JP2632055B2 - Processing solution and processing method for silver halide photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a processing solution and a processing method for a silver halide light-sensitive material, and more particularly to a development processing method with improved residual color and photographic properties. It is.

(Prior Art) With the advancement and development of the electronics field, rapidity has been required in all fields, and the field of silver halide photographic processing is no exception.

In particular, for example, in the development processing of a sheet-shaped photosensitive material such as a graphic arts photosensitive material, a X-ray photosensitive material, a photosensitive material for a scanner, and a photosensitive material for CRT image recording,
The need for rapid processing is increasing.

In addition, the more rapid processing is performed, the smaller the tank capacity required for developing a unit amount of photosensitive material per unit time, that is, there is an advantage that an automatic developing machine can be reduced. Is significant.

However, with the speeding up of the development processing, the problem that the sensitizing dye contained in the silver halide light-sensitive material does not elute during processing and remains colored in the light-sensitive material (so-called residual color) increases.

Conventionally, as a method for reducing the residual color, Research Disclosure, Volume 207, N
o. 20733 (July 1981), (1) a method of adding a water-soluble stilbene compound, a nonionic surfactant or a mixture of both to a developer, (2) development and bleaching A method in which the photographic element of the fixing solution is treated with an oxidizing agent to destroy the dye, (3) a method in which the bleaching bath is a persulfuric acid bleaching bath, and (4) JP-A-64-4739 and JP-A-64-4739. -1573
4, JP-A-1-9451, JP-A-1-35440, JP-A-1-21444
Nos. 1-35441, 1-159645, etc., using a processing liquid additive, but satisfactory results have not always been obtained.

(Object of the Invention) Accordingly, an object of the present invention is to provide a processing solution for a silver halide photosensitive material, which is suitable for rapid processing.
The second is to provide a method for rapid development processing,
A third object of the present invention is to provide a processing solution and a developing method for a silver halide light-sensitive material which have solved the problems of residual color and deterioration of photographic performance due to a sensitizing dye in rapid processing.

(Constitution of the Invention) An object of the present invention is to provide (1) a processing solution for a silver halide photosensitive material, wherein the processing solution is an aqueous solution containing a compound represented by the following general formula (I). Processing solution for a silver halide photosensitive material; General formula (I) (2) A method for processing a silver halide light-sensitive material, characterized in that the silver halide light-sensitive material is processed with a processing solution containing a compound represented by the above general formula (I).

Further, the compound represented by formula (I) will be described in detail.

As the unsaturated ring formed by Z, a benzene ring, a naphthalene ring or a 5- or 6-membered hetero ring is preferable. Examples of the 5- or 6-membered hetero ring include a pyridine ring, a pyrimidine ring, a pyrazine ring, a furan ring, a thiene ring, a pyrrole ring, a triazine ring, an imidazole ring, a quinazoline ring, a purine ring, a quinoline ring, an acridine ring, and an indole ring. , A thiazole ring, an oxazole ring, a selenazole ring, a furazane ring, or a heterocyclic ring in which these heterocycles are benzo-fused, naphtho-fused, or mutually fused.

Z includes those having a substituent, and specific examples of the substituent include a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, an amino group, an ammonium group, a sulfo group, a phosphonic group, a sulfonyl group, and a ureido. Group, acyl group, alkylthio group, arylthio group, carbamoyl group, sulfamoyl group, acylamino group, sulfonamide group, oxo group, halogen group, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group and the like. Can be (These groups may have a substituent.) R is an alkyl group (preferably an alkyl group having up to 4 carbon atoms, for example, methyl, ethyl, propyl), an aryl group (preferably an aryl having a benzene nucleus) Groups, such as phenyl), acyl groups (preferably having up to 10 carbon atoms such as acetyl, benzoyl), allyl groups, alkanesulfonyl groups (preferably having up to 3 carbon atoms such as methanesulfonyl, ethanesulfonyl, Propanesulfonyl) and arenesulfonyl groups (preferably arenesulfonyl groups having a benzene nucleus, such as benzenesulfonyl and p-toluenesulfonyl).

The alkyl group, aryl group, acyl group, alkane sulfonyl group, and arene sulfonyl group of R include those each having a substituent, and the substituent includes a hydroxy group, an alkoxy group, an aryloxy group, a carboxyl group, an amino group, An ammonio group (here, an amino group and an ammonio group include those having a substituent, and two or more substituents may be bonded to each other to form a ring such as a morpholino ring), a sulfo group, Morphone group, sulfonyl group, ureido group, acyl group, alkylthio group, arylthio group, carbamoyl group, sulfamoyl group (here, carbamoyl group and sulfamoyl group include those having a substituent.
Two substituents may be bonded to each other to form a ring such as a morpholino ring), an acylamino group, a sulfonamino group, an oxo group, a halogen group, a cyano group, a nitro group and the like. Further, if possible, these substituents and the above functional groups may further be substituted. Among the functional groups contained in the formula, carboxyl group, sulfo group, and phosphone group are alkali metals (for example, sodium,
Potassium) or a salt of a monovalent positive atom (for example, NH ₄ ⁺ ), and the amino group is a salt of hydrochloric acid, sulfuric acid, nitric acid,
It may form salts with various acids such as phosphoric acid and oxalic acid acetic acid. R is particularly preferably a hydrogen atom or an alkyl group, and the substituent of the alkyl group is preferably a dialkylamino group, a sulfonic acid group or a phosphonic acid group.

Among the compounds represented by the general formula (I), those having a molecular weight of 600
The following compounds are preferred, and the compounds having a molecular weight of 500 or less are more preferred. In addition, it is preferably water-soluble, especially for 100 cc of water at 20 ° C, 0.04 g or more,
Particularly, a compound that can dissolve at least 0.08 g is preferable.

The following shows specific examples of the compound used in the present invention,
The present invention is not limited to this.

Further, the compound represented by the general formula (I) or a salt thereof preferably satisfies condition 1.

Condition 1: anhydro-5,5'-dichloro-9-ethyl-3,3'-
2 × ⁴ × 10 ^-4 mol / l aqueous solution of bis (3-sulfopropyl) thiacarbocyanine hydroxide / pyridinium salt
And potassium chloride 1.0 × 10 ^-1 mol / l aqueous solution 1 ml,
To this mixture is further added 4 ml of an aqueous solution of the compound at 8.0 × 10 ^-2 mol / l, diluted with water and made up to 10 ml. 624nm of this aqueous solution
The molecular extinction coefficient at 1.0 should be 1.0 × 10 ⁵ or less.

The compounds of the present invention are described, for example, in JP-B-49-8852 and JP-B-49-11.
Nos. 063, 54-18338, West German Patent 2,349,527, Journal of Heterocyclic Chemistry, No. 14
Volume, 1045 pages (1977). (J. Heterocyclic Chem., 14 , 1
045 (1977). 15: 1027 (1978), Journal of Organic Chemistry, 24, 14
78 (1959), (J. Org. Chem., 24 , 1478 (195
9). 38, p. 3084 (1973), Journal
Of Chemical Society, 1949, 3311 (J.
Chem. Soc., 1949 , 3311).

 The synthesis examples of typical compounds of the present invention are shown below.

Synthesis Example Synthesis of Exemplified Compound I-6 164 g (1.0 mol) of 2-methylthiobenzimidazole was suspended in 1500 cc of water, and 1.65 g (0.005 mol) of sodium tungstate dihydrate and 280 ml of 35% hydrogen peroxide were added. In addition, the mixture was stirred on a hot water bath at 50 ° C. for 6 hours, and 181 g of 2-methanesulfonylbenzimidazole was collected by filtration.

70 g of 2-methanesulfonylbenzimidazole (0.36m
ol) and 1-chloro-2-diethylaminoethane hydrochloride
74 g (0.4 mol) and 119 ml of triethylamine were heated and refluxed for 3 hours in 700 ml of acetonitrile.

The precipitated triethylamine hydrochloride was separated by filtration, the filtrate was concentrated under reduced pressure, and extracted with ethyl acetate (1000 cc × 2). The ethyl acetate layer was dried over magnesium sulfate and concentrated under reduced pressure to give 1- (2-diethylaminoethyl) -2.
85.3 g of methanesulfonylbenzimidazole were obtained as crystals.

85 g of 1- (2-diethylaminoethyl) -2-methanesulfonylbenzimidazole, hydrazine monohydrate 2
After heating under reflux for 4 hours in 00 ml, extraction with ethyl acetate, drying with sodium sulfate, and drying under reduced pressure, isopropanol was added to the syrup-like residue, and further 20 ml of hydrochloric acid were added.
84 g of 1- (2-diethylaminoethyl) -2-hydrazinobenzimidazole dihydrochloride was obtained as crystals. After suspending 84 g of 1- (2-diethylaminoethyl) -2-hydrazinobenzimidazole dihydrochloride in acetonitrile, 19 ml of carbon disulfide and 80 ml of triethylamine are added and the mixture is completely dissolved by stirring at 60 ° C. After stirring was continued at 60 ° C. for 2 hours, crystals precipitated upon cooling with ice were collected by filtration, suspended in 500 ml of methanol, and completely dissolved by adding 20 ml of hydrochloric acid. When this was cooled again with ice, crystals were precipitated. The crystals were collected by filtration and treated with 8- (2-diethylaminoethyl) -3.
-Mercaptobenzimidazotriazole (1-6) 40
g was obtained.

mp258-260 ° Elemental analysis Calc: C.54.58 H.5.29 N.17.14 S.11.21 Fovrd: C: 54.60 H.5.25 N.17.01 S.11.30 The compound of the general formula (I) of the present invention is a silver halide photosensitive material. It shows the function that enables rapid processing of In particular, it functions to extremely reduce the amount of sensitizing dye remaining in the photographic material after processing.

In the photographic processing of the present invention, in the case of a black-and-white photosensitive material, the exposed silver halide photosensitive material is at least developed, fixed,
The process comprises washing (or stabilizing) and drying. In the case of a color photographic material, the exposed photographic material is subjected to at least color development, bleaching, and fixing (the bleaching and fixing are performed in the same bath, that is, a bleach-fixing bath). ), Washing (or stabilizing), and drying.

