JPH0422948A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To obtain the photographic processing compsn. which does not generate precipitate and sludge in spite of intrusion of metallic ions by incorporating at least one of specific compds. therein. CONSTITUTION:This compsn. contains at least one of the compds. expressed by formula I. In the formula, R, R1 and R2 respectively denote a hydrogen atom, alkyl group which may be substd. or aryl group; L1 denotes an alklene group or arylene group which may be substd. The preservable stability of the liquid is improved by adding the compds. expressed by the formula I in this case; in addition, the iron ions carried from a bleaching bath are concealed and the stability of the liquid is improved. The oxidation or decomposition of the processing liquid components by the effect of the metallic ions is suppressed and the performance of the processing liquid is maintained over a long period of time.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a processing composition for silver halide photographic materials, and more particularly to a composition containing a novel chelating agent for concealing metal ions harmful to photographic processing. The present invention relates to a photographic processing composition.

(Prior Art) In general, silver halide black and white photosensitive materials are processed through processing steps such as black and white development, fixing, and water washing after exposure to produce silver halide color photosensitive materials (hereinafter referred to as color photosensitive materials).

) is processed through processing steps such as color development, desilvering, washing with water, and stabilization after exposure. Silver halide color reversal light-sensitive materials are processed through processing steps such as black and white development after exposure, color development after reversal processing, desilvering, water washing, and stabilization.

In the color development step, exposed silver halide grains are reduced to silver by a color developing agent, and the generated 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 bleaching agent (bleaching), and is further exposed to light with unused silver halide by a fixing agent that forms soluble silver. removed from the layer (fixed). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. Details of these processing steps and their compositions can be found in The Theory of Photographic Processes (4th edition) by James.

“The Theory of Photography
icProcess"4'thedition
) (1977), Research Disclosure Nα
17643, pages 28-29, Nα18716, 651
It is described in the left column to the right column, pages 880 to 881 of Nα307105, etc.

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 carried out using automatic processors, ranging from large-scale photo labs equipped with large automatic processors to photo shops in recent years that have small automatic processors called minilabs installed in-store. Until now, photo processing has come to be performed in a variety of places, and as a result, there have been cases where processing performance has deteriorated.

One of the major causes is the mixing of metal ions into the processing solution. For example, metal ions such as calcium, magnesium, and iron contained in the water used when preparing the processing solution, and calcium and other metal ions eluted from the photosensitive material may be mixed into the processing solution, causing adverse effects.

For example, accumulation of calcium ions, magnesium ions, etc. reacts with processing liquid components, causing precipitation and sludge.
As a result, it adheres to the processed film and causes dirt, and also causes clogging of the filter in the developing machine. Furthermore, transition metal ions, typified by iron, often significantly reduce the storage stability of processing solutions, causing deterioration in photographic performance such as a decrease in image density and an increase in fog. In other cases, metal ions may remain in the processed film, resulting in poor image preservation.

Therefore, there has been a desire for a means to eliminate these harmful effects of metal ions.

Chelating agents that hide metal ions have been used to solve the above problems. For example, Tokuko Sho 48-
No. 30496, aminopolycarboxylic acids described in No. 44-30232 (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.), or JP-A-56
-97347, the organic phosphonic acids described in Japanese Patent Publication No. 56-39359 and West German Patent No. 2,227.639, or the organic phosphonic acids described in Japanese Patent Publication No. 52-102726 and Japanese Patent Publication No. 53-42730.
No. 54-121127, No. 55-126241, No. 55-65956, etc., and others, JP-A-58-195845, No. 58-2
Examples include compounds described in Japanese Patent Publication No. 03440 and Japanese Patent Publication No. 53-40900.

(Problems to be Solved by the Invention) Although some of these compounds have been put into practical use, their performance has not been fully satisfactory. For example, ethylenecyaminetetraacetic acid has a high hiding power for calcium ions, but when added to a developer, it accelerates the decomposition of the developer and developer preservative in the presence of iron ions, resulting in a decrease in image density and an increase in fog. This results in deterioration of the photographic quality.

For example, alkylidene diphosphonic acid does not cause such adverse effects even in the presence of iron ions, but
Processing solutions prepared with hard water that contains a lot of calcium have caused problems such as the formation of solids that can cause developing machine failures.

Particularly in recent years, in response to increasing social demands for environmental protection, the amount of replenishment of photographic processing solutions has been decreasing.As a result, the residence time of processing solutions in processing machines has become longer and Moreover, the deterioration of storage stability becomes a major problem. Therefore, it has been desired to develop an excellent new chelating agent that can effectively hide the metal ions accumulated in the processing solution without causing any harmful effects.

Therefore, a first object of the present invention is to provide a photographic processing composition that does not generate precipitation or sludge even when mixed with metal ions. The second object is to provide a stable processing composition that does not cause a decrease in the effective ingredients in the processing solution or produce components that cause adverse photographic effects even when mixed with metal ions. The third object is to provide a processing composition and a processing method using the same, which improves the deterioration in image storage stability caused by metal ions in the processing composition remaining on the processed photosensitive material. .

(Means for Achieving the Object) The above object has been achieved with a treatment composition containing at least one compound represented by the following general formula (I) and a treatment method using the same.

General formula (I) OH (wherein RSR and R2 each represent a hydrogen atom, an optionally substituted alkyl group, or an aryl group).

Ll represents an optionally substituted alkylene group or arylene group.

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

In general formula (I), R, R, and R3 each independently represent a hydrogen atom, an optionally substituted alkyl group, or an aryl group. R,R,,R.

The alkyl group represented by may be linear, branched or cyclic, and preferably has 1 to 10 carbon atoms.

More preferred alkyl groups are methyl and ethyl groups. The aryl group represented by R, R, and R2 preferably has 6 to 10 carbon atoms, and more preferably a phenyl group.

Substituents for the alkyl group and aryl group of R, R, and R2 include, for example, an alkyl group, an aralkyl group, an alkenyl group,
Alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamine group, ureido group, urethane group, aryloxy group, sulfamoyl group,
Carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, phosphono group, aryloquine carbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide basis,
Examples thereof include a sulfonamide group, a nitro group, and CN R1 (R1 represents a hydrogen atom, an optionally substituted alkyl group or an aryl group).

Furthermore, R,, R, and R may be connected to form a ring if possible.

Among the compounds represented by the general formula (I), compounds represented by the following general formula (n) or (I[[) are preferred, and compounds represented by the general formula (III) are more preferred.

