JPH03213856A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To solve a problem on color stains due to residual dyes and to eliminate problems of after color by executing post-rinsing and/or stabilizing treatment after development and fixation and specifying amounts of rinsing and/or stabilizing solution to be replenished. CONSTITUTION:This silver halide photographic sensitive material has at least one hydrophilic colloidal layer on each side of a support and at least one of them contains at least one kind of dye selected from the groups of compounds represented by formulae I - III, and it is subjected to the rinsing and/or stabilizing treatment after the development and fixation steps, and the amount of replenishing solution in the rinsing and/or the stabilizing treatment is regulated to <= 3 l/m<2> of this photosensitive material, thus permitting the obtained photosensitive material to be solved on problems of after color and stains due to sludge to be eliminated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide photographic materials.

[Conventional technology]

Conventionally, various dyes have been used in silver halide photographic materials for various purposes.

For example, a colored layer called a filter layer is generally provided outside the photosensitive emulsion layer (on the side farther from the support). This filter layer is used when it is necessary to control the spectral composition of light incident on the photosensitive emulsion layer. When there are a plurality of photosensitive emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between the emulsion layers.

Further, in order to prevent halation, a colored layer may be provided between the photosensitive emulsion layer and the support, or on the opposite side of the support from the photosensitive emulsion layer.

This is because incident light is scattered when passing through or after passing through the light-sensitive emulsion layer, and this scattered light is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material on the opposite side of the emulsion layer, and is reflected back into the emulsion layer. Blurred images caused by entering the
It suppresses so-called halation and is generally called an antihalation layer. In the case of multilayer color photosensitive materials, an antihalation layer may be formed between each layer.

Furthermore, the emulsion layer is colored in order to prevent deterioration in image sharpness caused by irradiation, that is, scattering of light in the emulsion.

As mentioned above, the silver halide emulsion layer and other layers are colored to absorb light of a desired wavelength.

[The problem that the invention attempts to solve]

In photosensitive materials provided with various colored layers as described above, dyes used for coloring may remain on the photosensitive materials after processing, resulting in undesirable coloring. Therefore, it is desirable that the dye for forming the colored layer be removed during processing by decoloring or dissolving during processing, and no residual color will occur.

However, on the other hand, if a dye that is eluted during processing is used to prevent residual color, sludge may be generated in the processing solution. This sludge may cause film stains on the photosensitive material to be processed.

In addition, the dyes used in the colored layers of photosensitive materials are required to satisfy conditions such as sufficient spectral absorption as well as having no adverse effect on photographic performance. No technique has yet been proposed that satisfies the above requirements and sufficiently solves the problems of residual color and staining caused by sludge.

The present invention was made in view of the above circumstances, and
An object of the present invention is to provide a method for processing a silver halide photographic material, which can form a colored layer with desired performance, solve the problem of residual color, and prevent staining due to sludge.

(Means for Solving the Problems) The object of the present invention is to provide at least one on each side of the support.
a hydrophilic colloid layer, and at least one of the hydrophilic colloid layers has a general formula (Ia) (Ib) (Ic
) (Detailed description below) A silver halide photographic photosensitive material containing a small amount of (sometimes referred to as the "dye of the present invention") arbitrarily selected from the group consisting of compounds represented by A processing method in which a material is processed in a processing step including development and fixing steps, in which washing and/or stabilization treatment is performed after the development and fixing steps, and the washing and/or stabilization treatment is performed.
Or, the amount of replenisher in the stabilization treatment is 3 I per 1 rf of the silver halide photographic light-sensitive material! This was achieved by the method for processing a silver halide photographic material characterized by the following.

The present invention will be further explained below.

First, the dye of the present invention represented by the general formula [Ia] [Ib] [Ic] will be explained.

- Numerical formula (I a) General formula (Ib) General formula [I C] In the formula, R+, R1, Rs, Ra, R* and R1 each represent an alkyl group, and Yl and Y each form a pyrrolopyridine ring Represents a group of nonmetallic atoms necessary for

- The ring of Y in formula (Ib) (Ic) includes.

R3Rt, R in general formula (Ia) (Ib) (Ic)
LR4, RLRs, Y+, Yt are each a group that allows the dye molecule to have at least two acid groups or -
CH2CH, represents a group capable of having at least two substituents having one or more OR groups. R represents a hydrogen atom or an alkyl group.

L represents a methine group, and Xθ represents an anion.

m represents an integer of 4 to 5, and n represents an integer of 1 or 2. When the dye forms an inner salt, n is l.

Examples of the acid groups in the general formulas [Ia], [Ib], and [Ic] include sulfonic acid groups, carboxylic acid groups, and phosphonic acid groups, and each of these acid groups includes its salts. Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

The alkyl group represented by R1, Rt, Rx, Ra, Rs and R6 preferably represents a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, i-propyl, butyl group, etc.), the acid substituent or -CH
It may have substituents other than 2CH and OR groups.

The alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.

Examples of substituents containing -CH2Cl and OR groups include hydroxyethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethylcarbamoylmethyl group, hydroxyethoxyethylcarbamoylmethyl group, N,N-dihydroxyethylcarbamoylmethyl group, Examples include hydroxyethylsulfamoylethyl group and methoxyethoxyethoxycarbonylmethyl group.