The compound of the general formula (I) of the present invention may be added to any of a developing solution, a color developing solution, a fixing solution, a bleaching solution, a bleach-fixing solution, a washing solution or a prebath thereof. In particular, it is preferable to add to a developing solution, a color developing solution, a fixing solution, a bleaching solution, a bleach-fixing solution or a prebath thereof. That is, the treatment liquid of the present invention is:
A developer, a color developer, a fixer, a bleach, a bleach-fix or a prebath thereof containing the compound represented by the formula (I).

The amount of the compound of the formula (I) to be added to the processing solution varies depending on the type of the processing solution, but is generally 5 × 10 4
^-5 mol / l to 10 ^-1 mol / l, preferably 10 ^-4 mol / l to ⁵ × 10
⁻² mol / l, particularly preferably 3 × 10 ⁻³ mol / l to 10 ⁻² mol / l
It is. Below this range, the effect of rapid process proper improvement cannot be obtained, and above this range, precipitation occurs in the processing solution or the cost increases.

Good.

Examples of p-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, and N-methylphenol.
(Β-hydroxyethyl) -p-aminophenol, N
-(4-hydroxyphenyl) glycine, 2-methyl-
There are p-aminophenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred.

1-phenyl- as a 3-pyrazolidone developing agent
3-pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4
-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-
And tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.

The developing agent is preferably used in an amount of usually 0.01 mol / l to 1.2 mol / l.

Examples of the sulfite preservative include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite.
The sulfite is preferably at least 0.2 mol / l, particularly preferably at least 0.4 mol / l. The upper limit is preferably up to 2.5 mol / l.

The pH of the developer is preferably in the range of 9 to 13.
More preferably, the pH is in the range of 10 to 12.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters.

Buffers such as Japanese Patent Application No. 61-28708 (borate), Japanese Patent Application Laid-Open No. 60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Further, a hardener may be used in the developer. As the hardener, a dialdehyde-based hardener or a bisulfite adduct thereof is preferably used. Specific examples thereof include glutaraldehyde and bisulfite adduct thereof.

Additives other than the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, and methanol. Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benzes such as 5-methylbenztriazole It may contain antifoggants such as triazole-based compounds.
ure, Vol. 176, No. 17643, Section XXI (December Issue, 1978) and, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hard water softener, It may contain an amino compound described in JP-A-56-106244.

In the developing treatment, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used in the developing solution.

As the developer, European Patent No. 0136682, JP-A-56
An amino compound such as an alkanolamine described in JP-A-106244 can be used.

"Photographic Processing Chemistry" by LFA Mason, Focal Press (19
66), pp. 226-229, U.S. Patent Nos. 2,193,015 and 2,591
Nos. 2,364 and JP-A-48-64933 may be used.

The fixing solution is an aqueous solution containing a thiosulfate as a fixing agent, and has a pH of 3.8 or more, preferably 4.2 to 7.0. More preferably, the pH is 4.5 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to about 6 mol / l.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like.

Tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more in the fixing solution. These compounds are used in an amount of 0.00
Those containing 5 mol or more are effective, and particularly 0.01 mol / l to 0.03 mol / l are particularly effective.

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water, or a patent application. The compounds described in JP-A-60-218562 can be included.

Reduce the swelling percentage of the photosensitive material (preferably 150
(% To 50%) It is more preferable that the treated hardening layer is made weaker, because rapid processing can be performed. That is, it is more preferable that there is no hardening during development, and it is more preferable that there is no hardening during fixing. However, the pH of the fixing solution may be set to 4.6 or more to weaken the hardening reaction. This makes it possible to form a replenisher consisting of one solution for each of the developing solution and the fixing solution, and there is also an advantage that the replenisher is prepared by simply diluting with water.

The silver halide light-sensitive material of the present invention is treated with washing water or a stabilizing solution after the developing and fixing steps. Here, the stabilizing liquid is the same as the water washing, and is different only in the name.

The replenishing amount of washing water or stabilizing solution photosensitive material 1 m ² per, 2l
The following (including 0, that is, washing with water) is preferable.

By doing so, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated.

As a method for reducing the amount of replenishment, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in a clean direction, that is, a processing solution that is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washing is performed.

In order to make the above-mentioned development processing water-saving processing or pipeless processing, it is preferable to apply a fungicide to the washing water or the stabilizing solution.

As the antifungal means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion-exchange resin described in JP-A-61-131632 are used. Method for making pure water, Japanese Patent Application No. 60-253807, 60-295894
Nos. 61-63030 and 61-51396 can be used.

Furthermore, LEWest, “Water Quality Criteria” Photo.
Sci, & Eng. Vol. 9 No. 6 (1965), MWBeach. “Microbiol
ogical Growths in Motion-Picture Processing "SMPTE
Journal Vol. 85, (1976), RODeegan, “Photo Proc
essing Wash Water Biocides "J.Imaging Tech 10, No.6
(1984) and JP-A-57-8542, JP-A-57-58143, and JP-A-57-58143.
-105145, 57-132146, 58-18631, 57-9
No. 7530, antibacterial agents described in Nos. 57-157244 and the like,
A fungicide, a surfactant and the like can be used in combination.

Further, a washing bath or stabilizing bath includes RTKreiman, JI
Isothiazoline compounds described in mage.Tech10, (6) p.242 (1984), Research Disclosure Volume 205, No. 2
Isothiazoline compounds described in No. 0526 (May, 1981), isothiazoline compounds described in Vol. 228, No. 22845 (April, 1983), and described in Japanese Patent Application No. 61-51396. The compound thus obtained can be used in combination as a bacteriostatic agent (Microbiocide).

In addition, "The chemistry of antibacterial and fungicide" by Hiroshi Horiguchi, Sankyo Publishing (Akira
57), and may contain compounds as described in the “Handbook of Bacterial and Fungicide Technology”, Japan Society of Bacterial and Fungicide / Hakuhodo (Showa 61).

When the silver halide light-sensitive material of the present invention is washed with a small amount of washing water, or when it is stabilized with a stabilizing solution, it is disclosed in Japanese Patent Application No. 61-1986.
More preferably, a squeeze roller washing tank described in 163217 is provided. It is also preferable to adopt a configuration of a washing step as disclosed in Japanese Patent Application No. 61-290619.

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the water subjected to the antifungal means to the washing or stabilizing bath according to the treatment, is disclosed in JP-A-60-23.
As described in Japanese Patent No. 5133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step.

The silver halide light-sensitive material of the present invention, in the case of a black-and-white light-sensitive material, when subjected to at least the above-mentioned development, fixing, washing or stabilization and automatic processing including a drying step, the process from development to drying 90 To complete within seconds, ie
The time from when the tip of the photosensitive material starts to be immersed in the developing solution to drying through a fixing and washing (or stabilization) process, until the tip comes out of the drying zone (so-called Dry to
Dry time) is preferably 90 seconds or less, particularly preferably 70 seconds or less. More preferably, the Dry to Dry time is within 60 seconds.

In the present invention, the `` development process time '' or `` development time '' is the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the next fixing liquid, "Fixing time" refers to the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution). "Washing time" refers to the time of immersion in the washing tank solution.

Further, the "drying time" is usually 33 ° C to 100 ° C, preferably 4 ° C.
A drying zone to which hot air of 0 ° C. to 80 ° C. is blown is installed in the automatic developing machine, and refers to a time in the drying zone.

In order to achieve the above-mentioned rapid processing within 90 seconds of Dry to Dry, the development time is within 30 seconds, preferably within 25 seconds, and the development temperature is preferably 25 ° C to 50 ° C, more preferably 30 ° C to 40 ° C. .

In the present invention, the fixing temperature and time are preferably from about 20 ° C to about 50 ° C for 6 seconds to 30 seconds, more preferably from 30 ° C to 40 ° C for 6 seconds to 20 seconds.

Rinse or stabilize bath temperature and time from 0 to 50 ° C for 6 seconds
It is preferably 20 seconds, more preferably 6 to 15 seconds at 15 ° C to 40 ° C.

In the present invention, the photographic material which has been developed, fixed and washed or stabilized is squeezed out of the washing water, that is, dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but is usually about 5 seconds to 30 seconds, particularly preferably 40 seconds.
C. to 80.degree. C. for about 5 to 20 seconds.

When developing with the photosensitive material / processing system of the present invention in dry to dry for 90 seconds or less, as described in Japanese Patent Application No. 61-297672 in order to prevent development unevenness peculiar to rapid processing. Applying a rubber roller to the roller at the exit of the developing tank, or increasing the discharge flow rate for stirring the developing solution in the developing solution tank to 10 m / min or more as described in Japanese Patent Application No. 61-297673. And furthermore, Japanese Patent Application No. 61
As described in JP-A-315537, it is more preferable to perform stronger stirring at least during development processing than during standby. The preferable circulation rate of the processing liquid is 9 l / min or more. Further, for the rapid processing as in the present invention, it is more preferable that the configuration of the roller of the fixing liquid tank is to increase the fixing speed or to use a facing roller. By using the opposing rollers, the number of rollers can be reduced, and the processing tank can be reduced. That is, it is possible to make the self-developing machine more compact.

The photographic light-sensitive material of the present invention is not particularly limited, and is used for general photographic materials. For example, photographic materials for laser printers for medical images and photographic materials for printing scanners, X-ray photographic materials for direct medical use, X-ray photographic materials for indirect medical use, photographic materials for CRT image recording, color negative materials for printing It can be used as a light-sensitive material, a color reversal light-sensitive material, a color photographic paper, and the like.

The above-mentioned light-sensitive material of the present invention can be produced, for example, by one or a combination of two or more of the following methods.

A silver halide having a small or no iodine content is used. That is, silver chloride having a silver iodide content of 0 to 5 mol%,
Silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like are used.

A water-soluble iridium salt is contained in a silver halide emulsion.

The amount of coated silver in the silver halide emulsion layer is reduced.
For example 1 to 5 g / m ² on one side, preferably 1 to 4 g / m ^2.
More preferably from 1 to 3 g / m ^2.