General formula (III) In the formula, R,, R, and L have the same meanings as in general formula (1), and RIll and R'' are R in general formula (I).
is synonymous with R2, Ll, L, , L, and ri each independently represent an optionally substituted alkylene group or arylene group, preferably a methylene group or an ethylene group. M represents a hydrogen atom or a cation (alkali metal, ammonium, etc.).

W represents a divalent linking group. The divalent linking group is preferably an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, a cyclohexane group, +W'-
0+. w2-1+W'-3+KW2~(W', W'' represents an alkylene group or an arylene group, m is 1-3
represents. ), W'-N-W"-(A is hydrogen, hydrocarbon, LA-COOM-LA-PO, M"M'-LA
-OH1-LA-3O,M'' (LA has 1 to 8 carbon atoms
represents an alkylene group or an arylene group having 6 to 10 carbon atoms, and M1 to M4 represent a hydrogen atom or a cation (alkali metal, ammonium, etc.). )), and combinations thereof may also be used.

These divalent linking groups may have a substituent, and examples of the substituent include those listed as substituents for the alkyl group and aryl group of R, R2.

Specific examples of W include the following.

(-CH,-)2 ,+CH1÷,,+CH,-)-,
, C.H.

CHCH2--CH, CHCH2- OH CH2CH20CHz CH! - -CH,CH20CH,CH20- -CH,CH,5CH2CH2- -CH2CH2SCH,CH25CH,CH2-CH2
CH2N CHr CH2- CH,C00H CH,CH,NCH,CH,NCH,CH-CH,C0
OH OH 03Na Specific examples of the compound represented by the general formula (I) are listed below, but the present invention is not limited thereto.

1°, CH,C0OH OH 6°7°8°OO 9°HO 0°HO ,,CH2C0OH OH OH OH 0H H l 1°H 15°19°20°I OO 25°27°0H O The compound of the present invention is , “Chelate Chemistry” edited by Ueno Barate (5)
), 1975, published by Nankodo, p. 318, or Inorganic Chemistry Vol. 27, p. 474, 1988
(Inorganic Chemistry.

Vol. 27.474 (1988)).

A synthesis example is shown below.

Synthesis example 1. Synthesis of Compound 7 Compound 7 was synthesized with reference to the description in "Chelate Chemistry" (5) edited by Ueno Sote, 1975, published by Nankodo, p. 318.

Hydroxylamine hydrochloride 5.6g (80, Ommol
) was suspended in methanol 30-, and potassium hydroxide 4.
5 g of methanol solution 30- was added.

The precipitated potassium chloride was separated by filtration, and the filtrate was mixed with ethylenediaminetetraacetic acid diethyl ester (synthesis method: Chelate Chemistry (5) edited by Ueno Sote, 1975, published by Nankodo, 31)
(See page 8) 6. A methanol solution of 7 g (20° Ommol) and 4.5 g of potassium hydroxide was added. After reacting at room temperature for 3 days, 20% hydrochloric acid was added,
The resulting paste was taken out, dissolved in a small amount of water, and the pH was adjusted to 9 with potassium carbonate. 3. Add methanol, collect the precipitated solid by filtration, and recrystallize it from water/methanol to obtain the monohydrate salt of target compound 7. 8g (10
, 8 mmol) was obtained. Yield 54% Synthesis Example 2. Synthesis of Compound 8 Acid anhydride of ethylenediaminetetraacetic acid under water cooling (see Buddhist Patent No. 1.548,885 for the synthesis method) 5. 1
2 g (20, Ommol) was suspended in 20 d of water,
Triethylamine 5.6-(40, Ommol) was added. Methylhydroxylamine hydrochloride 3 under nitrogen atmosphere
．． 67 g (44, Ommol) of water 1OWd! The solution was added slowly so as to maintain the internal temperature at 5-10°C. 4
After reacting for a period of time, the precipitated crystals were collected by filtration and recrystallized with water to obtain dihydrate salt 1 of target compound 8. 88 g (
4.87 mmol) was obtained. Yield 24% Melting point 138~
140°C (decomposition) Synthesis Example 3. Synthesis of Compound 9 Inorganic Chemistry Vol. 27, p. 474,
1988 (Inorganic Chemistry
, Vol.

27.474 (1988)).

N-isopropylhydroxylamine 29g (39Om
mol) and acid anhydride of ethylenediaminetetraacetic acid 10
g (39 mmol) in dimethyl sulfoxide 250
- and allowed to react at room temperature for 4 days. After distilling off the solvent under reduced pressure, tetrahydrofuran was added, and the precipitated solid was collected by filtration and recrystallized from methanol/diethyl ether to obtain the target product 57 in 9. 2 g (27 mmo
l) Obtained. Yield 69% Melting point 195-197°C (decomposition) Other compounds are synthesized in the same manner.

The amount of the compound represented by formula (I) to be added varies depending on the treatment composition to be added, but is usually used in the range of 10 to 50 g per 11 of the treatment composition.

More specifically, for example, when added to a black and white developer or a color developer, a more preferable amount is 0.0000000000000000000000000000000000000000000000000000000000000000. When added to a bleaching solution (for example, consisting of hydrogen peroxide, persulfuric acid, bromic acid, etc.), it is 0.1 to 20g per 11, and added to a fixing solution or a bleach-fixing solution. 1-40g per 11
, and when added to a stable column, it is 50 ■ per 11
~Ig.

The compounds represented by general formula (I) may be used alone or in combination of two or more.

The compound represented by the general formula (1) can be applied to any processing composition for processing silver halide photosensitive materials. For example, general black and white developer, infectious developer for lithium film, color developer, bleach, fixer, bleach-fixer, adjustment solution, stop solution, hardening solution, washing water, stabilizing solution, rinsing solution, cover. Examples include, but are not limited to, a washing liquid, a toning liquid, and the like.

By adding the compound of the present invention to a color developer and a black and white developer, precipitation can be prevented and the stability of the solution can be improved.

The color developing solution 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-diethylamine toluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene 4-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N= (β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N-ethylN-[β-(methanesulfone) (amido)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-methquin-4-[N-ethyl-N (β -Hydroxyethyl)aminocoaniline Among the above p-phenylenediamine derivatives, D-5, D-
6, D-12 is preferably used.

