JPH03119350A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent stain due to a residual color and sludge as well as to form a colored layer having desired performance by specifying the amt. of a replenisher in washing and stabilizing stages and the concn. of a Ca compd. in the replenisher. CONSTITUTION:When a silver halide photographic sensitive material contg. a dye represented by formula I is processed in processing stages including devel oping and fixing stages, the amt. of a replenisher in washing and stabilizing stages is regulated to <=3l per 1m<2> of the sensitive material and the concn. of a Ca compd. in the replenisher to <=10 mg/l (expressed in terms of Ca ions). In the formula I, each of R<1>-R<4> is optionally substd. alkyl, each of Z<1> and Z<2> is a group of nonmetallic atoms required to form an optionally substd. benzo or naphtho condensed ring, L is optionally substd. methine, X is an anion, n is 1 or 2, and when the dye forms an inner salt, n is 1. A colored layer having desired performance can be formed in the sensitive material and stain due to a residual color and sludge is prevented.

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 sometimes provided outside the light-sensitive 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 photosensitive material, a filter layer may be located between the emulsion layers.

Furthermore, in order to prevent haleysilane formation, 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 a haleysilane prevention 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.

[Problem that the invention seeks 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 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-mentioned problems and sufficiently solves the problems of residual color and staining of the 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.

c. Means for Solving Problems] The object of the present invention is to provide at least one on each side of the support.
It has a hydrophilic colloid layer, and at least one of the hydrophilic colloid layers contains a dye represented by the general formula [■] (described in detail later) (hereinafter also referred to as "the dye of the present invention" as appropriate). A processing method in which a silver halide photographic light-sensitive material containing at least one of the following is processed in a processing step having development and fixing steps, the processing method comprising washing with water and/or stabilizing treatment after the development and fixing steps. At the same time, the amount of replenisher in the water washing and/or stabilization treatment is 3! This was achieved by a treatment method characterized in that the concentration of calcium compounds in the replenisher is 1O2/l or less in terms of calcium ions.

The present invention will be further explained below.

First, the dye of the present invention represented by general formula (I) will be explained.

General formula [I] - In general formula [I], R', R'', R', R', R5, R'
may be the same or different from each other. represent.

However, R', R", R", R', R5, R", Z', Z
The group represented by "" represents a group that allows at least four of these to have acid substituents (for example, sulfonic acid groups or carboxylic acid groups). Particularly preferably, the dye molecule has four sulfonic acid substituents. Represents a group that allows it to have an acid group.

Here, the sulfonic acid group means a sulfo group or a salt thereof, and the carboxylic acid group means a carboxyl group or a salt thereof.

Examples of salts include alkali metal salts such as Na, ammonium salts, and organic ammonium salts such as triethylamine, tributylamine, and pyridine.

L represents a substituted or unsubstituted methine group, and X represents an anion. Specific examples of the anion represented by Xe include halogen ions (Cl3.Br, etc.), p-)luenesulfonic acid ions, ethyl sulfate ions, and the like.

n represents 1 or 2, and is 1 when the dye forms an inner salt.

R', R2, R: The alkyl group represented by I, R', R', Rh is preferably a lower alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, n-butyl group). group, isopropyl group, n-pentyl group, etc.), and may have a substituent (for example, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, etc.).

More preferably, R1 and R4 represent a lower alkyl group having 1 to 5 carbon atoms (eg, 2-sulfonithyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.) having a sulfonic acid group.

Examples of the substituent of the benzo-fused ring or naphtho-fused ring formed by the nonmetallic atom group represented by z', z'' include a sulfonic acid group, a carboxylic acid group, a hydroxyl group, and a halogen atom (for example, F, C1, Br etc.), cyano group, substituted amino group (e.g. dimethylamino group, diethylamino group,
ethyl-4-sulfobutyl group, di(3-sulfopropyl)amino group, etc.), or a substituted or unsubstituted carbon number 1-5 bonded to the ring directly or via a divalent linking group.
represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. (as a substituent, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, etc. are preferable)), and a divalent linking group is, for example, -〇- NHCONH30t N
HCOO-1-N)ICONH-2C0O--CO--
SO□- etc. are preferred.

