JPH06148840A - Photographic developing composition and processing method using same - Google Patents

Abstract

PURPOSE:To enhance the stability of a developing solution, to reduce the deterioration of a developing agent in the storage of the developing solution for a long period and at the time of continuous processing of a silver halide photographic sensitive material and to enhance the performance for preventing staining of the developing solution by incorporating a specified compound. CONSTITUTION:This developing composition contains at least one of the compounds represented by formula I in which X is a bonding group comprising 2C atoms; Y is a bonding group forming a 6-membered ring together with 2C atoms and the 2N atoms and this ring has 2 unsaturated bonds. This ring compound is added to the developing composition, such as a color developing solution or black-and-white developing solution, thus permitting excellent effects to be obtained on the stability of the developing solution with the lapse of time, staining-preventive ability, and fluctuation of photographic performance, such as stains, in the processing. This compound of formula I can restrain the deterioration of a developing agent likewise to the case of the color development, when it is used for the black-and-white developing solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide light-sensitive material, and more particularly to a processing method in which the stability of a developing solution is improved and contamination such as tar due to deterioration of the developing solution with time is improved. Furthermore, the present invention relates to a processing method capable of obtaining stable photographic properties in continuous processing.

[0002]

2. Description of the Related Art In the color development processing of a silver halide color photographic light-sensitive material, a color developing solution containing an aromatic primary amine color developing agent has been conventionally used for forming a color image, and nowadays a color developing solution is used. It plays a central role in the method of forming photographic images. However, the color developer has a problem that it is easily oxidized by air or metal, and when a color image is formed by using the oxidized developer, the stain is increased, the sensitivity and the gradation are changed. Therefore, it is well known that desired photographic characteristics cannot be obtained.

Further, with the recent rapid processing at high temperature and the reduction of replenishment amount, the above deterioration phenomenon tends to be further accelerated. As a result, liquid fatigue due to high temperature,
Due to the low replenishment, the development solution is colored and the decomposed product of the developing agent is accumulated due to long-term retention of the processing solution in the processing tank.

[0004] Conventionally, so-called preservatives have been developed in order to prevent the deterioration of the liquid as described above, but generally, these preservatives greatly impair the color forming property. Particularly, hydroxylamine and sulfite, which are generally and widely used, have a remarkable adverse effect on a light-sensitive material having a high silver chloride content used in recent rapid processing.

To address these problems, substituted hydrazine having a substituent has been investigated as a preservative. For example,
JP-A-63-170642 and JP-A-63-170643.
No. 1, JP-A-1-97953 and European Patent Application Publication 0
Examples thereof include alkyl-substituted hydrazines described in No. 285010 and No. 0254280. Some of these substituted hydrazines have little effect on photographic properties,
Not always enough.

[0006]

Therefore, the first object of the present invention is that the developer is excellent in stability and is deteriorated in the developing agent during long-term solution aging or during continuous processing of a silver halide photographic light-sensitive material. The present invention is to provide a processing method which has a small amount and which is excellent in preventing contamination of the developing solution. A second object of the present invention is to provide a treatment of the above light-sensitive material which is excellent in photographic properties and stain prevention.

[0007]

The above-mentioned problems are solved by using a developing composition for a silver halide light-sensitive material characterized by containing at least one compound represented by the general formula (I). I was able to.

[0008]

[Chemical 2]

By adding at least one of the compounds represented by the general formula (I) to a developing composition (for example, a color developing solution or a black and white developing solution), the stability of the solution over time, the anti-staining ability, and the photographic property variation in processing are changed. It was totally unexpected that it was excellent in (eg, stain, sensitivity).

This effect is (prevention of deterioration of the color developing agent) in the color development processing of the silver halide color light-sensitive material.
And (preservation performance) in a broad sense meaning (liquid coloration and tarring prevention) and (prevention of color development inhibition or stain generation), that is, excellent performance in terms of "photographic performance". is there.

The general formula (I) will be described in more detail. In the general formula (I), two carbon atoms constituting the linking group X, two carbon atoms constituting the linking group Y and two nitrogen atoms form a 6-membered ring, and two unsaturated bonds are formed in the ring. The basic skeleton of the compound is as follows.

[0012]

[Chemical 3]

In the formula of the basic skeleton, R ₁₁ , R ₂₁ , R ₂₂ ,
R ₃₁ , R ₃₂ , R ₄₁ , R ₅₁ , R ₅₂ , and R ₆₁ are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group,
It represents a sulfamoyl group, a carbamoyl group, an acyl group, an alkoxycarbonyl group, a cyano group, a nitro group, a halogen atom, a carboxy group, or a sulfo group. Preferably, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an amino group, an alkylamino group having 1 to 6 carbon atoms,
It is a sulfamoyl group, a cyano group, a chlorine atom, a carboxy group, or a sulfo group, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, an amino group, or 1 carbon atom. To 4 are alkylamino groups, carboxy groups, and sulfo groups. The alkyl group, aryl group and alkoxy group, alkylamino group, sulfamoyl group, carbamoyl group, acyl group, alkoxycarbonyl group may be substituted with other substituents, for example, the alkyl group and aryl group to be substituted are further substituted. The preferred substituents include a hydroxy group, an amino group, a carboxyl group, a sulfo group and a phosphono group. R ₁₁ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₅₁ ,
R ₅₂ and R ₆₁ may be the same or different and may be linked to each other to form a ring. Specific compounds of the general formula (I) are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

The compound represented by the general formula (I) is "Canad
ian Journal Chemistry ", Vol. 52, p. 3971, 1974," T
etrahedron ", 39, 2085, 1983," Pharmaceutical magazine ", 78
229, 1958, "Comprehensive Heterocyclic Chemis
try ", Volume 3, pp. 157-197," The Chemistry of Hete
It can be easily synthesized by the method described in rocyclic Compounds ", The Pyraziness, 1982, etc. Specific synthetic examples are shown below, but the invention is not limited thereto.

Synthetic Method of Compound IB-1 Ethylenediamine (18.5 g) was dissolved in 200 ml of tetrahydrofuran, and a tetrahydrofuran solution of diacetyl (20 g) was added dropwise. The mixture was refluxed at room temperature for 1 hour and heated under reflux for 1 hour. After cooling, potassium hydroxide was added for dehydration, the solvent was distilled off, and the residue was distilled under reduced pressure. Boiling point 60-63
° C / 20 mmHg (literature value: 60-63 ° C / 18 mmHg). Yield 16.5 g Yield 65%

Synthesis of Compound IB-9 1,2-Diaminocyclohexane (26 g) was dissolved in 200 ml of tetrahydrofuran, and a solution of diacetyl (20 g) in tetrahydrofuran was added dropwise. The mixture was refluxed at room temperature for 1 hour and heated under reflux for 1 hour. After cooling, potassium hydroxide was added for dehydration, the solvent was distilled off, and the residue was distilled under reduced pressure. boiling point
90-93 ° C / 2 mmHg yield 20g yield 53% Elemental analysis value: C: 73.5%, H: 9.89%, N:
17.09% (theoretical value C: 73.12%, H: 9.82)
%, N: 17.06%)

The content of these compounds in the developer is 0.5 g to 50 g, preferably 1.0 g to 30 g, and more preferably 1.5 g to 20 g per liter of the developer.
It is g. These compounds may be added directly to the treatment tank or may be contained in the replenisher. These compounds may be present in the light-sensitive material. Further, not only in the color developing solution, even if it is brought into the bleaching and bleach-fixing solution or the washing or stabilizing solution by bringing it from the prebath or adding it, it acts on the developing agent and its oxidant present in each solution. And can provide good performance.