Further, these p-phenylenediamine derivatives are preferably used as salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of aromatic primary amine color developing agent used is preferably o per color developer II.
．． oos~0.1, more preferably about 0.01-0.0
The concentration is 6 molar.

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

In addition, the aromatic primary amine color developing agent may be used directly (
Preferably, as a compound that preserves the stability, various hydroxylamines, such as the compounds described in JP-A No. 63-5341 and JP-A No. 63-106655, are preferred, and among them, compounds having a sulfo group or a carboxy group are preferred.

Hydroxamic acids as described in JP-A No. 63-43138, hydrazines and hydrazides as described in JP-A No. 61-146041, phenols as described in JP-A No. 63-44657 and JP-A No. 63-58443, and α- as described in JP-A No. 63-44656.
It is preferable to add hydroxyketones, α-aminoketones, and/or various saccharides described in 6:3-3 6244.

In addition, when used in combination with the above compounds, JP-A-6-3-4-23
No. 5, No. 63-24254, No. 6 3-2 1 64
No. 7, No. 63-146040, No. 6 3-2 784
Monoamines described in No. 1 and No. 6 3-2 5 6 5 4, etc., No. 63-30845, No. 63-146
Diamines described in No. 40, No. 63-43139, etc.
Polyamines described in No. 63-21647, No. 63-26655 and No. 63-44655, No. 63-53
Nitroxy radicals described in No. 551, No. 63-431
It is preferable to use the alcohols described in No. 40 and No. 63-535-49, the oximes described in No. 6356654, and the tertiary amines described in No. 63239447.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in IJ-180588, JP-A-54
-Alkanolamines described in No. 3582, JP-A-56
The polyethyleneimine described in US Pat. No. 3,746,544, the aromatic polyhydroxy compound described in US Pat. No. 3,746,544, etc. may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The amount of these preservatives added is 1f! of the developer! 0.00 per hit
The amount is 5 to 0.2 mol/l, preferably 0.01 mol to 0.05 mol/l.

The color developing solution used in the present invention can be used in a pH range of 9 to 12, preferably 9.5 to 11.5.
It is. The color developing solution can also contain other known developer component compounds.

In order to maintain the above p)1, it is preferable to use various buffering agents.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Hydroquine sodium benzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-sulfo-2-
Examples include sodium hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of buffer added to the color developer is 0. It is preferably 1 mol/1 or more, particularly 0°1 to 0.4 mol/l
It is particularly preferable that

In the present invention, various bovine rate agents can be used in combination within the range that does not impair the effects of the compound of the present invention.

The chelating agent is preferably an organic acid compound, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

N', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, ■, 2-diaminopropanetetraacetic acid, droxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1 ,2,4-
Tricarboxylic acid, 1-hydroquinethylidene-1,1-
Diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

These chelating agents are e.g. 0.0001 mol to 0.0
Can be used together at 5 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. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019, U.S. Patent No. 3,818,
Thioether compounds described in No. 247, etc., JP-A-52
-49829 and p described in No. 50-15554
-Phenylenediamine compound, JP-A-50-4377
No. 26, Special Publication No. 44-30074, Japanese Patent Publication No. 56-15
6826, quaternary ammonium salts described in US Pat. No. 52-43429, etc., and US Pat. 494. No. 903,
No. 3,128,182, No. 4,230.796, No. 3,253,919, Special Publication No. 11431-1973
No. 2,482°546, U.S. Patent No. 2,596
, 37-16088, 42-25, etc.
No. 201, U.S. Patent No. 3,128,183, Special Publication No. 4
1-11431, 42-23 El 83, and US Pat. No. 3,532,501, and imidazoles such as 2-methylimidazole and imidazole.

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

D-1 D-2 D D-4 D D The amount of these auxiliary developers added is 0.0 per color developer In.
005 mol to 0.03 mol, preferably 0.001 to 0
．． 01 mole.

Furthermore, any antifoggant can be added to the color developing solution, if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole,
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-hensitriazole,
Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyasaintridine, and adenine.

Further, the color developing solution may contain a fluorescent whitening agent.

As a fluorescent brightener, 4,4'-diamino-2,2'
-Disulfostilbene compounds are preferred. The amount added is 0
~5g/A' preferably 0. 1g to 4g7p.

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 50°C.
, preferably 33 to 55°C.

Processing time is 20 seconds to 5 seconds for color photosensitive materials.
1 minute, preferably 30 seconds to 3 minutes 20 seconds, more preferably 1 minute to 2 minutes 30 seconds, and in the case of color print materials, 10 seconds to 1 minute 20 seconds, preferably 20 seconds to 60 seconds. .

The black-and-white first developer used in color reversal processing in which the compound of the present invention can be used and the black-and-white developer for black-and-white silver halide photosensitive materials contain various well-known additives that are usually added. be able to.

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

Bleaching solutions in which the compounds of the invention can be used contain at least an oxidizing agent for oxidizing silver and a rehalogenating agent (or an organic ligand in its place). As the bleaching agent, known polyaminocarboxylic acid iron (III) complex salts, hydrogen peroxide, persulfates, bromates, etc. are used, and these may be used in combination. The amount of bleach used is 0.05 mol to 2 mol, preferably 0.05 mol to 2 mol per lβ of bleaching solution. It is 1 to 5 moles.

As the rehalogenating agent, halogenated compounds such as chloride, bromide, and iodide are commonly used, or instead of these, organic ligands that form poorly soluble silver salts may be used. Their amount is 0.1-2 mol/l, preferably 0.1-2 mol/l.
It is 3 to 1.5 mol/1.

The above-mentioned halides are added as alkali metal salts, ammonium salts, guanidine salts, amine salts, and the like. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, and ammonium bromide is preferred.

Adding a compound represented by the general formula (I) to a bleaching solution improves the shelf life of the bleaching solution, and this is particularly noticeable when hydrogen peroxide, persulfate, or bromate is used as the bleaching agent. .

The bleach-fix solution to which the compound of the present invention can be added contains, in addition to the bleaching agent, a fixing agent as described below, and, if necessary, the rehalogenating agent. The amount of bleach in the bleach-fix solution is the same as in the bleach solution. The amount of the rehalokenizing agent is 0 to 2.0 mol/l, preferably 0.01 to 1.0 mol/l.

By adding the compound of the present invention to a bleach-fix solution, the storage stability of the solution is improved.

The bleach or bleach-fix solution according to the invention may also include bleach accelerators, corrosion inhibitors to prevent corrosion of the processing bath, and pH of the solution.
) Buffers, optical brighteners, antifoaming agents, etc. to maintain I are added as necessary.

