JPH04127145A - Processing composition and processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow rapid processing with an excellent desilvering property without bleach fogging and with lessened generation of stains after processing by incorporating at least one kind of metal chelate compds. formed of specific compds. and the salts of specific metals into the above compsn. CONSTITUTION:At least one kind of the metal chelate compds. formed of the compds. expressed by formula I and the salts of the metals selected from Fe(III), Mn(III),Co(III),Rh(II), Rh(III),Au(III),Au(II), and Ce(IV). or the metal chelate compds. and org. acids are incorporated into this compsn. In the formula I, Z denotes the nonmetal atom group necessary for forming a 5- or 6-membered ring; L1 denotes an alkylene group, arylene group, etc.; X1 denotes a carboxy group, phosphono group, etc.; R1 to R4 respectively independently denote a hydrogen atom or alkyl group; Ra to Rc respectively independently denote a hydrogen atom, alkyl group or alkyl group; l and m denote 0 or 1. The processing compsn. which lessens the bleach fogging and has the bleach ability with the decreased stains with lapse of time is obtd. in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a processing composition for silver halide color photographic light-sensitive materials, and more specifically, to a processing composition containing a novel bleaching agent used in the bleaching step after color development. The present invention relates to a processing composition and a method for processing silver halide color photographic materials using the same.

(Prior Art) Silver halide color photographic materials (hereinafter referred to as color photographic materials) are basically processed by a color development step and a desilvering step after imagewise exposure.

In the color development step, exposed silver halide grains are reduced to silver by a color developing agent, and the resulting oxidized product of the color developing agent reacts with a coupler to form an image dye.

In the subsequent desilvering step, the developed silver produced in the development step is oxidized to silver salt by an oxidizing bleach (bleaching), and then sensitized with a fixing agent that forms soluble silver together with unused silver halide. removed from the layer (constant I
F) Bleaching and fixing may be carried out as independent bleaching and fixing processes, or may be carried out simultaneously as a bleach-fixing process. Details of these processing steps can be found in “The Theory of Photographic Ink Processes” by James, 4th edition (Jaw+es+ “The
ory of Photographic Processes
s''4'th edition) (1977).

In addition to the basic processing steps mentioned above, various auxiliary steps are added for the purpose of maintaining the photographic and physical quality of the dye image or the stability of the processing. Examples include a water washing process, a stabilization process, a hardening process, and a stopping process.

The above processing steps are generally performed using an automatic processor. Particularly in recent years, small automatic processing machines called minilabs have been installed in stores, and rapid processing services have become widespread for customers.

Against this background, there has been a strong demand in recent years for speeding up the treatment process, and it is also desired that the bleaching process be greatly speeded up.

However, the conventionally used ferric complex salt of ethylenediaminetetraacetic acid has a fundamental defect of weak oxidizing power, and the use of bleach accelerators (for example, U.S. Pat. No. 1,138
Although improvements have been made, such as the addition of mercapto compounds as described in No. 842, the goal of rapid bleaching has not yet been achieved.

Red blood salt, iron chloride, bromate, etc. are known as bleaching agents that achieve rapid bleaching. However, red blood salt has environmental protection issues, while iron chloride has problems such as metal corrosion. Bromate salts cannot be widely used due to the inconvenience of handling and the instability of the liquid.

Accordingly, there has been a desire for a bleaching agent that is easy to handle and achieves rapid bleaching without problems in draining waste liquid.

Recently, a bleaching agent of ferric complex salt of 1,3-diaminopropanetetraacetic acid has been disclosed as one that satisfies such conditions.

(Problem B to be Solved by the Invention) However, this bleach has several problems. That is, one of the problems with this bleaching agent is the performance problem of bleaching fog caused by bleaching. It has been disclosed that a buffering agent is added to the bleaching solution as a method of reducing this bleaching blade blur (for example, JP-A-1-213-65
No. 7), but the level of improvement is not fully satisfactory, especially in rapid processing in which color development takes less than 3 minutes, which still causes large bleach fog due to the use of a highly active developer. It causes

Furthermore, when a processing solution having bleaching ability made of the ferric 1,3-diaminopropanetetraacetic acid complex salt is used, there is a problem in that staining increases during storage after processing.

Another problem is that when a bleaching solution made of ferric 1,3-diaminopropanetetraacetic acid complex salt is used, the magenta pigment in the color image area increases in color and the gradation changes during storage after processing. Can be mentioned.

Another problem is that when performing a process in which the bleaching time is even shorter, the cyan dye in the image area becomes a leuco dye even if a bleaching solution made of the ferric complex salt of L3-diaminopropanetetraacetic acid is used. , causing poor color recovery. Therefore, there has been a desire for a new treatment composition and treatment method with bleaching ability that can replace this.

Therefore, a first object of the present invention is to provide a treatment composition that is easy to handle and does not cause environmental problems regarding waste liquid, and a treatment method using the same.

A second object of the present invention is to provide a processing composition having bleaching ability with excellent desilvering properties and a processing method using the same.

A third object of the present invention is to provide a processing composition that exhibits bleaching ability with less bleaching fog and a processing method using the same.

A fourth object of the present invention is to provide a treatment composition having bleaching ability with less staining over time and a treatment method using the same.

A fifth object of the present invention is to provide a processing composition and a processing method using the same, which have excellent rapid bleaching properties, do not cause poor color recovery, and have bleaching ability with little change in tone over time.

(Means for solving the problem) The above purpose is to provide a compound represented by the following general formula (1),
Fe(III), Mn(I[[), Co(1
) , Rh (II), Rh (I[[) , ＾u (
A silver halide characterized by containing at least one metal chelate compound formed from a salt of a metal selected from DI), Au (II) and Ce (IV), or the metal chelate compound and an organic acid. This was achieved by a processing composition for color photographic materials and a processing method using the same.

General formula (I) (wherein, Z represents a group of nonmetallic atoms forming a 5- or 6-membered ring, m Ll represents an alkylene group, an arylene group, or a group consisting of a combination thereof.

Xl represents a carboxyl group, a phosphono group, a sulfo group, or a hydroxy group; R1, Rt, R3 and R4 each independently represent a hydrogen atom or an alkyl group.

Ra, Rh and Rc each independently represent a hydrogen atom, an alkyl group or an aryl group. ! and m is O
Or represents 1. ) According to the present invention, after a silver halide color light-sensitive material is subjected to imagewise exposure and color development, it is treated with a processing composition containing at least the compound of the present invention, thereby bleaching the developed silver extremely quickly. There is also no significant bleach fog associated with conventional rapid bleaching agents, which is especially true when processing with the processing composition of the present invention follows rapid color development with a processing time of 3 minutes or less. It appears as a major effect when

In addition, the image storage stability after processing is good, and it is also convenient for handling.

Furthermore, when the treatment composition of the present invention contains an organic acid, in addition to the above-mentioned effects, poor color restoration does not worsen, and this appears as a great effect when speeding up the bleaching treatment.

Furthermore, when processing is performed to reduce the amount of bleaching solution replenished, the effects of the present invention are remarkable, the image storage stability after processing is good, and it is also preferable in terms of handling.

The compound represented by general formula (1) will be explained in detail below.

In the general formula (1), Z represents a group of nonmetallic atoms forming a 5- or 6-membered ring.

-C Aromatic rings (e.g. benzene, naphthalene, phenanthrene, anthracene), heterocycles (e.g. ehahyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan,
Pyran, pyrrole, imidazole, pyrazole, isothiazole, isoxazole, thianthrene, isobenzofuran, chromene, xanthine, phenoxathiin,
Indolizine, isoindole, indole, imidazole, quinolidine, isoquinoline, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteringine, carbazole, carboline, phenanthrene, acridine, pteridine, phenanthroline, phenazine, phenothiazine, phenoxazine, chroman, pyrroline , pyrazoline, indoline, isoindoline), cyclic alkenes (eg, cyclopentene, cyclohexeno), and the like. Moreover, these rings may be condensed with other rings.

Ci&c zen, naphthalene, pyridine, pyrazine, pyrimidine,
Pyrazine, quinoline, quinoxaline, and more preferably benzene.

-C Substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, and sulfamoyl groups. , carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonyl group Examples include amide group, sulfonamide group, and nitro group.

L+ represents a group consisting of an alkylene group, an arylene group, or a combination thereof. Ll may be substituted,
These substituents include -C, an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 6 to 1 carbon atoms.
2, more preferably a methylene group or an ethylene group, with a methylene group being particularly preferable.

X represents a carboxy group, a phosphono group, a sulfo group or a hydroxy group. As xl, a carboxy group or a hydroxy group is preferable, and a carboxy group is particularly preferable.

Rls Rx, R1 and R1 may be the same or different, and when aR1 to R4 each independently representing a hydrogen atom or an alkyl group is an alkyl group, they may be substituted, and examples of the substituent include -C Hydrogen atoms are preferred as R3, R1, Rs and R4.

Ra, Rh and Rc may be the same or different and each independently represents a hydrogen atom, an alkyl group or an aryl group.

The alkyl group represented by Ra, Rh, and Rc may be linear, branched, or cyclic (with 1 to 1 carbon atoms).
The alkyl group is preferably 0, and more preferably a methyl group or an ethyl group. The aryl group represented by Ra, Rh, or Rc preferably has 6 to 10 carbon atoms, and more preferably a phenyl group.

Ra%Rh, When Rc is an alkyl group or an aryl group, it may be substituted, and the substituent is preferably a carboxy group, a phosphono group, a sulfo group, or a hydroxy group. More preferably a carboxyl group or a hydroxyl group, particularly a carboxyl group, more preferably Ra,
Rb5Rc may be linked to form a ring.

! and m represent O or 1, respectively, l and m
At least one of them is preferably 1, and both f and m are 1.
It is particularly preferable that

In the present invention, preferred is a compound represented by the following general formula (II).

General formula (ff) (wherein, Z, X,, L3, R,, R,, R,, R4,
Rh, Rc, 1, and m have the same meanings as in general formula (I).

L and t have the same meanings as glue in general formula (1), and χ2 has the same meaning as X in general formula (1). ) More preferably, it is a compound represented by the following general formula (I[[).

General formula (II) (wherein, Z , X, , Ll, R1, R2, R8, R1
, Rh, Re.

1m has the same meaning as each of general formula (I). L2, L
3 and shi are each synonymous with L+ in general formula (1), and X2, X, and x4 are each synonymous with xl in general formula (1). ) Specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited thereto.

20°21°22°23°24°25°28°29°30°32°34°35°37°38°39°40°41°42°43°44° Regarding the compound represented by general formula (I) "Chelate Chemistry" by Keihei Ueno, Volume 5, Chapter 1 (Nankodo, 1975)
It can be synthesized based on the description in the annual publication).

Specific synthesis examples of representative compounds are shown below.