When the methine group represented by , 2-sulfoethyl group, etc.), halogen atoms (e.g., F, C1, Br, etc.), substituted or unsubstituted aryl groups (e.g., phenyl group, 4-
chlorphenyl group, etc.), lower alkoxy group (e.g.,
methoxy group, ethoxy group, etc.) are preferred.

Further, the substituents of the methine group represented by L may be bonded to each other to form a 6-membered ring (for example, a 4,4-dimethylcyclohexene ring) containing three methine groups.

Specific compound examples of the dye represented by the general formula [I] used in the present invention are shown below, and (1-1) (+-2) (r-3) (r-7) ( 1-8) (r-9) (1-4) (1-5) (CHx)* SO1θ (1-6) (1-10) (1-11) (1-123 (csoi)3NIIOsS- CH! Od Mouth 13] [■ 14) (T-15) (1-19) (1-20) *-0CHxCHtCHtS(hK (1-163 (1-173 (1-21) (I -22) Brown SOJHCHxCHmSOsNa so, e od (1-23) (1-253 N(CIIzljltCHzSOJ)z(r-243 (r-26)
~850 nm, Journal of the Chemical Society (J, Chem, Soc, 189
(1933)) and US Pat. No. 2,895.955.

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

Two or more of these dyes can also be used in combination.

The specific amount of dye used varies depending on the purpose and is difficult to set uniformly, but it is generally between 10-'g/rrr and 0.5g.
/rrr, especially 10-”glof ~0.2 g/rr
A preferred amount can be found within the range of f.

The dye represented by the general formula (I) of the present invention can be used in various colored layers. For example, it is particularly effective for the purpose of preventing irradiation silane. When used for this purpose, it is mainly added to the silver halide emulsion layer.

The dyes of the present invention are also particularly useful as antihalation dyes, in which case they are 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 4.0
g/rrf or less, preferably 3.5 g
It is more preferable that it is below /rrr.

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. can be used.

Preferably, a silver halide 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 may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly 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, silver halide grains having a (100) plane/(111) plane ratio of 5 or more are preferred. The (100) plane may be 100%.

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

In this method, a dye is preferentially adsorbed 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 are spectrally different. Select and use. The (100) plane/(111) plane ratio can be determined by adding such a dye to an emulsion and examining the spectra 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 the crystal phase of fine silver halide grains in photographic emulsions using dye adsorption phenomenon,” Journal of the Chemical Society of Japan ■, 942
~946 (1984).

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

-a, the PAg value during particle formation is maintained at a constant value of 8.10 or less, and silver nitrate aqueous solution and alkali halide aqueous solution are simultaneously added at a rate that is faster than the dissolution rate of the particles and at which re-nucleation is large. It can be preferably prepared by the controlled double jet method. More preferably, the pAg value is 7.80 or less, and still more preferably the PAg value is 7.60 or less. When silver halide grain formation is divided into two processes: nucleation and growth, P during nucleation
There is no limit to the Ag value (preferably the pAg value during growth is 8).
．． It is good to set it to 10 or less, more preferably 7.80 or less, still more preferably 7.60 or less. Although the soluble root salt and the soluble halogen salt may be reacted by a one-sided mixing method, 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 of Photographic Science (J, Photogr, 5
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used. Furthermore,
Particles having twin planes may also 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 the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size r is the frequency ni of particles having particle size ri.
The particle size r when the product n1Xri' of
Define as i. (3 significant digits, round the smallest digit to the nearest whole number.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and 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, the book by Glafkides, Zelikman et al.
ndlagender Photography
en Prozesse mit Silberhal
Ogeniden,,Akademiche Ve
rlagsgesellschaft.

(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, specific examples of which can be found in US Pat. No. 1,574.