Bleach accelerators include, for example, U.S. Pat. No. 3,893.8.
No. 58, German Patent No. 1,290,812, U.S. Patent No. 1,138,842, JP-A-53-95630,
Research Disclosure No. 17129 (197
Compounds having a mercapto group or disulfide group as described in 8), thiazolidine derivatives as described in JP-A-50-140129, 1,000-urea derivatives as described in U.S. Pat. No. 3,706,561, JP-A-49-Sho. 40943, German Patent No. 2°748.4
Polyethylene oxides described in No. 30, Japanese Patent Publication No. 1973-
Polyamine compounds described in No. 8836 can be used. Among these, mercapto compounds described in US Pat. No. 1,138,842 are preferred.

As the corrosion inhibitor, it is preferable to use nitrates, such as ammonium nitrate and potassium nitrate. The amount added is 0.05 mol/l to 0.5 mol/l, preferably 0°O1 to 2.0 mol/1, 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 to 8, preferably 3 to 7.5. When bleaching or bleach-fixing is performed immediately after color development, the pH of the solution should be set to 6 or less, preferably 5 to suppress bleaching edge blur in photographic materials.
．． It is best to use it at 5 or less. For color printing materials,
To prevent leucoization of the cyan dye, a pH in the range of 3 to 7 is preferred.As a pH buffer for this purpose, any pH buffer that is not susceptible to oxidation by bleaching agents and has a buffering effect within the above pH range may be used. But you can use it. For example, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid,
and organic bases such as pyridine, dimethylpyrazole, 2-methyl-0-oxacillin, and aminoacetonitrile. The amount of these buffers used is 0
-3 mol/l, preferably 0.5-2 mol/l.

Moreover, a plurality of these buffering agents may be used in combination.

The bleaching or bleach-fixing step can be carried out at a temperature range of 30 to 50 degrees, preferably 35 to 45 degrees. The bleaching process time is used in the range of 10 seconds to 5 minutes for photosensitive materials, preferably 10 seconds to 60 seconds, and 5 seconds to 70 seconds, preferably 5 seconds for print sensitive materials. ~60 seconds. Under these preferred processing conditions, good results were obtained that were rapid and without increased staining.

A known fixing agent may be used as the fixing solution or bleach-fixing solution. These are thiosulfates, thousocyanates, thioethers, amines mercaptos, thioons, thioureas,
Iodide salts, etc., such as ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-cythia-1,8-octanediol, imidazole, etc. . Among these, thiosulfates, particularly ammonium thiosulfates, are preferred for rapid fixing. Furthermore, even more 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, 1,000 urea, thioether, etc. In this case, the second fixing agent is in a range of 0.01 to 100 mol% based on ammonium thiosulfate. It is preferable to add it at

The amount of fixer is fixer or bleach-fixer 11! Hit 0.
The amount is 1 mol to 3 mol, preferably 0.5 to 2 mol.

The pH of the fixer depends on the type of fixer, but is generally between 3 and 3.
9, especially when using thiosulfate, 6.5~
8 is preferable in terms of obtaining stable fixing performance.

A preservative may be added to the fixing solution and/or the bleach-fixing solution to increase the stability of the solution 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. It is also preferable to use the sulfinic acid compound described in JP-A-60-283881.

It is also preferable to add a buffer to the fixing solution and/or the bleach-fixing solution in order to keep the pH of the solution constant. For example, phosphate, or imidazole, 1-methyl-
Examples include imidazoles such as imidazole, 2-methylimidazole, and ■-ethylimidazole, triethanolamine, N-allylmorpholine, and N-benzoylpiperazine. In the fixer according to the present invention,
Addition of the compound represented by the general formula (I) not only improves the storage stability of the solution, but also hides iron ions brought in from the bleaching solution, thereby improving the stability of the solution.

A similar effect can also be obtained by adding the compound of the present invention to the washing water or stabilizing solution.

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 Are there anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino acid type amphoteric surfactants, hetain 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 antibacterial agents and antifungal agents can be contained in the washing water to prevent water stains and mold from forming on the processed photosensitive material.

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, or talolophenol compounds such as trichlorophenol, or bromophenol compounds, or organotin or organozinc compounds, or thioanic acid or isothiocyanic acid compounds, or,
Acid amide compounds, diacin and triazine compounds, thiourea compounds, benzotriazole alkylguanidine compounds, quaternary ammonium salts such as benzalkonium chloride, or penicillin. Antibiotics, etc., Journal Antibacterial and Antifungal Agents (J, Antibact
, Anti-fung, Agents) Volt,
One or more general-purpose anti-spill agents described in Nα5, p, 207-223 (1983) may be used in combination.

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

Furthermore, it is preferable to use various bovine rate agents in combination within a range that does not impair the effects of the compound of the present invention.

Preferred compounds for the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenecyamine-N, N, N',
Examples include organic phosphonic acids such as N'-tetramethylenephosphonic acid, and hydrolysates of maleic anhydride polymers described in European Patent No. 345172 Al.

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.

Stabilizing solutions include, for example, organic acids, solutions with a buffering capacity of pH 3 to 6, and solutions containing aldehydes (e.g., formalin and glutaraldehyde), which can be added to the washing water. In addition, ammonium compounds such as ammonium chloride and ammonium sulfite, B15A1 can be contained as necessary.
Metal compounds such as, optical brighteners, patent application No. 63-3082
65, 63-318266, U.S. Pat. No. 4,859,574
Various dye stabilizers including N-methylol compounds described in , and stabilization methods using the same, hardeners, U.S. Patent No. 4
Alkanolamines described in No. 786583 and the like 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
It is preferable to use water that has been deionized to have a Mg concentration of 5/1 or less, water that has been sterilized using halogen, ultraviolet germicidal lamps, or the like.

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 each treatment liquid of the present invention, it is preferable that stirring of the treatment liquid be as strong as possible. Methods for strengthening the agitation include the method described in JP-A-62-183460 in which a jet of processing liquid collides with the emulsion surface of the photosensitive material, and the method described in JP-A-62-183460.
- A method of increasing the stirring effect using a rotating means described in No. 18346, and furthermore, moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade or squeeze roller provided in the liquid to create turbulence on the emulsion surface. Examples include a method of improving the stirring effect by increasing the circulation flow rate of the entire treatment liquid.