Y and other substituents that Y may have include:
Sulfo group (including salt), carboxyl group (including salt),
Examples include hydroxyl groups, cyano groups, halogen atoms (eg, fluorine, chlorine, bromine atoms, etc.).

The methine group represented by may also have a substituent (substituents include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl, 3-hydroxybrobyl, 2-sulfoethyl, etc.), halogen atoms (e.g., fluorine, chlorine, bromine, etc.), aryl groups (e.g., phenyl), alkoxy groups (e.g., methoxy, ethoxy, etc.). , the substituents of the methine group may be bonded to each other to form a 6-membered ring containing three methine groups (for example, a 4,4-dimethylcyclohexene ring).

The anion represented by Xe is not particularly limited, and specific examples thereof include a halogen ion, p-toluenesulfonate ion, and ethylsulfate ion.

The above formulas (Ia) (Ib) and (
Specific examples of the dye of the present invention represented by Ic) are shown below, but the present invention is not limited thereto.

Among the specific compound examples illustrated below, (3) (4) (l
O) ~ (13) (19) (20) (23) (2
6) (29) (32) is - a dye represented by formula (Ia), (1) (2X5) ~ (9) (14) ~ (18)
(21) (22) (24) (25) (27)
(3l) (33) or - A dye represented by formula (Ib); (28) (30) or - a dye represented by formula (Ic).

Specific compounds (1) (2) (3) (4) (5) (6) (7) (8) (9) (lO) (11) (12) (13) (14) (15) (16 ) (I7) (18) (19) (20) (21) (22) e (23) C10 (24) (25) (26) (27) (28) (JH*)ssOsθ (JH mountain 5OIN & (29 ) (30) (3l) (32) (33) The dye of the present invention is described in Journal of the Chemical Society (J, Chem, Soc,) p. 189 (1)
933), U.S. Pat.

Examples of the compound forming the mother nucleus of the dye of the present invention include the following compounds.

(A) (B) (C) Compound (A) is J, Chem, Soc, , 32
02 (1959) and British Patent No. 870.7
It can be synthesized by the method described in No. 53.

Compound (B) is J, Chem, Soc, 58
4 (1961).

Compound (C) can be synthesized by the method described in British Patent No. 841.588.

Using these cores, quaternization, sulfonation, etc. can be carried out as necessary. Or J, Chem.

Soc, 3202 (1959) and J, Che
N-alkyl-N-pyridylhydrazine was synthesized according to the synthesis method described in J. M. Soc., 584 (1961). A cyclization reaction was carried out via a hydrazone, and if necessary, acid treatment was performed to obtain l-alkyl-substituted - It is also possible to obtain a 3H-pyrrolopyridine derivative and use this as a starting material.

The above-mentioned dye is dissolved in a suitable solvent (e.g., water, alcohols such as methanol and ethanol, methyl cellosolve, etc., or a mixed solvent thereof) to obtain a hydrophilic material for forming a desired colored layer of a photosensitive material. It can be used by adding it to a coating solution for a colloid layer.

In the present invention, at least one of the compounds represented by the general formulas (I a), (I b), or (Ic) may be contained in the photosensitive material to be processed (
Furthermore, two or more types can be used in any combination (for example, compounds represented by the same general formula, compounds represented by different formulas, etc.).

The specific amount of dye used varies depending on the purpose, and is difficult to set uniformly, or is generally 10-'g/rrr-1,0g/
In particular, a preferable amount can be found in the range of 10-''g/rrf to 0.5g/rrf.

The dyes represented by the general formulas (Ia), (Ib), and (Ic) of the present invention can be used in various colored layers. For example, it is particularly effective for the purpose of preventing irradiation. When used for this purpose, it is mainly added to the silver halide emulsion layer.

The dye of the present invention is also particularly effective as an antihalation dye, and in this case it is generally added to the back side of the support or to a layer between the support and the emulsion layer.

The dyes of the invention can also be used as dyes to impart safelight safety, in which case they are generally used in silver halide emulsion layers, optionally in combination with dyes that absorb light at other wavelengths. Layer located on top (protective layer, etc.)
It is added to and used.

Additionally, the dyes of the present invention can be advantageously used as filter dyes.

In carrying out the processing method of the present invention, the amount of gelatin on the side containing the dye of the present invention of the photosensitive material to be processed is 3.5
g/rrf or less, preferably 3.0 g
It is more preferable that it is below /rd.

Furthermore, the swelling rate of the photosensitive material to be processed after fixing is 150%.
It is preferable that it is below, and more preferably that it is 100% or less.

Here, the swelling rate is: (a) The photosensitive material to be processed is heated at a temperature of 25°C and a relative humidity of 50%.
(b) Measure the thickness of the hydrophilic colloid layer; (C) Normally process using a developing/fixing means using the photosensitive material; and (d) Measure in step (b). It can be determined by measuring the percentage change in the layer thickness compared to the thickness of the hydrophilic colloid layer.

Further, in the treatment method of the present invention, the water washing or stabilization treatment time is preferably 15 seconds or less, more preferably 10 seconds or less.