Reduce the average grain size of silver halide in the emulsion. For example, it is 1.0 μm or less, preferably 0.7 μm or less.

As the silver halide grains in the emulsion, tabular grains, for example, those having an aspect ratio of 4 or more, preferably 5 or more are used.

The swelling percentage of the silver halide photosensitive material should be 200% or less.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedrons may be used, those having irregular crystal forms such as spheres, those having crystal defects such as twin planes, tabular particles or A composite form thereof may be used.

The tabular grain aspect ratio is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain.
In the present invention, the preferred form of the tabular grains is 4 to less than 20, preferably 5 to less than 10, aspect ratio. Further, the thickness of the particles is preferably 0.3 μm or less, particularly preferably 0.2 μm or less.

Tabular grains are preferably present in an amount of preferably 80% by weight, more preferably 90% by weight or more of all the grains.

The grain size of the silver halide may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The silver halide photographic emulsion of the present invention can be produced by a known method, for example, Research Disclosure No. 17643 (December 1978)
Mon), pp. 22-23, "I. Emulsion preparation
and types) ”and No. 18716 (November 1979), 64
The method described on page 8 can be followed.

The photographic emulsion used in the present invention is described in "Graduation of Chemistry and Physics", published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique, Paul Montel, 196
7), “Digital Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966) "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman eta).
l., Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like.

In forming the silver halide grains used in the present invention, for example, ammonia, rodankari, rodanammon, as a silver halide solvent in order to control the growth of the grains.
Thioether compounds (for example, US Pat. No. 3,271,157,
No. 3,574,628, No. 3,704,130, No. 4,297,439
No. 4,276,374, etc.) and thione compounds (for example, JP-A Nos. 54-144,319, 53-82,408, and 55-77,73).
No. 7, etc.) and amine compounds (for example, JP-A-54-100,717).

In the present invention, a water-soluble rhodium salt or a water-soluble iridium salt as described above can be used. In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof.

A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. PA in the liquid phase where silver halide is formed as a form of the double jet method.
A method of keeping g constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size is obtained.

The silver halide emulsion used in the present invention is preferably chemically sensitized.

In case of chemical sensitization, normal sulfur sensitization, reduction sensitization,
Noble metal sensitization and combinations thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine;
Potassium chloroaurate, auras, thiosulfate and potassium chloroparadate
Noble metal sensitizers such as Palladate): reduction sensitizers such as tin chloride, phenylhydrazine and reductone.

The silver halide emulsion of the present invention is optionally spectrally sensitized by a known spectral sensitizing dye. Examples of the spectral sensitizing dye to be used include, for example, Hemmer, "Heterocyclic Compounds, Cyanine Soybeans and Relatively Compounds, John Wheely and Sons (1964) (FMHamer," Heterocyclic ").
Compounds-The Cyanine Dyes and Related Compounds
", John Wiley & Sons (1964) and Starmer," Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry ", John Wheely and Sons (1977) (DMSt)
urmer. “Heterocyclic Compounds-Special Topics in
Heterocyclic Chemistry ", John Wiler & Sons (1977), cyanine, merocyanine, rhodocyanine, styryl, hemicyanine, oxonol, benzylidene, holopolar and the like can be used.
Particularly, cyanine and merocyanine are preferred. Most preferred is benzimidazolobenzoxazolocarbocyanine.

Sensitizing dyes that can be preferably used in the present invention include JP-A-60-133442, JP-A-61-75339, JP-A-62-6251, and JP-A-60-62591.
And cyanine dyes and merocyanine dyes represented by the general formulas described in JP-A-212827, JP-A-50-122292, JP-A-59-1801553 and the like. Specifically, pages (8) to (11) of JP-A-60-133442 and (5) of JP-A-61-75339 are described.
To (7), pages (24) to (25), pages (10) to (15) of JP-A-62-6251, and (5) to (5) of JP-A-59-212827.
Page (7), pages (7) to (9) of JP-A-50-1222928,
A sensitizing dye which spectrally sensitizes silver halide to a blue region, a green region, a red region or an infrared region of the spectrum described in pages (7) to (18) of JP-A-59-180553 is used. Can be mentioned.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510) Described)), cadmium salt,
An azaindene compound may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

The above sensitizing dye is used in an amount of 5 × 10 ⁻⁷ mol to 5 × 10 ⁻² mol, preferably 1 × 10 ⁻⁶ mol to 1 × 10 ⁻³ mol per mol of silver halide.
Mol, particularly preferably 2 × 10 ^-6 mol to 5 × 10 ^-4 mol, in the silver halide photographic emulsion.

The sensitizing dye can be directly dispersed in the emulsion layer. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Also, ultrasonic waves can be used for dissolution. Further, as a method for adding the sensitizing dye, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is dispersed. As described in JP-B-46-24185, etc., by dispersing in a water-soluble solvent without dissolving a water-insoluble dye, and adding this dispersion to the emulsion; A method of mechanically pulverizing and dispersing a water-insoluble dye in an aqueous solvent as described in -45217, and adding this dispersion to an emulsion; a surfactant as described in U.S. Pat. No. 3,822,135; A method of dissolving a dye in an emulsion and adding the solution to an emulsion; a method of dissolving using a compound that causes a red shift as described in JP-A-51-74624, and adding the solution to the emulsion; The dyes described in JP-A-50-80826 contain substantially water. A method of dissolving in an acid, and adding the solution to the emulsion. Others
U.S. Pat.Nos. 2,912,343 and 3,342,6
Methods described in No. 05, No. 2,996,287 and No. 3,429,835 can also be used. The above sensitizing dyes may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but may of course be dispersed in any step of the preparation of the silver halide agent. .

Other sensitizing dyes can be used in combination with the above sensitizing dyes. For example, U.S. Patent Nos. 3,703,377, 2,688,545, 3,397,060, 3,615,635,
No. 3,628,964, UK Patent No. 1,242,588, No. 1,293,
No. 862, No. 43-4936, No. 44-14030, No. 43-1077
No. 3, U.S. Pat.No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Pat.Nos. 2,615,613, 3,615,632, 3,617,295
And sensitizing dyes described in JP-A No. 3,635,721 and the like can be used.

In order to rapidly process the silver halide light-sensitive material, the swelling percentage of the silver halide light-sensitive material is preferably 200% or less.

On the other hand, if the swelling percentage is too low, the speed of development, fixing, washing with water and the like will decrease.

The preferred swelling percentage is 200% or less and 30% or more, particularly preferably 150% or less and 50% or more.

To control the swelling percentage to 200% or less, those skilled in the art can easily control the swelling percentage by increasing the amount of a hardening agent used for a photosensitive material, for example.

The percentage of swelling was determined by (a) incubating the photographic material at 38 ° C. and 50% relative humidity for 3 days, (b) measuring the thickness of the hydrophilic colloid layer, and (c) subjecting the photographic material to 21 ° C. distilled water. D) and (d) measuring the percentage change in layer thickness compared to the thickness of the hydrophilic colloid layer measured in step (b).

Examples of the hardening agent that can be used in the present invention include aldehyde compounds, compounds having an active halogen described in U.S. Patent No. 3,288,775, and reactive ethylenically unsaturated groups described in U.S. Patent No. 3,635,718. And organic compounds such as epoxy compounds described in US Pat. No. 3,091,537 and halogenocarboxaldehydes such as mucochloric acid. Among them, vinyl sulfone hardeners are preferred. Further, a polymer hardener can also be preferably used.

As the polymer hardener, a polymer having an active vinyl group or a group which is a precursor thereof is preferable. Among them, an active vinyl group or a precursor thereof is preferably formed by a long spacer as described in JP-A-56-142524. Particularly preferred are polymers in which the following groups are bonded to the polymer backbone. The amounts of these hardeners to achieve the above-mentioned swelling percentage vary depending on the type of hardener used and the kind of gelatin used.

When the silver halide light-sensitive material of the present invention is subjected to rapid processing, it is preferable to incorporate an organic substance which flows out in the development processing step into the emulsion layer and / or the other hydrophilic colloid layer. When the substance to be discharged is gelatin, a gelatin species which is not involved in the cross-linking reaction of gelatin by a hardener is preferable. For example, acetylated gelatin and phthalated gelatin correspond to these, and those having a small molecular weight are preferable. On the other hand, as a polymer substance other than gelatin, polyacrylamide as described in U.S. Pat.No. 3,271,158, or also a polyvinyl alcohol, a hydrophilic polymer such as polyvinylpyrrolidone can be used effectively, and dextran and saccharose can be used. , Pullulan, and other saccharides are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. In addition, Research Disclosure Volume 176, No. 17643, VI
The antifoggants and stabilizers described in the section (December issue, 1978) can be used.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 1, 4,168,977, No. 4,166,742, No. 4,311,781
No. 4,272,606, No. 4,221,857, No. 4,243,73
The hydrazine derivative described in No. 9 or the like can be applied to a silver halide light-sensitive material capable of obtaining ultra-high contrast and high photographic characteristics with high sensitivity.

The present invention is also applicable to silver halide color light-sensitive materials. Hereinafter, the case of a silver halide color light-sensitive material will be described in detail.

In the present invention, in the case of a color photographic light-sensitive material, the first step of processing refers to the processing step which is carried out first, and in the processing of a color negative film, this usually corresponds to a color developing solution.

After the photosensitive material is immersed in the processing solution of the first step,
The present invention exerts its effect when the so-called wet treatment time until the treatment liquid in the final step is removed is 6 minutes or less,
When the time is 30 minutes or less, the effect becomes more remarkable, and the time is more preferably 5 minutes or less.

Among the wet processing times of 6 minutes or less, it is preferable that the fixing or bleach-fixing time is 2 minutes or less, and it is preferable that the fixing or bleach-fixing time is 1 minute and 30 seconds or less from the viewpoint of clear effect. or,
The present invention is applied when the total replenishment amount of each processing solution is 2500 ml or less per 1 m ^{2 of the} color photographic light-sensitive material, and especially 2000 ml
Or less, more preferably 1800 ml or less.

Above all, the replenishment amount of the fixing solution or the bleach-fixing solution is preferably 1200 ml or less, more preferably 800 ml or less, particularly preferably 600 ml or less because the effect of the present invention becomes remarkable.