It is preferable that the processing method of the present invention is 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. Further, in order to carry out rapid processing using the processing composition of the present invention, it is preferable to shorten the crossover between processing tanks in an automatic processor. 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 automatic development according to the processing method of the present invention, the consumption of processing solution components accompanying the processing of the photosensitive material is compensated for, and undesirable components eluted from the photosensitive material are added to the processing solution. In order to suppress accumulation, it is preferable to add a replenisher depending on the amount of processed photosensitive material. Further, two or more processing baths may be provided for each processing step, in which case it is preferable to use a countercurrent method in which the replenisher is poured from the rear bath to the front bath. In particular, a cascade of 2 to 4 stages is preferred in the water washing step and stabilization step.

The amount of replenisher is preferably reduced as long as changes in the composition of each processing solution do not affect photographic performance or cause other problems such as staining of the solution.

In the case of color photographic materials, the amount of color developer replenisher is 100 to 1500 J, preferably 1
00- to 1000-, and in the case of color print materials, 20- to 220-1, preferably 30- to 160-
It is.

In the case of color photographic materials, the amount of bleach replenisher is
10-500-1 preferably 10TLl-1 per d
It is 60-. For printing materials, 20-300
-1 is preferably from 50 to 150.

In the case of photographic materials, the amount of bleach-fix supplementary solution is 100 mA to 1000 mA per xi of light-sensitive material, preferably 200 mA to 100 mA per xi of light-sensitive material.
1300- and for printing materials, 2 Chd.
'-300d, preferably 50rn! -200-. The bleach-fix solution may be replenished as a single solution, the bleach composition and the fix composition may be replenished separately, or the oat flow solution from the bleach bath and/or fix bath may be mixed together. By doing so, it can also be used as a bleach-fixing replenisher.

In the case of photographic materials, the amount of fixing replenisher is 300 to 3000 d, preferably 300 to 100 d per 1 d of light-sensitive material.
0-, and for printing materials, 20m1 to 300
J, preferably 50d to 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 the purpose of preserving the circular tomb, it is also preferable to use a combination of various regeneration methods.

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 bleaching agent in the bleaching solution and/or bleach-fixing solution becomes reduced during the bleaching process. If this reduced metal chelate accumulates, not only will the bleaching performance deteriorate (in some cases, the image dye will turn into a leuco dye, causing a decrease in image density.
Preferably, the bleach and/or bleach-fix solution is continuously regenerated in conjunction with processing. Specifically, it is preferable to blow air into the bleach solution and/or the bleach-fix solution using an air pump to reoxidize the reduced metal chelate with oxygen. In addition, it can also be regenerated by adding an oxidizing agent such as hydrogen peroxide, persulfate, or bromate.

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.

Photographic materials that can be processed with the processing composition of the present invention include ordinary black-and-white silver halide photographic materials (for example, black-and-white photographic materials, black-and-white photographic materials for X-ray, black-and-white photographic materials for printing), Ordinary multilayer silver halide color photographic materials (
For example, color negative film, color reversal film, color positive film, color negative film for movies, color photographic paper, color reversal photographic paper,
Direct positive color photographic paper), infrared light sensitive materials for laser scanners, and diffusion transfer photosensitive materials (for example, silver diffusion transfer photosensitive materials, color diffusion transfer photosensitive materials), and the like.

The photographic light-sensitive material according to the present invention has various layer configurations on one or both sides depending on the purpose of the light-sensitive material (for example, a silver halide emulsion layer sensitive to each of red, green, and blue, an undercoat layer, an antihalation layer, (filter layer, intermediate layer, surface protective layer) or arrangement.

Support for the photographic light-sensitive material according to the present invention; Coating method; Types of silver halide used in the silver halide emulsion layer, surface protective layer, etc. (for example, silver iodobromide, silver iodochlorobromide, silver bromide,
silver chlorobromide, silver chloride), its grain shape (e.g. cubic, tabular, spherical), its grain size, its fluctuation rate, its crystal structure (e.g. core/shell structure, multiphase structure, homogeneous phase structure), Its manufacturing method (e.g., single-shot method, double-jet method), binder (e.g., gelatin), hardener, antifoggant, metal doping agent, 710 silver gemide solvent, thickener, emulsion precipitating agent, dimensions Stabilizers, anti-adhesion agents, stabilizers, anti-stain agents, dye image stabilizers, anti-stain agents,
Chemical sensitizers, spectral sensitizers, sensitivity-enhancing agents, supersensitizers, nucleating agents, couplers (e.g., pivaloylacetanilide-type and benzoylacetanilide-type yellow couplers, 5
- Pyrazolone type and pyrazoloazole type magenta couplers, phenol type and naphthol type cyan couplers, DIR
couplers, bleach accelerator-releasing couplers (competitive couplers, colored couplers), coupler dispersion methods (e.g. oil-in-water dispersion using high-boiling solvents), plasticizers, antistatic agents,
Lubricants, coating aids, surfactants, brighteners, formalin scavengers, light scattering agents, matting agents, light absorbers, ultraviolet absorbers, filter dyes, irradiation dyes, development improvers, matting agents, There are no particular restrictions on preservatives (e.g. 2-phenoxyethanol), anti-pepper agents, etc.
92, pp. 107-110 (1971
) and Research Disclosure Magazine (Re)
search disclosure (hereinafter referred to as RD magazine) Nα17643 (December 1978), RD magazine Nα18716 (November 1979), RD magazine Nα3
07105 (November 1989) can be referred to.

The photographic material according to the present invention may contain a developing agent. As a developing agent that can be contained in a sensitive material,
rDevelop on page 29 of the above RD magazine Nα17643
Examples include those described in the section ing agentsJ. Hydroquinone and pyrazolidones are particularly preferably used.

The photographic light-sensitive material according to the present invention may use a coupler that develops yellow, cyan, or magenta as described above, and includes ■C-G of the above-mentioned RD magazine Nα17643 and ■-C to G of the above-mentioned RD magazine Nα3071.05. Various couplers described in the patent described in JP-A No. 62-215272
There are some that are described in detail in the issue.