Next, the photosensitive material to be processed in the present invention will be described in more detail as follows. The light-sensitive material may contain the dye of the present invention in at least one of the silver halide emulsion layer and/or other hydrophilic colloid layer, and other structures are not particularly limited. For example, as the silver halide used in the silver halide emulsion layer, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. can be used. You can use one of these.

Preferably, a silver chloride emulsion having a silver chloride content of 50 mol % or more is used.

Further, the average grain size of the silver halide grains is preferably 0.4 μm or less. The particle size follows the definition and measurement method described below.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the interior and surface layer of the grain, and the latent image is mainly formed on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

In the light-sensitive material, silver halide grains may have any shape.

One preferred example is one having a (100) plane as a crystal surface.

In particular, the ratio of (100) plane/(111) plane is 71 or more than 5.
0 silver saponide grains are preferred. It may be a (100) plane or 100%.

The (100) plane/(111) sedimentation ratio of particles can be measured by Kubelkamunk's dye adsorption method.

In this method, the dye preferentially adsorbs to either the (100) plane or the (111) plane, and the association state of the dye on the (100) plane and the association state of the dye on the (111) plane differ spectrally. Select and use. The (100) plane/(111) sedimentation ratio can be determined by adding such a dye to an emulsion and examining the spectroscopic spectrum in detail with respect to the amount of the dye added.

The detailed ratio of (100) planes on the silver halide grain surface is as follows:
Tadaaki Tani [Identification of crystal phase of silver halide fine grains in photographic emulsion using dye adsorption phenomenon] Journal of the Chemical Society of Japan 6.942
~946 (1984).

Preferred silver halide grains having a ratio of (100) planes/(111) planes of 5 or more can be prepared by various methods.

- For boat fishing, the pAg value during particle formation is maintained at a constant value of 8.1O or less, and silver nitrate aqueous solution and alkali halide aqueous solution are simultaneously added at a rate faster than the dissolution rate of the particles and at a rate high enough to prevent re-nucleation. It can be preferably prepared by the controlled double jet method. More preferably, the pAg value is 7.80 or less, and even more preferably, the pAg value is 7.60 or less. When silver halide grain formation is divided into two processes: nucleation and growth, the p
There is no limit to the Ag value, and the pAg value during growth is preferably 8.
．． It is good to set it to IO or less, more preferably 7.80 or less, still more preferably 7.60 or less. Further, the method for reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, or a simultaneous mixing method is better in order to obtain good monodispersity.

Also, U.S. Patent Nos. 4.183.756 and 4.225
．． No. 666, JP-A-55-26589, JP-A-55-
Specifications such as No. 42737, The Journal Sai, P.
Photographic Science (J, Photogr,
Particles having shapes such as an octahedron, a tetradecahedron, and a dihedron can also be prepared by the method described in the literature such as 5ci), 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains may be of a single shape or may be a mixture of grains of various shapes.

Also, emulsions with any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions)
Alternatively, an emulsion with a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several types.

Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In this specification, the average particle size r is defined as the particle size "1" when the product ni x ri2 of the frequency ni and ri3 of particles having the particle size ri is maximum.

In the case of spherical silver halide grains, the grain size referred to here means the diameter thereof, and in the case of grains having shapes other than spherical, the diameter when the projected image is converted into a circular image of the circumferential area.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print. (The number of grains to be measured shall be 1,000 or more indiscriminately.) Particularly preferred highly monodispersed emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, see Glafkides, Zelikman et al., or H. Frleser, ed.
g-ender Photography
Prozesse mit Silberha-1ag
eniden SAkademicche Verla
gsgesellschaft.

(1968) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metals, etc. can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat. .689, same 2
．． No. 278.947, No. 2728, No. 668, No. 3.
No. 656.955.

As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in US Pat.
No. 487.850, No. 2.419.974, No. 2.5
No. 18.698, No. 2.983.609, No. 2.98
3.610 and 2.694.637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used.
No. 83, No. 2.448.060, British Patent No. 618.
It is described in No. 061.

Also, there are no particular restrictions on the conditions such as p)I, pAg, temperature, etc. during chemical sensitization.The pH value is preferably 4 to 9, especially 5 to 8, and the pAg value is 5 to 11, especially 7 to 8. It is preferable to keep it at 9. In addition, the temperature is 40 to 90°C1
Particularly preferred is 45 to 75°C.

In addition to sulfur sensitization and gold/sulfur sensitization, the silver halide emulsion used can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, and the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

In carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,3
Various stabilizers can also be used, including a, 7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like. Furthermore, if necessary, a silver halide solvent such as a thioether, or a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

Silver halide grains used in emulsions are treated with cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts during the grain formation and/or growth process. Metal ions can be added and included within the particles and/or on the surface of the particles.

Unnecessary soluble salts may be removed from the emulsion after the growth of silver halide grains is completed, or they may be left in the emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide photographic material to which the present invention is applied may further contain a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like.

Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid group, etc. can be applied.

Sensitizing dyes can be used at concentrations equivalent to those used in conventional negative-working silver halide. In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion. The amount of sensitizing dye per mole of silver halide is approximately 1. OX 10-' to about 5X10-' moles are preferred, and it is particularly preferred to use a concentration of sensitizing dye of about 4X10-' to 2X10-' moles per mole of silver halide.