When the replenishing amount of the color developing solution is 700 ml or less, more preferably 500 ml or less. In addition, the replenishment amount of the bleaching solution is preferably 600 ml or less, more preferably 300 ml or less.

Further, when the present invention is applied to a color photographic light-sensitive material, the effect is remarkable for a photographic color photographic light-sensitive material using a silver iodobromide emulsion, and the total thickness of all photographic constituent layers excluding a support is particularly 20 μm or less. And the film swelling speed T1 / 2 of the binder of the photographic emulsion layer exhibits a more excellent effect in a color photographic light-sensitive material having a thickness of 10 seconds or less, and the thickness of all photographic constituent layers is 18
It is preferable that the film swelling speed T1 / 2 is 8 seconds or less at μ or less.

Here, the photographic constituent layer means all hydrophilic colloid layers involved in image formation on the same side as the support having the silver halide emulsion layer, and in addition to the silver halide emulsion layer, for example, antihalation Layer (black colloid silver antihalation layer, etc.), subbing layer, interlayer (mere interlayer,
Or a filter layer, an ultraviolet absorbing layer, etc.), a protective layer and the like.

The thickness of the photographic constituent layer is the total thickness of the above hydrophilic colloid layers, and the measurement is performed with a micrometer.

The silver halide color photographic light-sensitive material of the present invention has a binder film swelling speed T1 / 2 of the silver emulsion layer of 25 seconds or less. That is, gelatin is usually used as a hydrophilic binder used for coating a silver halide of a silver halide color photographic light-sensitive material, but a high-molecular polymer may be used. Is T1
/ 2 must be less than 25 seconds. The swelling rate T1 / 2 of the binder can be measured according to any technique known in the art, for example, A. Green
n) Photographic Science and Engineering (Phot.Sci.Eng.), Vol. 19, No. 2, 1
It can be measured by using a serometer (swelling meter) of the type described on pages 24 to 129, and T1 / 2 is 30 ° C. in a color developing solution,
The maximum swelled film thickness of 90% reached when the treatment is performed for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach half the film thickness. That is, 1/2 of the film thickness when the film thickness due to swelling is saturated.
The film swelling speed is defined as the time T1 / 2 until the film reaches the temperature.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder.

As hardeners, aldehyde-based and aziridine-based (for example, PB Report 19,921, U.S. Pat. Nos. 2,950,197 and 2,96
4,404, 2,983,611, 3,271,175, JP-B-46-4
0898, JP-A-50-91315, etc.), isoxazolium-based (for example, those described in U.S. Pat. No. 3,321,323), epoxy-based (for example, U.S. Pat. No. 3,047,394,
West German Patent 1,085,663, British Patent 1,033,518, Japanese Patent Publication 48
−35495, etc.), vinyl sulfone type (for example, PB Report 19,920, West German Patent No. 1,100,942, 2,3)
37,412, 2,545,722, 2,635,518, 2,742,30
8, 2,749,260, UK Patent 1,251,091, U.S. Patent
3,539,644, 3,490,911, etc.), acryloyl-based (for example, those described in US Pat. No. 3,640,720), carbodiimide-based (for example, US Pat. No. 2,938,892)
No. 4,043,818, No. 4,061,499, JP-B-46-38715
No., etc.), triazines (for example, West German patent)
2,410,973, 2,553,915, U.S. Patent 3,325,287,
JP-A-52-12722, etc.) Polymer type (for example, British Patent No. 822,061, U.S. Pat. Nos. 3,623,878 and 3,39)
6,029, 3,226,234, JP-B-47-18578, 18579
No. 47-48896), maleimides, acetylenes, methanesulfonates, N
-Metrol hardeners can be used alone or in combination. Useful combination techniques include, for example, West German Patent 2,
447,587, 2,505,746, 2,514,245, U.S. Patent
No. 4,047,957, No. 3,832,181, No. 3,840,370, JP 4
8-43319, 50-63062, 52-127329, Shoko 4
Combinations described in JP-A-8-32364 are exemplified.

 The processing steps to which the present invention is applied are exemplified.

1.Color development-bleach-fix-wash 2.Color development-bleach-fix-wash-stable 3.Color development-bleach-bleach-fix-wash-stable 4.Color development-bleach-fix-stable 5.Color development-bleach-stable Fixing-Stable 6. Color developing-Bleaching-Bleaching-Stable 7. Color developing-Fixing-Bleaching-Washing-Stable 8. Color developing-Fixing-Bleaching-Stable 9. Black-white developing-Washing-Color developing-Reversing- Adjustment-Bleaching-Fixing-Washing-Stable Next, details of the processing solution will be described.

The color developing agents used in the color developing solution and the color developing replenisher are aromatic primary amine compounds, and include known compounds widely used in various color photographic processes. However, in the present invention, a preferred color developing agent is (1) 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate (2) 4- (N-ethyl-N-β- Methanesulfonamidoethylamino) -2-methylaniline sulfate (3) 4-((N-ethyl-N-β-methoxyethylamino) -2-methylaniline-p-toluenesulfonate (4) 4- ( N, N-diethylamino) -2-methylaniline hydrochloride (5) 4- (N-ethyl-N-dodecylamino) -2-
Methylaniline sulfate (6) N, N-dialkyl-p-phenylenediamine-based color developing agents such as N, N-diethyl-p-phenylenediamine hydrochloride. These compounds are present in the color developer at 0.00
It is added in the range of 5-0.05 mol / l, preferably 0.01 to 0.01 mol / l.
-0.04 mol / l, particularly preferably in the range of 0.015-0.03 mol / l. Further, it is preferable to add the replenisher for color development so as to have a higher concentration than the above concentration. Specifically, how high the concentration should be depends on the setting of the replenishment amount, but is generally 1.05 to 2.0% of the color developing solution (mother solution).
Times, more often in the range of 1.2-1.8 times.

The color developing agents may be used alone or in combination depending on the purpose. Preferred examples of the combination include (1) and (2), (1) and (3), and (2) and (3) among the above color developing agents.

In the present invention, the bromine ion concentration of the color developing solution is 0.00
The content is preferably in the range of 5 to 0.02 mol / l, and for this purpose, the bromide content of the replenisher is preferably set to 0.005 mol / l or less. In general, the lower the replenishment volume,
The bromide content in the replenisher should be set low. In particular, in the present invention, it is preferable that the replenisher does not contain bromide in order to greatly reduce the replenishment amount.

The bromide includes potassium bromide, sodium bromide, lithium bromide, hydrobromic acid and the like.

Examples of the color developing solution and the color developing replenisher include hydroxylamine, diethylhydroxylamine, triethanolamine, compounds described in West German Patent (OLS) No. 2622950, hydrazines described in JP-A-63-146041, Preservatives such as sulfites and bisulfites are used.

In addition, various chelating agents are also added for the purpose of softening water and hiding a metal. In the present invention, at least one compound represented by the following general formula (A) and / or (B) is particularly contained. Is preferred.

General formula (A) General formula (B) In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and represents a hydrogen atom,
Represents an alkali metal atom or ammonium.

R is particularly preferably a methyl group or an ethyl group.
Is preferably a hydrogen atom or a sodium atom.

Specific examples of the compounds represented by formulas (A) and (B) are described below.

In the color developing solution used in the present invention, in addition to the above compounds, a pH buffer such as an alkali metal carbonate, borate or phosphate; iodide, benzimidazoles, benzothiazoles, mercapto compounds Organic solvents such as diethyl glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium, amines, and thiocyanate; nucleating agents such as sodium borohydride. An auxiliary developing agent such as 1-phenyl-3-pyrazolidone: a viscosity imparting agent; in addition to the compounds represented by formulas (A) and (B), ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid , Iminodiacetic acid, hydroxyethyliminodiacetic acid, research
Various chelating agents such as organic phosphonic acids described in Disclosure 18170 (May 1979) can be used alone or in combination.

In the present invention, the pH value of the color developing solution and its replenisher is usually 9 or more, preferably 9.5-12, particularly preferably 9.5-11.0. In the above range, the replenisher for the color developer is preferably set to a value higher by about 0.05 to 0.5.

The temperature in the color development process is 30 to 45 ° C., and it is preferable to use a high temperature in order to achieve a larger low replenishment process.
It is preferably carried out at 38-42 ° C.

The present invention can be carried out in any of an automatic developing machine and manual processing, but is preferably carried out in an automatic developing machine. In the processing of the automatic developing machine, the number of color developing solution tanks may be one or more. However, if a plurality of tanks are used and a multi-stage forward replenishing method in which the front tank is replenished and sequentially flows into the rear tank is used, the replenishment is further reduced. be able to. The contact area between the developer and the air in the tank is preferably as small as possible. Specifically, a floating lid, a seal with a liquid having a high boiling point and a specific gravity smaller than that of the developer, JP-A-63-216050
The use of a shielding means such as a tank structure narrowed to the opening described in the above item further enhances the effects of the present invention.

Further, as a means for enhancing the effect of the present invention, it is preferable to replenish water according to the amount of evaporation in order to correct the evaporation and concentration of the developer. The water to be replenished is preferably deionized water that has been subjected to an ion exchange treatment or deionized water that has been subjected to a treatment such as reverse osmosis or distillation.

The color developing solution and the color developing replenisher are prepared by sequentially adding and dissolving the above-mentioned chemicals in a certain amount of water, and the above-mentioned deionized water is preferably used as the preparation water.

In the present invention, the photosensitive material after color development is a bleaching solution,
Alternatively, it is processed with a bleach-fix solution. As the bleaching agent used in these, a complex salt of ferric ion and a chelating agent such as aminopolycarboxylic acid, polycarboxylic acid, aminopolycarboxylic acid and the like is generally used. Examples of preferred chelating agents used as complex salts with these ferric ions include (1) ethylenediaminetetraacetic acid (2) diethylenetriaminepentaacetic acid (3) cyclohexanediaminetetraacetic acid (4) 1,3-diaminopropanetetraacetic acid ( 5) Nitrilotriacetic acid (6) Iminodiacetic acid (7) Glycol ether diamine tetraacetic acid, etc., but particularly (1), (2),
(3) and (4) are preferred in terms of finishing performance and quickness of bleaching.