Example 1 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 provided, and various photographic constituent layers were further applied to form 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 ([!xY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (C
pd-7> To 0.7 g, 27.2 cc of ethyl acetate and 4.1 g each of solvents (Solv-3) and (Solv-7) were added and dissolved, and this solution was diluted with 10% sodium dodecylbenzenesulfonate containing 8 cc of 10% sodium dodecylbenzenesulfonate. Emulsified dispersion A was prepared by emulsifying and dispersing it in 185 cc of an aqueous gelatin solution. On the other hand, silver chlorobromide emulsion A (cubic, 3=7 mixture (silver molar ratio) of large size emulsion A with an average grain size of 0.81 bm and small size emulsion A with an average grain size of 0.70*. Coefficient of variation of grain size distribution were 0.08 and 0.10, respectively, and each size emulsion contained 0.3 mol% silver bromide locally on a part of the grain surface).This emulsion contained the blue-sensitive sensitizing dye shown below. AB! ! For large size emulsion A per mole,
2.0xlO-' mol each, and 2.5 x 10'' mol each for small size emulsion A. Also, chemical ripening of this emulsion was performed on the sulfur sensitized side and the gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-35-dichloro-s-1 riazine sodium salt was used.

Further, Cpd-10 and Cpd-11 were added to each layer in a total amount of 25.0 mg/rd and 50.0 mg/rd, 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 (CHz)) (CL)s so, O5OJ-N(C,Hs)z Sensitizing dye B for blue-sensitive emulsion layer (cuzL (cnzL S(hO5O3H-N(CJs)3 (2.OX 10-' mol each for large size emulsion A and 2.5X 10-' mol each for small size emulsion A per mole of silver halide) Sensitizing dye for green-sensitive emulsion layer C (per mole of silver halide, 4.0XlO-' mole for large size emulsion B, 5XlO-' mole for small size emulsion B)
．． 6 X 10-' mol) and the sensitizing dye DSOse 5O3H-N(CJs)s for the green-sensitive emulsion layer (per mol of silver halide, for large size emulsion B 7.
0x10-' moles, and 1.0 for small size emulsion B
X10-'mol) Sensitizing dye for red-sensitive emulsion layer E CtHs Ie C5L (halogenated v
& 0.9X1 per mole for large size emulsion C
0-' mole, and for small size emulsion C 1. lX1
For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-' moles per mole of silver halogenide.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide, respectively.
．． 5XIO-' moles, 7.7 X 10-' moles, 2.
5 x 10-' 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 mole of silver halide to lXl0-'
2×10” moles were added.

In addition, in order to prevent irradiation, the following dyes (the coating amount is shown in parentheses) were added to the emulsion layer, and (10wg/-〇(40+gg/m)) (Layer composition) The composition of each layer is shown below. , the number is the coating amount (g/rrf)
The silver halide emulsion represents the silver conversion X coating weight.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti(h) 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 (Solv-3) 0.1
8 Solvent (Solv-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) 0.082
Container (Solv-1)
0.16 Solvent (Solv-4>
0.08 Fifth layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion B with an average grain size of 0.55 m and small size emulsion B with an average grain size of 0.39 m+)
=3 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.10 and 0.08, respectively, and each size emulsion is Ag.
0.12 gelatin (Br O, 8 mol% 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 (Cp
d-9) 0.02 solvent (Sol
v-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (U Sea 1) 0.47 Color mixture prevention agent (Cpd-5) 0.05
Container (Solv-5)
0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.58n and small size emulsion C with an average grain size of 0.45m):
4 mixture (Ag molar ratio). The coefficient of variation of the grain size distribution is 0.09 and 0o11, 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 (C
pd-8) 0.05 solvent (So
lv-6) 0.14 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.02
Solvent (Sol Sea 5) 0.
08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl ano-Col (degree of modification 17%) 0.17 Liquid paraffin 0.03 (1:1 mixture with EXYII yellow coupler tHs (molar ratio ) (ExM) Magenta coupler (ExC) 1=1 mixture (molar ratio) of cyan coupler I and H I (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color Image stabilizer (CPd-4) Color image stabilizer 0Ja (Cpd-5) Color mixture inhibitor H H (Cpd-6) 2:4:4 mixture (weight ratio) of color image stabilizer (Cpd-7) Color image Stabilizer - (CL-CJ!8- (Cpd-8) 1:1 mixture (weight ratio) with color image stabilizer (Cpd-'9) Color image stabilizer (Cpd-10> Preservative (Cpd-11) ) Preservative (IIV-1) Ultraviolet radiation series CsH++ (t) 4 = 2:4 mixture (weight ratio) (Solv-1) Solvent (Solv-2) 11 mixture with melting medium (volume ratio) ( SQIV-3) Solvent (Sol Sea 4) Solvent (Solv-5) Solvent C00C-H+t (CL)s COOCsH+v (Solv-6) Solvent C,H, C) IcH (CL) 80 with 20 mixture (volume ratio) (Solv-7) Solvent aH ycHcH (CHz) tcOOc*H+t\1 Next, the following treatment liquid was prepared.

It is.

Color developer Water Potassium bromide Potassium chloride Triethanolamine Potassium carbonate Fluorescent brightener (W) IITEX・4B (manufactured by Sumitomo Chemical) Preservative (A) N-ethyl-N-(β-methanesulfonamidoethyl) -3 -Methyl-4-amine composition is as follows: 0.015g 3.1g 10.0g 7g ■, Og 5mmol Add water to 1000dpH (25
°C) 10.05 The above developer was designated as Sample 101, and the compounds to which the compounds of the present invention and comparative compounds were added in the amounts shown in Table 1 were designated as Samples 102 to 112.

Preservative (A) Bleach-fix solution Ammonium thiosulfate (70%) Sodium sulfite Iron(II) Ammonium ethylenediaminetetraacetic acid 4001n! 10〇- 7g 5g Thorium g Add water 10001n! pH(
25℃) 6.0 Ion exchange water (calcium, magnesium 3pp each)
m or less) 5 ppm of ferric ions in each of the above color developers
and 150 ppm of calcium ions are added and the aperture ratio is 0.10.
cm-' in a beaker at 38°C for 20
I let the day pass.

Using a sensitometer (Model FWH, manufactured by Fuji Photo Film Co., Ltd.), the above-mentioned color photosensitive material was subjected to gradation exposure using a three-color separation filter for sensitometry.

Exposure is 0. The exposure time was 1 second and the exposure amount was 250 CMS.

After exposure, processing was performed according to the following steps using the freshly prepared color developer (fresh solution) and the aged color developer (aged solution) prepared above.