No. 944, No. 2,410.689, No. 2.278.9
No. 47, No. 2゜728, No. 668, No. 3,656,95
It is stated in No. 5.

As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat.
No. 487,850, No. 2,419,974, No. 2.5
No. 18.698, No. 2.983.609, No. 2,98
No. 3.610 and No. 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.

In addition, there are no particular restrictions on the conditions such as PH, PAg, temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, especially 5 to 8, and the PAg value is 5 to 11, especially 7 to 9. It is preferable to keep it. Further, the temperature is preferably 40 to 90°C, particularly 45 to 75°C.

In addition to the sulfur sensitization and gold/sulfur sensitization described above, the silver halide emulsion used can also be subjected to a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or 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 1,000-onythyl, 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, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc., and 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 nucleus, and the like can be applied.

The sensitizing dyes can be used in 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. OXl0-' to about 5X10-' moles are preferred, especially about 4 sensitizing dyes per mole of silver halide.
It is preferred to use a concentration of between Xl0-' and 2X10-' molar.

The sensitizing dyes can be used alone or in combination of two or more. More specifically, the aggravating dyes which are advantageously used include, for example, the following:

That is, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Patent No. 2,231,658, US Patent No. 2,493,748, and US Patent No. 2,503.776. No. 2.519.001, No. 2
, 912.3l9, 3.656.956, 3.
No. 672.897, No. 3,694.217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
, 242.5B8, Special Publication No. 44-14030, 5
No. 2-24844, JP-A-48-73137, JP-A 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. 2,776.280,
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. be able to.

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,
No. 3,672,898, No. 3679.428, No. 3,703,377, No. 3,769,301, No. 3
, No. 814.609, No. 3.837.862, No. 4,
No. 026,707, British Patent No. 1,344.281;
It is described in Japanese Patent Publications 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.

The silver halide photographic material to which the present invention is applied may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful.

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 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), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-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 K. Mees.
Theory of the photography
ic 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.

Further, the silver halide photographic light-sensitive material may contain an alkyl acrylate latex described in U.S. Pat. No. 3,411,911, U.S. Pat. .

The silver halide photographic material may contain various additives as described below. As a thickener or plasticizer, for example, U.S. Pat. No. 2,960,404, Japanese Patent Publication No. 43-4939
No., West German Application Publication No. 1,904,604, Japanese Unexamined Patent Publication No. 4
8-63715, Belgian Patent No. 762.833, U.S. Pat. No. 3,767.410, and Belgian Patent No. 588,143, such as styrene-sodium maleate Hardeners such as polymers and dextran sulfates include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based, isocyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, acyloyl-based, etc. Various hardeners and ultraviolet absorbers include, for example, U.S. Patent No. 3,253,921 and British Patent No. 1,309.34.
Compounds described in each specification etc. of No. 9, especially 2-(
2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'hydroxy-3',5'-di-
tertiary butylphenyl)benzotriazole, 2-(2-
Hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5-di-tertiary butylphenyl)-5-chlorobenzotriazole, etc. can be mentioned. Further, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548.53L; No. 1,216,389, U.S. Patent No. 2.026゜202, U.S. Patent No. 3,514,293,
Special Publication No. 44-26580, No. 43-17922, No. 43-17926, No. 43-3166, No. 48-2
Use of anionic, cationic, nonionic or amphoteric compounds described in No. 0785, Buddhist Patent No. 202,588, Belgian Patent No. 773,459, JP-A-48-101118, etc. Among these, anionic surfactants having a sulfone group,
For example, succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 48-89979
No. 2,882.157, U.S. Patent No. 2.972.
No. 535, JP-A-48-20785, JP-A No. 48-431
No. 30, No. 4B-90391, Special Publication No. 46-2415
No. 9, No. 46-39312, No. 48-43809,
There are compounds described in various publications of JP-A-4733627.