The ferric ion complex salt may be used in the form of a complex salt or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate,
A ferric ion complex salt may be formed in a solution using ferric ammonium sulfate, ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid. When used in the form of a complex salt, 1
Different kinds of complex salts may be used, or two or more kinds of complex salts may be used. Such examples are particularly (1) and (4)
Is preferred. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. Further, one or more chelating agents may be used. In any case, the chelating agent may be used in excess of the amount of forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylate iron complexes are preferable, and the amount of addition is 0.1 to 1 mol / l, preferably 0.2 to 0.4 mol / l in a bleaching solution of a color photographic light-sensitive material for photography such as a color negative film. In the bleach-fix solution, 0.05 to 0.5 mol /
l, preferably 0.1 to 0.3 mol / l. Further, in a bleaching solution or bleach-fixing solution of a color photographic light-sensitive material for printing such as color paper, 0.03 to 0.3 mol / l, preferably
0.05 to 0.2 mol / l.

In the bleaching solution or the bleach-fixing solution, a bleaching accelerator can be used if necessary. As specific examples of useful bleaching accelerators, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention may contain bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium) rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Addition of one or more inorganic acids and organic acids having pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can do.

The above-mentioned bleaching solution is usually used in the range of pH 3 to 7, preferably 3.5 to 6.5, particularly preferably 4.0 to 6.0. The pH of the bleach-fix solution is 4 to 9, preferably 5 to 8, particularly preferably 5.5 to 7.5. When the pH is higher than the above range, poor bleaching tends to occur, and when the pH is low, poor coloring of the cyan dye tends to occur.

The fixing agent used in the bleach-fixing solution of the present invention or the fixing solution used after processing with the bleaching solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate, ammonium thiocyanate Thiocyanates such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol and water-soluble silver halide solubilizers such as thioureas; Two or more kinds can be used as a mixture. Also, JP-A-51-1553
A special bleach-fixing solution comprising a combination of the fixing agent described in No. 54 with a large amount of a halide such as potassium iodide or the like can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent per one is preferably 0.5 to 3 mol, particularly 1 to 2 mol in the processing of color photographic light-sensitive material for photography, and in the processing of color photographic light-sensitive material for printing,
It is in the range of 0.5 to 1 mol.

The pH range of the fixing solution in the present invention is preferably from 4 to 9,
Particularly, 5 to 8 is preferable. If the pH is lower than this, the solution is remarkably deteriorated, and if the pH is higher than this, ammonia volatilizes from the ammonium salt contained and stains are easily generated.

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

The bleach-fixing solution and the fixing solution used in the present invention may be a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. ), Metabisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, aromatic sulfinic acids such as benzenesulfinic acid, paratoluenesulfinic acid, and salts thereof. It contains. These compounds are preferably contained at about 0.02 to 0.50 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

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

After the fixing step or the bleach-fixing step, processing steps such as water washing and stabilization are generally performed, and simple steps such as performing only a water-washing step or a stable processing step without a substantial water-washing step are performed. Various processing methods can be used.

The washing step removes processing liquid components adhered to or occluded in the color photographic material or unnecessary components in the color photographic material, thereby maintaining good image stability and film properties after processing. do. On the other hand, the stabilizing step is a step of improving the storability of an image to a level that cannot be obtained by washing with water.

The rinsing step may be performed in one tank, but is often performed by a multi-stage countercurrent rinsing method of two or more tanks. The amount of water in the washing step can be arbitrarily set according to the type and purpose of the color photosensitive material. For example, Journal of Motion Picture and Television Engineering, Vol. 64, pp. 248-253 (May, 1955) “Water
Flowrates in Immersion Washing of Motion Picture Film Water Flow Rates i
n Immersion-Washing of Motion Picture Film, SRGo
ldwasser).

When the amount of washing water is reduced, the generation of bacteria and mold becomes a problem, but as a countermeasure, it is preferable to use washing water in which calcium and magnesium are reduced as described in JP-A-62-288838. Fungicides and deterrents, such as the Journal of Antibacterial
And Antifungal Agenz (J. Antibac
t.Antifug.Agents) vol.11, No.5, p207-223 (1983)
And the compound described in "Chemistry of Fungicide and Fungicide" by Hiroshi Horiguchi) can be added. Further, as a water softener, a chelating agent such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can be added.

When you save the amount of washing water, as its water, although normally the color light-sensitive material 1 m ² per 100ml~1500ml used,
In particular, the range of 200 ml to 800 ml is preferably used from the viewpoint of achieving both color image stability and water saving effect.

The pH in the washing step is usually in the range of 5-9. In addition, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers for adjusting the membrane pH after the treatment (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide,
Ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. are used in combination), similar chelating agents that can be added to washing water, fungicides, formalin-releasing compounds such as formalin and hexamethylenetetramine, and other applications. A fluorescent whitening agent can be added, and various ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate, and ammonium thiosulfate can be added.

The pH of the stabilizing bath is usually 3 to 8, but a low pH range of 3 to 5 may be preferably used depending on the kind of the light-sensitive material and the purpose of use.

The present invention can be applied to processing of various color light-sensitive materials. Typical examples include a color negative film for general use or movies, and a color reversal film for slides or televisions.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler that provides the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important,
Specific examples of the equivalent or 2-equivalent couplers are described above in RD17643, VII
-In addition to the couplers described in the patents mentioned in sections C and D,
The following can be preferably used in the present invention.

Typical examples of the yellow coupler that can be used include known oxygen atom-eliminable yellow couplers and nitrogen atom-eliminable yellow couplers. α-
Pivaloyl acetanilide couplers are excellent in the fastness of coloring dyes, especially in light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers having a ballast group. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.

Cyan couplers usable in the present invention include hydrophobic and non-diffusible naphthol-based couplers and phenol-based couplers, and a preferred example is an oxygen atom-eliminable double-equivalent naphthol-based cap error. Couplers capable of forming a cyan dye which is robust to humidity and temperature are preferably used.A typical example is an alkyl group such as an ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. A phenolic cyan coupler, a 2,5-diacylamino-substituted phenolic coupler, a phenolic coupler having a 2-phenylureido group and an acylamino group at the 5-position, and a phenolic coupler described in European Patent No. 161626A. And aminonaphthol cyan couplers.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such couplers are specific examples of magenta couplers in U.S. Pat.No. 4,366,237 and the like, and yellow in European Patent No. 96,570 and the like.
Specific examples of magenta or cyan couplers are described.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in U.S. Pat. No. 4,367,282.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers described in the aforementioned RD17643, Section VII-F, are useful.

In the light-sensitive material of the present invention, a coupler which releases a nucleating agent or a development accelerator or a precursor thereof in an image-like manner during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. In addition, DIR described in JP-A-60-185950 and the like
Redox compound releasing couplers, such as the couplers described in EP 173,302A, which release dyes that recolor after release can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,27 and the like. Further, the steps of the latex dispersion method, effects, specific examples of latex for impregnation are described in U.S. Pat.
No. 363, West German Patent Application (OLS) Nos. 2,541,274 and
No. 2,541,230.

Next, specific examples of the present invention will be described, but the present invention is not limited to these examples.

Example 1 Preparation of emulsion 30 g of gelatin and 6 g of potassium bromide were added to water 1 and an aqueous silver nitrate solution (as silver nitrate) was stirred in a container maintained at 60 ° C.
5 g) and 0.15 g of potassium iodide were added by a double jet method over 1 minute. Further, an aqueous nitric acid solution (145 g as silver nitrate) and an aqueous potassium bromide solution containing 4.2 g of potassium iodide were added by a double jet method. At this time, the flow rate was accelerated so that the flow rate at the end of the addition was five times that at the start of the addition. After the addition is complete,
After removing soluble salts at ℃, the temperature was raised to 40 ℃, and 75 g of gelatin was added to adjust the pH to 6.7. The resulting emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. In this emulsion,
Chemical sensitization was performed in combination with gold and sulfur sensitization.

Preparation of photographic material 101 As a surface protective layer, in addition to gelatin, polyacrylamide having an average molecular weight of 8000, sodium polystyrene sulfonate,
Polymethyl methacrylate fine particles (average particle size 3.0
μm), an aqueous gelatin solution containing polyethylene oxide, a hardener and the like.

Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt as a sensitizing dye in the emulsion at a ratio of 500 mg / l mol Ag, Potassium iodide 200mg / l mol
Ag was added at the rate. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5
-Triazine and nitrone, trimethylolpropane as a dry antifoggant, a coating aid, a hardening agent as a coating solution, by coating and drying simultaneously with the surface protective layer on both sides of the polyethylene terephthalate support,
Photographic materials were created. The coated silver amount of this photographic material is 2 g / m ² per side.

Preparation of developer kit The following parts (A), (B) and (C)
(A concentrated solution) was prepared.

Part (A) Developer (used solution) For 10 l Potassium hydroxide 291 g Potassium sulfite 442 g Sodium bicarbonate 75 g Boric acid 10 g Diethylene glycol 120 g Ethylenediaminetetraacetic acid 17 g 5-Methylbenzotriazole 0.6 g Hydroquinone 300 g 1-phenyl-4,4-dimethyl -2-Pyrazolidone 20g Water was added to adjust 2.5l pH to 11.0.

Part (B) For developer (use solution) 10l Triethylene glycol 20g 5-Nitroindazole 2.5g Glacial acetic acid 3g 1-Phenyl-3-pyrazolidone 15g Add water 250ml Part (C) For developer (use solution) 10l Glutaraldehyde 99 g Sodium metabisulfite 126 g Water was added to 250 ml to prepare a starter having the following composition.

Starter Glacial acetic acid 270 g Potassium bromide 300 g Add water 1.5 l Preparation of developer 2.5 l of part (A), 250 ml of part (B) in about 6 l of water
Add and dissolve 250 ml of Part (C) while stirring sequentially,
Finally, the total volume was adjusted to 10 l with water.

Next, a starter was added to the working solution 1 at a ratio of 20 ml.