The sensitizing dyes may be used alone or in combination of two or more. More specific examples of sensitizing dyes that can be advantageously used include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080 and US Pat. No. 2.231. No. 658, No. 2.493.748, No. 2.503, No. 776, No. 2.519.001, No. 2
．． No. 912.329, No. 3, No. 656.956, No. 3.
No. 672.897, No. 3.694.217, No. 4.0
No. 25.349, No. 4.046.572, British patent l
, No. 242, 588, Special Publication No. 44-14030, No. 5
No. 2-24844, JP-A No. 48-73l37, No. 61
-172140 etc. can be mentioned. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
2.945.763, British Patent No. 505°979,
Typical examples include cyanine dyes, merocyanine dyes and composite cyanine dyes as described in Japanese Patent Publication No. 48-42172. Furthermore, sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 2.270.378, No. 2.442.710, No. 2.454.629, No. 2.776, No. 280,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent Publication No. 49-17725, Japanese Patent Application Publication No. 50-62425, Japanese Patent Application Publication No. 61-29836, Japanese Patent Publication No. 60-80841, etc. I can do it.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. A typical example is
U.S. Patent No. 2.688.545, U.S. Patent No. 2.977, 22
No. 9, No. 3.397.060, No. 3.522.052
No. 3.527.641, No. 3.617.293, No. 3.628゜964, No. 3.666, 480,
3.672.898, 3.679, 428, 3.703.377, 3.769.301, 3
．． 814.609, 3.837.862, 4.
No. 026.707, British Patent No. 1.344.281,
It is described in Japanese Patent Publication No. 1.507.803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, Japanese Patent Application Publication No. 110618-1980, Japanese Patent Publication No. 52-109925, etc.

When dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer of the silver halide photographic light-sensitive material, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
benzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), mercaptopyridines , the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7 A number of compounds known as stabilizers can be added, such as tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is in The Theory of the Photographic Process, by Mees.
e Theory of the photograp
hic Process, 3rd edition, 1966), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat. No. 3.954.474;
The descriptions in No. 982.947, No. 4.021.248, or Japanese Patent Publication No. 52-28660 can be referred to.

In addition, silver halide photographic light-sensitive materials include U.S. Pat. No. 3.411.911 and U.S. Pat.
and Japanese Patent Publication No. 45-5331.

The silver halide photographic material may contain various additives as described below. As thickeners or plasticizers, for example, U.S. Pat.
-63715, Belgian Patent No. 762.833,
U.S. Patent No. 3.767,410, Belgian Patent No. 5
Substances described in the specifications of No. 88.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl Sulfone type, isocyanate type, sulfonic acid ester type,
Examples of hardening agents and ultraviolet absorbers such as carbodiimide, mucochloric acid, and acyloyl include US Pat. No. 3.253.921 and British Patent No. 1.309.349.
Compounds described in each specification etc. of No. 2, especially 2-(
2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2(2'hydroxy-3',5'-di-3
butylphenyl)benzotriazole, 2-(2-hydroxy-3'-tertiary butyl-5'-butylphenyl)
Examples include -5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5-di-tertiary butylphenyl)-5-chlorobenzotriazole, and the like. Furthermore,
Coating aids, emulsifiers, permeability improvers for processing liquids, etc.
As antifoaming agents or surfactants used to control various physical properties of photosensitive materials, British Patent No. 548,532, British Patent No. 1.216.389, U.S. Patent No. 2.026.202, No. 3.514.293, Special Publication No. 44-26580, No. 43-17922, No. 4
No. 3-17926, No. 43-3l66, No. 48-20
785, French Patent No. 202.588, Belgian Patent No. 773.459, JP-A-48-101118, etc., using anionic, cationic, nonionic or amphoteric compounds. Of these, anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are particularly preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979, and U.S. Pat.
No. 35, JP-A-48-20785, JP-A No. 48-43l3
No. 0, No. 48-90391, Special Publication No. 46-24159
No. 46-39312, No. 48-43809, and Japanese Unexamined Patent Publication No. 47-33627.

When manufacturing photosensitive materials, the pH of the coating solution is 5.3 to 7.
It is preferable that it be in the range of 5. In the case of multilayer coating, it is preferable that the pH of the coating solution obtained by mixing the coating solutions for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. If the pH is less than 5.3, the progress of hardening will be slow, which is undesirable, and if the pH is greater than 7.5, it may have an adverse effect on photographic performance, which is not preferred.

The photographic constituent layers of the light-sensitive material may contain matting agents such as silica as described in Swiss Patent No. 330.158, French Patent No. 1
．． No. 296.995, the glass powder described in British Patent No. 1.
Inorganic particles such as carbonates of alkaline earth metals or cadmium, zinc, etc. as described in No. 173.181; starch as described in U.S. Pat. No. 2.322.037; Starch derivatives described in No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, Swiss Patent No. 330.158
organic particles such as polystyrene or polymethyl methacrylate as described in U.S. Pat. No. 3,079,257, polyacrylonitrile as described in U.S. Pat. .

In the photographic constituent layer of the light-sensitive material, slipping agents such as higher aliphatic higher alcohol esters described in U.S. Pat. No. 2,588,756 and U.S. Pat. Casein described in British Patent No. 1
, 263.722;
British Patent No. 1.3l3.384, U.S. Patent No. 3.04
2.522 and 3.489.567, etc. may be included. Dispersions of liquid paraffin and the like can also be used for this purpose.