Synthesis example 1. Synthesis of Compound 1/2HCf Sand Synthesis Example 1-(1) Synthesis of Compound 1a 134 g (0,507 sol) of α,α'-dibromo-0-xylene and 210 g (1,13 sol) of phthalimide potassium salt
1) was dissolved in 1.51 dimethylformamide, and 80
After heating and stirring at ℃ for 2 hours, 21 parts of water was added, and
Stirred for 0 minutes. The precipitated solid was collected by filtration, washed with water, and dried with air to obtain 191 g of the target substance 1a.
(0,482 sol) was obtained. Yield 95%.

Synthesis Example 1-(2) Synthesis of Compound Myo 173 g (0,4
36 sol) and 60.0 g of hydrazine 1 (
1.20 mol) was dissolved in methanol Il and heated under reflux for 3 hours. The precipitated solid was filtered off, the filtrate was concentrated under reduced pressure, and then 122 g (1.20 mol) of concentrated hydrochloric acid was added. While stirring at room temperature, 500 d of acetonitrile was added, and the precipitated solid was collected by filtration. After washing with acetonitrile, drying removes the target material.
69g (0,809sol) was obtained. Yield 95%.

Synthesis Example 1-(3) Synthesis of Compound 1 Synthesis Example 1. - J,b synthesized in <2) 59.9 g
(0,286+wol) was dissolved in 100 - of water, and 22.9g (0,573*ol) of sodium hydroxide was added. Next, 140g of sodium chloroacetate (1,20m
200 d of aqueous solution of ol) and 48.0 g of sodium hydroxide
100 d of an aqueous solution of (1,20+*ol) was gradually added. During this time, the reaction temperature was kept at 50-55°C, and p
A small amount of phenolphthalein was added as an H indicator to maintain a pale red color. After heating and stirring for another 1 hour,
The mixture was allowed to cool, and 122 g (1.20 mol) of concentrated hydrochloric acid was added. The precipitated solid was collected by filtration, and 45.6 g of sodium hydroxide was added.
(1,14 mol) in 600 ml of an aqueous solution, filtered, and the filtrate was mixed with 116 g of concentrated hydrochloric acid (1,14 mol
l) was added.

The precipitated white crystals were collected by filtration, thoroughly washed with water, and then dried with air to give 75.1 g (0.2 g) of the target compound 1.
04sol) obtained. Yield 71%. Melting point 247-249°
C (decomposition).

The metal salt constituting the metal chelate compound of the present invention is Fe
(III), Mn (I[[), Co
(II) , Rh (II) , Rh (II
I), Au (II), Au (III) and Ce
(IV). Among them, Fe (DI), M
n (ml), Ce (IV) is preferred, especially Fe
(I[[) is preferred.

The metal chelate compound of the present invention may be an isolated metal chelate compound.

The metal chelate compounds of the present invention may be used in combination of two or more.

Of course, in the present invention, the compound represented by general formula (1) and the metal salt, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate, are used. etc. may be used by reacting them in a solution. The compound represented by the general formula (1) is used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably larger when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30.

The metal chelate compound of the present invention may be contained in a small amount in the fixing solution or at an intermediate temperature between the color development and the desilvering process, but by containing 0.05 to 1 mol per processing solution III, it can be used in the bleaching solution or in the bleaching solution. Effective as a bleaching agent in fixer solutions.

Hereinafter, preferred embodiments of processing liquids (generally referred to as bleaching liquids or bleach-fixing liquids) having bleaching ability will be described. The metal chelate compound of the present invention is effective as a bleaching agent when it is contained in a bleaching solution of 0.05 to 1 mol per 11 of the processing solution as described above.
It is more preferable to contain 1 to 0.5 mol.

According to another aspect of the present invention, it is preferable that the treatment liquid having bleaching ability further contains an organic acid in addition to the above-mentioned metal chelate compound.

Preferred examples of the organic acids used in the present invention include formic acid, acetic acid, propionic acid, glycolic acid, monochloroacetic acid, monobromoacetic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, and aminobutyric acid. , valeric acid, isovaleric acid, benzoic acid, monosubstituted benzoic acids such as chloro and hydroxy, monobasic acids such as nicotinic acid; asparagine, aspartic acid, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine , amino acid compounds such as leucine; tribasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, tartaric acid, malic acid, oxaloacetic acid, phthalic acid, isophthalic acid, and terephthalic acid; as well as citric acid, etc. Tribasic acids, sulfonic acids, sulfinic acids, imides, aromatic sulfonamides, etc. can be mentioned, but of course the compounds are not limited to these exemplified compounds.

In the present invention, organic acids having a pKa of 1.5 to 6.5 are preferred among these, and more preferably organic acids having a pKa having a carboxyl group.
Organic acids having a pH of 2.0 to 5.5 are preferred, and among these, monobasic acids are particularly preferred, with acetic acid and/or glycolic acid being most preferred.

In the present invention, the amount of these organic acids used is 0.05 mol or more per 1N of the processing solution having bleaching ability and its replenisher, preferably 0.1 to 3.0 mol/i, more preferably , 0.3 to 2.0 mol/i.

Moreover, these organic acids may be used in combination of two or more types, and instead of these organic acids, the organic acid salt and the inorganic acid may be used at the same time.

When the metal chelate compound of the present invention is used as a bleaching agent in a processing solution having bleaching ability, it may be used in combination with other bleaching agents as long as the effects of the present invention are achieved. Examples of such bleaching agents include: Pa of the given compound (III
), Co(I[l) or Mn(I[l) chelate bleaches, beloxonisulfate, hydrogen peroxide, bromate, etc.

The compounds forming the above chelate bleach include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetic acid tetra(trimethylammonium) salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic acid Tetrasodium salt, ethylenediaminetetraacetic acid trisodium salt, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N-(β-oxyethyl)N, N', N'-)
acetic acid, ethylenediamine N-(β-oxyethyl)-
N,N',N'-)triacetic acid trisodium salt, ethylenediamine-N(β-oxyethyl)-N,N',
N'-1-diaminopropane tetraacetic acid triammonium salt, 1,2-diaminopropane tetraacetic acid, 1,2-diaminopropane tetraacetic acid disodium salt, 1,3-diaminopropane tetraacetic acid, 1,3-diaminopropane tetraacetic acid disodium salt Ammonium salts, nitrilotriacetic acid, nitrotriacetic acid trisodium salt, cyclohexanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylene Diaminetetraacetic acid, 1,3-diaminopropano-
Ru N, N, N', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N
, N, N', N'-tetramethylenephosphonic acid and the like, but are not limited to these exemplified compounds.

The processing liquid having bleaching ability containing a metal chelate compound according to the present invention contains the metal chelate compound or the above-mentioned organic acid as a bleaching agent, and also contains chloride as a rehalogenation agent to promote the oxidation of silver. It is preferred to add halides such as , bromide, iodide. The amount of rehalogenating agent is between 0.01 and 2.0 mol/l. Furthermore, instead of the halide, an organic ligand that forms a poorly soluble silver salt may be added.The halide is added as an alkali metal salt, an ammonium salt, or a salt of guanidine, amine, or the like. Specific examples include sodium bromide, ammonium bromide, potassium chloride, and guanidine hydrochloride, with ammonium bromide being preferred. The amount of rehalogenating agent in the bleaching solution is between 0.1 and 2.0 mol/2, preferably between 0.3 and 1.5 mol/l.

The bleach-fix solution containing the metal chelate compound or the metal chelate compound and an organic acid according to the present invention contains the metal chelate compound as a bleaching agent, and also contains a fixing agent (described later) and, if necessary, the rehalogenating agent. can be included. The amount of rehalogenating agent used in the bleach-fix solution is
0.001 to 2.0 mol/2, preferably 0.01 to 2.0 mol/2
The bleach or bleach-fix solution of the present invention having a concentration of 1.0 mol/l also contains a bleach accelerator, a corrosion inhibitor to prevent corrosion of the processing bath, a buffer to maintain the pH of the solution, an optical brightener, Antifoaming agents and the like are added as necessary.

Bleach accelerators include, for example, US Pat. No. 3,893,858 and German Patent No. 1,290,8.
No. 12, U.S. Patent No. 1,138,842, Japanese Unexamined Patent Publication No. 1983
-95630, Research Disclosure No. 17
Compounds having a mercapto group or disulfide group described in No. 129 (1978), JP-A-50-140129
Thiazolidine derivatives described in US Pat. No. 3,7
Thiourea derivatives described in No. 06,561, polyethylene oxides described in German Patent No. 2,748,430, polyamine compounds described in Japanese Patent Publication No. 45-8836,
Imidazole compounds described in JP-A-49-40493 can be used.

Among these, mercapto compounds described in US Pat. No. 1,138,842 are preferred.

Further, as the corrosion inhibitor, it is preferable to use a nitrate, such as ammonium nitrate or potassium nitrate. The amount added is 0.05 to 0.5 mol/l, preferably 0.01 to 2.0 mol/l, more preferably 0.05 mol/l.
~0.5 mol/l.

The pH of the bleaching solution or bleach-fixing solution of the present invention is 2.0 to 8.
．． 0, preferably 3°0 to 7.5. When bleaching or bleach-fixing is performed immediately after color development, the pH of the solution should be set to 6.0 or less, preferably 5.0 or less, to prevent bleach fog.
It is best to use it at 5 or less. Furthermore, at pH 2.0 or lower, the metal chelate of the present invention becomes unstable, and therefore, at pH 2.0 or lower,
, 0 to 5.5 are preferred.

In order to adjust the pH of the treatment liquid having bleaching ability to the above range, the above organic acid and an alkaline agent (for example, aqueous ammonia,
KOHSNaOH, imidazole, monoethanolamine, jetanolamine) may be used in combination. Among them, ammonia water is preferred.

During processing, it is preferable to perform aeration after the bleaching process to oxidize the produced iron(II) complex salt.This regenerates the bleaching agent and maintains extremely stable photographic performance.

The bleaching or bleach-fixing step can be carried out at a temperature ranging from 30°C to 50''C, preferably from 35°C to 45°C.

The time for the bleaching process is used in the range of 10 seconds to 5 minutes for photographic photosensitive materials, preferably 10 seconds to 60 seconds, and more preferably 10 seconds to 30 seconds. In the case of printed photosensitive materials, the time is 5 seconds to 70 seconds, preferably 5 seconds to 30 seconds. Under these preferred processing conditions, good results were obtained that were rapid and without increased staining.

A fixing agent is used in the fixing solution or bleach-fixing solution. These are thiosulfates, thiocyanates, thioethers,
Examples include amines mercaptos, thiones, thioureas, and iodide salts. Examples of these fixing agents include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-cythia 1.8 octanediol, imidazole, and the like. Among these, thiosulfates, particularly ammonium thiosulfate, are preferred for rapid definition. Furthermore, rapid fixing can be achieved by using two or more types of fixing agents together. For example, in addition to ammonium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether, etc. , in which case the second fixing agent is 0.01 to 10% of ammonium thiosulfate.
It is preferable to add it in a range of 0 mol%.