For fixing, Fuji F (manufactured by Fuji Photo Film Co., Ltd.) to which the compound of the present invention (see Table 1) was added was used.

Ethylenediaminetetraacetic acid disodium salt
Water containing 0.5 g / l of dihydrate (antifungal agent) was used.

Next, the following developing process was performed by a roller transport type automatic developing machine system. Processing temperature Temperature Processing time Image 35 ° C 12.5 seconds Fixing 30 ° C 10 seconds Rinse and squeeze 20 ° C 12.5 seconds Drying 50 ° C 12.5 seconds Table 1 shows the residual color after processing. (Measured value).

As shown in Table 1, when the fixing solution containing the compound of the present invention was used, it was found that the residual color after the processing was small in each case.

Example 2 In the same manner as in Example 1, the photosensitive was subjected to X-ray exposure,
Developing treatment was carried out using the same developing solution, fixing solution and washing solution formulation as in Example 1.

The residual color after the processing is shown below by measuring the transmission optical density of the non-image area with green light.

When the fixing solution containing the compound of the present invention was used, it was found that the residual color after the processing was small.

Example 3 Photographic materials 301 to 307 were prepared using the following sensitizing dyes as sensitizing dyes in the same manner as in Example 1, and processed similarly on an automatic developing machine.

In each case, the residual color was reduced when treated with a fixing solution containing the compound of the present invention.

Example 4 A 0.3 micron cubic silver iodobromide emulsion containing 2.5 mol% iodide was treated with anhydro-5,5-dichloro-9-ethyl-
230 mg of 3,3'-bis (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt (sensitizing dye)
1 mol of silver, 1.3 g of a hydrazine derivative (the following compound) / 1 mol of silver, and 30 parts of polyethylene glycol (molecular weight: about 1000)
0 mg / 1 mol of silver, and a dispersion of 5-methylbenztriazole, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and polymethylene acrylate, 2-hydroxy-1,3,5 -Triazine sodium salt was added.
Further, as a hardener, 1,3-divinylsulfonyl-2-propanol was added in an adjusted amount so that the swelling percentage became 120%.

The coating solution thus prepared was coated on a polyethylene terephthalate film support together with a protective layer at a silver coating amount of 3.
5g / m ² , gelatin coating amount (with emulsion layer and protective layer) 3.0
g / m ² to give a film.

These films were exposed through a sensitometric exposure wedge using a 150-line magenta contact screen, developed with a developer having the following composition at 40 ° C. for 15 seconds, and then fixed with a fixer GR-F1 manufactured by Fuji Photo Film Co., Ltd. Fixing, washing and drying.

The automatic developing machine used here was a dry to dry machine set at 65 seconds.

(Developer composition) Tetrasodium ethylenediaminetetraacetate 1.0 g Sodium hydroxide 9.0 g 5-sulfosalicylic acid 44.0 g Potassium sulfite 100.0 g 5-methylbenztriazole 0.5 g Potassium bromide 6.0 g N-methyl-p-aminophenol 1 / 2H ₂ SO ₄ 0.4 g Hydroquinone 54.0 g Sodium p-toluenesulfonate 30.0 g Water 1 pH 11.7 The same aqueous solution as used in Example 1 was used as the washing water, and 250 ml of large total size (20 inch × 24 inch) was used. Refilled. Similarly, Compound I-6 of the present invention was added to Fixer GR-F1.
1.6 g / l was added for treatment.

When the residual color after the treatment was measured in the same manner as in Example 1, the residual color density was 0.058 less than that of the treatment solution not using the compound of the present invention.

Example 5 While controlling 60 ° C., pAg = 8.0 and pH = 2.0, 2.0 mol% of silver iodide having an average grain size of 0.20 μm by a double jet method.
A monodispersed cubic silver iodobromide emulsion containing A part of this emulsion was used as a core and grown as follows. That is, a solution containing the core particles and gelatin at 40 ° C., pAg 9.0, pH 9.
At 0, the ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide are added by the double jet method, and silver iodide is added.
A first coating layer containing 30 mol% was formed. And further pAg =
At 9.0, pH = 9.0, an ammoniacal silver nitrate solution and a potassium bromide solution are added by a double jet method to form a second coating layer of pure silver bromide, and a cubic monodisperse iodobromide having an average particle size of 0.57 μm. A silver emulsion was prepared and designated as E-1. The average silver iodide content of this emulsion was 2.0 mol%.

The following sensitizing dyes A and B were added to E-1 in the amounts shown below, and 8 × 10 ⁻⁷ mol of chloroaurate, 7 × 10 ⁻⁶ mol of sodium thiosulfate, and 7 × 10 ^{−4 of} ammonium thiocyanate were added. Mole, and optimally sensitized with gold and sulfur to give 4-hydroxy-
6-Methyl-1,3,3a, 7-tetrazaindene was stabilized with 2 × 10 ^-2 mol and the gelatin concentration was adjusted so that the amount of gelatin was 2.25 g / m ² (per side).

Further, the following additives were added to the emulsion and the protective film solution, respectively, and the following hardener was added so that the melting time was 20 minutes.

That is, as an additive for an emulsion layer, 2 × 10 ^-4 mol of the compound of the present invention (see Table 6) per mol of silver halide, 400 ml of t-butyl-catechol, polyvinylpyrrolidone (molecular weight: 10,
000) 1.0 g, styrene / maleic anhydride copolymer 2.5 g,
Trimethylolpropane 10g, diethylene glycol 5
g, nitrophenyl-triphenylphosphonium chloride 50 mg, 1,3-dihydroxybenzene-4-ammonium sulfonate 4 g, 2-mercaptobenzimidazole-5-sodium sulfonate 15 mg, 1,1-dimethylol-1-bromo-1-nitromethane 10 m
g, etc. were added.

Along with the above emulsion, a hardening agent and various additives described below were added so that the melting time was 20 minutes 1.15 g / m
^{2 A} silver halide emulsion layer (viscosity:
11 cp, surface tension 35 dyn / cm, coating thickness 50 μm), and a protective layer (viscosity 11 cp, surface tension 25 dyn / cm, coating thickness 20 μm) were simultaneously coated with two layers at a coating speed of 60 m / min to obtain photographic material 401. Was. The silver amount was 45 mg / dm ² in each case.

The following compounds were added as additives for the protective layer. That is, per 1 g of gelatin, 7 mg of matting agent composed of polymethyl methacrylate having an average particle size of 5 μm, and colloidal silica 70 having an average particle size of 0.013 μm
mg and the like were added.

The hardener amount of each sample was adjusted so that the melting time measured by the following method was 20 minutes.

That is, the time from immersion of a sample cut to 1 cm × 2 cm in a 1.5% sodium hydroxide solution kept at 50 ° C. to the start of elution of the emulsion layer was defined as the melting time.

Further, the sensitivity and fog were measured as follows. That is, the sample is sandwiched between two optical wedges whose density gradients are mirror-symmetrically aligned, and exposed to light from a light source having a color temperature of 5400 ° K at the same time and equally for 1 / 12.5 seconds from both sides.

The processing was performed according to the following steps using a roller transport type automatic developing machine having a total processing time of 45 seconds.

Processing temperature Processing time Insertion-1.2 seconds Developing + migrating 35 ° C 14.6 seconds Fixing + migrating 33 ° C 8.2 seconds Rinse + migrating 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Drying 45 ° C 8.1 seconds Total-45.0 seconds In this embodiment, an apparatus having the following specifications was used.

That is, in this example, a rubber roller is used as the roller,
The material used was silicone rubber (hardness: 48 degrees) at the transition portion, and EPDM (hardness: 46 degrees), a kind of ethylene propylene rubber, in the treatment liquid. Surface roughness Dmax of the roller = 4 μm,
The number of rollers was 6 in the developing section, and the total number was 84.
The number of opposing rollers is 51, and the ratio of the number of opposing rollers / the total number of rollers is 51/84 = 0.61. Developer replenishment amount is 2
0cc / quarter, fixer replenishment amount 45cc / quarter, washing water volume 1.5l /
min. The air volume in the drying section is 11 m ² / min, the heater capacity is 3
KW (200V) was used.

 The total processing time is 45 seconds as described above.

The following developer-1 was used as the developer. The following fixing solution-1 was used as the fixing solution.

From the obtained characteristic curve, base density + fog density + 1.0
And the relative sensitivity was determined.

Composition of developer and fixer Next, the residual color property was evaluated. The transmission optical density of the non-image area was measured with green light.

Further, for each sample, the sensitivity was also obtained when the line speed of the 45-second automatic developing machine was reduced to half and the conventional 90-second processing was performed. Table 6 shows the results.

As is clear from Table 6, the sample according to the present invention has sensitivity,
It is excellent in fog, residual color, etc., which indicates that it is suitable for ultra-rapid processing.

Compared with the conventional 90-second processing, the remaining color can be reduced and the processing time can be reduced to half while maintaining high sensitivity compared to the conventional system, that is, the processing capacity is doubled. You can see that.

Example 7 A silver halide emulsion composed of silver chlorobromide (5 mol% silver bromide average particle size: 0.25 μ) containing 1 × 10 ^-5 mol of Rh per mol of silver was prepared.

Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) as a sensitizing dye in the above emulsion
500 m of oxacarbocyanine hydroxide sodium salt
g / 1 mol Ag was added. Further polystyrene potassium sulfonate was added as a 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium and thickeners as hardeners, coating silver amount to a polyethylene terephthalate film is to 4g / m ² It applied so that it might become. On this emulsion layer, a gelatin solution was applied as a protective layer so that the amount of gelatin became 1.0 g / m ² . As a coating aid for this protective layer, p
-Sodium dodecylbenzenesulfonate and the same thickener as in the emulsion layer were used.

The thus-obtained sample was exposed through a light wedge using a P-607 type printer manufactured by Dainippon Screen Co., Ltd., and then developed using the following developing solution and fixing solution formulation.

<Developer> Fuji Photo Film Fixer LD-8-35, 38 ° C, 20 seconds <Fixer> Fuji Photo Film Developer LF308 <Automatic developing machine> Fuji Photo Film FD-800RA Example 8 A sulfur-sensitized silver halide emulsion composed of 93% by mole of silver bromide and 7% by mole of silver iodide was prepared. The average diameter of silver halide grains contained in this emulsion was 0.7 μm. 1 kg of this emulsion contained 0.52 mol of silver halide.

