mol for the yellow coupler,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

The light-sensitive material used in the present invention, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, amines, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler,
You may contain a sulfonamide phenol derivative etc.

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, methylenedioxy. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or phenolating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by (bissalicylaldoximate) nickel complex and (bis-N, N-dialkyldithiocarbamate) nickel complex can also be used.

Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 give good results in preventing the yellow dye image from deteriorating due to heat, humidity and light. Further, in order to prevent the deterioration of the magenta dye image, particularly the deterioration due to light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether described in JP-A-55-89835. The chromans given give favorable 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, an ultraviolet absorber is contained in either one of the layers adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When an ultraviolet absorber is added to the protective layer, another protective layer may be further applied 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.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based brightening agent. 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. A multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one red-sensitive emulsion layer on a support.
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, or 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 anti-halation 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 and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Use of various synthetic hydrophilic polymer substances such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can 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, (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products 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. Typical examples of these additives are Research Disclosure 17643 (December 1978) and 18716.
(November 1979).

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, polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, polycarbonate film, polystyrene film and the like are available, and these supports can be appropriately selected according to the purpose of use.

[Example-1] A processing solution having the following formulation as a color developing solution (Sample Nos. 1 to 1)
8) was prepared.

Color developer Compound (A) shown in Table 1 below Amount shown in Table 1 below Compound (B) shown in Table 1 below Amount shown in Table 1 below Sodium sulfite 0.2g Potassium carbonate 30g Ethylenediaminetetraacetic acid Disodium 1 g Sodium chloride 1.5 g 4-Amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline sulfate 5.
0g Whitening agent (4,4'-diaminostilbene type) ^* 3.0g Add water to 1000 ml pH 10.05 * UVITEX-CK manufactured by Ciba-Geigy Color developer solution prepared in this way (No. 1
18) in a test tube with an aperture ratio (opening area / sample area) of 0.06
It was put so as to become cm ⁻¹ and left at 35 ° C. for 4 weeks. After 4 weeks, the decrease due to evaporation was corrected with distilled water, and the residual ratio of the aromatic primary amine color developing agent was measured and calculated by liquid chromatography.

As is clear from Table 1, when using hydroxylamine and diethylhydroxylamine alone (Sample Nos. 1 and 2)
On the other hand, the residual ratio of the developing agent by adding a compound such as triethanolamine or polyethyleneimine, sodium sulfite or cyclohexanediaminetetraacetic acid is not sufficient although it is improved (Sample No. 3 4, 5, 6).

However, as is apparent from Sample Nos. 7 to 14, by using the compound represented by the general formula (I) and the compound represented by the general formula (II), the residual ratio of the developing agent is remarkably improved, and It can be seen that the stability of the developer is improved.

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

Preparation of first layer coating solution 19.1 g of yellow coupler (a) and color image stabilizer (b)
To 4.4 g, 27.2 ml of ethyl acetate and 7.9 ml of 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-sensitizing sensitizing dye is added to a silver chlorobromide emulsion (containing 1 mol% of silver bromide and 70 g / kg of Ag) in an amount of 5.5 per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 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 B was obtained, and the coating solution for the first layer was prepared.
Each of the components shown in Table B is used to form the coating liquid for the second to seventh layers as well.
It was prepared in the same manner as the layer coating solution. 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 the emulsion of each layer.

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

The structural formulas of the compounds used in this example, such as couplers, are as follows.

(J) Solvent (iso ₇ H ₁₈ O ₃ P = O The multilayer color photographic printing paper prepared as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

(Processing process) (Temperature) (Time) Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Stability 1 35 ℃ 20 seconds Stability 2 35 ℃ 20 seconds Stability 3 35 ℃ 20 seconds Dry 70 ℃ to 80 ℃ For 60 seconds stability, 3 tanks countercurrent from stability 3 to stability 1 was used. The formulation of each treatment liquid used is as follows.