When manufacturing photosensitive materials, the pH of the coating solution is 5.3 to 7.
It is preferable that it is in the range of 5. In the case of multilayer coating, it is preferable that the pH of the coating liquid obtained by mixing the coating liquids 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
．． 296,995, British Patent No. 1,
Inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc as described in US Pat. No. 173.181; starch as described in US Pat. No. 2.3l2.037; Starch derivatives described in .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. Nos. 2,588,756 and 3,121,060, and U.S. Pat. Casein described in British Patent No. 1
．． Higher aliphatic calcium salts as described in No. 263,722;
British Patent No. 1,313,384, U.S. Patent No. 3,04
2,522 and 3,489,567, etc. may be included. Dispersions of liquid paraffin can also be used for this purpose.

The photosensitive material to which the present invention is applied may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Volume 176 I.
Lem 17643 (December 1978) and Lem 18
7 Vol. 1 tem 18716 (November 1979), the silver halide photographic light-sensitive material has, for example, an emulsion layer and other photographic constituent layers on one side of a flexible support commonly used in photographic light-sensitive materials. It can be constructed by coating on both sides. 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. (e.g. polyethylene, polypropylene, ethylene/
paper coated or laminated with a butene copolymer) or the like. 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
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 application, the treatment method of the present invention can be applied to a dip coating method, a roller coating method, or a curtain coating method.
This is a processing method in which a photosensitive material to be processed is processed through processing steps including development and fixing steps.

Furthermore, 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 equal to one volume of the photosensitive material to be processed. 31 or less per liter, and the concentration of calcium compounds in the replenisher is 10 μ/l or less as calcium ions.

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 as follows:
The amount is 3 liters or less per photosensitive material to be processed. 3 here! The expression below also includes the case where the liquid amount is zero, that is, no liquid replenishment is performed.

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 developing machine. Furthermore, the number of stock tanks can be reduced. That is, the washing water (and diluting water for the developing solution and fixing solution, 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 case where the replenishment amount of the washing water (or stabilizing liquid) is zero means a washing method using a so-called water washing method.

In the present invention, the concentration of calcium compounds in the replenisher in the water washing and/or stabilization treatment is 10 μ/l or less as calcium ions, preferably 5 μ/l.
/! Below, more preferably 3■/l or less, particularly preferably 1■/l! It is as follows.

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.

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

Further, an H-type cation exchange resin can also be used, but in this case, the pH of the treated water becomes acidic, so 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 Diaion 5K-IB or Diaion PK-21 manufactured by Mitsubishi Kasei.
6 etc. can be mentioned. The substrate for these ion exchange resins is preferably one in which the amount of divinylbenzene charged is 4 to 16% 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-divinylbenzene copolymer as a base and have a tertiary amine or quaternary ammonium group as an exchange group. Resins are preferred. Examples of such anion exchange resins include:
For example, the product name Diaion 5A-, also manufactured by Mitsubishi Kasei ■
10A or Diaion PA-418.

As the reverse osmosis treatment device that can be used, any known device can be used without any restriction, but the reverse osmosis membrane has an area of 3 mm or less and a working pressure of 30 kg/m or less, particularly preferably 2n (hereinafter referred to as 20 kg/m). It is desirable to use an ultra-compact device of less than 30%.Using such a small device allows for good workability and a sufficient water-saving effect.Furthermore, it is also possible to pass activated carbon, a magnetic field, etc.

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/cJ is normally used, a pressure of 30 kg/cj or less is sufficient to achieve the purpose of the present invention, and a so-called low-pressure reverse osmosis device with a pressure of 10 kg/c+fl or less is also sufficient. Can be used.

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 af# or less in terms of magnesium ions, more preferably 5 .mu./l or less.

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-mold measures can be used as a washing or stabilizing liquid.

When water treated with anti-mildew means is used in conjunction with washing or stabilizing liquid, the formation of water scale can be effectively prevented.
1! For example, 0 to 3j2, preferably 0 to 11, of water can be saved per water.