The amount of fixer is fixer or bleach-fixer 17! Hit 0.
The amount is 1 to 3.0 mol, preferably 0.5 to 2.0 mol. The pi of the fixer depends on the type of fixer, but is generally 3.
．． 0 to 9.0, and particularly when using thiosulfate, 6.5 to 8.0 is preferable in order to obtain stable fixing performance.

Add a preservative to the fixer and/or bleach-fixer,
It is also possible to improve the stability of the liquid over time.

In the case of fixers or bleach-fixers containing thiosulfates, sulfites and/or bisulfite adducts of hydroxylamine, hydrazine, aldehydes (
For example, a bisulfite adduct of acetaldehyde, particularly preferably a bisulfite adduct of aromatic aldehyde described in JP-A-1-298935, is effective. Also, JP-A-6
It is also preferable to use the sulfinic acid compound described in No. 2-143048.

In addition, the fixing solution and/or bleach-fixing solution has a liquid pi (
It is also preferable to add a buffer to keep the constant.

Examples include phosphates, imidazoles such as imidazole, l-methyl-imidazole, 2-methyl-imidazole, and l-ethyl-imidazole, triethanolamine, N-allylmorpholine, N-benzoylpiperazine, and the like. Furthermore, by adding various chelating agents to the fixing solution, it is possible to hide iron ions brought in from the bleaching solution and improve the stability of the solution.

Examples of such preferred chelating agents are shown below.

1-Hydroxyethylidene-LL-diphosphonate ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid nitrilotrimethylenephosphonic acid ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid cyclohexanediaminetetraacetic acid 1,2-propanediaminetetraacetic acid The fixing process is The temperature can be 30°C to 50°C, preferably 35°C to 45°C. The fixing process time for photographic materials is 35 seconds to 2 minutes, preferably 40 seconds.
seconds to 1 minute and 40 seconds, and for printed photosensitive materials, 10 seconds to 1 minute and 40 seconds.
The time is from 10 seconds to 30 seconds, preferably from 10 seconds to 30 seconds.

The desilvering process according to the present invention is carried out in combination with a bleaching process and/or a bleach-fixing process, typical examples of which are shown below.

■ Bleach-fix ■ Bleach-bleach-fix ■ Bleach-wash-fix ■ Bleach-fix ■ Fix-bleach-fix The present invention can also be applied to desilvering treatment using a stop bath, a water wash bath, etc. after color development processing. .

In the desilvering treatment steps such as bleaching, bleach-fixing, and fixing treatments of the present invention, it is preferable that stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, a method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, and JP-A-6218
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there are methods to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the solution, creating turbulence on the emulsion surface, and methods to increase the circulation flow rate of the entire processing solution. It will be done. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. Improving agitation is achieved by adding bleach into the emulsion film,
It is believed that this speeds up the supply of the fixing agent and, as a result, increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the bleach accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The above-mentioned strong stirring is preferably used for color developing solutions, water washing, stabilizing solutions, and the like.

The color developer in the color development step of the present invention contains a known aromatic primary amine color developing agent. A preferred active ingredient is a p-phenylenediamine derivative, representative examples of which are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocyaniline 4-amino-3-methyl-N-ethyl-N- (β-(methanesulfonamido)ethyl)aniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-dimethyl-p-phenylenediamine 4-amino-3-methyl-N-ethyl-N -methoxyethylaniline 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline 4-amino-3-methyl-N-ethyl N-β-butoxyethylaniline 2-methoxy-4-[N- Ethyl-N-(β-hydroxyethyl)aminocyaniline Among the above p-phenylenediamine derivatives, D-5, D-
6, D-12 is preferably used.

In addition, these p-phenylenediamine derivatives are preferably used as salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate.The amount of aromatic primary amine color developing agent used depends on color development. Liquid 1! Preferably o
, oos to 0.1 mol, more preferably about 0.01 to 0
．． The concentration is 0.06 molar.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts may be added to the color developing solution as preservatives. Can be added.

Alternatively, the aromatic primary amine color developing agent may be directly applied to
Preservative compounds include various hydroxylamines, such as compounds described in JP-A-63-5341 and JP-A-63106655, hydroxamic acids described in JP-A-6343138, in which compounds having a sulfo group or a carboxy group are preferred; Hydrazines and hydrazides described in No. 63-146041, No. 63-44657 and No. 6
Phenols described in No. 3-58443, No. 63-446
α-hydroxyketones and α-aminoketones described in No. 56 and/or various types described in No. 63-36244 *
It is preferable to add a. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
Monoamines described in No. 327841 and No. 63-25654, No. 63-30845, No. 63-146
Diamines described in No. 40, No. 63-43139, etc.
No. 63-21647, No. 6326655 and No. 6
Polyamines described in No. 3-44655, No. 63-535
Nitroxy radicals described in No. 51, No. 6343140
Alcohols described in No. 63-53549 and oximes described in No. 63-56654 and No. 63-2
Preferably, the tertiary amines described in No. 39447 are used.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 82, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
If necessary, the aromatic polyhydroxy compound described in No. 746°544 may be contained. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The amount of these preservatives added is 0.0 per color developer if
05 to 0.2 mol, preferably (1,01 mol to 0.0
It is 5 moles.

The color developing solution used in the present invention is ρ119.0 to 12
It can be used in the range of 9.5 to 1, preferably 9.5 to 1.
1.5, which is a zero color developing solution, may contain other compounds of known developer components.

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

Specific examples of buffering agents 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, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (5-potassium sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of buffering agent added to the color developing solution is preferably 0.1 mol/2 or more, particularly preferably 0.1 to 0.4 mol/l.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, and N.

N,N-)rimethylenephosphonic acid, ethylenediamine-
N, N-N', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2- Phosphonobutane-1
, 2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxyhensyl)ethylenediamine-N,N'-diacetic acid, and the like.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient to sequester metal ions in the color developing solution, for example, from 0.001 mol to 0.05 mol per If, preferably 0.0 mol.
03 to 0.02 mol.

Any development accelerator can be added to the color developing solution if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 75987, No. 38-7826, No. 44-1238
No. 0, No. 45-9019, U.S. Patent No. 3,818,2
Thioether compounds described in No. 47, etc., JP-A-52-
P- described in No. 49829 and No. 50 to 15554
Phenylenediamine compounds, JP-A-50-13772
No. 6, Special Publication No. 1973-30074, Japanese Patent Publication No. 156-1973
Quaternary ammonium salts described in US Pat. No. 826, US Pat. No. 52-43429, etc., US Pat.
．． No. 128.182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.
No. 6, amine compounds described in No. 3,582,346, Japanese Patent Publication No. 3746088, No. 42-25201,
U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-114
No. 31, No. 42-23883, U.S. Patent No. 3,532
．． Examples include polyalkylene oxides described in No. 501, etc., and imidazoles such as 2-methylimidazole and imidazole.

It is also preferable to add 1-phenyl-3-pyrazolidones as an auxiliary developing agent for rapid development.For example, the following compounds may be mentioned.

AD-1 AD AD-3 AD AD-5 AD- The amount of these auxiliary developers added is 0.00 per color developer If.
05 mole to 0.03 mo/I, preferably 0.001 to
It is 0.01 mole.

The color developing solution used in the present invention may further contain an arbitrary anti-capri agent, if necessary.

As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used.

Examples of organic anti-capri agents include hensitriazole, 6-nidropenzimitasole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl- Typical examples include nitrogen-containing heterocyclic compounds such as henzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developing solution used in the present invention may contain a fluorescent whitening agent, and the preferable fluorescent brightening agent is a 4,4'-diamino-2,2'-disulfostilbene compound. The amount added is O~5g/f, preferably 0.1g~4g/f.
It is j2.

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

The processing temperature in the color developing solution in the present invention is 20 to 55°
C1 is preferably 30 to 55°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 20 seconds. More preferably, the time is 1 minute to 2 minutes and 30 seconds.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal processing of color photosensitive materials. Various well-known additives that are used in black-and-white developing solutions used in processing solutions for black-and-white silver halide light-sensitive materials can be included in the black-and-white first developing solution for color reversal light-sensitive materials.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole,
Examples include water softening agents such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds.

The processing method of the present invention basically consists of the color development step and the subsequent desilvering step. Furthermore, it is preferable to provide a water washing and/or stabilization step following this.

The washing water used in the washing step can contain various surfactants in order to prevent uneven water droplets when drying the photosensitive material after processing. These surfactants include:
Polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester salt type anionic surfactant, alkylnaphthalene sulfonate type There are anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino acid type amphoteric surfactants, and betaine type amphoteric surfactants. It is preferable to use a nonionic surfactant, especially an alkylphenol ethylene oxide adduct, since it may combine with various ions mixed in with the treatment to form an insoluble substance. As the alkylphenol, octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 moles. Furthermore, it is also preferable to use a silicone surfactant that has a high antifoaming effect.

In addition, various anti-grouping agents and anti-mold agents can be contained in the washing water in order to prevent the formation of water scale and mold on the photographic material after processing.

Examples of these antibacterial agents and antifungal agents include thiazolylbenzimidazole compounds as shown in JP-A-57-157244 and JP-A-58-105145; Kaisho 57-8
Isothiazolone compounds as shown in No. 542, oral phenolic compounds such as trichlorophenol, bromophenolic compounds, organotin and organozinc compounds, or
Thiocyanic acid and isothiocyanic acid compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, hensitriazoles alkylguanidine compounds, and quaternary compounds such as benzalkonium chloride. Ammonium salts or antibiotics such as penicillin, etc., are used in the Journal of Antibacteria and Antifungal Agents (J.

Antibact, Antifung, Ag
ents) Voll, Nll 5,
p.

207-223 (1983) may be used in combination.

Furthermore, various fungicides described in JP-A No. 48-83820 can also be used.

Moreover, it is preferable to contain various types of Kirei-HIJ.

Preferred compounds for the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediamine-N, N, N', N'
- organic phosphonic acids such as tetramethylenephosphonic acid,
Alternatively, a hydrolyzate of maleic anhydride polymer described in European Patent No. 345172A I can be mentioned.

Further, it is preferable that the washing water contains a preservative that can be contained in the above-mentioned fixing solution or bleach-fixing solution.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, organic acids and pH 3~
A solution having a buffering capacity of 6.6, a solution containing an aldehyde (for example, formalin or glutaraldehyde), etc. can be used. The stabilizing liquid can contain all the compounds that can be added to the washing water, and if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, Bi, Aj! various dye stabilizers including the N-methylol compounds described in Japanese Patent Application No. 63-308265, No. 63-308266, and U.S. Pat. No. 4,859,574, stabilization methods using the same, Film agents such as alkanolamines described in US Pat. No. 4,786,583 can be used.

Further, the water washing step and the stabilization step are preferably performed by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages.

The replenishment amount is 1 to 5 of the amount brought in from the previous bath per unit area.
0 times, preferably 2 to 30 times, more preferably 2 to 15 times
It's double.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, Mg concentration is 5mg/j1! It is preferable to use deionized water, water sterilized by halogen, ultraviolet germicidal lamp, etc. below.