This emulsion was weighed into a pot of 1 kg each, and sensitizing dye SD was 32 m.
g / 1 kg of emulsion was added and mixed and stirred at 40 ° C. 4 more
-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene: 0.01 g / emulsion 1 kg, 1-hydroxy-3,5-dichlorotriazine soda 0.1 g / emulsion 1 kg, and sodium dodecylbenzenesulfonate 0.1 g g / emulsion of 1 kg were sequentially added and coated on a polyester terephthalate film base to obtain a photographic light-sensitive material.

The film sample was subjected to light wedge exposure using a sensitometer having a light source having a color temperature of 2854K with a dark red filter (SC-74) manufactured by Fuji Photo Film Co., Ltd. attached to the light source. After exposure, the film was developed with a developing solution having the following composition at 20 ° C. for 3 minutes, stopped, and then fixed using the following fixing solution and further washed with water.

Table 8 shows the residual colors (transmission optical densities of non-image portions) after the processing.

Developer Water 500 ml N-methyl-p-aminophenol 2.2 g Sodium sulfite anhydrous 96.0 g Hydroquinone 8.8 g Sodium carbonate monohydrate 56.0 g Potassium bromide 5.0 g Compound of the present invention 1.7 g Add water 1 Fixer Fuji Fixer LF308 made by Photographic Film In each case, the developer containing the compound of the present invention showed little residual color.

Example 9 Using a double jet method, a cubic, monodispersed silver chloroiodobromide emulsion having an average grain size of 0.3 μm (coefficient of variation: 0.13, silver iodide 0.1%).
1 mol% and 33 mol% of silver bromide were prepared.

This emulsion was desalted by a conventional method, subjected to gold-sulfur sensitization, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and the sensitizing dyes shown in Table 9 were added to the emulsion. The dye was sensitized by adding 150 mg per mol of silver halide contained therein.

500 mg of potassium bromide, 100 mg of sodium p-dodecylbenzenesulfone, 30 mg of 5-nitroindazole, 20 mg of 5-methylbenzotriazole per mole of silver halide
mg, 1.5 g of a styrene / maleic acid copolymer and 15 g of a styrene / butyl acrylate copolymer latex (average particle size 0.25 μm) were added.

Further, a tetrazolium salt compound of the following structural formula was added at 1 × 10 ⁻³ mol per mol of silver, and then a coated silver amount of 4.0 g /
Coating was carried out on a subbed support described in Example 1 of JP-A-59-19941 so that the amount of m ² and the amount of gelatin became 2.1 g / m ² .

At this time, 1-decyl-2- (3-isopentyl) succinate was used as a spreading agent so that the amount of gelatin became 1.2 g / m ^2.
A protective layer containing 30 mg / m ^{2 of} sodium 2-sulfonate and 25 mg / m ² of formalin as a hardening agent was simultaneously and multi-layer coated to prepare a sample. These samples were processed at 28 ° C. for 30 seconds using a GR-27 automatic developing machine manufactured by Konica Corporation, Konica Developer CDM-651K and Konica Fixer CFL-851 containing the compounds shown in Table 7.

 The back layer was applied according to the following formulation.

(Back layer formulation)

Gelatin 4g / m ² Matting agent polymethyl methacrylate (particle size 3.0
4.0μ) 10mg / m ² latex Polyethyl acrylate 2g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40mg / m ² Dye Mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ² Sensitizing dye A 1- (β-hydroxyethyl) -3-phenyl-5-
[(3-α-sulfopropyl-α-benzoxazolidene) -ethylidene] thiohydantoin sensitizing dye B anhydro-5,5′-dichloro-9-ethyl-3,3′-
Di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt Sensitizing dye C Potassium-4- [5-chloro-2- {2- [1-
(5-hydroxy-3-oxapentyl) -3- (2-
Pyridyl) -2-thiohydantoin-5-ylidene] ethylidene {-3-benzoxazolinyl] butanesulfonate In each case, the residual color was reduced when treated with a fixing solution containing the compound of the present invention.

Example 10 Preparation of Emulsion 30 g of gelatin and 6 g of potassium bromide were added to water 1 and an aqueous silver nitrate solution (as silver nitrate) was stirred in a container maintained at 60 ° C.
5 g) and 0.15 g of potassium iodide were added by a double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide were added by a double jet method. At this time, the flow rate was accelerated so that the flow rate at the end of the addition was five times that at the start of the addition. After the addition is complete,
After removing soluble salts at ℃, the temperature was raised to 40 ℃, and 75 g of gelatin was added to adjust the pH to 6.7. The resulting emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. In this emulsion,
An emulsion was prepared by performing chemical sensitization using gold and sulfur sensitizations in combination.

Preparation of photographic material As a surface protective layer, in addition to gelatin, sodium polystyrene sulphonate, polymethyl methacrylate fine particles (average particle size 3.0 μm), polyethylene oxide, a ^10-3 mol methanol solution of a compound of the present invention (see Table 10) in 200 m.
An aqueous gelatin solution containing 1/1 mol Ag and a hardener was used. The above emulsion sensitizing dye anhydro-5,5'-di-
Chloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbanine hydroxide sodium salt 500 mg / 1 mol Ag and potassium iodide 200 mg / 1 mol Ag were added. Further, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine,
A photographic material was prepared by adding trimethylolpropane as a dry antifoggant, a coating aid, and a hardening agent to form a coating solution, and coating and drying both sides of the polyethylene terephthalate support simultaneously with the surface protective layer. The coated silver amount of the photographic material is 3.7 g / m ^{2 on} both sides.

Processing Method The formulas of the developing solution and the fixing solution (1) are as follows.

Developer Diethylenetriaminepentaacetic acid 2g 1-phenyl-3-pyrazolidone 2g Hydroquinone 30g 5-Nitroindazole 0.25g 5-Methylbenzotriazole 0.02g Potassium bromide 1g Anhydrous sodium sulfite 60g Potassium hydroxide 30g Potassium carbonate 5g Boric acid 6g Diethylene glycol 20g Glutaraldehyde 5g Add water to make the total amount 1 (pH adjusted to 10.50) Fixer (I) Ammonium thiosulfate 175g Sodium sulfite (anhydrous) 20.0g Boric acid 8.0g Disodium ethylenediaminetetraacetate dihydrate 0.1g Aluminum sulfate 15.0 g sulfuric acid 2.0 g glacial acetic acid 22.0 g Compound I-6 of the present invention 1.7 g 1.7 g water was added to 1.0 l (the pH was adjusted to 4.20). In the tank of the automatic processing machine, a liquid was used as a developing solution, in which 20 ml of an aqueous solution (starter) containing 2 g of potassium bromide and 4 g of acetic acid (90%) was added to the replenisher 1 described above. Each time, the replenisher was replenished at a constant rate. As the fixing solution, a solution having the same composition as the replenisher was used in the tank of the automatic developing machine.

The following colors (500th sheet) of the sensitizing dye in the processing solution when the above-mentioned photographic materials were processed in various sizes under the following conditions under the following conditions:

Example 11 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layered manner to produce a multilayer color photosensitive material 1101.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, for the sensitizing dye and the compound of the present invention,
The coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

(Sample 1101) 1st layer; antihalation layer Black colloidal silver silver 0.18 gelatin 0.48 2nd layer; intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U- 1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.12 Gelatin 1.24 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0) .
6 μ, variation coefficient 0.15) silver 0.55 sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 sensitizing dye IV 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.45 4th layer (2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.3
7 μ, average aspect ratio 5.5, average thickness 0.2 μ) silver 1.0 sensitizing dye I 5.1 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.3 × 10 ^-4 sensitizing dye IV 3.0 × 10 ^-5 EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.50 5th layer (3rd red-sensitive emulsion layer) Silver iodobromide emulsion (16 mol% of silver iodide, average grain size 1.1μ) Silver 1.60 Sensitizing dye IX 5.4 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.4 × 10 ^-4 sensitizing dye IV 3.1 × 10 ^-5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 2.00 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 gelatin 1.00 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size) 0.
6μ, average aspect ratio 6.0, average thickness 0.15μ) silver 0.40 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-4 sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX -7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.90 Eighth layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.1%)
7μ, coefficient of variation 0.18) silver 0.80 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 0.010 EX-1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.30 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (12 mol% silver iodide, average particle size 1.0μ)
Silver 1.2 sensitizing dye V 3.5 × 10 ^-5 sensitizing dye VI 8.0 × 10 ^-5 sensitizing dye VII 3.0 × 10 ^-4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 gelatin 2.00 10th layer (yellow filter layer) Yellow colloidal silver silver 0.05 EX-5 0.08 HBS-3 0.03 gelatin 1.10 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, Average particle size 0.
6μ, average aspect ratio 5.7, average thickness 0.15) silver 0.24 sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 gelatin 1.50 twelfth layer (second blue-sensitive emulsion layer) monodisperse iodine Silver bromide emulsion (silver iodide 10 mol%, average grain size 0.
8μ, coefficient of variation 0.16) silver 0.45 sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 gelatin 0.55 layer 13 (third blue-sensitive emulsion layer) silver iodobromide emulsion (Silver iodide 14 mol%, average grain size 1.3μ)
Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.85 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average particle size 0.07μ)
Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.20 Fifteenth layer (second protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.90 In addition to the above components, a gelatin hardener H-1 and a surfactant were added.

The sample 1101 has a thickness of all photographic constituent layers in the present invention of 22.
μ, and the membrane swelling speed T1 / 2 was 12 seconds.

Next, the amount of gelatin and the amount of hardener in each layer of the sample 1101 were reduced, and the sample 1102 having a thickness of 19μ and T1 / 29 seconds, a thickness of 17μ, and a thickness of T1 / 2
A sample 1103 of 7 seconds was produced.