Silver halide photographic materials can be constructed, for example, by coating an emulsion layer or other photographic constituent layers on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports may generally be subjected to a subbing treatment to improve adhesion with emulsion layers and the like.

The undercoating treatment is as per JP-A-52-104913 and JP-A-59-1.
No. 8949, No. 59-19940, No. 59-1894
Preferably, the treatments described in each publication No. 9 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

Margins Below Next, the processing method of the present invention is a processing method in which a photosensitive material to be processed is processed in a processing step including development and fixing steps.

Further, in the processing method of the present invention, after the development and fixing steps, water washing and/or stabilization processing is performed, and the amount of replenisher in the water washing and/or stabilization processing is reduced per 1 m of photosensitive material to be processed. It is 3 liters or less.

Preferred processing steps in the present invention include development, fixing, washing, or stabilization and drying steps.

In the processing method of the present invention, the amount of replenisher in the water washing and/or stabilization treatment after the development/fixing step is 3 liters or less per 1 rrf of the photosensitive material to be processed. Here, 3 liters or less also includes the liquid volume being zero, that is, no liquid replenishment.

In the present invention, the dye of the present invention has excellent dissolution and removability, and excellent effects can be obtained with this amount of replenisher. According to the present invention, it is possible to save water, and it is also possible to eliminate the need for piping for an automatic processor. Furthermore, it becomes possible to reduce the number of stock tanks. That is, the washing water (and water for diluting the developer and fixer if necessary) or the stabilizing solution can be supplied from one common stock tank, making it possible to further downsize the automatic developing machine.

Note that the above-mentioned case where the amount of replenishment of the washing water (or stabilizing liquid) is zero means a washing method using a so-called water washing method.

In the present invention, it is preferable that the concentration of calcium compounds in the replenisher in the water washing and/or stabilization treatment is 1O2/l or less in terms of calcium ions. More preferably, it is 5 ■/l or less, more preferably 3 ■/l or less, particularly preferably 1 ■/l or less.

Various means can be used to adjust the concentration of calcium in the replenisher in the water washing treatment or stabilization treatment to the above level. Preferably, ion exchange resins and/or reverse osmosis equipment are used.

As the ion exchange resin, various cation exchange resins can be used, or it is preferable to use a Na type cation exchange resin in which Ca is replaced with Na.

Further, it is also possible to use an H-type cation exchange resin, or in this case, since the pH of the treated water becomes acidic, it is preferable to use it together with an OH-type anion exchange resin.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such ion exchange resins include Mitsubishi Kasei's mounting product name Diaion SK-IB or Diaion PK-21.
I can list 6 and so on. The base material of these ion exchange resins is preferably one containing 4 to 16% divinylbenzene based on the total amount of monomers charged during production. Anion exchange resins that can be used in combination with H-type cation exchange resins include strongly basic anion exchange resins that have a styrene-divinylhensen copolymer as a base and have a tertiary amine or quaternary ammonium group as an exchange group. Resin is preferred. An example of such anion exchange resin is Diaion 5A-1, also manufactured by Mitsubishi Kasei Corporation.
Examples include 0A or Diamond Ion PA-418.

As for the reverse osmosis treatment equipment that can be used, any publicly known equipment can be used without any restriction.The area of the reverse osmosis membrane should be 3rrf or less, the operating pressure should be 30kg/rd or less, and particularly preferably 2rrl or less, 20kg/rr? It is desirable to use the following ultra-compact devices: When such a small device is used, the workability is good and a sufficient water saving effect can be obtained. Furthermore, it is also possible to pass activated carbon or a magnetic field.

The reverse osmosis membranes included in the reverse osmosis treatment equipment include cellulose acetate membranes, ethyl cellulose polyacrylic acid membranes,
A polyacrylonitrile film, a polyvinylene carbonate film, a polyethersulfone film, etc. can be used.

In addition, although a liquid feeding pressure of 5 to 60 kg/al is normally used, a pressure of 30 kg/c[Ir or less is sufficient to achieve the purpose of the present invention. But it can be used enough.

The structures of reverse osmosis membranes include spiral type and tubular type.
A type, hollow fiber type, pleated type, or rod type can be used.

Further, in the present invention, the concentration of the magnesium compound in the replenisher in the water washing and/or stabilization treatment is preferably 10 .mu./l or less, more preferably 5 .mu./l or less in terms of magnesium ions.

In order to control the amount of magnesium compound in the replenisher as described above, the means for controlling the amount of calcila compound described above can be similarly used.

In the present invention, washing with water means washing with water components of the processing liquid attached to or occluded in the photosensitive material to be processed, components of the photosensitive material that are no longer needed during the processing process, and the like. Therefore, this can be said to be a process for ensuring performance after processing.

Further, in the present invention, the stabilization treatment is a step of improving the storage stability of an image to a level that cannot be obtained by washing with water, and is generally composed of a liquid containing a component that has an image stabilizing effect.

As the washing or stabilization treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. For example, water treated with anti-mildew measures can be used as a washing or stabilizing solution.