Further, tap water may be used as the water for correcting the evaporation content, but it is preferable to use deionized water or sterilized water, which is preferably used in the above-mentioned washing step or stabilization step.

In the present invention, it is preferable to replenish not only bleach and bleach-fix solutions but also other processing solutions with an appropriate amount of water, correction solution or processing replenisher in order to compensate for concentration caused by one shot.

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

The processing method of the present invention is preferably carried out using an automatic processor. Regarding the conveyance method in such an automatic developing machine, Japanese Patent Application Laid-Open Nos. 60-191257 and 60-19125
No. 8, No. 60-191259. Furthermore, in order to perform rapid processing, it is preferable to shorten the crossover between processing tanks in an automatic developing machine.

An automatic processor with a crossover time of 10 seconds or less is described in JP-A-1-319038.

When continuous processing is performed using an automatic processor according to the processing method of the present invention, it is possible to compensate for the consumption of processing solution components accompanying processing of the photosensitive material, and to remove undesirable components eluted from the photosensitive material from the processing solution. In order to suppress the accumulation of water, it is preferable to add a replenisher according to the amount of processed photosensitive material.Moreover, two or more processing baths may be provided in each processing step, in which case the replenisher should be added The second method is to use a countercurrent method where water flows from the rear bathtub to the front bathtub.
preferable. Particularly in the water washing step and the stabilization step, it is preferable to use a cascade of two or more stages.

It is preferable to reduce the amount of replenisher as long as a 1 Jlih change in each processing solution does not affect photographic performance or cause other liquid staining problems.

In the case of color photographic materials, the amount of color developer replenisher is 100d to 1500ad per 120cm of light-sensitive material! , preferably from 100 d to 1000 m, and in the case of color print materials, from 20 d to 500 d, preferably from 30 d to 200++ d per 11 photosensitive materials.

In the case of color photographic materials, the amount of bleach replenisher is equal to 1
10d to 500Jd per mt, preferably 1(ld
~160d. For print materials, photosensitive material 1
- per 20M1~3001d, preferably 50d~
15 (d.

In the case of photographic materials, the amount of bleach-fix replenisher is
100+d to 3000d per st, preferably 20
0id1300m, and in the case of printing materials, 20d to 300d, preferably 5(
ld~200 males. The bleach-fixing solution may be replenished as a single solution, or the bleaching composition and fixing composition may be replenished separately, or by mixing the overflow liquid from the bleaching bath and/or fixing bath. It may also be used as a bleach-fix replenisher.

In the case of photographic materials, the amount of fixing replenisher is 300 d to 3000 d per Z of photosensitive material. d, preferably 300d
~1000 m, and in the case of print materials, 20 m1 per 112 of photosensitive materials! ~300d, preferably 50
M1~200-.

The amount of washing water or stabilizing solution to be replenished is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the bath per unit area.

In order to further reduce the amount of the replenisher for environmental conservation, it is also preferable to use various regeneration methods in combination.

Regeneration can be carried out by circulating the processing solution in an automatic developing machine, or by once removing it from the processing tank, performing appropriate regeneration processing, and then returning it to the processing tank as a replenisher. Also good.

The developer can be regenerated by ion exchange treatment using an anion exchange resin, removal of accumulated substances by electrodialysis treatment, etc., and/or addition of a chemical called a regenerant. The regeneration rate is preferably 50% or more, more preferably 70% or more. Although commercially available anion exchange resins can be used, it is also preferable to use a highly selective ion exchanger described in JP-A-63-11005.

The metal chelate bleach in the bleach and/or bleach-fix solution becomes reduced during the bleaching process. Accumulation of this reduced metal chelate not only reduces bleaching performance, but also causes image dyes to become leuco dyes, resulting in a decrease in image density. It is preferable to use a continuous regeneration method in conjunction with the processing. Specifically, air is blown into the bleach and/or bleach-fix solution using an air pump, and the reduced metal chelate is reoxidized with oxygen. It is preferable to do air training, etc.
It can also be regenerated by adding oxidizing agents such as hydrogen peroxide, persulfates, and bromates.

The fixer and bleach-fixer are regenerated by electrolytically reducing accumulated silver ions. In addition, it is also preferable to remove accumulated halogen ions using an anion exchange resin in order to maintain fixing performance.

In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

A light-sensitive material suitable for the processing of the present invention may have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There are no particular restrictions on the number and order of the silver halide emulsion layer and the non-irradiating layer. A typical example is a silver halide photographic light-sensitive material having a light-sensitive layer on a support, which is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities; The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally as follows: A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer between each layer may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may contain color mixing inhibitors, ultraviolet absorbers, stain inhibitors, etc. as commonly used.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the S support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (RL) order, or BH/BL/GL/GH/R) I/RL order,
Alternatively, they can be installed in the order of BH/BL/GO/GL/RL/R)l.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all constituent layers of the color photosensitive material excluding the support and the undercoat layer and hack layer of the support is 20.0 μm. The following is preferable in order to achieve the object of the present invention. More preferably 18.0
It is less than μ.

These film thickness regulations are determined by the color developing agent incorporated into these layers of the color photosensitive material during and after processing. By influencing. In particular, the increase in color of magenta, which is thought to be caused by the chloroplast color layer, is greater than the increase in color of other cyan and yellow colors.

Note that it is desirable that the lower limit value in the film thickness regulation be reduced within a range that does not significantly impair the performance of the photosensitive material based on the above regulation. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is 1.0μ.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The sensitive material to be measured is stored at 25° C. and 150% RH for 7 days after its preparation. First, measure the total thickness of this sensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to calculate the total thickness of the coated layer of the above-mentioned sensitive material excluding the support. The thickness can be measured using, for example, a film thickness measuring device (Anritsu) using a contact-type thick electrical conversion element.
Electric Co, Ltd.

) [-402B 5tand, ). Note that the coating layer on the support can be removed using an aqueous sodium hypozincate solution.

Next, use a scanning electron microscope to take a cross-sectional photograph of the sensitive material (magnification is preferably 3,000 times or more), measure the total thickness on the support and the thickness of each layer, and calculate the previous film thickness. The thickness of each layer can be calculated by comparing it with the total thickness measured by the measuring device (absolute value of the actual thickness).

Swelling rate of the photosensitive material of the present invention [(equilibrium swelling film thickness at 25°C, Hgo - total dry film thickness at 25°C, 55% RH/
Dry total film thickness at 25°C and 55%RH)X100) is 50
-200% is preferable, and 70-150% is more preferable. If the swelling ratio deviates from the above value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the swelling speed of the photosensitive material of the present invention is 90% of the maximum swelling film thickness in a color developing solution (30"C 13 minutes 15 seconds).
When 0% is the saturated swelling film thickness and the time required to reach 1/2 of this is defined as the swelling rate T1/2, T18 is 1
Preferably it is 5 seconds or less. More preferably, Tl8 is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the color brightening material used in the present invention may have any silver halide composition. That is, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, or silver iodochlorobromide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Sou 17643
(December 1978), pp. 22-23, Na3071
05 (November 1989), pp. 863-865 “1.
Emulsion preparation
on and types)” and Nl11B71
6 (November 1979), 648 pages, "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chemic et Ph1s
ique Photographique.

Paul Montel+ 1967), Duffin,
Published by Photographic Emulsion Chemistry J Focals Publishing (G, F, D
uffin, Photographic Emul
sion Chemistry (Focal
Press, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L
, Zelikman et al., Making
and Coating Photographic
Emulsion, FocalPress, 19
It can be prepared using the method described in 64).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
nce and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 414,310, No. 4,4
33.048, British Patent No. 4,439,520 and British Patent No. 2.112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a phase structure, or silver halides of different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver halide or lead oxide.

A mixture of grains of various crystal forms may also be used.Silver halide emulsions that have been subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such processes are listed in Research Disclosure No. 1764.
3, No. 18716 and NCL 307105, 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 two Research Disclosures, and the relevant descriptions are shown in the table below.

Type of additive RD17643 (December 197B) 1?D18716 (November 1979 1?1) 307105 (November 19B9) 1 Chemical sensitizer 2 Sensitivity increasing agent Page 23 Page 648 Right column Page 866 Page 648 Right column Brightener 24 pages 647 pages Right column 868 pages 77 Anti-tein agent 25 pages Right column 650 pages Left column - 872 pages Right column 9 Hardener 10 Binder 26 pages 26 pages 651 Pages Left column 651 pages Left column 874 - 875 pages 873-874 Matting agents 878-
879 Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned RDNI117643,
c-c, N[l 307105, Vll-C-G2.

As a yellow coupler, for example, U.S. Patent Box 3.93
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4,401,752, No. 4,248,
No. 961, Special Publication No. 58-10739, British Patent No. 1,
No. 425,020, US Pat. No. 1,476.760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat. Preferably a rooster one.

As magenta couplers, 5-pyrazolone and hibirazoloazole compounds are preferred, and European Patent No. 73.6
No. 36, U.S. Patent Box 4,310,619, U.S. Patent Box 4,35
No. 1,897, No. 3,061,432, No. 3.725
．． No. 064, No. 4,500,630, No. 4,540,
No. 654, No. 4,556,630, Research Disclosure (RD) Sou 24220 (June 1984)
, RDNCL24230 (June 1984), JP-A-60-33552, JP-A-60-43659, JP-A-6
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, W O(P
Particularly preferred are those described in CT No. 88104795. The effects of the present invention on bleaching fog and staining are particularly remarkable for pyrazoloazole couplers.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Box 4,052,212.
No. 4.146.396, No. 4.228.233, No. 4,296,200, No. 2,369,929,
2,801.171, 2,772,162, 2,895,826, 3,772.002, 3
, No. 758,308, No. 4,334,011, No. 4,
No. 327.173, West German Patent Publication Box 3,329,729
European Patent No. 121,365A, European Patent No. 249.453
No. A: U.S. Patent No. 3,446,622, U.S. Patent No. 4,333
, No. 999, No. 4,753,871, No. 4.45L5
No. 59, No. 4,427,767, No. 4,690,88
No. 9, No. 4,254.212, No. 4,296,199
Preferably, those described in JP-A No. 61-42658 and the like are preferred.

Colored couplers to correct unnecessary absorption of color dyes are research disclosure (RD) inhibitors 176
Section 43 ■-G, U.S. Patent Box 4.163゜670, Japanese Patent Publication No. 57-39413, U.S. Patent Box 4,004,92
No. 9, No. 4.138.258, British patent cylinder 1,146
, No. 368 is preferred. In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during capping, as described in U.S. Patent No. 4,774,181, and couplers that react with developing agents as described in U.S. Patent No. 4,777,120. It is also preferable to use a blurr which has a dye precursor group as a leaving group which can form a dye.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
Preferred are those described in No. 570, European Patent No. 96.570, and German Patent Publication No. 3,234.533.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,367,282, No. 4,409,320, No. 4,576.910, British Patent No. 2.102.173
It is stated in the number etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in Research Disclosure (RD) 17643, Items ① to F, and in JP-A-57-151944 and JP-A-57-154.
No. 234, No. 60-184248, No. 63-3734
No. 6, U.S. Patent Box 4,248,962, U.S. Patent Box 4,782
, No. 012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
Those described in JP-A No. 2.131,188, JP-A-59-157638, and JP-A No. 59170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. 4,310,618, etc., DIR redonx compound emitting couplers, DIR couplers emitting couplers, DIR described in JP-A-60-185950, JP-A-62-24252, etc.
Coupler-releasing redox compound or DIR Redo, Cous-releasing redox compound 1, European Patent No. 173.302
Research Disclosure (RD) no.