EX-11; same as EX-, but R = H HBS-1; tricresyl phosphate HBS-2; dibutyl phthalate HBS-3; bis (2-ethylexyl) phthalate Samples 1101, 1102, and 1103 prepared as described above were 35 mm wide.
Fed a standard exposure in a camera then cut into, and mixed processing processed by one day by each 1 m ² of the following using an automatic developing machine
This continued for 10 days.

The magenta transmission density of the unexposed portion of each sample processed at the first (fresh processing) and the last (running processing) of the above processing was measured with an X-Rite 310 photographic densitometer (running processing)-( Fresh processing), that is, a change in magenta density due to running.

In addition, each sample of the running process was 60 ° C and 70% relative humidity.
Was stored for one week, and the change in magenta transmission density during this period was evaluated.

 The above results are shown in Table-11.

In the above, the wet processing time from immersion of the photosensitive material in the color developing solution to removal of the stabilizing solution is 5:00 seconds. The total amount of replenishment is 1730 ml.

(Bleaching solution) Common to mother liquor and replenisher (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 160.
0 Disodium ethylenediaminetetraacetate 10.0 Ammonium bromide 160.0 Ammonium nitrate 10.0 Bleach accelerator 0.010 mol Ammonia water (27%) 5.0ml Add water (tap water) 1.0l pH 5.3 (Bleaching / fixing solution) Common for mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate Ammonium dihydrate 80.0 Disodium ethylenediaminetetraacetate Salt 5.0 Ammonium sulfite 15.0 Aqueous ammonium thiosulfate solution (700 g / l) 300.0 ml Aqueous ammonia (27%) 6.0 ml Compound of the present invention See Table 11 Add water 1.0 l pH 7.2 (tap water) All mother liquor, replenisher common tap water Is passed through a mixed-bed column filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400) to obtain the following water qualities. did.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water (tap) Water) 1.0l pH 5.0−8.0 As shown in Table 11, according to the present invention, it is possible to control the increase in the magenta density of the unexposed portion due to running to a level that does not cause any harm. In addition, an increase in the magenta density in the unexposed area under high-temperature and high-humidity storage was also able to be suppressed at the same time. It is apparent that the above effects can be further improved by reducing the thickness of the photographic constituent layer and increasing the swelling speed T1 / 2.

Example 12 On a cellulose triacetate film support provided with an undercoat, layers having the following compositions were applied in a multi-layered manner to prepare a multilayer color photosensitive material 1201.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown per mol of 1 mol of silver halide in the same layer.

First layer (anti-halation layer) Black colloidal silver 0.2 Gelatin 1.2 UV absorber UV-1 0.05 Same UV-2 0.1 Same UV-3 0.1 Dispersed OIL-1 0.02 Second layer (Intermediate layer) Fine grain silver bromide (average grain 0.15 gelatin 1.2 Third layer (first red-sensitive emulsion layer) monodisperse emulsion (silver iodide 6 mol%, average particle size 0.4 μm, coefficient of variation 15%) 1.42 gelatin 1.1 sensitizing dye A 2.0 × 10 ^-4 sensitizing dye B 1.0 × 10 ^-4 sensitizing dye C 0.3 × 10 ^-4 Cp-b 0.35 Cp-c 0.052 Cp-d 0.047 D-1 0.023 D-2 0.035 HBS-1 0.10 HBS-2 0.10 4th Layer (intermediate layer) Gelatin 1.0 Cp-b 0.10 HBS-1 0.05 Fifth layer (second red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 6 mol%, average grain size 0.5 μm, variation coefficient 15%) 1.38 gelatin 1.2 Sensitizing dye A 1.5 × 10 ^-4 Sensitizing dye B 2.0 × 10 ^-4 Sensitizing dye C 0.5 × 10 ^-4 Cp-b 0.150 Cp-d 0.027 D-1 0.005 D-2 0.010 HBS-1 0.050 HBS- 2 0.060 6th layer (3rd layer Red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 7 mol%, average grain size 1.1 μm, variation coefficient 16%) 2.08 gelatin 1.7 Cp-a 0.060 Cp-c 0.024 Cp-d 0.038 D-1 0.006 HBS-1 0.012 Seventh layer (intermediate layer) Gelatin 1.2 Cpd-A 0.05 HBS-2 0.05 Eighth layer (first green sensitive layer) Monodisperse silver bromide emulsion (silver iodide 3 mol%, average grain size 0.4 μm)
m, coefficient of variation 19%) 0.64 gelatin 1.2 monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7μ)
m, coefficient of variation 18%) 1.12 gelatin 1.2 sensitizing dye D 1 × 10 ^-4 sensitizing dye E 4 × 10 ^-4 sensitizing dye F 1 × 10 ^-4 Cp-h 0.20 Cp-f 0.61 Cp-g 0.084 Cp -K 0.035 Cp-1 0.036 D-3 0.041 D-4 0.018 HBS-1 0.25 HBS-2 0.45 Ninth layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 7 mol%, average Particle size 1.0μ
2.07 Gelatin 1.7 Sensitizing dye D 1.5 × 10 ^-4 Sensitizing dye E 2.3 × 10 ^-4 Sensitizing dye F 1.5 × 10 ^-4 Cp-f 0.007 Cp-h 0.012 Cp-g 0.009 HBS -2 0.088 10th layer (intermediate layer) Yellow colloidal silver 0.06 gelatin 1.4 Cpd-A 0.3 HBS-1 0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, 0.31 Monodispersed silver iodobromide emulsion (5 mol% silver iodide, average particle size 0.9 μm, coefficient of variation 17%) 0.38 Gelatin 2.0 Sensitizing dye G 1 × 10 ^-4 Sensitizing dye H 1 × 10 ^-4 Cp-i 0.63 Cp-j 0.57 D-1 0.020 D-4 0.015 HBS-1 0.05 12th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (iodide 8 mol% silver, average particle size 1.3μ
m, coefficient of variation 18%) 0.77 gelatin 0.7 sensitizing dye G 5 × 10 ^-5 sensitizing dye H 5 × 10 ^-5 Cp-i 0.10 Cp-j 0.10 D-4 0.005 HBS-2 0.10 Layer 13 (intermediate layer) Gelatin 0.7 Cp-m 0.1 UV-1 0.1 UV-2 0.1 UV-3 0.1 HBS-1 0.05 HBS-2 0.05 14th layer (protective layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average Particle size 0.05μ
m, coefficient of variation 10%) 0.1 Gelatin 1.5 Polymethyl methacrylate particles (average 1.5 μ) 0.1 S-1 0.2 S-2 0.2 Other surfactant K-1 and gelatin hardener H-1 were added.

The amount of gelatin and the amount of hardener of Sample 1201 were reduced, and the following samples were prepared in all.

Sample Thickness of photographic constituent layer Film swelling speed T1 / 2 1201 24μ 12 seconds 1202 19μ 8 seconds 1203 16μ 6 seconds After exposing the above sample to the camera, each sample was 1 m ² per day as in Example-11. Mixing treatment was continued for a total of 10 days.

 The processing performed is as follows.

 Processing and evaluation of the sample were performed in the same manner as in Example-11.

The above wet processing time is 4 minutes and the replenishment amount is 1330 ml in total
It is.

(Stable liquid) Common to mother liquor and replenisher (unit: g) Tap water 1.0 l Formalin (37%) 1.2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 6.0 mg 2-methyl-4-isothiazoline-3 -One 3.0 mg surfactant; 0.4 [C ₁₀ H ₂₁ OCH ₂ CH ₂ O ₁₀ H] ethylene glycol 1.0 The results are shown in Table-12.

As in the case of Example-11, the present invention is effective in suppressing the increase in magenta density in the unexposed area and suppressing the increase in cyan density in the unexposed area under high temperature and high humidity storage.

Example 13 A multilayer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) To 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and 8.2 g of the solvent (Solv-3) were added and dissolved.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide
The following blue-sensitive sensitizing dyes were added to the large-sized emulsion at a concentration of 2.0 × 10 ^-4 mol per mol of silver, and the small-sized emulsion was added to the small-sized emulsion. ^Were prepared by adding 2.5 × 10 ^-4 mol of each and then sensitizing with sulfur. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
6.0 × 10 ^-4 mol, 8.4 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
10 × 10 ^-5 mol, or 1.5 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

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

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion has AgBr0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Variation in grain size distribution The coefficients are 0.09 and 0.11, AgBr0 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing 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 (denaturation degree
17%) 0.17 Liquid paraffin 0.03 (Solv-3) Solvent O = PO-C ₉ H ₁₀ (iso)) ₃ First, each sample was subjected to continuous processing (running test) using a paper processing machine until replenishment of twice the tank capacity for color development in the next processing step.

Processing temperature Temperature Replenisher * Tank capacity Color development 38 ° C 20 seconds 161ml 17l Bleaching and fixing 35-38 ° C 20 seconds 215ml 17l Rinse 35-38 ° C 7 seconds ― 10l Rinse 35-38 ° C 7 seconds ― 10l Rinse 35-38 ° C 6 seconds 350 ml 10l drying 70 to 80 ° C. 30 seconds * replenishment rate (as a tank countercurrent system to rinse →.) per photosensitive material 1 m ² is had the following composition of each processing solution.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Compound I-6 of the present invention 1.7 g Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Bromide Ammonium 40g Add water 1000ml pH (25 ℃) 6.0 Rinse solution (Tank solution and replenisher are the same) Ion exchange water (Calcium and magnesium 3ppm or less each) Bleaching and fixing containing the compound of the present invention obtained as above In the case of processing with the solution, the reflection density based on the residual color of the sensitizing dye in the unexposed area was reduced by 0.055 compared with the case of processing with the bleach-fixing solution not containing the compound of the present invention, which was remarkably improved.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-58-160948 (JP, A) JP-B-7-119974 (JP, B2) JP-B-62-32777 (JP, B2) European Patent Publication 173540 ( EP, A3)

Claims (2)

(57) [Claims] 1. A processing solution for a silver halide light-sensitive material, wherein the processing solution comprises an aqueous solution containing a compound represented by the following general formula (I). liquid. General formula (I) 2. A method for processing a silver halide light-sensitive material, comprising processing the silver halide light-sensitive material with a processing solution containing the compound represented by the formula (I).