When water treated with anti-mildew is used in conjunction with washing or stabilizing liquid, the formation of water scale can be effectively prevented.
For example, it is possible to save water by θ to 3 liters, preferably θ to 11 liters per 100 liters.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, 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 will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated by the fixer, resulting in even more efficient processing. Water washing or stabilization is performed. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more significant stabilizing effect can be obtained.

The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Furthermore, anti-mildew measures can be applied to the washing or stabilizing bath.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-13l632. How to make pure water, JP-A-60-
No. 253807, No. 60-295894, No. 61-6
The method using the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L, E, West t″Water Qua
lity Cr1teria” Photo Sci &
Eng, Vol, 9 Na6 (1965), M
,W,Be-ach''Microbiological
Growths in Motion-Pic-tu
re Processing”SMPTE Journal
al Vol, 85. (1976), R,0,Deeg.
an, “Photo Processing Was
h Water Bi.

cides''J, Imaging Tech, Vol.
10.46 (1984) and JP-A No. 57-8542,
No. 57-58143, No. 58-105145, No. 5
No. 7-132146, No. 58-1863l, No. 579
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in Japanese Patent Nos. 7530 and 57-157244 can also be used together.

Furthermore, for the washing bath, R.T., Kreimen, J.I.
mage, Techlo, (6) 242 (198
Isothiapurine compounds described in 4), research
Disclosure Volume 205, Item 20526 (
Isothiacillin compounds described in the same volume 228, Item 22845 (1983, May issue)
Isothiacillin compounds described in JP-A-61-51396 (April issue, 2013), compounds described in JP-A-61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
O-phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-thiarizosin)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4,4'-trichloro2°-hydroxydiphenyl ether, etc. There is.

Furthermore, in addition to the silver image stabilizer, various surfactants may be added to the washing water for the purpose of preventing uneven water droplets.

As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook J" published by Kogaku Tosho.

The temperature and time of water washing or stabilizing solution by the above method are preferably 5 seconds to 30 seconds at 0°C to 50°C, or 15°C
~40°C for 5 seconds to 20 seconds, more preferably 1
5 to 10 seconds at 5°C to 40°C is preferred.

The washing water used in the washing process and its replenisher can contain a bactericidal agent, an anti-spill agent as described above, or a water softener, but it is not necessary to use these.

The stabilizing solution used in the stabilization process or its replenisher can contain compounds used in washing water for washing or its replenisher, or other compounds that generally have an image stabilizing effect are added.

Typical examples include water-soluble iodides such as potassium iodide and ammonium iodide, and JP-A-58-114
Examples include heterocyclic mercapto compounds such as 1-phenyl-5-mercaptotetrazole described in JP-A No. 035.

The pH of the washing water or stabilizing liquid is usually preferably 4 to 9.
However, it is more preferably 5-8.

However, depending on the use and purpose, acidic (pH
4 or less) may be used.

It is preferable to combine various cleaning promotion means with the water washing or stabilization step. As such a promoting means, ultrasonic oscillation in the liquid, air foaming, jet impingement on the surface of the photosensitive material, compression using a roller, etc. can be used.

Next, specific steps of the treatment method of the present invention will be illustrated below.

1. Color development - bleaching - (washing) constant fixation - (washing with water) (stable) 2. Color development - bleach fixing - (washing) - (stable) 3. Black and white development constant fixation - washing 4. Black and white development constant fixation - stable 5. Black and white development Constant fixing - Water washing - Stability The steps marked in parentheses above can be omitted depending on the type, purpose and use of the photosensitive material to be processed, but water washing and stabilization cannot be omitted at the same time.

In the present invention, at least one step of water washing and/or stabilization treatment is performed after the development and fixing steps. In the present invention, the fixing time and developing time are each 20
It is preferably less than 1 second, more preferably less than 15 seconds.

Also, the processing time is so-called y to dry time, or 6
It is preferable that it is 0 seconds or less.

Margin below In the present invention, when a black and white developer is used in the development step,
As the developing agent, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferable since it is easy to obtain good performance.

Of course, a p-aminophenol developing agent may also be included.

Examples of the dihydroxybenzene developing agent that can be used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3-dibromohydroquinone, Examples include 2,5-dichlorohydroquinone, and hydroquinone is particularly preferred.

The developing agents for l-phenyl-3-pyrazolidone or its derivatives that can be used in the present invention include l-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-
3-Virazolitone etc.

Examples of the p-aminophenol developing agent that can be used in the present invention include N-methyl-p-aminophenol,
p-aminophenol, N-(β-hydroxyethyl>
-p-aminephenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, p
-benzylaminophenol etc., especially N-
Methyl-p-aminophenol is preferred.

The developing agent is usually 0. Preferably, it is used in an amount of O1 mol/It-1.2 mol/l.

Sulfite preservatives may be used in the present invention, such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. There is. The amount of sulfite added is 0.
．． It is preferably 2 mol/1 or more, particularly 0.4 mol/1 or more.

Further, the upper limit is preferably up to 2.5 mol/I.

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

The alkaline agents used to set the pH are optional and include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide;
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol; l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents, surfactants, and antifoaming agents as necessary. agent, water softener, JP-A-56-
It may also contain the amino compounds described in No. 106244.

In the present invention, a silver stain preventive agent such as the compound described in JP-A No. 56-2434 may be used in the developer.