Further, the compound represented by the general formula (I) is
You may use it for black and white developer. When used in black and white developer,
As in the case of color, deterioration of the developing agent can be suppressed.

Representative examples of the color developing agent used in the present invention are shown below, but the invention is not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino)
Toluene P-3 2-amino-5- (N-ethyl-N-laurylamino) toluene P-4 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline P-5 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-6 N, N-diethyl-p-phenylenediamine P-7 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline P-8 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline P-9 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline

P-10 4-amino-3-methyl-N-ethyl-N- (2-hydroxyethyl) aniline P-11 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline Further, these p-phenylenediamine derivatives are used in salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, and naphthalene-1,5-disulfonates. It is common to It is preferably about 0.003 mol to about 0.1 mol, and more preferably 0.01 mol to 0.05 mol per liter of color developer.

In the color developing solution, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added as necessary. Although it can be added, the concentration of the sulfite compound is preferably low in the present invention, and the preferable addition amount thereof is 0.07 mol or less, and more preferably 0.05 mol or less per liter of the color developing solution. , May not be included at all. Carbonyl bisulfite adducts are preferred because they can substantially reduce the concentration of sulfite or bisulfite compounds. Also in this case, it is preferable to control the concentration of free sulfite or bisulfite within the above range. Further, as a compound that directly preserves the aromatic primary amine color developing agent, various hydroxylamines described in JP-A-63-5341 and JP-A-63-106655 (in particular, those having a sulfo group or a carboxy group) Compounds are preferred), hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, phenols described in JP-A-63-44657 and 63-58443, 63-4
Examples thereof include α-hydroxyketones and α-aminoketones described in No. 4656 and various sugars described in No. 63-36244. Also, in combination with the above compound,
JP-A Nos. 63-4235, 63-24254, and 6
No. 3-21647, No. 63-146040, No. 63-
Monoamines described in No. 27841 and No. 63-25654, No. 63-30845, No. 63-1464
0, 63-43139 and the like diamines, 63-21647, 63-26655 and 6
Polyamines described in 3-44655, 63-53
Nitroxy radicals described in No. 551, 63-43
The alcohols described in Nos. 140 and 63-53549, the oximes described in No. 63-56654, and the tertiary amines described in No. 63-239447 can be used. Other preservatives include JP-A-57-44
148 and 57-53749, various metals, 59-180588, salicylic acids, 54-3582, alkanolamines, 5
The polyethyleneimine described in 6-94349, the aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0. In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
-Potassium hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. The addition amount of the buffer is preferably 0.1 mol or more, and particularly preferably 0.1 to 0.4 mol per liter of the color developing solution.

In addition, it is preferable to use various chelating agents as a precipitation preventing agent for calcium and magnesium in the color developing solution or for improving the stability of the color developing solution. As a chelating agent, an organic acid compound is preferable,
Examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Typical examples of these are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid,
Ethylenediamine ortho-hydroxyphenylacetic acid, 2-
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N '
-Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid etc. are mentioned. Two or more of these chelating agents may be used in combination, if necessary. The amount of the chelating agent added may be an amount sufficient to block the metal ions in the color developing solution, and is, for example, about 0.1 g to 10 g per liter of the color developing solution.

If desired, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution in the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and color contamination prevention. Here, "substantially" means that the amount of the developer is not more than 2 ml, preferably not at all, per liter of the color developing solution. Other development accelerators include JP-B-37-1
No. 6088, No. 37-5987, No. 38-7826
Nos. 44-12380, 45-9019, U.S. Pat. No. 3,818,247, and the like, thioether compounds, JP-A-52-49829 and JP-A-50-15.
P-phenylenediamine compounds described in JP-A No. 554, JP-A-50-137726, JP-B-44-30074.
No. 5, JP-A-56-156826, JP-A-52-43429.
Quaternary ammonium salts described in US Pat.
No. 94,903, No. 3,128,182, No. 4,
230,796, 3,253,919, Japanese Patent Publication No. 41-11431, and U.S. Pat. No. 2,482,546.
No. 2,596,926, No. 3,582,34
Amine compounds described in No. 6, etc., JP-B-37-1608
8, 42-25201, U.S. Pat. No. 3,128,
No. 183, Japanese Patent Publication Nos. 41-11431, 42-238
No. 83, U.S. Pat. No. 3,532,501, and other polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. The amount of the development accelerator added is about 0.01 to 5 g per liter of the color developing solution.

In the present invention, if necessary,
Any antifoggant can be added. 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-
Nitrogen-containing substances such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine. A heterocyclic compound can be mentioned as a typical example. The addition amount of the antifoggant is about 0.001 g to 1 g per liter of the color developing solution. The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4,4′-diamino-2,2′-disulfostilbene compound is preferable. The amount of the fluorescent whitening agent added is 0 to 5 g, preferably 0.1 to 4 g, per liter of the color developing solution, and if necessary, alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid. You may add various surfactants, such as.

The processing temperature in the color developing solution is suitably 20 to 50 ° C, preferably 30 to 45 ° C. The treatment time is suitably 20 seconds to 5 minutes, preferably 20 seconds to 4 minutes. Further, in the present invention, in order to accelerate the processing, it is also preferable to provide an alkaline processing bath (hereinafter referred to as a pre-development bath) before the color developing step. In this case, this pre-development bath may contain compounds that can be contained in all color developing solutions other than the color developing agent. The processing time of the pre-development bath is preferably 10 to 60 seconds, more preferably 10 to 30 seconds.