11449, 24241, JP-A-61-201247
Bleach accelerator releasing coupler described in US Patent No. 4, US Pat.
Examples thereof include Gantt-emitting couplers described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322,027, etc.; Specific examples of boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) Phthalates, etc.), esters of phosphoric or phosphonic acids [(triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, triptoxyethyl phosphate) , trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc.), benzoic acid ester 1i (2-ethylhexylbenzoate,
dodecyl benzoate, 2-ethylhexyl-P-hydroxybenzoate, etc.), amides (N,N diethyldodecaneamide, N,N-diethyl laurylamide, 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 ntrate, etc.), aniline derivatives (N, N- Examples include dibutyl 2-butoxy-5-tert-octylaniline, etc.) hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Examples include hexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation are disclosed in U.S. Pat.
41,230, etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

Suitable supports that can be used in the present invention include, for example, 28 true of the aforementioned Research Disclosure (RD) Nα17643, and 64 from the right column of page 647 of the same Nα18716.
It is written in the left column of page 8.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or motion pictures, color reversal film for slides or television, color paper, direct positive color paper, color positive film, and color reversal paper. The color reversal film may be of the so-called internal type (containing the coupler in the light-sensitive material) or of the external type (containing the coupler in the developer).

(Example) The present invention will be explained in more detail with reference to Examples below.
The invention is not limited thereby.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the brightening layer) The coating amount is expressed in g/m of silver for silver halide, colloidal silver and couplers, and in moles per 1 mole of silver halide in the same layer for aggravating dyes. Shown in numbers.

1st layer: antihalation layer black colloidal silver silver coating amount 0.2 gelatin
2.2UV-10,1 11V-20,2 pd-1 Sol Sea 1 olv-2 olv-3 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) 0,05 0.01 0. 01 0.08 Silver coating amount 0.15 Gelatin 1.0Cpd-2
0,2 Third layer: First red-glare emulsion layer Silver iodobromide emulsion (^gr 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 1
Tetrahedral grains) Silver coating weight 0.26 silver iodobromide emulsion (Agl
4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μ
, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle)! ! Coating amount 0.2 gelatin 1.0E
xS-14,5Xl0-'mol ExS-21,5Xl0-'mol ExS-30,4X 10-'mol εxs-40,3 xC-1 xC-7 xC-2 xC-3 xC-6 4th layer: 2 Red-sensitive emulsion layer Silver iodobromide emulsion (Agl 16 mol%, internal high Agl type,
Equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 4.0) Silver coating amount 0.55 Gelatin 0.7ExS-1
3Xl0-'ExS-21xlO-'ExS-30,3XIF'ExS-40,3Xl0-' ExC-30,05 ExC-40,10 ExC-60,08 5th layer: 3rd red-sensitive emulsion layer xio-' Mol 0.15 0.15 0.009 0.023 0.14 Silver iodobromide emulsion (Agl 10.0 mol%, internal high AgT
Type, equivalent sphere diameter 1.2 μ, variation coefficient of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 0.9 Gelatin 0.6ExS-12
XIO-' ε to S-20,6 -4
0,1 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (Agl 10.0 mol%, internal high Agr
Type, equivalent sphere diameter 0.7 μ, variation of equivalent sphere diameter 14%, 1
Tetrahedral grains) Silver quantity fabric 1092 Silver iodobromide emulsion (Ag
l 14.0 mol%, internal high AgI type, equivalent sphere diameter 0.4
μ, 22%, tetradecahedral particles) Gelatin xS-5 xS-6 xS-7 xM-1 xM-6 xM-2 xM-5 Solv-1 Solv-4 Coefficient of variation of equivalent sphere diameter Silver coating amount 0.1 1 .2 5 Xl0-' 2 Xl0-' I Xl0-' 0.20 0.25 o, i.

0.40 0.03 8th layer: 2nd green emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type,
Equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35ExS-
53,5Xl0-' ExS-61,4X 10-'ExS-70,7X10-' ExM-10,09 ExM-30,01 Sθl Sea 10,15 Solv-40,03 9th layer: Intermediate layer gelatin 0.5 10th layer: 3rd green emulsion layer Silver iodobromide emulsion (Agl 10.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.2 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Silver coating amount 1.0 0.8 2 Xl0-' 0.8 Xl0-' 0 .8 Xl0-' 0.01 0.04 o, oos O2O3 Gelatin xS-5 εχS-6 εxS-"I xM-3 xM-4 εxC-4 Solv-1 11th layer: Yellow filter layer Cpd-30,05 Gelatin (1,5Solv-
10,1 12th layer: Intermediate layer gelatin 0.5Cpd-20
, 1 13th layer: 1st blue sensitive layer silver iodobromide emulsion (Agl 10 mol%, internal high iodine type,
Equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, ■ Tetrahedral grains) Silver content, ] Silver iodobromide emulsion 8 g 14° 0 mol%, internal high iodine type, equivalent sphere diameter 0. 4μ
, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particles) Silver coating amount 0.05 Gelatin 1
．． 0ExS-83X 10-' ExY-10,25 ExY-30,32 ExY-20,02 Sol Sea 1 0.2.0
14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 19.0 mol%, internal high Agl
Type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%, 1
Tetrahedral particles) Silver coating amount 0.19 gelatin
0.3 ExS-82 2 gelatin
0.36 16th layer: 3rd blue emulsion layer silver iodobromide emulsion (ttgr 14.0 mol%, internal high Ag
L type, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount 1.0 Gelatin 0.5ExS-8
1.5 Oool 18th layer: 2nd protective layer Fine grain silver bromide (equivalent sphere diameter 0.07 μ) Silver coating 10.18 Gelatin 0.7 Polymethyl methacrylate particles (diameter 1.5 μ) 0.2 Ll O, 02H-1
0.4 Cpd-51,0 V-1 l13 H3 1+CII□-C+f--□10CH, -C→-2COO
CIIn -5 xM-1 xM-2 C1□Hzs xM-4 xY-1 xY-2 xY-3 ExS-1 ExS-4 Js C,lIS ExS-5 ExS-8 ExS-7 Js Sol Sea 1 Sol Sea 2 olv -3 Sol Sea 4 pd-1 pd-2 pd-3 pd-4 pd-5 υ■ CJ++ (n) -1 CJ+? 5OJHcHzc)lzcH2OcH2cH
Je (CH3)3CH,=C)lsO2cl(ZCO
NH-C)IfC)Iz=C)lsOzcHzcONH
-CHZ The prepared sample was cut and processed into a width of 351 m.
Wedge exposure was applied to the mouth (color temperature of the light source: 4800°K), and processing was performed using a cine-type automatic processor in the processing steps shown below. However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative replenishment amount of the color developer reached three times the volume of the mother solution tank, and then the samples were processed.

The composition and pH of the bleaching solution at this time were changed as shown in Table 1, and the conditions for the aeration of the bleaching solution were as follows: The treatment was carried out while foaming at 200 d/min.

Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8°C 23d iop
Bleach 50 seconds 38,0°c
5H15/! Fixation 1 minute 40 seconds 38.0℃
30d lOf water washing (1) 30 seconds
38.0℃ -51 water washing (2) 20 seconds 3
8.0℃ 30dl stable 20 seconds
38.0″C20d!M Drying 1 minute 55°C The amount of replenishment is the amount per 1m of 35+us width.Washing is the countercurrent method from (2) to (1).In addition, the amount of developer brought into the bleaching process, The amount of fixer carried into the washing process was 2.5 m and 2.0 d per 1 m length of the 35-width photosensitive material, respectively.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher axis)
Diethylenetriaminepentaacetic acid 1.0 1.11-Hydroxyethylitine-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β~hydroxyethylamino)- 2- Add methylaniline sulfate solution to pH (bleaching solution) 3.0 4.0 30.0 1.4 1.5mg 2.4 4.5 1.0℃ 10.05 Mother liquor axis) 30.0゜1 .0 ff1 10.10 Replenisher axis) Iron nitrate 0.20 mol 0, 30 mol Chelate compound (listed in Table 1) 0.31 mol 0.47
Molar ammonium bromide 100g 15
0g ammonium nitrate 20g 30
g Glycolic acid 55g 83g
Add water 1. Of 1. On!
P H5,05,0 Here, the chelate compound refers to an organic acid that constitutes the organic acid ferric ammonium salt used in the bleaching agent.

(Fixer) Common to mother solution and replenisher (g) Ethylenediaminetetraacetic acid secondary ammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g/1) 260.
Add 0d water 1.0! p
) l 7.0 (Washing water) Common tap water for mother liquor and replenisher was used with H-type strongly acidic cation exchange resin (Amberlite I R-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite I R-120B manufactured by Rohm and Haas). Water was passed through a hot bed column filled with Light I RA-400) to bring the calcium and magnesium ion concentration to 31χg/I! , followed by sodium isocyanurate dichloride 20 mg/j!
and 150 mg/12 sodium sulfate were added.

The p)l of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 1.2id surfactant 0.4 (C+oHz+-
0+CHzCHzO±rrH) ethylene glycol
1.0 Add water
1.0IP H5,0-7,0 For each of the photographic materials subjected to the above treatment, the amount of residual silver in the highest color density area was measured by fluorescent X-ray analysis. The results are shown in Table 1.

In addition, the density of these treated samples was measured, and the Dmin value measured using green light (CG light) was read from the characteristic curve.

Next, as a standard bleaching solution without bleaching blade blur, change to the following processing solution formulation, bleaching processing time is 390 seconds, processing temperature is 38°C, replenishing solution amount is 25d/35+wm, sample length is 1m.
The process was performed without changing anything else.

(Standard bleaching solution) Mother liquor (g) Replenishment solution (g) Ethylenediaminetetrasentate ferric sodium trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 100 120 Ammonium nitrate 30 .0 35.0 Ammonia water (2
7χ) 6.5d 4.0d Add water 1. ONl, OfP H6,05,7 The treated samples obtained using the above standard bleaching solution were subjected to concentration measurements in the same way, and the D-in values were read from the characteristic curve.These obtained Dmin values are the standard. The difference between each sample, ΔDmin, was determined based on the Dmin value of the bleaching solution. In addition,
The Dmin value obtained using the standard bleaching solution at this time was 0.60.

Bleached Capri (ΔDmin) = (Dmin of each sample)
- (D■in of standard bleaching solution) - The results are shown in Table 1.