The following color developing agent shown in Table 2 0.01mol brightener (4,4'-diaminostilbene type) was added to 3.0g of potassium bromide 0.01g Water 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%) 120ml Sodium sulfite 16g Glacial acetic acid 7g Water added 1000ml pH 5.5g Stabilizer Formalin (37%) 0.1ml 1-Hydroxyethylidene-1,1-diphosphone Acid (60
%) 1.6 ml Bismuth chloride 0.35 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid / 3Na 1.0 g EDTA 0.5 g Sodium sulfite 1.0 g 5-Chloro-2-methyl-4- isothiazolin-3-one 50 mg Add water On the other hand, a part of the above color developing solution was placed in a beaker 1 and left at an open rate of 35 ° C. for 21 days, and then this aged solution was used for the above processing step.

The treatment using the color developing solution (aging liquid) left for 21 days was designated as the aging liquid test, and the treatment using the color developing liquid (fresh liquid) before being left was designated as the fresh liquid test.

The photographic characteristics obtained by the fresh liquid test and the aged liquid test are shown in Table 2.

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.

From the results in Table 2, in Experiment Nos. 1 to 4, the Dmin and the gradation changed with the passage of time, and the contrast became higher, whereas in Experiment No. 5
It can be seen that in the range of to 12, the changes in Dmin and gradation are small even after aging, and the stability of photographic properties is remarkably improved. Further, among Experiment Nos. 5 to 8, in Experiment No. 8, the changes in Dmin and gradation were the smallest, and it was found that Compound D was the most preferable among the color developing agents.

* Color developing agents a to d represent the following compounds.

** Compounds (a), (b), (c), and (d) are the same as in Table A. [Example-3] Same as Example 2 except that the bromine ion content of the green-sensitive layer emulsion was 80 mol%. Then, a color photographic paper was prepared, and the change in photographic property after exposure to a wedge shape was evaluated by the occurrence of fog.The developer of Comparative Example showed a large increase in fog in the aged liquid, whereas The developer of the invention did not increase fog with time, and maintained good photographic properties.

[Example-4] A color photographic paper prepared in the same manner as in Example 2 was exposed to a wedge shape, and then various color developers were subjected to a running process (continuous process) in the following processing steps until replenishment was performed in an amount of 3 times the tank volume. Processing) The test was performed.

(Processing process) (Temperature) (Time) (Replenishment amount) Color development 35 ℃ 45 seconds 160ml / m ² Bleaching fixing 35 ℃ 45 seconds 100ml / m ² Rinse 30 ℃ 20 seconds Rinse 30 ℃ 20 seconds Rinse 30 ℃ 20 seconds 200ml / m ² Dry 60 ° -70 ° C 30 seconds Rinsing was a three-tank counter-current system from the rinse to the rinse.

 The formulation of each treatment liquid used is as follows.

Bleach-fixing solution (tank solution and replenisher are the _{same) EDTAFe (III) NH 4 ·} 2H 2 O 60g EDTA · 2Na · 2H 2 O 4g Ammonium thiosulfate (70%) was added to 120ml sodium sulfite 16g glacial acetic 7g water 1000 ml pH 5.5 Rinse solution (tank solution and replenisher are the same) EDTA ・ 2Na ・ 2H ₂ O 0.4g Water is added and 1000 ml pH 7.0 Treatment is carried out in the above treatment process using the above treatment liquid, at the start of running treatment and running treatment The BGR density (stain) of the unexposed area at the end was measured by a Fuji type self-recording densitometer. Further, the sample at the end of the running treatment was left at 80 ° C. (5 to 10 RH) for one month, and then the BGR concentration in the unexposed area was measured again.

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

From the results of Table 3, in Experiments Nos. 1 and 2, as a result of the running treatment, the stain was significantly increased, while in Experiment No. 3
It can be seen that in ~ 7, the increase in the stain is extremely small. In addition, even if we look at the changes over time after the end of processing, Experiment Nos. 3 to 7
In comparison with Experiment Nos. 1 and 2, the increase in stain is very small.