The processing method of the present invention can be preferably used for color reversal processing. In the reversal process, after the black and white development, the reversal process is performed if necessary, and then the color development is performed. The black-and-white developing solution used at this time is called a black-and-white first developing solution which is commonly used for reversal processing of color light-sensitive materials. Various well-known additives that are used by being added to the liquid can be contained. Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, hard water softeners such as polyphosphates, development inhibitors consisting of trace amounts of iodides and mercapto compounds You can

The processing after color development of the present invention specifically refers to a desilvering step and an auxiliary step. The desilvering process of the present invention is carried out by a combination of a bleaching process, a fixing process and a bleach-fixing process, a typical example of which is shown below. Bleach-fix Bleach-bleach-fix Bleach-bleach-fix-fix Bleach-wash-fix-bleach-fix-bleach-fix Bleach-fix-fix

The processing solutions having bleaching ability (collectively referred to as bleaching solutions or bleach-fixing solutions) will be described below.
For a processing solution having a bleaching ability, 0.
It is necessary to contain 01 to 1 mol of bleach, and
05-0.5 mol is more preferable, and 0.1-0.5 mol is particularly preferable. As the bleaching agent used in the processing solution having a bleaching ability, there are Fe (II), Co (II
Examples thereof include I) or Mn (III) chelate bleach, persulfate (for example, peroxodisulfate), hydrogen peroxide, bromate and the like. Examples of the compound forming the chelate bleaching agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ', N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilo-N-2-carboxy-
N, N-diacetic acid, N- (2-acetamido) iminodiacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid, 1,3-diaminopropanol-N, N, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-N,
Examples thereof include N, N ', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N, N, N', N'-tetramethylenephosphonic acid and their sodium salts and ammonium salts. Among the above, 1,3-diaminopropane tetraacetic acid, nitrilo-N-2-carboxy-N, N-
Diacetic acid and N- (2-acetamido) iminodiacetic acid are particularly preferred.

A processing solution having a bleaching ability preferably contains a halide such as chloride, bromide or iodide as a rehalogenating agent for promoting the oxidation of silver. Further, an organic ligand that forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include potassium bromide, sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, and the like, with potassium bromide or sodium bromide being preferred. The amount of rehalogenating agent in the bleaching solution is 2
The amount is suitably mol / liter or less, preferably 0.01 to 2.0 mol / liter, more preferably 0.1 to 1.
It is 7 mol / liter. The bleach-fixing solution contains a fixing agent (described later) and may further contain all the compounds contained in the fixing solution described later. If necessary, the rehalogenating agent may be included. When the rehalogenating agent is used in the bleach-fixing solution, the amount thereof is 0.001-2.
It is 0 mol / liter, preferably 0.001 to 1.0 mol / liter.

The bleaching solution or bleach-fixing solution according to the present invention may further contain a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffering agent for maintaining the pH of the solution, a fluorescent whitening agent, a defoaming agent and the like. It is added as needed. Examples of the bleaching accelerator include US Pat. No. 3,893,858, Dotsui Patent No. 1,290,812, and US Pat. No. 1,138,8.
42, JP-A-53-95630, Research Disclosure No. 17129 (1978), compounds having a mercapto group or a disulfide group, JP-A-50-140129, thiazolidine derivatives, US Pat. , 706,561, thiourea derivatives, German Patent 2,748,430, polyethylene oxides, JP-B-45-8836, polyamine compounds, JP-A-49-40493, imidazole compounds. Etc. can be used. Of these, the mercapto compounds described in US Pat. No. 1,138,842 are preferable. As the corrosion inhibitor, nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate or the like is used. The amount added is 0.01 to 2.0 mol / liter, preferably 0.1.
It is from 05 to 0.5 mol / liter. In the bleaching solution or the bleach-fixing solution according to the present invention, the total ammonium ion concentration is preferably 0.3 g ion / liter or less. This embodiment is preferable from the viewpoint of image storability and environmental protection, and in the present invention, it is more preferably 0.1 mol / liter or less.

The pH of the bleaching solution or the bleach-fixing solution according to the present invention is 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is carried out immediately after color development, the pH of the solution is preferably 7.0 or less, more preferably 6.4 or less in order to suppress bleaching fog. Particularly in the case of a bleaching solution, 3.0 to 5.0 is preferable. When the pH is 2.0 or less, the metal chelate according to the present invention becomes unstable. Therefore, pH 2.0 to 6.4 is preferable. PH for this
As a buffering agent, it is difficult to be oxidized by a bleaching agent,
Any material having a buffering effect in the H range can be used. For example, acetic acid, glycolic acid,
Examples thereof include organic acids such as lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid and ureidopropionic acid, and organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline and aminoacetonitrile. A plurality of these buffers may be used in combination. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferable, and acetic acid and glycolic acid are preferably used alone or in combination. The total amount of these buffers used is suitably 3.0 mol or less, preferably 0.5 to 2.0 mol, per liter of the processing solution having a bleaching ability. In order to adjust the pH of the processing solution having a bleaching ability to the above range, the above-mentioned acid and alkaline agent (for example, aqueous ammonia, KOH, Na
OH, imidazole, monoethanolamine, diethanolamine) may be used in combination. Of these, KOH is preferred.

The bleaching or bleach-fixing step is carried out at 30 ° C to 6 ° C.
It can be performed in a temperature range of 0 ° C, but is preferably 35 ° C to 50 ° C.
Is. The time for the bleaching and / or bleach-fixing treatment step is 1
It is used in the range of 0 second to 2 minutes, preferably 10 seconds to 1 minute. In these preferred processing conditions,
Good results are obtained quickly and without an increase in stain.

A known fixing agent is used for the bleach-fixing solution or the fixing solution. These are thiosulfates, thiocyanates, thioethers, amines, mercaptos, thiones, thioureas, iodides, mesoions and the like, for example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, thiosulfate. Guanidine sulfate, potassium thiocyanate, dihydroxyethyl-thioether,
3,6-dithia-1,8-octanediol, imidazole and the like can be mentioned. Of these, thiosulfates, particularly ammonium thiosulfate, are preferred for rapid fixing. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, niourea, thioether, etc. in this case, and in this case, the second fixing agent is in the range of 0.01 to 100 mol% with respect to ammonium thiosulfate. It is preferable to add it. The amount of the fixing agent is 0.1 to 3.0 mol, preferably 0.5 to 2.0, per liter of the bleach-fixing solution or the fixing solution.
It is a mole. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to 9.0, and particularly when thiosulfate is used, 6.5 to 8.0 provides stable fixing performance. It is preferable above.

A preservative is added to the bleach-fixing solution or the fixing solution,
It is also possible to enhance the stability of the liquid over time. In the case of a bleach-fixing solution or a fixing solution containing thiosulfate, sulfite as a preservative, and / or bisulfite adduct of hydroxylamine, hydrazine, aldehyde (for example, bisulfite adduct of acetaldehyde, particularly preferred) The bisulfite adduct of aromatic aldehyde described in JP-A 1-298935) is effective. Also, JP-A-62-14304
It is also preferable to use the sulfinic acid compound described in No. 8.
It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
Examples thereof include N-allylmorpholine and N-benzoylpiperazine. Furthermore, by adding various chelating agents to the fixing solution, it is possible to conceal iron ions brought in from the bleaching solution and improve the stability of the solution. Such a preferable chelating agent is 1-hydroxyethylidene-
1,1-diphosphonic acid, ethylenediamine-N, N,
Examples thereof include N ', N'-tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and 1,2-propanediaminetetraacetic acid. The fixing step can be performed in the range of 30 ° C to 60 ° C, preferably 35 ° C to 50 ° C. The fixing process time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute 40 seconds.