In the present invention, the developing solution includes JP-A-56-10624
Amino compounds such as alkanolamines described in No. 4 can also be used.

In addition, F. A. Mason, "Photographic Brothecine Chemistry", Focal Press (1966), pp. 226-229, US Patent No. 2.
No. 193.015, No. 2.592.364, JP-A-4
Those described in No. 8-64933 may also be used.

In this specification, "developing time" and "fixing time J" refer to the time during which the photosensitive material to be processed is substantially in contact with the developer and fixer, respectively, and when an automatic developing machine is used, the photosensitive material This refers to the time from when the product is immersed in the developing tank solution of an automatic processor until it is immersed in the next fixing solution, and the time from when it is immersed in the fixing tank solution until it is immersed in the next washing tank solution (stabilizing solution).

Furthermore, "washing time" refers to the time during which the product is immersed in the washing tank liquid.

Furthermore, "drying time" refers to the time it takes to enter the drying zone, which is usually installed in an automatic processor with a drying zone where hot air of 35°C-ioooC and preferably 40°C to 80°C is blown. say.

The development temperature and time are preferably about 25°C to 50°C and 15 seconds or less, more preferably 30°C to 45°C and 5 seconds to 15 seconds.

The fixer is generally preferably an aqueous solution containing thiosulfate, and preferably has a pH of 4.0 or higher, more preferably 4.0 or higher.
It is 2 to 5.5.

Examples of the fixing solution include sodium thiosulfate and ammonium thiosulfate, but it generally contains thiosulfate ions and ammonium ions, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to 0.6 mol/l.

In the present invention, the fixing solution may contain an acidic hardener. Furthermore, tartaric acid, citric acid, or derivatives thereof can be used alone or in combination of two or more kinds in the fixer. Generally preferably, these compounds are present in fixer solution 1.
It is effective if it contains 0.005 mol or more per 1 mol, especially 0
．． O1 mol/l to 0.03 mol/l is particularly effective.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution may optionally contain a preservative (e.g. sulfite, bisulfite), a pH buffer agent (e.g. acetic acid, nitric acid), a pH adjuster (e.g. sulfuric acid), a chelating agent with water softening ability, or a special patent agent. 60-213562.

The fixing temperature and time are preferably about 20° C. to about 50° C. and 15 seconds or less, and more preferably 30° C. to 40° C. and 5 seconds to 15 seconds.

When a fixer concentrate is used and dilution water is used, the fixer concentrate usually consists of two agents or may consist of one agent.

Usually, it is preferably pH 4.5 or higher, more preferably pH 4.
It is 65 or more. If the pH is less than 4.5, the thiosulfate may decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used.

In the pH range of 4.5 or higher, there is little generation of sulfur dioxide gas,
It also improves the working environment. The upper limit of pF is not so strict, but if it is fixed at too high a pH, the membrane p
A pH of up to 7 is desirable because the H content increases, membrane swelling increases, and therefore the drying load increases.

In the present invention, it goes without saying that the developer and/or fixer may be a so-called working solution that does not require dilution water (that is, is replenished as an undiluted solution).

When using concentrates, the amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, or in general, the ratio of concentrate to dilution water is Preferably, the ratio is 1:0 to 8, and the total amount of these developer and fixing wave troughs is 50 to 50% of the light-sensitive material lr&
- to 1500d is preferable.

In the practice of the present invention, a method may be used in which the developed, fixed, and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method.

Drying can be carried out at about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, usually about 5 seconds to 1 minute, more preferably at 40°C to 80°C.
°C for about 5 seconds to 30 seconds.

The present invention exhibits an even more excellent effect of shortening the drying time.

According to the method of the present invention, the so-called dry-to-dry processing time from development, fixing, washing, and drying is 1
The processing time is preferably within 0.00 seconds, more preferably within 60 seconds, still more preferably within 50 seconds, as described above.

Here, "Dry to Dry" refers to the time from the moment the leading edge of the photosensitive material to be processed enters the film insertion section of the automatic processor to the moment the leading edge of the photosensitive material comes out of the automatic processor after being processed.

In the following margin [Examples] The present invention will be specifically described below with reference to Examples. However, as a matter of course, the present invention is not limited to this.

Example 1 E
Silver chlorobromide particles containing 30 mol% of silver bromide were obtained while controlling Ag to 120 mV and pH to 3.0. These particles were cubic crystal particles with an average particle size of 0.24 μm, and the width of the particle size distribution was 11%. The ratio of (100 planes)/(111 planes) was 9515. After adding 0.6 g of potassium bromide per mole of silver halide and sensitizing it with gold and sulfur, the following sensitizing dyes <A> and <B> were added at 20 μm each.
In addition, per mole of silver halide, 4
- Add 1 g of hydroxy-6=methyl-1,3,3a,7-chitrazaindene, and add 700 mg of the following compound <C>
, 60% sodium n-dodecylbenzenesulfonate
0■, 2g of styrene-maleic acid copolymer, 3g of ethyl acrylate polymer latex, and the amount of silver was 3.5 on the polyethylene terephthalate film.
g/rrr, and the amount of gelatin was applied to be 1.8 g/rd. This formed a silver halide emulsion layer.