Next, using the above sample, the increase in stain during sample storage after treatment was stored under the following conditions, and the D of the uncolored area was
It was determined from the change in concentration of s+in before and after storage.

Dark/heat condition 2 60° C., 70% RH 24-week stain increase (ΔD)=(Ds+1n after storage)−(low in before storage) The results are also shown in Table 1.

Comparative Compound E From the results in Table 1, it can be seen that the compounds of the present invention can reduce the amount of residual silver compared to the comparative compounds, and at the same time exhibit excellent effects on bleaching fog and staining during color image storage after processing.

Example 2 Sample 311 described in JP-A-2-28637 was treated as follows.

Processing method step Processing time Processing temperature Replenishment amount Tank capacity Color development 1 minute 45 seconds 43℃ 25d 11 Bleaching 20 seconds 40℃ 5d
4ffi bleach fixing 20 seconds 40℃
41 fixation 20 seconds 40℃
16d lWash (1) 20 seconds 40
℃ 21Wash (2) 10 seconds
40℃ 30Illll! 2IV.

Stable 10 seconds 40'C20d
21 Drying 1 minute 60℃ Replenishment amount is 35 @ II amount per 1 m length The washing process is (
It was a countercurrent system from 2) to (1), and all the overflow of the bleaching solution was introduced into the bleach-fixing system.

In addition, all the overflow liquid from washing (1) is allowed to overflow to the fixing bath, and all the overflow liquid from the fixing bath is allowed to overflow to the bleach-fixing bath.The amount of fixing liquid brought into the washing process in the above process is 35-m/m/m. It was 2 d per 1 m length of photosensitive material having a width of m.

The formulation of the treatment liquid used is shown below.

(Color developer) Mother liquid axis) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylthene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 5.8 Potassium carbonate
40.0 40.0 Potassium bromide
1.3 Potassium iodide 1.5 m Hydroxylamine sulfate 2.4 3.62-Methyl-4-[N-ethyl-N-(β hydroxyethyl) Aminocoaniline sulfate solution was added to pHC potassium hydroxide (50 )] (Bleach solution) Chelate compound (compounds are listed in Table 2) Nitrate/iron ammonium bromide Ammonium nitrate Add water and H (Fixer) Ammonium thiosulfate aqueous solution (700 g/l) Ethylenediamine tetranoic acid 9.2 1. OI! 10.20 Mother liquor 0.30 mol 0.27 mol 100° 17.5 g 1.0/ 4.5 Mother liquor 80 m 12.6 g 13.4 1.0 β 10.35 Replenisher 0.42 mol 0.38 mol 40 g 25.0g 1, Ol 4.5 Replenisher 40d1 FIg Ammonium Sulfite 27.5g 82.5
g Imidazole 28g Add 84g water 11 If pH7,88
,0 (bleach-fix solution) A mixture of bleach solution: fix solution: washing solution = 5:16:30 (volume ratio).

(Water solution) Same as the washing solution in Example 1, stable solution) Common to mother liquor and replenisher (Unit: g) Formalin (37χ) 2.0d Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0. 3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1. Oj2p H5,0-
8,0 The obtained treated sample is subjected to concentration measurement, and the Dn+in value measured with green light is read from the characteristic curve.
Using the standard bleaching solution used in Example 1, JP-A-2-286
Sample 311 described in No. 37 was treated and the low-in value was determined in the same manner as above. Based on the Dmin value of this standard bleaching solution, the bleaching fog, Δ
Dmin value was calculated. D due to the standard bleaching solution at this time
+min value was 0.57. The results are shown in Table 2.

Subsequently, using the above-treated sample, a test was conducted for staining during image storage after processing under the same conditions as in Example 1, and staining was evaluated using the same method. These results are also shown in Table 2.

Further, samples uniformly exposed to give a gray density of 1.5 were processed in the same manner as before, and the amount of silver remaining in these samples was quantified by the fluorescence xia method.

These results are also shown in Table 2.

Comparative compounds A, B, CSD and E in the second study were the same as in Example 1. The results in Table 2 show that the compounds of the present invention can reduce the amount of residual silver compared to the comparative compounds, and at the same time exhibit excellent effects on bleaching edge blur and staining during color image storage after processing.

Example 3 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was applied, and various photographic constituent layers were further applied to obtain the layer structure shown below. A multilayer color photographic paper was produced. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-1)
-7) 27.2 cc of ethyl acetate and 4.0 g of each of solvents (Solv-3) and (Solv-7) were added to 0.7 g.
1 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average particle size 0.
88s large size emulsion A and 0.70-small size emulsion A
3-nia mixture (silver molar ratio) with The coefficient of variation of particle size distribution is 0.08 and 0.08, respectively. IO1 emulsions of each size (containing 0.3 mol % silver bromide locally on a part of the grain surface) were prepared.

In this emulsion, the blue-sensitive sensitizing dyes A and B shown below were contained in a ratio of 2.0% to 1 mole of silver for large-size emulsion A, respectively.
OXl0−' moles, and for small size emulsion A,
2.5 Xl0-' moles were added, respectively.

Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to obtain the composition shown below.
A layer coating solution was prepared.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy-3,5-dichloro-5-) riazine sodium salt was used as the gelatin hardening material for each layer.

Further, Cpd-10 and Cpd-11 were added to each layer so that the total amounts were 25.0+mg/m'' and 50.0mg/m'', respectively.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

Sensitizing dye A for blue-sensitive emulsion layer ose SO,H ・N(CJs)s Sensitizing dye B for blue-sensitive emulsion layer (per mole of silver halide, 2.0 XIO of each for large-sized emulsion layer A) -' mol, or 2.5 XIO-' mol each for small size emulsion A) Sensitizing dye C for green-sensitive emulsion layer (4.0'-' mole, 5.6 Xl0-' mole for small size emulsion B) and sensitizing dye D for green-sensitive emulsion layer (per mole of silver halide, 7.OX10 for large size emulsion MB) -' mol, and 1.OXl0-' mol for small size emulsion B) Red-sensitive red-sensitive emulsion layer dye E゛■ e (per mole of silver halide, 0.9 for large size emulsion C) For the red-sensitive emulsion layer, the following compounds were added in an amount of 2.6 Xl0-' moles per mole of silver halide. .

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was added at 8.0% per mole of silver halide, respectively.
5 Xl0-' mol, 7.7 X'IO-' mol, 2.
5 Xl0-' moles were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene was added per 11 moles of halogenation, respectively.
'mol and 2X10-'mol were added.

In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m''). Silver halide emulsions represent the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ii02) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive emulsion layer) The above-mentioned silver chlorobromide emulsion A 0.30 gelatin 1 .86 yellow coupler (ExY) 0.82 color image stabilizer (
Cpd-1) 0.19 solvent (SO
IV-3>0.18 solvent (S
plv-7) 0.18 Color image stabilizer (Cpd-7) 0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (
Solv-1) 0.16 Solvent (Solv-4) 0.08 Fifth layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion B with average grain size 0.55-, and 0.39 - l with small size emulsion B:
3 (Ag molar ratio), the coefficient of variation of particle size distribution is 0.10 and 0.08, respectively, and each size emulsion has Ag
0.12 Gelatin (0.8 mol% Br was locally contained on a part of the particle surface)
1.24 magenta coupler (ExM)
0.23 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.16 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-9)
0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorption layer (UV-1) 0.47 Color mixing prevention (Cpd-5) 0.05 Solvent (Solv-5) 0.24
Fifth layer (red-causing emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.58 m and small size emulsion C with an average grain size of 0.45 m):
4 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.09 and 0.11, and each size emulsion is AgBrO,
(6 mol% was locally contained on a part of the particle surface)
0.23 gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-6)
0.18 color image stabilizer (Cpd-7)
0.40 color image stabilizer (Cpd-8)
0.05 solvent (Solv-6)
0.14 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (
Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0,17 Liquid paraffin 0.03 (ExY) Yellow coupler R= 11 with 1 mixture (molar ratio) (ExM) Magenta coupler (ExC) Cyan coupler L: 1 mixture (molar ratio) (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd- 3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Sd-6) 2:4 mixture (weight ratio) of color image stabilizer (Cpd-7) Color image stabilization Average molecular weight: 60.000 (Cpd-8) 1:I mixture (weight ratio) with color image stabilizer (Cpd-9) Color image stabilizer (Cpd) Preservative (Cpd Preservative (UV-1) Ultraviolet absorber 4:2:4 mixture of C3H (weight ratio) (Solv-1) Solvent (Solv-2) 1:1 mixture with solvent (volume ratio) (Solv-4) Solvent (Sol Sea 5) 8 medium C00CsH+ 7 (Ct+,)*C00CsH+t (Solv-6) 80:20 mixture (volume ratio) with solvent (Solv-7) Solvent CsH+70HCH (CHz)tcOOcsH+t\1 Next, the following treatment liquid was prepared.

It is.

41st grade water Ethylenediamine N, N.

N’, N’-tetramethylene Phosphonic acid potassium bromide potassium chloride triethanolamine potassium carbonate Fluorescent brightener 01HITEX・4B・ (manufactured by Sumitomo Chemical) The composition is as follows. 001d 2.0g O,015g 3.1g 10.0g 7g 1.0g diethylhydroxylamine N-ethyl-N-(β-meta (sulfonamide ethyl) 3-methyl-4-amino Ani! hmm add water pH (25°C) 1 foot long water Ammonium thiosulfate (70%) sodium sulfite iron chloride Chelate compounds (listed in Table 3) ammonium add water pH (25°C) North 2nd nail Ion exchange water (calcium, 3pp+11 or less) The above photosensitive material was processed as follows.

Magnesium is 4.2g each 5.0 1000iif 10.05 00ad 00M1 17° 0.30 mol 0.33 mol 000d 6.8 Five sciences and engineering parts ■ Piece ■ Color development Bleach fixing at 38°C for 45 seconds Rinse at 35'C for 25 seconds ■ 35 Rinse at 35°C for 20 seconds ■ Rinse at 35°C for 20 seconds Dry at 80°C 60
Further, samples uniformly exposed so as to have a gray density of 1.5 were processed in the same manner as before, and the amount of silver remaining in the highest density part of these samples was quantified by fluorescent X-ray method. The results are shown in Table 3.

Comparative Compound A° is the same as Comparative Compound A of Example 1. From the above results, it was found that when the compound of the present invention was used, the amount of residual silver was smaller than that of Comparative Compound A.

Example 4 Fujicolor 5UPERHG400 (serial number 3111
30) and Fujicolor REALA (serial number 8610
16) was carried out in Processes 201 to 218 of Example 2, and the same effects as in Example 2 were confirmed.