After the processing step having fixing ability, usually,
Perform a washing process. After processing with a processing solution with fixing ability,
It is also possible to use a simple treatment method in which a stabilizing treatment using the stabilizing solution of the present invention is carried out without substantially washing with water. Although tap water can be used as the water used in these washing steps, it is sterilized by water, halogen, an ultraviolet germicidal lamp, etc., which has been deionized to a Ca or Mg ion concentration of 5 mg / liter or less by an ion exchange resin or the like. Preference is given to using water. Further, tap water may be used as water for correcting the evaporation of each treatment liquid, but deionized water or sterilized water which is preferably used in the above washing step is preferable.

It is preferable that the washing water and the stabilizing solution contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. As these surfactants, polyethylene glycol type nonionic surfactants,
Polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt Type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants are preferred, but it is preferable to use nonionic surfactants, especially alkylphenol ethylene oxide addition. The thing is preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Further, it is preferable that the washing water and the stabilizing solution contain various antibacterial agents and antifungal agents in order to prevent water stains and molds generated on the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents include thiazolylbenzimidazole compounds as shown in JP-A-57-157244 and 58-105145, and JP-A-57-8542. Isothiazolone compounds, chlorophenol compounds such as trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds,
Diazine and triazine compounds, thiourea compounds,
Benztriazole compounds, alkylguanidine compounds, quaternary ammonium compounds such as benzalkonium chloride, antibiotics such as penicillin, Journal Antibacterial &
Antifungus Agent (J. Antibact. Anti
fung. Agents) Vol 1. No. 5, p.207-223 (19)
The general-purpose antifungal agent described in 83) and the like may be used in combination of two or more kinds. Also, JP-A-48-8382
Various bactericides described in No. 0 can also be used.

It is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysates of maleic anhydride polymers described in European Patent 345172A1.

The stabilizing solution stabilizes the dye image.
Compounds such as formalin, hexamethylene tetrami
And its derivatives, hexahydrotriazine and its derivatives
Conductor, dimethylol urea, N-methylol pyrazole
Contains any N-methylol compound, organic acid, pH buffer, etc.
Get caught The preferred addition amount of these compounds is 1
0.001 to 0.02 mol per ton but stable
The lower the free formaldehyde concentration in the liquid, the more
This is preferable because the scattering of dehydration gas is reduced. like this
From this point of view, hexamethylene ether is used as a dye image stabilizer.
Japanese Patent Application No. 3- such as tramin and N-methylolpyrazole
N-methylolazoles described in 318644, N,
N'-bis (1,2,4-triazol-1-yl) py
Azolyl described in Japanese Patent Application No. 3-142708 such as perazine
Methylamines are preferred. Also, if necessary
Ammonium such as ammonium chloride and ammonium sulfite
Compounds, metal compounds such as Bi and Al, optical brighteners,
Hardener, alkano described in US Pat. No. 4,786,583.
Included in ruamine and the above fixer and bleach-fixer
It is also preferable to include a preservative capable of these
Among them, the sulfi described in JP-A No. 1-231051
Acid compounds (eg benzenesulfinic acid, toluene
Sulfinic acid or sodium and potassium of these
Etc.) is preferable, and the addition amount of these is Stabilizer 1
1 x 10 per liter^-Five~ 1 x 10 ^-3Mol is preferred
Especially 3 × 10^-Five~ 5 x 10^-FourMolar is more preferred.
As a stabilizer, pH is usually used in the range of 4 to 10.
However, 6-9 is preferable. The processing temperature for the stabilizer is 3
0-45 degreeC is preferable. If the processing time is short,
Therefore, the effect of the present invention becomes remarkable, and 10 seconds to 2 minutes, especially 10
~ 60 seconds is preferred. Furthermore, in 10 to 25 seconds,
Is also preferable, because the effect is remarkable, and the image storability is deteriorated
It is possible to perform the processing for a short time without causing it.

The processing method of the present invention is used when continuous processing is performed using an automatic processor. The replenisher for each processing solution supplements the consumption and deterioration of processing solution components over time in the processing of photosensitive materials and in automatic developing machines, and suppresses the accumulation of unwanted components that elute from photosensitive materials in the processing solution. In order to keep the performance constant, it is preferably added depending on the amount of the processed light-sensitive material. Therefore, the former compound has a higher concentration than the tank liquid, and the latter compound has a lower concentration. Further, two or more processing baths may be provided in each processing step, and in that case, it is preferable to adopt a countercurrent system in which the replenisher is poured from the rear bath to the front bath. In particular, it is preferable to use a cascade of 2 to 4 stages in the washing process and the stabilizing process. Also,
The color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the developing time or further reduce the replenishing amount. Further, by using a processing tank having a slit-shaped small cross-sectional area as described in JP-A-2-67556, a post-bath is provided so that the developing solution can flow in the direction opposite to the traveling direction of the photosensitive material. A method of replenishing from the near side and overflowing from the opposite side is also preferable. Conversely, the developer may be replenished so that the developing solution can flow in the same direction as the traveling direction of the photosensitive material. The replenishment amount of each processing solution is preferably reduced as long as the compositional change in each processing solution does not cause photographic performance or other inconveniences due to contamination of the solution.

The color developing replenisher contains a compound contained in the color developing solution. Compounds for compensating the consumption and deterioration of the processing solution components with the processing of the light-sensitive material and the lapse of time in the automatic processor are a color developing agent and a preservative, and the replenisher contains 1.1 to 10 parts of the tank solution. Included in 4 times the amount. Further, a compound that suppresses the accumulation of undesired components eluted from the light-sensitive material in the processing solution is a development inhibitor represented by a halide (for example, potassium bromide). 0.6 times included. The halide concentration in the replenisher is usually 0.006 mol / liter or less, but it is necessary to reduce the concentration as the replenisher is lowered, and it may not be contained at all. In addition, a compound that is unlikely to change its concentration due to processing or aging is usually contained in approximately the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Further, the pH of the color developing replenisher is higher than that of the tank solution by about 0.1 to 1.0 in order to prevent the pH of the tank solution from being lowered by the processing. This difference in pH also needs to be increased as the amount of replenishment decreases.

The replenishing amount of the color developing solution is 3000 ml or less per 1 m ² of the light-sensitive material, preferably 50 to 600 ml, more preferably 50 to 300 ml. The replenishing amount of the bleaching solution is 20 to 90 per 1 m ² of the light-sensitive material.
It is 0 ml, preferably 50 to 550 ml, more preferably 50 to 250 ml. The replenishing amount of the bleach-fixing solution is ^{20 to} 1500 ml, preferably 30 to 6 per m ² of the light-sensitive material.
It is 00 ml, and more preferably 50 to 200 ml.
The bleach-fixing solution may be replenished as a single solution, or the bleaching composition and the fixing composition may be separately replenished, or the bleaching bath and / or the overflow solution from the fixing bath may be mixed. It may be used as a bleach-fix replenisher.
The replenishing amount of the fixing solution is ^{20 to} 1500 per 1 m ² of the light-sensitive material.
ml, preferably 30 to 600 ml, more preferably 50 to 200 ml. The replenishing amount of the washing water or the stabilizing solution is preferably 200 to 1500 ml, and more preferably 300 to 600 ml per 1 m ^{2 of the} light-sensitive material to be processed. The washing process and the stabilizing process are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount carried in from the previous bath per unit area.