[Example-5] As shown in Table C, the first layer (lowermost layer) to the seventh layer (uppermost layer) were sequentially formed on corona-discharge-treated double-sided polyethylene laminated paper to form a printing paper sample. did.
Preparation of the coating solution for each layer is as follows. The details of the structural formulas of the coupler, color image stabilizer and the like used in the coating liquid will be described later.

The coating liquid for the first layer was prepared as follows. That is, a mixture of 200 g of yellow coupler, 93.3 g of anti-fading agent, 10 g of high boiling point solvent (p) and 5 g of solvent (q) and 600 ml of ethyl acetate as an auxiliary solvent was heated and dissolved at 60 ° C.,
It was mixed with 3,300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution of alkanol B (trade name; alkylnaphthalene sulfonate, manufactured by Dyupon). Next, this liquid was emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off from the dispersion under reduced pressure to give a sensitizing dye for a blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-.
Emulsion 1,4 with acetylamino-1,3,4-triazole
Add to 00g (including 96.7g as Ag, 170g gelatin),
Further, 2,600 g of a 10% gelatin aqueous solution was added to prepare a coating solution. The coating solutions for the second layer to the seventh layer have the first composition according to the composition of Table C.
Prepared according to layers.

However, each of the cyan couplers shown in Table 4 below was used as the cyan coupler of the fifth layer to produce photographic paper.

n 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole o 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole p di (2-ethylhexyl) phthalate q dibutyl Phthalate r 2,5-di-tert-amylphenyl-3,5-di-tert-
Butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-amyl-2,5-dioctyloxybenzene u 2,2′-methylenebis (4-methyl-6-tert-butylphenol The following substances were used as the sensitizing dye for the emulsion of each layer.

Sensitizing dye for emulsion in blue-sensitive layer; anhydro-5-methoxy-
5'-methyl-3,3'-disulfopropylselenacyanine hydroxide sensitizing dye for green-sensitive layer emulsion; anhydro-9-ethyl-5,
5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive layer emulsion sensitizing dye; 3,3'-diethyl-5-methoxy-9,9 '-(2,2-dimethyl -1,3-Propano) thiadicarbocyanine iodide Further, 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole was used as a stabilizer for each emulsion.

The following dyes were used as the anti-irradiation dye.

4- (3-carboxy-5-hydroxy-4- (3-
(3-carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-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 Also, 1,2-bis (vinylsulfonyl) ethane was used as a hardening agent.

 The couplers used are as follows.

The multilayer color printing paper obtained as described above was subjected to the following processing steps after wedge-shaped exposure.

(Processing step) (Time) (Temperature) Color development 3 minutes 30 seconds 33 ° C Bleaching fixing 1 minute 30 seconds 33 ° C Rinse (3 tank cascade) 2 minutes 30 ° C dryness 1 minute 80 ° C On the street.

Color developer Water 800 ml Sodium sulfite Amount shown in Table 4 below N, N, '-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 0.1 g Nitrilo-N, N, N-trimethylenephosphone Acid (40%)
1.0 g Potassium bromide 1.0 g Additives C and D shown in Table 4 below Amount shown in Table 4 Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulphate 5.5g Fluorescent brightener (4,4'-diaminostilbene type) 1.0g Add water and 1000ml KOH pH 10.10 Bleach-fix solution Ammonium thiosulfate (70%) 150ml Sodium sulfite 15g EDTA ・ Fe _{(III) · NH 4 · 2H} 2 O 60g EDTA 10g optical brightener (4,4'-diaminostilbene type) 1.0g 2-mercapto-5-amino-3,4-thiadiazole 1.0g water to make 1000ml PH 7.0 with ammonia water rinse solution 5-chloro-2-methyl-4-isothiazoline-3-
On 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.g 1-hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.5 g Fluorescent whitening agent (4,4′-diaminostilbene type) 1.0 g Ammonia water (26%) 2.0 ml Water was added to 1000 ml KOH pH 7.5 In the above treatment, in the same manner as in Example 2. The Dmin and gradation of cyan were measured using the aged solution after leaving a part of the fresh solution and the color developing solution for 21 days.