Example 5 On a subbed cellulose triacetate film support,
A sample 102, which is a multilayer color brightening material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/% of silver for silver halide and colloidal silver, the amount expressed in g/rrf for coupler additives and gelatin, and the amount expressed in g/rrf for coupler additives and gelatin. The number of moles is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

Uv: ultraviolet absorber, Solν: high boiling point solvent, Ex
F: dye, ExS i sensitizing dye, ExC: cyan coupler, ExM: magenta coupler, ExY
; Yellow coupler, Cpd ; Additive 1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.33ExM-20,
11 UV-13,0xlO~2 UV-26,0X10-” UV-37,0X10-” 5olv-10,16 Solv-20,10 Ex F-11,0X10-” Ex F-24,0xlO -"E x F -3s, oxio-" Cp d -6t, oxlo-3 2nd layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4.0 mol%, uniform-Agl type,
Equivalent ball diameter 0.4. , coefficient of variation of equivalent sphere diameter 30%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount 0.35 Silver iodobromide emulsion (Agl 6.0 mol%, core shell ratio 1)
:Gl type to internal height of 2, equivalent sphere diameter 0.45js, coefficient of variation of equivalent sphere diameter 23%, plate-shaped particles, diameter/thickness ratio 2.0) Gelatin xS-1 xS-2 xS-5 xS-7 xC-1 xC-2 xC-3 xC-5 3rd layer (medium-sensitivity green-sensitive emulsion layer) Coated silver amount 0.18 0.77 2.4X10-'1.4X10-'2.3X10-' 4, lX10 -' 0.09 4, OX 10-"8.0X10-" 0.08 Silver iodobromide emulsion (Agl 6.0 mol%, core shell ratio 1
:2 internal height Agl type, ball equivalent diameter 0.65. , coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.80 1.46 2.4X10-' 1.4 X 10-' 2.4 X 10-'4.3X10-" 0.19 2, OX 10-" 0,10 0.19 2, OX 10-"2.0X10-" 5.7 X 10-" 5.7 X 10-" Gelatin xS-1 xS -2 xS-5 xS-7 xC-1 xC-2 xC-3 xC-5 xC-6 xM-3 V-2 V-3 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide hole R ( Agr 9.3 mol%, multi-structured particles with a core-shell ratio of 3:4:2, All content from inside to 2
4.0.6 mol%, equivalent sphere diameter 0.75 m, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 2.5) Gelatin xS-I xS-2 xS-5 xS-7 xC -I xC-4 xC-6 olv-I olv-2 5th layer (intermediate layer) Gelatin pd-1 Polyethyl alcohol olv-1 Coated silver amount 1.49 1.3B 2.0X10-' 1, I X 10-'1.9X10-' 1.4 -” 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4.0 mol%, uniform-Agl type,
Equivalent sphere diameter 0.33-1 Coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.19 0.44 1.5X10-'4.4X10-' 9. 2X10-' 0.17 3.0X10-" 0.13 1.0X10-" Gelatin ExS-3 xS-4 xS-5 xM-1 xM-3 olv-1 olv-4 7th layer (mid-sensitivity green emulsion Layer) Silver iodobromide emulsion (Agl 4.0 mol%, uniform-Agl type,
Equivalent sphere diameter O, SS*, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter/thickness ratio 4.0) Coated silver amount 0.24 Gelatin 0.54 xS-3 2, lX10-' E x S -46, 3 8th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 18.8 mol%, silver ratio 3:4:2
Multi-layer structure particles, Agl content of 240.3 mol% from inside, equivalent sphere diameter of 0.75 mm, coefficient of variation of equivalent sphere diameter of 23%,
Plate-shaped particles, diameter/thickness ratio 1.6) Coated silver amount 0.49 0.61 4.3X10-' 8.6 X 10-' 2.8 X 10-5 8.0X10-"3.0XIO-"3.0X10-" Gelatin xS-4 xS-5 xS-8 xM-I xM-2 xY-1 Ex C-11,0X10-2 Ex C-41,0X10-" 5olv-10,23 S o l v-2s, oxto-”S o l v
-4i,oxto-"Cp d -81,0X10-
2 9th layer (middle layer) Gelatin 0.56Cp
d -14,0X10-” Polyethyl acrylate latex 5.OX 10-”
SOLV-13,0X10-”UV-43
, oXlo-" UV -54,0X10-" 1st O layer (donor layer for interlayer effect on red-sensitive layer) Iodobromide 11 emulsion (AgI 8.0 mol%, core-shell ratio 1:2
GL type, equivalent sphere diameter 0.65 m, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.67 Silver iodobromide emulsion (Ag14.0) Mol%, uniform Agl type, equivalent sphere diameter 0.4 mm, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.20 0.87 6.7 ×10 -' 0, 16 0.30 3, OX 10-" Gelatin xS-3 xM-4 olv-1 olv-6 11th layer (yellow filter layer) Yellow colloidal silver gelatin p d-2 olv-1 Pd-1 Pd -6 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7-1 coefficient of variation of equivalent sphere diameter 15%, plate-like grains , diameter/thickness ratio 7.0) Coated silver amount 0.50 9, OX 10-" 0.84 0.13 0, 13 8.0 X 10-"2.0X10-' 0.25 Silver iodobromide emulsion (AgI 3.0 mol%, uniform Agl type, equivalent sphere diameter 0.3 m, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount 0.30 Gelatin 2.18E x
S -69,0X10-' ExC-10,14 ExY-20,17 Ex Y -31,09 Solv-10,54 13th layer (middle layer) Gelatin 0.40ExY
-40,19 Solv-10,19 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10.0 mol%, internal high Agl
Type, equivalent sphere diameter 1.0-1 Coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0
．． 40 Gelatin ExS-6 xY-2 ExY-3 xC-1 olv-1 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Agl 2.0 mol%, uniform Ag
Type I, equivalent sphere diameter 0.07m) Coated silver amount 0.12 Gelatin 0.63U V
-40,11 UV -50,18 S o l v-52,0xlO-" Cp d-50,10 Polyethyl acrylate latex 9.OX 10-"
16th layer (second protective layer) Fine-grain silver iodobromide emulsion (AgIO, 2 mol%, homogeneous -Ag
r type, equivalent sphere diameter 0.07 m) Coated silver amount 0.36 0.49 2.6X10-'1.0X10-" 0.20 1.0X10-"9.0X10-" Gelatin 0.85B-1
(Diameter 1.5m) 8.0X10-”B
-2 (diameter 1.5+s) 8.0X10
-"B -32,0X10-"W-42,0xlO-" H-10,18 In addition to the above, the sample thus prepared also contained 1.2 benzisothiazoline-3-ions (an average of 2
00 ppm), n-butyl-p-hydroxybenzoate (approximately 1,000 ppm), and 2-phenoxyethanol (approximately 10,000 ppm) were added.

Furthermore, B-4, B-5, F~1, F-2, F3, F-4
, F-5, F-6, F-7, F-8, F-9, F-10
, F-11, F-12 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

In addition to the above ingredients, each layer contains surfactants W-1 and W-2.
, W-3 were added as coating aids and emulsifying and dispersing agents.

V V-2 V-3 U ■ y =70 : 30 (wt%) o Iv ■ Tricresyl phosphate olv Dibutyl phthalate olv Trihexyl phosphate ExF-1 ExF-3 xC xC-3 xC-4 xC-5 E x M -1 xM xY-1 xY I xY-3 xY C6H+ s pd ■ C, F,, 50□N (Cdb) C) IzCOOKxS OONa F-12 B-1 H 0aNa The prepared sample was cut into 35 paper towels. The film was processed and subjected to wedge exposure at the mouth (color temperature of the light source: 4800''K), and processed using a cine-type automatic processor in the processing steps shown below.

However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative replenishment amount of the color developer reached three times the volume of the mother solution tank, and then the samples were processed.

The composition of the bleaching solution at this time was as shown in Table 1, and the conditions for aeration of the bleaching solution were 200 d/min of foaming from the piping section, which had many 0.2m+φ pores installed at the bottom of the bleaching solution tank. I processed it while doing so.

Processing process Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 37.8°C23I & bleaching 2
5 seconds 38.0°C5d fixation 1 minute 40 seconds
38.0℃ water washing (1) 30 seconds 38.
0℃ water washing (2) 20 seconds 38.0″C temperature
20 seconds 38.0℃ drying 1 minute
At 55°C, the amount of replenishment is per meter of 35mm width.The amount of washing is countercurrent from (2) to (1).The amount of developer carried into the bleaching process and the amount of fixing solution carried into the washing process are Each length of 1 meter of light-sensitive material was 2.0 d.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

0d tank capacity 0ffi 0f 30111! 0H1 (color developer) diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate Mother liquor (8) Replenishment solution ((to) 1.0 1.1 3.

4.0 30.0 1.4 1.5g 2.4 30.0 Add water and H (bleaching solution) Ferric nitrate chelate compound (listed in Table 4) 1.02 10.05 Mother liquor 0.20 Dry 0.31 mol 1, Qf 10.10 Replenisher 0.30 mol 0.47 mol Ammonium bromide 100 g 150
g Ammonium nitrate 20g 30
g acetic acid
0.72 mol 1.09 mol Add water
1.0ffi 1. Oji! pH4
,03,8 Here, the chelate compound refers to a compound that constitutes the ferric chelate compound used in the bleaching agent with a metal salt.

(Fixer) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid secondary ammonium salt 17 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution 260.0〆 (700g/1) Add water to 1.0j2pH
7.0 (Washing water) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amber 54 Days R-120B manufactured by Rohm and Haas) and OH-type strongly acidic and basic anion exchange resin (Amberlite IRA, manufactured by Rohm and Haas). -4
Water was passed through a hotbed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3 μ/l or less, and then 20 μ/l of sodium isocyanurate dichloride and 1501 mg/l of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37χ) 1.2■ Surfactant (C+of(it O+CHtCHzO-)-Tr-H
) D ethylene glycol 1
．． 0 Add water t, o ep
)l 5.0-7.0
For each of the photographic materials subjected to the above treatment, the amount of residual silver in the highest color density area was measured by fluorescent X-ray analysis. The results are shown in Table 4.

Further, the density of these processed samples was measured, and from the characteristic curve, the color density at the highest color density portion was measured using red light (R light), and 1(li!) was read.

Next, as a standard bleaching solution without defective color recovery, change to the following processing solution formulation, set the bleaching time to 600 seconds, and set the processing temperature to 3.
Processing was carried out at 8° C., with the amount of replenisher being 25 d/35 m wide, and with sample length 1 m, without any other changes.

(Standard bleaching solution) Mother liquor (6) Replenisher solution (6) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 12t1.
D Ethylenediaminetetraacetic acid disodium salt 1a, ott, θ Ammonium bromide 140 140 Ammonium nitrate 30.8 35.0 Aqueous ammonia (27χ) 6.5d 4. (l
d Add water 1. ONl, 0ffi
pH 6,05,7 The concentration of the treated sample obtained using the above standard bleaching solution was measured in the same manner, and the value was read from the characteristic curve.

These obtained values were taken based on the reference bleaching solution values, and the difference ΔD11 between each sample was determined. The DI value obtained by processing with the standard bleaching solution was 2.1 for the photographic material used in this example.

Poor color recovery (ΔD11)=.

(Dll of reference bleach solution) - (Each sample paste) The results are shown in Table 4.