At that time, sodium l-decyl-2-(3-isopentyl)succinate-2-sulfonate was added as a spreading agent at 30μ/rrf so that the amount of gelatin was 1.0g/rrf.
As a hardening agent, l-hydroxy-3,5-dichlorotriazine sodium salt 30 μ/d, formalin 25 μ/n (
, and a protective layer containing the following fluorine-containing surfactant E was applied in a multilayer manner onto a film on which a backing layer had been applied in advance.

Thereby, Sample-1 was obtained which had an emulsion layer and a surface protective layer on one side of the support and a backing layer on the opposite side. The backing layer of Sample-1 contained a comparative dye, which will be described later, in the amount shown in Table 1.

In addition, Samples 2 to 6 were prepared in which the backing layer contained the dye of the present invention in the type and amount shown in Table 1.

<B> aθ E: Na03S-CI(COOCHt (C
Ft)sHCH,C00(Jl, (CF2),H) The obtained sample was passed through a contact screen (gray negative 150L
), optical wedge and Kodak Wratten filter Nα8
After LO-5 seconds of flash exposure with a xenon flash through an 8A flash, the following composition was used: Experiment 11kll processed under the following conditions.
-18 were conducted and evaluated.

The residual color of the obtained image and the generation of sludge from the processing liquid used in the processing were evaluated as follows.

The results of the above evaluation for each treatment are shown in Table -■.

Residual color: visually evaluated in 5 stages, 5 is no residual color, l
A value of 3 or more was considered to be a practical level, with a very large amount of remaining color remaining.

Generation of sludge: After continuously processing 300 sheets of large size (20" x 24") film, the presence or absence of dirt on the film was checked.

<Developer prescription> (Composition A) Pure water (ion exchange water) 150ml
Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) 100-potassium carbonate 50g hydroquinone
15g 5-Methylbenzotriazole 200■ 1-phenyl-5-mercaptotetrazole 30■ Potassium hydroxide Adjust the pH of the solution to 10.4 Silver potassium 4.5g (composition) Pure water (ion-exchanged water) 3@l Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25■ Acetic acid (90%
aqueous solution) 0.3d5-nitroindazole 110■l-phenyl-3-
Pyrazolidone 700 ■Water 500 when using developer
d in the order of composition A and composition II! It was finished and used.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0sZ sodium sulfite 17g
Sodium acetate trihydrate 6.5g boric acid
6g sodium citrate dihydrate 2g acetic acid (90% w/v aqueous solution) 13.6d (composition) Pure water (ion exchange water) 17- Sulfuric acid (50% w/v aqueous solution) 4.7
g Aluminum sulfate (A i , Os equivalent content is 8.1% W/V aqueous solution) 2
6.5g Washing water〉 (Mother solution and replenisher common) (I) Washing water (I Water was passed through a mixed bed column filled with theanioexchange resin (Amberlite IR-400) and used at the following water quality.

(It) Washing water (I) and tap water, Water below I used it as a pawn.

(■ Tap water.

The water quality is as follows.

(calcium, and magnesium is each calci ram ion, and amount as magnesium ion It was displayed in

) As can be understood from Margin Table-1 below, when the processing method of the present invention is applied to a photographic material sample colored with a dye (
In experiments Nα4 to 18), it was possible to realize a process in which residual color was suppressed and no staining due to sludge was generated. On the other hand, the comparative treatment methods (Experiments Na 1 to 13) caused problems with residual color and caused stains due to sludge.

〔Effect of the invention〕

As described above, according to the processing method of the present invention, it is possible to form a colored layer with desired performance on a photosensitive material, solve the problem of residual color in the photosensitive material, and furthermore, it does not cause staining due to sludge. It is also possible to provide a method for processing silver photosensitive materials.

Claims (1)

[Scope of Claims] 1. Each side of the support has at least one hydrophilic colloid layer, and at least one of the hydrophilic colloid layers has the following general formula [I a] [ I b] [ A processing method comprising processing a silver halide photographic material containing at least one dye arbitrarily selected from the group consisting of the compounds represented by Ic] in a processing step including development and fixing steps, , water washing and/or stabilization treatment is performed after the development and fixing steps, and the amount of replenisher in the water washing and/or stabilization treatment is 3 liters or less per 1 m^2 of the silver halide photographic light-sensitive material. A method for processing the silver halide photographic material, characterized in that: General formula [I a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I c] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula , R_1, R_2, R_3, R_4, R_5 and R
_6 each represents an alkyl group, and Y_1 and Y_2 each represent a nonmetallic atomic group necessary to form a pyrrolopyridine ring. In the ring of Y_1 in the general formula [I b] [I c], ▲
There are mathematical formulas, chemical formulas, tables, etc.▼Includes bonds, and within the ring of Y_2 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Includes bonds. R_1 in the general formula [I a] [I b] [I c],
R_2, R_3, R_4, R_5, R_6, Y_1, Y
_2 each represents a group that allows the dye molecule to have at least two acid groups or a group that allows it to have at least two substituents that have one or more -CH_2CH_2OR groups. R represents a hydrogen atom or an alkyl group. L represents a methine group, and X^■ represents an anion. m represents an integer of 4 to 5, and n represents an integer of 1 or 2. When the dye forms an inner salt, n is 1.