Table 4 shows the increase in Dmin and gradation of the aged liquid with respect to the fresh liquid.

From the results of Table 4, in comparison with Experiment Nos. 1 to 3, Experiment No. 4 to
With No. 15, it is found that even if a developer left for 21 days is used, changes in Dmin and gradation are small and the photographic properties are extremely stabilized. Especially when "C-5" or "C-38" is used as the cyan coupler (Experiment No. 6, 7, 10, 1)
1, 13, 15) and when the concentration of sulfurous acid in the developer is low (Experiment No. 10, 11, 13, 15), the preservative property of the developer is high,
It can be seen that the photographic property becomes more stable.

The cyan couplers A) and B) in Table 4 are as follows.

Example 6 The rinsing liquid of Example 4 was added with an ion exchange solution (calcium,
When the same treatment as in Example 4 was performed except that magnesium was used in an amount of 3 ppm or less), preferable results were obtained in the present invention.

Example 7. A multilayer color photographic paper sample having the same constitution as in Example 2 except that the silver chloride content of each of the silver chlorobromide emulsions of the first layer, the third layer and the fifth layer was changed as described below. 210, 211 and 212 were created.

This color photographic paper sample was subjected to the fresh solution test and the aged solution test in the same manner as in Example 2 by using the developer of Experiment No. 8 in Table 2 of Example 2.

 The photographic properties thus obtained are shown in Table 5.

Sample 210 Silver chloride 90 mol% silver chlorobromide emulsion 〃 211 〃 80 〃 〃 212 〃 70 〃 (Note) The amount of silver used is the same As is clear from the results in Table 5, Sample No. 21 of the present invention
According to 0 and 211, the change in the Dmin and the gradation is small even when treated with the aged liquid as compared with the treatment with the fresh liquid, but a comparative example (Sample No. 212,
In the case of using an emulsion containing 70 mol% of silver chloride), the photographic properties of Dmin and gradation are significantly changed by the treatment with the aged liquid as compared with the treatment with the fresh liquid.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 61-159640 (JP, A) JP 62-178959 (JP, A) JP 62-246051 (JP, A) JP 62- 242939 (JP, A) JP 62-247366 (JP, A) JP 62-255945 (JP, A) JP 58-95345 (JP, A) JP 58-108533 (JP, A) JP-A-58-95736 (JP, A) International publication 87/4534 (WO, A)

Claims (3)

[Claims] 1. The silver halide in the silver halide emulsion layer has a silver chloride content of 80 to 100 mol%, and has the following general formula (C
-I) or (C-II), a silver halide color photographic light-sensitive material containing at least one cyan coupler in at least one silver halide emulsion layer, an aromatic primary amine color developing agent. And at least one compound represented by the following general formula (I) and at least one
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing a compound represented by the following general formula (II). General formula (C-I) (In the formula, R ³¹ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ³² represents an alkyl group or an aryl group. R ³³ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. And R ³³ .
^May combine with R ³² to form a ring. Z ¹ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidant of an aromatic primary amine type color developing agent. ) General formula (C-II) (In the formula, R ³⁴ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ³⁵ represents an alkyl group having 2 or more carbon atoms. R ³⁶ represents a hydrogen atom, a halogen atom or an alkyl group. Z ² 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 (I) (In the formula, M may be the same or different and represents a hydrogen atom, alkaline metal, and ammonium ion.
Represents an integer of 4. ) General formula (II) (In the formula, R ²¹ and R ²² are an unsubstituted or substituted alkyl group,
It represents an unsubstituted or substituted alkenyl group or an unsubstituted or substituted aryl group, and R ²¹ and R ²² may be linked to form a nitrogen-containing heterocycle. ) 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color developer contains substantially no benzyl alcohol. 3. The aromatic primary amine color developing agent is 4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline compound), The method for processing a silver halide color photographic light-sensitive material according to claim 2.