Next, using the above sample, the change in gradation during sample storage after processing was stored under the following conditions, and was determined from the modulation changes before and after storage. Note that the gradation Cr here
G) refers to the color density (Dot) measured with G light at a point where an exposure amount of 1/10 of the exposure amount that gives the maximum color density measured with green light (G light) is given from the characteristic curve, and the maximum color density (Dot). It is expressed as the difference from the color density (De) where an exposure amount that is 1/1000 of the exposure amount that gives the color density is applied.

Floor'J (IG) = DGI Dcz Storage conditions: Dark/
Heat, 60℃, 70%RH, 4-week gradation change (ΔTG)
= (TG after storage) (TG before storage) The results are also shown in Table 4.

From the results shown in Table 4, it can be seen that the present invention exhibits superior effects in terms of the amount of residual silver, defective color recovery, and gradation changes during storage of color images after processing, compared to the comparative examples.

Example 6 Sample 102 described in Example 5 was treated in the same manner as in Example 5 by varying the bleaching time during the treatment process, and the same measurements as in Example 5 were made for poor color restoration. However, bleach solution (
The treatment was carried out in a system containing 0.72 mol of acetic acid in the mother liquor. The results are shown in Table 5.

Comparative Example Compound B in Table 5 is the same as Example 5. From the results in Table 5, it can be seen that the present invention exhibits a superior effect on poor color restoration in rapid bleaching treatment compared to Comparative Example.

Example 7 On a subbed cellulose triacetate film support,
Sample 103, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is g for silver halide and colloidal silver.
/ The amount of silver expressed in M, and for the coupler addition and gelatin in g/rd, and for the sensitizing dye in moles per mole of silver halide in the same layer. Ta.

1st layer: antihalation layer black colloidal silver gelatin V-1 V-2 pd-1 p d-2 olv-1 olv-2 2nd layer: intermediate layer fine particulate bromide 1i1i! (Agl 1.0 mol%, equivalent sphere diameter 0.07 mm) Silver coating amount 0.20 2.20 0.11 0.20 4.0X10-"1.9X10-" 0.30 1.2 X 10-" !!Coating amount 0.15 Gelatin 1.00E x
C-46,0X10-" Cp d-32,0X10-" Third layer: First red emulsion layer Silver iodobromide emulsion (Agl 5.0 mol%, surface height Agl type, equivalent sphere diameter 0.9- Coefficient of variation of 1 sphere equivalent diameter 21%, tabular grain, diameter/thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (Ag [4.0 mol%, internal high AgI type,
Equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) Silver coating amount 0.40 Gelatin 1.90E x
S -14,5X10-'mol Ex S -21,
5xlO-'MoleEx S-34,0X10-SMoleExC-1,0,65 ExC-31,0X10-"ExC-42,3X10-"S o lv -10,32th 4 layers: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Agl 8.5 mol%, internal high Agl type, equivalent sphere diameter 1.0 m, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness Ratio 3.0) Silver coating amount 0.85 Gelatin 0.91E x
S -13,0X10-'mol Ex S -21,
0X10”'MoleEx 5 layers: 3rd red-sensitive emulsion 1 layer silver iodobromide emulsion (Agl 11.3 mol%, internal high AgT
Type, equivalent sphere diameter 1.4 mm, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Silver coating amount 1.50 1.20 2.0X10-'mol 6.0X10- 'Mole 2, OX 10-'Mole 8.5 6 olv-I olv-2 6th layer: Intermediate layer gelatin 1.00Cp d
-48,0X10-" So 1 v -1s, oxxo-" 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Agl 5.0 mol%, surface height agr type, equivalent sphere diameter 0.9 m , coefficient of variation of equivalent sphere diameter 21%, tabular grain, diameter/thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (Agl 4.0 mol%, internal high Agl type, equivalent sphere diameter 0) .44, coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) Gelatin xS-4 xS-5 xS-6 xM-I xM-2 xM-5 Silver coating amount 0.16 1.20 5, OX 10 -'Mole 2.0X10-'Mole 1, OX 10-'Mole 0.50 0.10 3.5X10-" 5olv-10,20 S o l v-33,0X10-" 8th layer: 2nd green feeling Emulsion layer Silver iodobromide emulsion (Agl 8.5 mol%, internal high Agl type, equivalent sphere diameter 1.0 m, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating Amount 0.57 0.45 3.5 X 10-' mol 1.4 X 10-' morph, 0X10-' mol 0.12 7, l xS-4 xS-5 xS-6 xM-1 xM-2 xM-3 olv-1 olv-3 9th layer: Intermediate layer gelatin olv-1 10th layer: 3rd green-sensitive milk layer 0.50 2. 0X10-” Silver iodobromide emulsion (^gr tt, a mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 m, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20E x
S -42,0 x 10-'mol Ex S -58,0
X10-'mol Ex S -68,0 25 11th layer: Yellow filter layer gelatin 0.50Cp d
-65,2X10-” 5olv-10,12 12th layer: Intermediate layer gelatin 0.45Cpd-
30,10 13th layer: 1st blue emulsion layer Silver iodobromide emulsion (8g 12 mol%, average-Agl type, equivalent sphere diameter O, SS*, coefficient of variation of equivalent sphere diameter 25%, tabular grains, Diameter/thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00EχS-
73,0X10-'mol ExY-10,60 ExY-22,3X10-''5olv-10,15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 19.0 mol%, internal height Agl
Type, equivalent sphere diameter 1.0I111, coefficient of variation of equivalent sphere diameter 16
%, octahedral particles) Gelatin xS-7 xY-I olv-1 15th layer: Intermediate layer silver coating amount 0.19 0.35 2.0 Silver bromide (Agl 2 mol%, uniform Agl type, equivalent sphere diameter 0.13) Silver coating amount 0.20 Gelatin 0.36 No. 16
Layer: Third blue emulsion layer silver iodobromide emulsion (Agr 14.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.7-1 Coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) m Coating amount 1.55 Gelatin 1.00E x
S -8t, 5xio-'mol Ex Y -10,2
1 S o I v -17,0X10-” 17th layer: 1st
Protective layer gelatin 1.80UV-
10,13 U V -20,21 S o 1 v -11,0X10-” S o 1 v
-21.0
Diameter 1.5-) 2.0X10-”B-
2 (diameter 1.5m) 0.15B
-33,0X10-"W-12,0X10-"H-10,35 Cp d -71,00 In addition to the above, the sample thus prepared also contained 1.2benzisothiaprin-3-one (relative to gelatin). average of 20
0 ppm), n-butyl-p-hydroxybenzoate (approximately 1,000 ppm) and 2-phenoxyethanol (approximately 10,0 OOIIIP!1) were added.

Furthermore, B-4, B-5, W-2, W-3, F-1, F-
2, F-3, F-4, F-5, F-6, F7, F-8,
Contains F-9, F-10, F-11, F-12, F-13 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

v-i V-2 xC-1 xC-2 (n) Cth Ls xC xC-5 C+dbs xM-4 I JIs Ex M -6 xY-2 pd pd C6H13 H (p d-6 olv xS-2 xS 4: xS-5 ExS-6 ExS-7 ExS OOH shiυυshiH3 03Na n=2~4 CHI 瓢CH-So□-CHz C0NHCHzOO
NaNHC,H.

The produced sample was processed and exposed in the same manner as in Example 5, and the same treatment was performed. The treatment steps were also the same as in Example 5, and the compositions of the treatment liquids other than the bleaching solution were also the same as in Example 5. However, the bleaching treatment time was 40 seconds.

The composition of the bleaching solution used in Example 6 is shown below.

(Bleach solution) Mother liquor (g) Replenisher (9) Ferric nitrate chelate compound (listed in Table 2) Ammonium bromide Ammonium nitrate Organic acid (listed in Table 2 12) Add water and add H 0.20 mol 0.30 mo1 0.31 mole 0.47! 00g 50g 0g 0g 0.10 mole 10.30 mole 0.14 mole 10.42
Mol 1.01 1.01 4.2 4.6 For each photographic photonic material subjected to the above treatment, the gradation change (Δre) was determined from the same measurements as in Example 5. The results are shown in Table 6.

From the results shown in Table 6, it can be seen that the present invention exhibits superior effects in terms of gradation changes during color image storage after processing, compared to the comparative example.

Example 8 Example described in JP-A-2-44345, Sample 10
1 was processed and exposed in the same manner as in Example 5, and the same treatment was performed. Regarding the processing process, the bleaching time was 30 seconds, and the ratio (C/R) of the amount of developer brought into the bleaching process (C) to the amount of bleach solution refilled (R) was determined as shown in Table 7. The same processing steps as in Example 5 were used, except that the bleach solution replenishment was varied to change the Furthermore, the composition of the processing solution other than the bleaching solution was the same as in Example 5.

The composition of the bleaching solution used in Example 8 is shown below.

(Bleach solution) Mother solution Replenisher Ferric nitrate 0.20u O,3
0u chelate compound 0.31 mol 0
．． 47ft (listed in Table 7) Ammonium Bromide 100g 150
g Ammonium nitrate 20g 30g Glycolic acid 0.5 mol 0.75 mol Add water 1. OR,1,01p
H3,53,3 Example 5 for each photographic material subjected to the above treatment
The amount of residual silver was determined from the same measurements as above. The results are shown in Table 7.

From the results shown in Table 7, it was found that the present invention was superior in desilvering performance compared to the comparative example even when a treatment method was used to reduce the amount of bleaching solution replenished.

(Effects of the Invention) By using the composition having bleaching ability containing the metal chelate compound of the present invention, there is no bleaching blade blur, there is little staining after processing, and rapid processing with excellent desilvering properties can be performed. .

Further, by treating with a composition further containing an organic acid, rapid treatment with less defective color recovery, less gradation change after treatment and excellent desilvering properties can be achieved.

Procedural amendment September 11, 1991

Claims (5)

[Claims] (1) A compound represented by the following general formula (I) and Fe
(III), Mn(III), Co(III), Rh(II), R
A silver halide color photographic photosensitive material containing at least one metal chelate compound formed from a salt of a metal selected from h(III), Au(III), Au(II) and Ce(IV). Treatment compositions for materials. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. X_1 represents a group consisting of a carboxy group, a phosphono group, a sulfo group, or
Represents a hydroxy group. R_1, R_2, R_3 and R_4 each independently represent a hydrogen atom or an alkyl group. R_a, R_b and R_c each independently represent a hydrogen atom, an alkyl group, or an aryl group. l and m
represents 0 or 1. ) (2) A processing composition for a silver halide color photographic light-sensitive material, wherein at least one of l or m in general formula (I) according to claim (1) is 1. (3) In general formula (I) according to claim (1), l
and a processing composition for silver halide color photographic materials, wherein m is 1. (4) A composition for a silver halide color photographic light-sensitive material, wherein the processing composition according to claim (1) further contains an organic acid. (5) A silver halide color photographic light-sensitive material, which is characterized in that the imagewise exposed silver halide color photographic light-sensitive material is processed with the processing composition according to claim (1) or (2) after color development. Processing method.