Further, it is preferable to use a method in which the overflow liquid of the water washing step or the stabilization step is caused to flow into a bath having a fixing ability as a pre-bath because the amount of waste liquid can be reduced.

When processing with the above-mentioned black-and-white developing solution or color-developing solution in an automatic developing machine, the area (opening area) in which the developing solution (color-developing solution and black-and-white developing solution) comes into contact with air should be as small as possible. preferable. For example, when the value obtained by dividing the opening area (cm ² ) by the volume of the developing solution (cm ³ ) is taken as the aperture ratio, the aperture ratio is preferably 0.01 (cm ^-1 ) or less, more preferably 0.005 or less.

In order to further reduce the amount of the replenisher for environmental protection, it is also preferable to use various regenerating methods in combination. Regeneration may be performed while circulating the processing solution in the automatic processor, or after removing the processing solution from the processing tank, performing appropriate recycling processing and returning it to the processing tank as a replenishing solution again. Is also good. In particular, the developer can be regenerated and used.

Since the metal chelate bleaching agent in the bleaching solution and / or the bleach-fixing solution becomes a reducing state with the bleaching treatment, the bleaching solution and / or the bleach-fixing solution should be continuously regenerated in cooperation with the treatment. It is preferable to take. In particular,
It is preferable to blow air into the bleaching solution and / or the bleach-fixing solution with an air pump to reoxidize the metal chelate in a reduced state by oxygen, so-called aeration. In addition, it can be regenerated by adding an oxidizing agent such as hydrogen peroxide, persulfate or bromate. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. In addition, it is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

The light-sensitive material in the present invention may have a coated silver amount of 1.2 g / m ² or more and a dry film thickness of 16 μm or less. The silver halide color photographic light-sensitive material is generally at least on a support. At least one layer of silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer is provided. In the present invention, there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a light-sensitive material having a photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support, and the photosensitive layer is A unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally arranged in order from the support side to a red-sensitive layer. The color-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are installed in this order. However, even if the above installation order is reversed depending on the purpose,
Further, the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038 may contain a coupler and the like, and include a color mixing inhibitor, an ultraviolet absorber, an anti-staining agent, etc., as commonly used. You can leave.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, a low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL) /, or BH / BL / GL / GH / RH / RL,
Alternatively, they can be installed in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 62-
No. 63936, the blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.
It can also be arranged in the order of. In addition, Japanese Patent Publication Sho-49-154
As described in Japanese Patent Publication No. 95, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a halogen having a lower sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer is arranged and three layers having different sensitivities are sequentially lowered toward the support. 3 with different sensitivities
Even when it is composed of layers, it is disclosed in JP-A-59-202464.
As described in the above publication, in the same color-sensitive layer, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

Swelling rate of the light-sensitive material of the present invention [(25
° C., the equilibrium swollen film thickness -25 ° C. in in H ₂ O, dried whole thickness / 25 ° C. at 55% RH, dry whole thickness at 55% RH) ×
100] is preferably 50 to 200%, and 70 to 150%
Is more preferable. If the swelling ratio deviates from the above value, the amount of the color developing agent remaining becomes large, and the film properties such as photographic performance, desilvering property, and film strength are adversely affected.

Further, the film swelling speed of the light-sensitive material in the present invention is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38 ° C., 3 minutes 15 seconds), and the saturated swollen film thickness is When the time required to reach the film thickness of 1/2 is defined as the swelling speed T1 / 2, T1 / 2 is preferably 15 seconds or less. It is more preferably 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the light-sensitive material used in the present invention is silver iodobromide, silver iodochlorobromide,
It may be any of silver iodochloride, silver chlorobromide, silver bromide and silver chloride. Of these, preferred silver halide is about 0.1
Silver iodobromide, silver iodochloride or silver iodochlorobromide containing up to 30 mol% of silver iodide. Particularly preferred is 0.1-15
% Silver iodide chloride, and most preferably silver iodochloride containing 0.1 to 8% silver iodide.

The silver halide grains of the photographic emulsion are cubic,
Having regular crystals such as octahedron, tetradecahedron,
It may have an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "I.
Bmulsion preparation and types "and
No. 18716 (November 1979), p.648, "The Physics and Chemistry of Photography" by Graphide, published by P.Glafkides, Chimie et Physique Photographique P.
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photograph
ic Emulsion Chemistry (Focal Press, 1966), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by VLZelikman et al Making and Coating Ph
otographic Emulsion, Focal Press, 1964) and the like.

US Pat. Nos. 3,574,628, 3,655,394 and British Patent 1,413,74.
Monodisperse emulsions described in No. 8 and the like are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, P
hotographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
No. 4,226, No. 4,414,310, No. 4,4
It can be prepared by the method described in 30,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a phase structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are Research Disclosure No. 17643 (December 1978), No.
18716 (November 1979) and No. 307 of the same.
105 (November 1989), and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures (RD), and the relevant portions are described below. Additive type RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866, 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column to page 866 to 868, strong Color sensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, and stabilizer 6. Light absorber, flux 25 Page 26 Page 649 Right column ~ Page 873 Filter dye, Page 650 Left column UV absorber 7. Stain prevention page 25 Right column 650 Page left column 872 Agent ~ Right column 8. Dye image stabilization Page 25 650 page Left column 872 Page agent 9. Hardener 26 page 651 left column 874 to 875 page 10. Binder page 26 651 page left column 873 to 874 page 11. Plasticizer and lubrication page 27 650 page right column 876 agent 12. Coating aid , Tables 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static protection, page 27, page 650, right column, pages 876 to 877, anti-static agent, matting agents, pages 878 to 879

The silver iodochloride emulsion preferable in the present invention will be described below. In the present invention, silver iodochloride contains substantially no silver bromide. The phrase "substantially free of silver bromide" means that the molar content of silver bromide is 1 mol% or less. The case where silver bromide is not contained at all is preferable.
A preferred silver iodochloride emulsion of the present invention is a high silver chloride silver iodochloride emulsion containing at least 85 mol% of silver chloride. The molar content of silver chloride is preferably 90 mol% or more, more preferably 93 mol% or more, and particularly preferably 95 mol% or more. The silver iodide content is 0.1.
It is preferably at least mol% and at most 10 mol%, more preferably at least 0.1 mol% and at most 5 mol%. The silver halide emulsion may be an internal latent image type emulsion or a surface latent image type emulsion.