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 an even 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. 61-13163L. How to make pure water, JP-A-60-
No. 253807, No. 60-295894, No. 61-6
3030 and 61-51396 can be used. Furthermore, L, E, West "Water Qualt"
ty Cr1teria” Photo Sci & E
ng, Vol, 9 Na6 (1965), M, W
, Be-ach “Microbiological
Growths in Motion-Pic-tur
e Processing' SMPTE Journal
al Vol, 85. (1976), R.O., Deeg.
anI”Photo Processing Wa
sh Water Bi.

cides''J, Imaging Tech, Vol.
10. No. 6 (1984) and JP-A-57-854
2, No. 57-58143, No. 58-105145, No. 57-13l146, No. 58-18631, No. 5797530, No. 57-157244, etc. It can also be used in combination with surfactants, etc.

Furthermore, for the washing bath, R.T. Kreimen, J.I.
mage, Techlo, (6) 242 (198
Isothiazoline compounds described in 4), research
Disclosure Volume 205, I tem20526
(1981, May issue), volume 228 of the same, Hem 22845 (198
Isodeacylin compounds described in JP-A-61-51396 (April issue, 1983), etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-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-trichloro-2°-hydroxydiphenyl ether, etc. There is.

The amount of water kept in a water stock tank with anti-fungal measures added as dilution water for the processing solution stock solution such as the developing solution and fixing solution is preferably 0.01 to 10 g/l, more preferably 0.
．． It is 1 to 5 g/2.

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

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

Various compounds can be added to the stabilizing liquid for the purpose of stabilizing the image. For example, adjusting the membrane pH (e.g. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and Holimarin. In addition, various additives such as chelating agents, bactericidal agents (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardening agents, etc. may be used. , two or more of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a membrane pH adjusting agent for the processing solution in order to improve image storage stability.

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

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 a compound used in washing water for washing or its replenisher, but in addition, -Ji12 may contain a compound that has an image stabilizing effect. It will be done.

Formaldehyde (formalin) is a typical example.
and aldehyde compounds such as geltaraldehyde.

However, for a color photosensitive material using a 2-equivalent magenta coupler, an aldehyde compound such as formalin may not be used.

In addition, various buffers (e.g. borate, metaborate,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. are used in combination), and other fluorescent brighteners are added depending on the purpose. Ammonium chloride, ammonium sulfite, ammonium sulfate,
Various ammonium salts such as ammonium thiosulfate can be added.

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.

In the present invention, the time for water washing or stabilization treatment is generally preferably carried out between 0 seconds and 5 minutes, but in order to speed up the treatment, a shorter time is preferable, and specific 5 seconds to 60 seconds, particularly preferably 5 seconds to 3 seconds.
It is 0 seconds.

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. In addition, the temperature of the water washing or stabilization step is preferably 20 to 50°C.
'C range, more preferably 25-45°C, and even more preferably 30-40°C.

Next, specific steps of the treatment method of the present invention are illustrated below, but the steps of the present invention are not limited to these.

1. Color development - bleaching - (washing with water) constant fixing - (washing with water) - (stable) 2. color development - bleach-fixing - (washing with water) - (stable) 3. color development - bleaching - bleach-fixing - (washing with water) - ( 4. Color development - Bleach - Bleach fixing - Constant fixing - (Water washing) - (Stable) 5. Color development - Bleach - Constant fixing - Bleach fixing - (Water washing) - (Stable -) 6. Black and white development - Water washing - (Reversal) ) - Color development - (Preparation) -
Bleach constant fixation - (Water washing) - (Stable) 7, Black and white development - Water washing -
(Reversal) - Color development - (Preparation) - Bleach fixing - (Washing) -
(Stable) 8, Black and white development - Water washing - (Reversal) - Color development - (
Preparation) - Bleaching - Bleach-Fixing 1 (Water washing) 9. Black and white development constant fixing - Water washing 10. Black and white development constant fixing - Stability Steps marked in parentheses above can be omitted depending on the type, purpose and use of the photosensitive material to be processed. However, 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
The time is preferably at most seconds, more preferably at most 15 seconds.