Processing plate process 1 Toyo plate color development 38°0 45 seconds bleach fixing 3
Rinse at 56C for 45 seconds■ Rinse at 35℃ for 20 seconds■ Rinse at 35℃ for 20 seconds■ Dry at 35°C for 20 seconds
80°0 60 seconds Aged color for yellow minimum density (Dmin) and magenta sensitivity (logarithm value of exposure that gives density 0.5 + ogE) when processed with fresh color developer (fresh solution) Increase in yellow minimum density Dmin when processed with developer (aging solution) (
ΔDmin) and the amount of change in magenta sensitivity (ΔS) were calculated.

In addition, the remaining amount of the crude drug in the aged solution was determined by high performance liquid chromatography. In addition, the presence or absence of precipitation in the developing solution was observed after the passage of time. The results are summarized in Table 1.

As is clear from Table 1, according to the configuration of the present invention, △D
It can be seen that the values of min and ΔS are small, and fluctuations in photographic properties are suppressed.

Furthermore, it can be seen that the amount of the crude drug remaining is such that sufficient performance can be obtained by using the compound of the present invention.

Furthermore, it can be seen that the occurrence of precipitates was greatly improved compared to the comparative example.

Particularly, among conventional compounds, those which have a large effect of preventing precipitation formation have poor preservation of herbal medicines, while those whose main drug decomposes only a little have insufficient prevention of precipitation formation.

In contrast, it can be seen that the compounds of the present invention do not produce precipitates and provide stable developing solutions.

Example 2 On a subbed cellulose triacetate film support,
A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rrr of silver for silver halide, colloidal silver and coupler, and the number of moles per mole of silver halide in the same layer for sensitizing dye. It was shown in

1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-10,l UV-20,2 Cpd-10,05 Solv-10,01 Solv-20,01 Solv-30,08 2nd layer: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1. 0Cpd-2
0,2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgIlO, 0 mol%, internal high AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, 14
(hedron grains) Silver coating amount 0.26 Silver iodobromide emulsion (Ag 14.0 mol%, internal high AgI type,
Equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle) Silver coating amount 0.2 Gelatin 1.0ExS-14
,5X10-'molExS-21,5X10-'molExS-30,4XIO-''molExS-40,3xlO-'molExC-10,15 ExC-70,15 ExC-20,009 ExC-30,023 ExC -60,14 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag 116 mol%, internal cylinder AgI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter /thickness ratio 4.0) Silver coating amount 0.55 Gelatin 0.7ExS-13
X10"'ExS-21XIO-'ExS-30,3X10-'ExS-40,3XlO-' ExC-30,05 ExC-40,10 ExC-60,08 5th layer: 3rd red-sensitive emulsion layer iodobromide Silver emulsion (Agl 10.0 mol%, internal high Agl type, equivalent sphere diameter 1.2 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like grains, diameter/thickness ratio 6°0) Silver coating amount 0.9 Gelatin 0 .6E
xS-12xlO-' ExS-20,6X10 ExS-30,2xlO-' ExC-40,07 ExC-50,06 Solv-10,12 Solv-20,12 6th layer: Intermediate layer gelatin 1,0Cpd-40
, 1 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (Ag 110.0 mol %, internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 14
(Hedron grains) Silver coating amount 0.2 Silver iodobromide emulsion (Ag 114.0 mol%, internal cylinder AgI type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, 14
Face piece particles) Silver coating amount 0.1 Ceratin 1. 2ExS-5
5X10 ExS-62X10 ExS-71XIO ExM-10,20 ExM-60,25 ExM-20,10 ExM-50,0'3 Solv-10,40 Solv-40,03 8th layer: 2nd green-sensitive emulsion layer Silver bromide emulsion (AgrlO mol%, internally high iodine type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3.0) Silver coating amount 0.4 Ceratin 0 .35ExS-5
3,5X10 ExS-61,4xlO"ExS-70,7X10-' ExM-10,09 ExM-30,01 Solv-10,15 Solv-40,03 9th layer: Intermediate layer gelatin 0.5 10th layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (Ag 110.0 mol%, inner cylinder AgI type, equivalent sphere diameter 1.2 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like grains, diameter/thickness ratio 6°0 ) Silver coating amount 1.0 Gelatin 0.
8ExS-52X10""ExS-60,8X10-'ExS-70,8XlO-' ExM-30,01 ExM-40,04 ExC-40,005 Solv-10,2 11th layer: Yellow filter layer Cpd-30, 05 Gelatin 0. 5Solv-
10,1 12th layer: Intermediate layer gelatin 0.5Cpd-20
, 1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgIIO mol%, internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating amount 0.1 Silver iodobromide emulsion (Ag 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-83
X10-' ExY-10,25 ExY-30,32 ExY-20,02 Solv-10,20 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ag119.0 mol%, internal cylinder AgI type, Equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%, 14
Face piece particles) Silver coating amount 0.19 Gelatin 0. 3ExS-8
2X10 ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0
．． 13μ) Silver coating amount 0.2 Gelatin 0.36 16th layer:
Third blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 14.0 mol%, internal tube Agl type, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%, plate-like grains, diameter/thickness ratio 5°0 ) Silver coating amount 1゜0 gelatin 0. 5E
xS-81,5XIO-” ExY-10,2 Solv-10,07 17th layer: 1st protective layer gelatin 1,8UV-10,
l UV-20,2 Solv-10,01 Solv-20,01 18th layer: 2nd protective layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.18 Gelatin 0. 7 Polymethyl methacrylate particles (diameter 1.5μ) 0.2 W-1002 H-10,4 Cpd-51,0 ExC-1 0H (1) C4HIOCOCNH ExC-2 H ExC-3 H ExC ExC-7 ExC-4 H H H (n)C+□H2゜ExC-5 0H OCH2CH,5CHCOOH C+tH21 xM-1 L Average molecular weight 40゜I xM-2 xM-4 l xM-5 xM-6 I xY-2 xY xS xS xS-3 (CHri3S03NH(C2H4)s xS-4 C,H.

2H5 xS-8 olv ■ olv-2 olv olv-4 pd-1 pd-2 H H pd-3 CsH+5(n) pd-5 C) Is W-1 CsH+ ysOJHcH*c) IzCH20CH2C
HJe(C)Is )aCHx=CH3OzCHzCO
N)! CHfCH3=CHSOxCHtCON)
IC) 12 Next, the following treatment solution was prepared.