The emulsion grains may have a uniform crystal structure inside, or may have different halogen compositions inside and outside, and may have a layered structure of three or more layers. Therefore, the silver halide emulsion of the present invention can have a distribution or structure with respect to the halogen composition in its grains. A typical example thereof is a core-shell type or double structure type grain having a halogen composition in which the inside of the grain is different from the surface layer. In such particles, the shape of the core part and the entire shape with the shell may be the same or different. Specifically, the core portion has a cubic shape, and the shell-containing particles may have a cubic shape or an octahedral shape. On the contrary, the core part may be an octahedron and the particles with shell may have a cubic or octahedral shape. Further, although the core portion is a regular regular particle, the particle with shell may be slightly deformed or may have an irregular shape. In addition, it is not just a double structure, but a triple structure or more multilayer structure,
A silver halide having a different composition can be thinly applied to the surface of the double-structured grain of the shell.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called bonded structure can be prepared. The crystal to be bonded can be generated by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. In this case, the surface of the host crystal is, for example,
The halogen conversion initiation inhibitor which is an adsorbing organic compound such as mercaptoazoles, nucleic acid decomposition products, and dyes described in No. 102453 can be used. The use of this halogen conversion initiation inhibitor is also useful when performing halogen conversion on the host crystal. Such a bonded crystal has a uniform core composition even if the host crystal has a uniform halogen composition.
It can be formed even if it has a shell type structure. In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan and silver carbonate may be combined with silver halide to form a junction structure. Also, a non-silver salt compound such as PbO may be used as long as it can form a junction structure. The grains having these structures are, for example, core-shell type grains having a high silver iodide content in the core portion and a low silver iodide content in the shell portion, or conversely, containing silver iodide in the core portion. Particles having a low amount and a high shell portion may be used. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. In addition, the boundary portion where the halogen composition of grains having these structures is different,
The boundary may be a clear boundary, an unclear boundary by forming a mixed crystal due to a composition difference, or a positively continuous structure change.

In the present invention, an emulsion composed of grains having a certain structure is preferably used rather than one having a uniform composition within the grains with respect to the halogen composition. In particular, a grain having a halogen composition in which silver iodide is smaller in the grain surface than in the grain is more preferably used. A typical example thereof is a core-shell type emulsion containing a higher content of silver iodide in the core than in the shell. The constituent molar ratio of the core part and the shell part may be any ratio as long as it is between 0: 100 and 100: 0, but in order to make it distinctly different from particles having a uniform structure, it is 3: 97-98: 2. Is preferred. When the shell portion is formed by so-called halogen conversion utilizing the difference in solubility of silver halide, the core portion is not uniformly covered, but at least 98: 2 is acceptable. More preferable ratio of core to shell is 5:95 to 8
It is between 5:15, and more preferably 15: 85-7.
It is between 0:30. Although the difference in the silver iodide content between the core part and the shell part depends on the molar ratio of the core part and the shell part,
It is preferably 0.5 mol% or more. More preferably, it is 5.0 mol% or more. When the silver iodide contents in the core portion and the shell portion are not so different from each other, that is, when the composition difference is small, the grain is not so different from that of a grain having a uniform structure and the feeling is low. If the composition difference is large, desensitization or the like due to pressure is likely to occur, so it is necessary to devise a means for reducing them. The appropriate composition difference depends on the composition ratio of the core part and the shell part, and is 0:
The closer the composition ratio is to 100 or 100: 0, the larger the composition difference is, and the closer the composition ratio is, the smaller the composition difference is.

The silver iodochloride grains preferably used in the present invention, even if they are normal crystals not containing twin planes, are described in The Photographic Society of Japan and the Basic Silver Salt Photographs of the Photographic Industry (Corona Publishing Co., Ltd., p.163). For example, a single twin containing one twin plane, a parallel multiple twin containing two or more parallel twin planes, a non-parallel multiple twin containing two or more non-parallel twin planes, etc. It can be selected and used according to the.
A cubic having a (00) plane, an octahedron having a (111) plane, and a dodecahedral grain having a (110) plane disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Furthermore, Journal of Imaging Science 3
Volume 0, page 247, as reported in 1986
(Hl1) face particles typified by (211), (hh1) face particles typified by (331), (hk0) face particles typified by (210) face, and (3
21) (hk1) plane particles, which are typified by planes, require a certain adjustment method, but can be selected and used according to the purpose. A tetrahedral grain in which the (100) face and the (111) face coexist in one grain, (10
Particles in which (0) face and (110) face coexist or (111) face and (11
0) Particles in which two surfaces or a large number of surfaces coexist, such as particles in which surfaces coexist, can be selected and used according to the purpose.

The shape of the silver iodochloride grains preferably used in the present invention may be a tetradecahedron or a dodecahedron other than the above-mentioned cube or octahedron, or may be an irregular shape. In particular, in the case of junction type particles, although not indefinite, junction crystals are uniformly generated at the corners or edges of the host crystal or on the surface, and a regular particle shape is exhibited. It may also be spherical. In the present invention, cubic particles and octahedral particles are more preferably used. Tabular grains are also preferably used, but the ratio of the grain diameter in terms of circle to the grain thickness is 2 or more, preferably 2 to 15, and particularly preferably 3 to 8 are tabular grains having a projected area of all grains of 50 or less. Emulsions that account for more than 100% have excellent rapid developability. Those tabular grains having the above-mentioned structural properties are more useful. When preparing tabular grains, for example, JP-A-64-
General formula (I) or general formula (II) described in 70741.
It is preferable to use the crystal habit controlling agent represented by the following formula. Further, these crystal habit controlling agents can be preferably used also when forming the normal crystal silver halide grains described above. The silver iodochloride emulsion used in the present invention is E
A treatment for rounding the particles as disclosed in P-0096727B1, EP-0064412B1 and the like,
Alternatively, DE-2306447C2, JP-A-60-22
Surface modification may be performed as disclosed in 1320.

For the silver iodochloride emulsion used in the present invention, the above-described method for preparing a silver halide emulsion can be used. 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.

The soluble silver salt aqueous solution or soluble alkali halide water-soluble one or both solutions to be added
It is also effective to prepare more than one kind and change the concentration or composition of two or more kinds of the prepared aqueous solutions, respectively, if necessary. The addition method disclosed in Japanese Examined Patent Publication No. 61-31454 is an example, and it can be used if necessary. A method of accelerating the addition rate as disclosed in JP-B-48-36890, US Pat. No. 4,24.
The method disclosed in JP-A No. 2,445, which raises the addition concentration with time is a preferable method for preparing the silver iodochloride emulsion used in the present invention. It is preferable as a method for preparing the silver iodochloride emulsion used in the present invention that a part of the grains is converted with a different anion during grain formation or at an appropriate time after grain formation. Before the desalting process, after the desalting process and before chemical aging,
It can be performed during chemical aging, after chemical aging, and before coating. Conversion is preferably performed before chemical sensitization or before dye adsorption. As the anion used for the conversion, a compound that forms a sparingly soluble silver salt than the silver iodochloride grains used is desirable.

It is preferable in some cases to use two or more kinds of anions together. The amount of anions used is preferably 0.01 to 10 mol% with respect to the total amount of silver halide. It is preferably 0.1 to 3 mol%. It is particularly preferable to form a localized portion having a high silver iodide content in the silver iodochloride grain. In order to form a layer mainly composed of localized silver iodide, a water-soluble silver salt and a water-soluble iodide salt may be added to form a shell after forming high silver chloride grains, or only the water-soluble iodide salt may be added. You may add and heat-age it.