In addition, the processing time, so-called dry-to-dry time,
60 In the present invention, when a black and white developer is used in the development step, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferred as the developing agent because 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 1-phenyl-3-virazolidone or its derivatives that can be used in the present invention include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxy Examples include methyl-3-pyrazolidone and 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

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-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, p
-benzylaminophenol, among others, N-
Methyl-p-aminephenol is preferred.

The amount of developing agent is usually 0.01 mol/! ~1.2 mol/I! ,
Preferably, it is used in an amount of .

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

Moreover, the upper limit is 2.5 mol/I2. It is preferable to set it up to.

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 25 moderators 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; 1-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. , hard water softener, JP-A-1987-
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-56-2434, can 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 be used.

In addition, F. A. Mason, “Photographic
``Brosecin Chemistry'', published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2.19.
No. 3.015, No. 2.592.364, Japanese Unexamined Patent Publication No. 1973-
64933 and the like may be used.

In the present invention, "development time" and "fixing time" respectively refer to the time from when the photosensitive material to be processed is immersed in the developing tank solution of an automatic processor until it is immersed in the next fixing solution. This refers to the time from when the product is immersed in the next washing tank solution (stabilizing solution).

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

In addition, "drying time" refers to the drying zone installed in automatic processors where hot air is normally blown at 35°C to 100°C, preferably 40°C to 80°C. This refers to the time spent.

The development temperature and time are preferably about 25°C to 50°C for 15 seconds or less, more preferably 30°C to 40°C.
5 seconds to 15 seconds at 5°C.

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 changed as appropriate, and is generally about 0.1 to 0.6 mol/! It is.

In the present invention, the fixer 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.
Those containing 0.005 mol or more per 1 are effective, especially 0
．． 01 mol/2~0.03 mol/! 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, 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 is usually composed of two agents, but may be composed of one agent.

The fixer stock solution can stably exist as a single agent usually at a pH of 4.5 or higher, more preferably at a pH of 4.
, 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. When the pH is in the range of 4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of the pH is not so strict, but if the fixation is carried out at too high a pH, the pH of the membrane will become high even after subsequent washing with water, and the membrane will swell and the drying load will increase, so a pH of up to 7 is desirable.

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, but in general, the ratio of concentrate to dilution water is Preferably, the ratio is 1:0 to 8, and the total amount of these developing solutions and fixing methods is 50 ml per 1 ml of light-sensitive material.
/ to 1500- 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, but usually it is about 5 seconds to 1 minute, but more preferably at 40°C to 80°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, and as described above, the processing time is more preferably within 60 seconds, and still more preferably within 50 seconds.

Here, "y to dry" means that from the moment the leading edge of the photosensitive material to be processed enters the film insertion section of the automatic processor, the leading edge of the photosensitive material is processed and can be removed from the automatic processor. [Example] Below , the present invention will be specifically explained 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 the Ag content to 12% and the 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)/(11,1 plane) 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 dye <A> was added, and then 1 mole of silver halide was added.
Per mole, 1 g of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added as a stabilizer, 700 mg of the following compound <B>, 6001 figs of sodium n-dodecylbenzenesulfonate, and styrene-maleic acid co-added. Added 2g of polymer, added 3g of high molecular weight polymer latex of ethyl acrylate, and coated on polyethylene terephthalate film so that the amount of silver was 3.5g/n (and the amount of gelatin was 1.8g/rrf. A silver halide emulsion layer was formed.At that time, sodium l-decyl-2-(3-isopentyl)succinate-2-sulfonate was added as a spreading agent at 30 μ/p so that the amount of gelatin was 1.0 g/nf. , 1-hydroxy-3,5-dichlorotriazine sodium salt as a hardening agent 30 μ/
A protective layer containing formalin 25 cm/bo and the fluorine-containing surfactant shown in Table 1 was coated in a multilayer manner on 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 protective layer of Sample-1 contained Dye A, which is a comparative dye, in the amount shown in Table-1.