(Color developer) Mother liquor (g) Diethylenetriaminepentaacetic acid Compounds in Table 2 Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2.4 4-(N-Ethyl-N 1.0 1.0 0. 01 mol (same as the amount of mother liquor) 4.04.9 30.0 30.0 1.4 1.5 ■ Replenisher (g) 3.6 β-hydroxyethylamino)-2 Add methylaniline sulfate solution pH (Bleach solution) 4.5 1.01 10, 05 6.4 1.01 10.10 Mother liquor replenisher 1.3-Propanediaminetitraacetate iron (nI) Ammonium 0.55M Ammonium bromide 85g Ammonium nitrate 20g Glycol Acid 55g Add water 1.01 p8 4.0 (Fixer) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid ammonium salt Ammonium sulfite 14° 0.83 mol 25g 0g 3g 1.01 3.8 1゜Ammonium thiosulfate aqueous solution (700g/l) Add 260.0yd water 1. 0J2 pH 7,0 (Washing water) Common tap water for mother liquor and replenisher was mixed 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). R.A.
Water was passed through a mixed bed column packed with -400) to reduce the concentration of calcium and magnesium ions to 3/i or less, followed by sodium dichloride isocyanurate 20/l.
and 150 μ/I 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 (37%) 1.2J Surfactant
0.4(C,,Hl,-0(-CH
fCH! O+-, oH) ethylene glycol
1.0 Add water 1.01
]) H5,0-7,0 5 ppm of ferric ions and 150 ppm of calcium ions were added to the above color developing solution, and samples 201 to 207 were heated at 38°C in a circulating reagent aging tester with an aperture ratio of 0.11 cm-'.
It was then left to age for 30 days.

Further, the sample prepared above was cut and processed into a width of 35 m+n, and wedge exposure was applied to white light (color temperature of the light source: 4800°K).

After exposure, samples 201 to 20 prepared as described above
Processing was carried out according to the following steps using the color developing solution immediately after preparing No. 7 and the aged developing solution.

Processing process Processing time Processing temperature Color development 3 minutes 15 seconds 37.8°C Bleaching
50 seconds 38.0°C fixation
1 minute 40 seconds 38.0°C water washing m 30 seconds
38.0°C Water washing (2120 seconds 38.0°C Stable 20 seconds 38.00C Based on the maximum concentration when processed with fresh color developer (fresh solution), the G concentration after each time elapsed. Concentration decrease (△Dm
ax) was calculated. Further, the residual rate of the developing agent and hydroxylamine after time was determined by analysis. Furthermore, the color developing solution after a period of time was visually inspected for the presence or absence of precipitation. These results are summarized in Table 2.

As is clear from Table 2, when no chelating compound is added and when a conventional chelating agent is added, prevention of precipitation and securing of liquid stability are at an insufficient level. It can be seen that a great effect can be obtained only by adding the compound represented by formula (I).

Table 2 *○ indicates no precipitate at all. It was determined by

Example 3 Compounds 7.8.9 and 1 of the invention were added to the fixer solution of Example 2.
Sample solutions 301 to
It was set at 312. These sample solutions were mixed with an aperture ratio of 0. 1cm-
The solution was incubated at 38 degrees for 30 days, and the turbidity of the solution was observed. While the fixer without any additives became extremely cloudy over time, all of the fixers containing the compound of the present invention maintained a transparent state, indicating that no precipitate was generated.

Example 4 The stabilizer solution of Example 2 was used as it was for comparison, and exemplified compounds 7, 8, 9, and 12 were added thereto at a ratio of 100 μ/1 to prepare samples 401 to 405. Using these stabilizers, except for the stabilizer, Example 2
The treatment was carried out using the method described in Example 2 using the fresh solution. The processed film was heated under 45 degrees and 70% humidity.
The magenta stain increases (△
Dmtn) was determined.

The results obtained are shown in Table 4. It can be seen that the stabilizing solution of the present invention to which the exemplified compound is added suppresses the increase in staining and improves image storage stability.

Table-4 Example 5 The following bleaching solution was prepared.

This was used for comparison, and Compounds 7 to 9 of the present invention were added to this.
Samples 501 to 505 were prepared.

In order to examine the bleaching performance, the same photosensitive material as in Example 2 was used, the same color developing solution as Sample 201 of Example 2, and the same fixing solution, stabilizing solution, and washing water as in Example 2 were also used.

Regarding samples 501 to 505, the liquid immediately after preparation and 40°C
After aging for 3 days, the solution was subjected to the following treatment, and the amount of residual silver in the highest concentration area was analyzed using fluorescent X-rays. At the same time, the residual amount of hydrogen peroxide was analyzed.

Process Processing time Processing temperature Color development 3 minutes 15 seconds 38°C bleaching
5 minutes 40℃ fixation 1 minute 4
0 seconds 38°C water washing (1130 seconds 38°C water washing (2) 20 seconds 38°C stability 20 seconds 38°C *By titration with potassium permanganate solution under sulfuric acid acidity.

It can thus be seen that even in bleaching solutions using hydrogen peroxide as an oxidizing agent, the stability of the solutions is improved by using the compounds of the present invention.

Example 6 The same evaluation as in Example 2 was conducted using Sample 201 of Example 2 of JP-A-2-90151, Photosensitive Material 9 of Example 3 of JP-A-2-93641, and the photosensitive material of Example 1. I had a similar effect.

Example 7 Using sample-1 of Example 1 of JP-A-2-58041, a developer (B) was prepared by replacing disodium ethylenediaminetetraacetate in the developer (A) with the same amount of compound 8. However, when each developer was aged at 40° C. for 4 days and then subjected to running treatment, an improvement in sedimentation was observed.

(Effects of the Invention) The treatment composition of the present invention has the following excellent effects.

(1) Oxidation or decomposition of processing liquid components due to the action of metal ions is suppressed, and the performance of the processing liquid is maintained over a long period of time.

(2) There is no precipitation in the liquid due to the accumulation of metal ions, so there are no problems such as staining of the film or clogging of the filter of an automatic processor.

(3) The image storage stability of the photosensitive material after processing is improved.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment

Claims (2)

[Claims] (1) A photographic processing composition characterized by containing at least one compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R, R_1 and R_2 are hydrogen atoms,
Represents an optionally substituted alkyl group or aryl group. L1 represents an optionally substituted alkylene group or arylene group. (2) A method for processing a silver halide photographic material, which comprises processing the silver halide photographic material with the photographic processing composition according to claim (1).