In the process of silver halide grain formation or physical ripening, even if 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, etc. coexist. Good. In particular, the iridium salt is used in an amount of 10 ⁻⁹ to 10 ⁻⁴ mol / mol, more preferably 10 ⁻⁸ to 10 ⁻⁵ mol / mol, based on silver halide. This is particularly useful in obtaining rapid developability and stability at high illuminance or low illuminance, which is out of the proper exposure illuminance range, as compared with an emulsion prepared without using an iridium salt. Emulsions doped with a large amount of polyvalent impregnated ions as disclosed in JP-A-62-260137 are preferable for improving reciprocity law failure and can be used in the silver iodochloride emulsion of the present invention. In any case, the chloride concentration during particle formation is preferably 5 mol / liter or less, and 0.07 to 3 mol / l.
A concentration of liter is particularly preferred. The temperature during particle formation is 1
The temperature is 0 to 95 ° C, preferably 40 to 90 ° C. The pH at the time of particle formation is not particularly limited, but a neutral to weakly acidic range is preferable.

The silver halide salt emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation. Known silver halide solvents (e.g., ammonia, rhodancal or U.S. Pat. No. 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-53-144319, and JP-A-53-144319). 54-100717
Physical ripening in the presence of thioethers and thione compounds described in JP-A No. 54-155828 or JP-A No. 54-155828, a monodisperse emulsion having a regular crystal form and a nearly uniform grain size distribution is obtained. To be In order to remove the soluble silver salt from the emulsion before and after physical ripening, a Nudel water washing method, a fusculation sedimentation method or an ultraleakage method is used.

The average grain size of silver halide grains (in the case of spherical grains or grains close to spheres, the grain diameter is represented, and in the case of cubic grains, the edge length is represented as the grain size, and the average is based on the projected area), It is preferably 4μ or less and 0.1μ or more, and particularly preferably 2μ or less and 0.15μ or more. The particle size distribution may be narrow or wide. A so-called monodisperse silver halide emulsion having a narrow grain size distribution such that 90% or more, particularly 95% or more of all grains fall within ± 20% of the average grain size in terms of number of grains or weight can be used in the present invention. it can. 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 are mixed in the same layer or different layers. Can be applied in multiple layers. Further, 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. In the present invention, it is particularly preferable to use two or more monodisperse emulsions as a mixture or as a multilayer.

Next, the chemical sensitization of a silver iodochloride emulsion preferable in the present invention by a gold compound will be described. Regarding the gold sensitization method using a gold compound, for example, US Pat.
The methods described in 48,060 and 3,320,069 can be applied. The gold sensitizer used in the present invention is particularly a gold complex salt, for example, US Pat. No. 2,399,
The compounds described in No. 083 can be preferably used. Of these, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate, and 2-aurosulfobenzothiazolemethochloride are particularly preferred. The content of the gold sensitizer in the silver halide grain phase is preferably 10 ⁻⁹ to 10 ⁻³ mol, and particularly preferably 10 ⁻⁸ to 10 ⁻⁴ mol, per mol of silver halide. To strengthen the gold sensitization, TH James, “The Theory of the Photographic P
rocess "4th edition, (Macmillan Co. Ltd., New York, 197
It is also useful to use a thiocyanate as described in 7), page 155, or a tetrasubstituted thiourea compound as described in JP-B-59-11892.

The gold sensitized silver halide emulsion contains 80% or more, preferably 85%, of the gold sensitizer contained in this emulsion.
Or more, more preferably 90% or more, particularly preferably 93
% Or more is present in the silver halide grain phase, and by suppressing the ratio of the gold sensitizer remaining in the binder phase of the silver halide emulsion to a low level, a light-sensitive material having excellent fog reduction and stability over time is provided. be able to. In addition, it is possible to make the action and effect of so-called stabilizers and antifoggants represented by tetrazaindenes and mercaptotetrazoles remarkable.

Various color couplers can be used in combination in the present invention. Typical examples thereof are RD No. 1 mentioned above.
7643, VII-CG and RD No.307105, VII-CG
Are described in the patents listed in. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. ,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
Those described in 511, 649, European Patent 249,473A, Japanese Patent Application Laid-Open No. 3-215148, Japanese Patent Application No. 3-63680, Japanese Patent Application No. 3-157480, Japanese Patent Application No. 3-101798, etc. are preferable. .

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
No. 32, No. 3,725, 064, RD No. 24220
(June 1984), JP-A-60-33552, RD
No. 24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730.
No. 55-118034, No. 60-185951
U.S. Pat. Nos. 4,500,630 and 4,540,
No. 654, No. 4,556,630, WO (PCT) 8
Those described in 8/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers. US Pat.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334, 011, No. 4,327, 1
73, West German Patent Publication No. 3,329,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,433,99.
No. 9, No. 4,753, 871, No. 4,451, 5
No. 59, No. 4,427, 767, No. 4,690,
889, 4,254,212 and 4,29
Those described in JP-A No. 6,199 and JP-A No. 61-42658 are preferable.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in RD No. 17643, Item VII-G,
U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-394
13, U.S. Pat. Nos. 4,004,929 and 4,1.
38,258, British Patent 1,146,368 and JP-A-3-251843 are preferred. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and US Pat. No. 4,777,120.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in JP-A No.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910 and British Patent 2,102,173.

A coupler that releases a photographically useful residue upon coupling is also preferably used. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,1.
31,188, JP-A-59-157638, 59.
Those described in -170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers as described in No. 7 and the like, European Patent No. 173,30
RD No. 11449, RD No. 24241, a coupler which releases a dye that recolors after the separation described in No.
Bleach accelerator releasing couplers described in 1-201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, leuco dye releasing couplers described in JP-A-63-75747, U.S. Pat. Fourth 4,774
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like, and specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di- 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylfetyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-)
Octylaniline), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, 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 and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230.

These couplers may also be impregnated with a loadable latex polymer (for example, described in US Pat. No. 4,203,716) in the presence or absence of the above-mentioned high-boiling organic solvent, or insoluble in water. It can be dissolved in a polymer soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, International Publication Number WO8
The homopolymers or copolymers described on pages 12 to 30 of the specification of 8/00723 are used. In particular, use of an acrylamide polymer is preferable in terms of color image stabilization and the like.

Suitable supports which can be used in the present invention are, for example, RD No. 17643, page 28 and No. 18 mentioned above.
716, right column, page 647 to left column, page 648. The present invention can be applied to various light-sensitive materials. Color negative film for general use or movies,
It is preferably used for a slide or a reversal film for television.