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

<A><B> The obtained sample was exposed to a contact screen (gray negative 15
0L), optical wedge and Kodak Wratten filter N
After a 10-S second flash exposure with a xenon flash through an α88A, a current holding solution, a fixing solution, and a washing solution having the following compositions (washing solution I according to the present invention) were prepared.

Experiments Nα1 to 18 were carried out using the washing liquid (1) and the comparative washing liquid (2) using a roller type automatic processor GR-27 manufactured by Konica (2) under the conditions shown in Table 1, and evaluations were made.

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 1.

Residual color: A five-level visual evaluation is performed, with 5 being no residual color and 1 being
A rating of 3 or higher is considered to be a practical level, with a large amount of residual color remaining.

Generation of sludge: The presence or absence of dirt on the film was checked after 300 sheets of large size film were continuously subjected to odor cleaning.

<Developer prescription> (Composition A) Pure water (ion exchange water) 150mZ
Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 50g Potassium sulfite (55% w/v aqueous solution) 100mZ Potassium carbonate 50g Hydroquinone 15g 5-methylbenzotriazole 200 ■ 1-phenyl-5-mercaptotetrazole 30 ■ Potassium hydroxide pH of working solution 10.4 Potassium silver bromide 4.5g (composition) Pure water (ion exchange water > 3m! Diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3 rn15-nitroindazole 110 ■1-phenyl-
3-pyrazolidone 700 ■ Water 5 when using developer
The above compositions were dissolved in 00 mI in the order of composition A and composition 11 and used.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% w/v aqueous solution) 24
0d Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate dihydrate 2g acetic acid (90% w/v aqueous solution) 13.6m7 (composition) Pure water (ion exchange water) 17mZ sulfuric acid (50% Tsuba/ν aqueous solution) 4.7g aluminum sulfate (A/ !, 0. converted content is 8.1% y/v aqueous solution) 26
．． 5g <Washing water> (common to mother liquor and replenisher) (1) Washing water (I
R-1208) and an OH-type anion exchange resin (Amberlite IR-400) was passed through a hot bed type column and used at the following water quality.

r Calcium 0.5 / 1 (n) Washing water (I) and tap water were mixed and used in the following water quality.

(I[[)Tap water. The water quality is as follows.

(Calcium and magnesium are expressed as calcium ions and magnesium ions, respectively.

) Dye A As understood from Table 1, when the processing method of the present invention is applied to a photosensitive material sample colored using a dye (
Experiments Nα5-8, 10-18), it was possible to realize a process in which residual color was suppressed and no staining was caused by sludge. On the other hand, the comparative treatment methods (Experiments 1 to 4.9) have problems with residual color and stains due to sludge.

The following margins [Effects 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 also solve the problem of residual color caused by sludge. It is possible to provide a method for processing silver halide photosensitive materials that does not cause stains.

Claims (1)

[Claims] 1. The support has at least one hydrophilic colloid layer on each side, and at least one of the hydrophilic colloid layers contains a dye represented by the following general formula [I]. A processing method in which a silver halide photographic light-sensitive material containing at least one type of silver halide is processed in a processing step having a development and fixing step, the method comprising performing a water washing and/or stabilization treatment after the development and fixing steps, and The amount of replenisher in the water washing and/or stabilization treatment is 1 m^2 of the silver halide photographic light-sensitive material.
3 liters or less per replenisher, and the concentration of the calcium compound in the replenisher is 10 mg/l or less as calcium ions. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R^1, R^2, R^3, R^4,
R^5 and R^6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and Z^1 and Z^
2 represents a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring, respectively. However, R^1, R^2, R^3, R^4, R^5, R
^6, Z^1 and Z^2 denote groups which allow the dye molecule to have at least 4 acid groups. L represents a substituted or unsubstituted methine group, and X^e represents an anion. n is 1 or 2, and is 1 when the dye forms an internal salt.