[0089]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth layer (medium-sensitive blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0106]

[Table 1]

In Table 1, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) Low molecular weight gelatin was used for the preparation of tabular grains according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0108]

[Chemical 9]

[0109]

[Chemical 10]

[0110]

[Chemical 11]

[0111]

[Chemical 12]

[0112]

[Chemical 13]

[0113]

[Chemical 14]

[0114]

[Chemical 15]

[0115]

[Chemical 16]

[0116]

[Chemical 17]

[0117]

[Chemical 18]

[0118]

[Chemical 19]

[0119]

[Chemical 20]

[0120]

[Chemical 21]

[0121]

[Chemical formula 22]

[0122]

[Chemical formula 23]

Next, the following processing solutions were prepared. The composition is as follows. (Color developer) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 1.3 mg Additive I (Compounds of General Formulas (I) and (II)) See Table 1 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulphate 4.5 Add water 1. 0 liter pH 10.05

(Bleach) (Unit: g) 1,3-Diaminopropanetetraacetic acid Ammonium ferric acid monohydrate 130 Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Water is added to 1.0 liter pH [ammonia water Prepared in 4.4

(Bleaching Fixing Solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0)

(Fixer) (Unit: g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / liter, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 15
0 mg / l was added. The pH of this solution is 6.5
It was in the range of 7.5.

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The sample 101 prepared as described above
After being cut to a width of mm and exposed to gray gradation for sensitometry, 1 liter of the color developer prepared as described above was allowed to stand in a 1 liter beaker for 1 week at room temperature (hereinafter referred to as an aged solution). ) And a color developing solution (hereinafter referred to as a fresh solution) immediately after the preparation, and processing was performed under the following conditions using an automatic developing machine. The processing steps are shown below.

[0130]

The minimum concentration (Dmin) of yellow when treated with a fresh liquid with respect to the minimum concentration (Dmin) of yellow over time
The amount of increase (ΔDmin) was calculated. Further, the residual amount of the developing agent in the aged liquid was quantified by high performance liquid chromatography. The results are shown in Table 1 together with the liquid of the aged liquid.

[0132]

[Table 2]

As is clear from Table 1, when the additive of the present invention is used, the value of ΔDmin is small and the generation of stain is suppressed (compared to Comparative Examples Nos. 1 and 2).
No. 3 to 13). The residual amount of the developing agent is large, and the liquid state is good with no coloring.

Example 2 In Example 1, the additives were IA-5, IC-3 and IC.
When tested in the same manner as in Example 1 in place of −4, the value of ΔDmin was small and the residual amount of the developing agent was large.

Example 3 In Example 1, 3.9 g of sodium sulfite was added to the color developing solution per liter, but the amounts of sodium sulfite and additive I were changed as shown in Table 2. The test was conducted. Other conditions were the same as in Example 1. The results are shown together in Table 2.

[0136]

[Table 3]

As is clear from Table 2, in the comparative example, when the amount of sodium sulfite added was reduced, ΔDmin increased, the liquid became more colored, and the severe one produced tar (N
o. 1-3). On the other hand, when the additive of the present invention is used (for example, No. 5 to 7), ΔDmin shows a small value, and the liquid is also good without coloring. Further, it can be seen that the use of the additive of the present invention gives good results even if the amount of the additive used is reduced.

Example 4 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to prepare a A multilayer color photographic paper (102) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, a silver chlorobromide emulsion A (a cube, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.88 μm and a small size emulsion A having a grain size of 0.70 μm (silver mole ratio). The variation coefficient of the grain size distribution is , 0.08 and 0.10 respectively, and silver bromide 0.
3 mol% localized on a part of the particle surface) was prepared.
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added to the large-sized emulsion A per mol of silver of 2.0 ×, respectively.
10 ⁻⁴ , and for small size emulsion A, 2.
5 × 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A are mixed and dissolved,
The first layer coating liquid was prepared so as to have the composition shown below.
The emulsion coating amount indicates a coating amount equivalent to silver.

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-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 is 25.0 mg / m ² and 50 mg / m ² , respectively.
It was added so as to be m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0141]

[Table 4]

[0142]

[Table 5]

[0143]

[Table 6]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0145]

[Chemical formula 24]

[0146]

[Chemical 25]

[0147]

[Chemical formula 26]

[0148]

[Chemical 27]

[0149]

[Chemical 28]

[0150]

[Chemical 29]

[0151]

[Chemical 30]

[0152]

[Chemical 31]

[0153]

[Chemical 32]

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

[0155]

[Table 7]

[0156]

[Table 8]

[0157]

[Table 9]

[0158]

[Table 10]

Next, the following processing solutions were prepared. The composition is as follows. [Color developer] Water 800 ml Ethylenediaminetetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium chloride 6.5 g Potassium bromide 0.03 g Potassium carbonate 27.0 g Fluorescent brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Sodium sulfite 0.1 g Disodium-N, N-bis [sulphonatoethyl) hydroxylamine 5.0 g Triisopropylnaphthalene (β) sulfonic acid Sodium 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g Water was added to 1000 ml pH (25 ° C / With potassium hydroxide and sulfuric acid) 10.00

[Bleach-fixing solution] Water 600 ml Ammonium thiosulfate (700 g / liter) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Water was added. 1000 ml pH (25 ° C / acetic acid and aqueous ammonia) 5.8

[Rinse Solution] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml PH 6.5

The sample 102 prepared as described above was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). After exposure, 1 liter of color developer prepared as described above was allowed to stand in a 1 liter beaker for 2 weeks at room temperature (hereinafter referred to as aged solution) and color developer immediately after preparation (hereinafter referred to as fresh solution). (Hereinafter referred to as a liquid), and the processing was performed under the following conditions using an automatic processor. (Rinse was a three-tank countercurrent system from (3) to (1).)

The minimum concentration of yellow (Dmin) of the aged liquid against the minimum concentration of yellow (Dmin) when treated with fresh liquid
The amount of increase (ΔDmin) was calculated. Further, the residual amount of the developing agent in the aged liquid was quantified by high performance liquid chromatography. The results are shown in Table 3 together with the liquid of the aged liquid.

[0164]

[Table 11]

As is clear from Table 3, when the additive of the present invention is used, the value of ΔDmin is small and the generation of stain is suppressed (compared with Comparative Examples Nos. 1 and 2).
No. 3 to 13). The residual amount of the developing agent is large, and the liquid state is good with no coloring.

[0166]

By using the compound of the present invention, deterioration of a developing solution such as a color developing solution with time can be suppressed, and as a result, the stability of the developing solution is excellent, and the solution can be stored for a long time or in a silver halide photograph. Light-sensitive materials, especially during continuous processing of color light-sensitive materials, there is little deterioration of the developing agent, and
It was possible to provide a processing method excellent in preventing the contamination of the developer.

Claims (3)

[Claims] 1. A photographic developer composition containing at least one compound represented by the general formula (I): ## STR1 ## The general formula (I) represents a 6-membered ring consisting of two carbon atoms constituting the linking group X, two carbon atoms constituting the linking group and two nitrogen atoms, and two unsaturated atoms in the ring. Represents a compound having a bond. 2. A method for processing a silver halide light-sensitive material, which comprises using the developing solution according to claim 1. 3. A method of processing a silver halide light-sensitive material according to claim 2, which contains an aromatic primary amine color developing agent.