JPS63257752A - Processing of silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enable satisfactory development with a small amt. of a replenisher by forming at least one silver halide emulsion layer with an emulsion contg. a prescribed amt. of silver iodide, incorporating a prescribed polymer and replenishing a prescribed amt. of a processing soln. having fixing capacity. CONSTITUTION:At least one photosensitive silver halide emulsion layer of a silver halide photosensitive material is formed by coating a supporting body with one or more emulsion layers contg. one or more kinds of silver iodide selected among silver iodide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. Silver chloride or silver bromide may be used besides the silver iodide. The pref. amt. of iodine (AgI) in the photosensitive material is >=4X10<-3>mol./m<2>. A polymer providing cation sites is incorporated into the photosensitive material. The photosensitive material is exposed, color-developed and processed with a processing soln. having fixing capacity. The processing soln. is replenished by <=300ml, preferably 50-250ml, especially preferably 50-200ml per 1m<2> photosensitive material.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method for processing silver halide photosensitive materials such as black-and-white and color photographs, particularly an excellent method for reducing the amount of replenishment of a processing solution having fixing ability. The present invention relates to a method for processing silver halide photosensitive materials that can be subjected to development processing.

C. Prior Art] A number of techniques have been developed to reduce the amount of various waste liquids generated during the development process of silver halide photosensitive materials and prevent pollution problems. A method of significantly reducing the amount of washing water using an aqueous solution (
Japanese Unexamined Patent Publication No. 57-8542), A method for significantly reducing the amount of washing water by adopting a multi-stage countercurrent system and specifying the amount of replenishment (Japanese Unexamined Patent Publication No. 57-8543), Processing bath with fixing ability and washing bath An example of this method is to provide a preliminary washing step between the two to reduce the amount of washing water (Japanese Unexamined Patent Publication No. 57-157243).

On the other hand, the amount of replenishment of the processing liquid having fixing ability has so far been about 400 ml per 1 m<2> of light-sensitive material, but there is a desire to reduce this amount. However, simply reducing the amount of processing solution having fixing ability has a negative effect on desilvering properties, and it has not been possible to easily reduce the amount of cough fluid.

On the other hand, in order to increase the graininess and sensitivity of photosensitive materials, 1. Silver iodide has been used as silver halide, but when processing such photosensitive materials, iodide ions accumulate in the processing bath that has fixing ability, resulting in a significant decrease in desilvering performance. This makes it even more difficult to reduce the fixing ability of the processing liquid.

[Problems to be Solved by the Invention] Therefore, the present invention provides a method for processing a low-pollution silver halide photosensitive material in which desilvering performance does not decrease even when the replenishment amount of a processing solution having fixing ability is reduced. The purpose is to provide a method.

[Means for solving problems]

The present invention uses a photosensitive material having a photosensitive layer formed from a silver halide emulsion containing 1 mol% or more of silver iodide and a polymer that provides cation sites, and a processing liquid having a fixing ability. This was done based on the knowledge that the above problems could be solved by setting the replenishment amount to a specific amount.

That is, the present invention provides a method of processing an exposed silver halide photosensitive material with a processing solution having fixing ability after color development, in which the silver halide photosensitive material has at least one layer of photosensitive silver halide on a support. The light-sensitive material has an emulsion layer, at least one layer of which is formed of a silver halide emulsion containing 1 mol% or more of silver iodide, and the light-sensitive material contains a polymer that provides cation sites and has a fixing ability. Provided is a method for processing a silver halide photosensitive material, characterized in that the amount of replenishment of a processing solution having the following is 300I11β or less per m 2 of the photosensitive material.

The silver halide grains in the photographic emulsion used in the color photographic light-sensitive material of the present invention are cubic, octahedral, rhombidodecahedral, and monododecahedral.
It may have a regular crystal shape such as a tetrahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite shape of these crystal shapes. It can be anything. In addition, Research Disclosure (Research Disclosure)
closure) 225e pages 20-58 (19B
The grains may be tabular grains having an aspect ratio of 5 or more as described in (January 2003).

Further, the particles may have an epitaxial structure, or may have a multilayer structure in which the inside and the surface of the particle have different compositions (for example, halogen composition).

Further, it is preferable that the average size of the particles is 0.5 μ or more. More preferably, the average size is 0.7 μ or more and 5.0
It is less than μ.

Also, the particle size distribution may be broad or narrow. The latter is also known as a so-called monodispersed emulsion, and has a dispersion coefficient of 20% or less, more preferably 15% or less. (Here, the dispersion coefficient is the standard deviation divided by the average grain size.) These photographic emulsions are
Chimie et Phyai Photographic (Chimie et Phyai P, G1a-fkides)
que Photographique) (Paul
(Paul Montel, 1967) G.F. Dauphin, (G.F. Duffjn)
Author Photographic Emulsion Chemistry (
Photographic Emulsion Che
mistry) (The Focal Press (The F
Making and Coating Photographic Ink Emulsion by V. L. Zelikman et al.
Pho-tographic Emulsion (The Focal Pres)
s), 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. .

These photographic emulsions may be any combination of silver chloride, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.

However, in the photosensitive material to be processed in the present invention, the silver halide emulsion layer containing silver iodide in an amount of 1 mol % or more, preferably 5 mol % to 25 mol %, more preferably 7 to 20 mol %, may be reduced. Both are characterized by having one layer.

Therefore, one or more silver iodides selected from silver iodide, silver iodobromide, silver chloride iodobromide, and silver chloroiodide are used to form one or more emulsion layers. is applied onto a support to form a color photosensitive material. At this time, in addition to silver iodide, silver chloride, silver bromide, etc. can be optionally used.

Also, is the coating silver amount of the photosensitive material of the present invention 1 to 20 g/rr?
, especially 2 to 10 g/n (preferably, the total iodine content (AgI) contained in the silver halide photosensitive material is 4
It is preferable that it is 101 mol/d or more. More preferably 6X10-' mol/rrr or more is 4X10-''
mol/d or less.

At the stage of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, or a complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof, etc. may be present.

The polymer providing cation sites contained in the photosensitive material to be processed in the present invention includes the development process,
In particular, it is a polymer having a cation site in a processing liquid that has a fixing ability, and an anion conversion polymer is preferable.

Here, examples of the anion conversion polymer include quaternary ammonium salt (or phosphonium salt) polymers, or tertiary amine polymers that become cations by addition of hydrogen ions or the like in the treatment liquid.

These polymers are widely known as mordant polymers and antistatic polymers from the following publications.

Specifically, JP-A-59-166,940, U.S. Patent No. 3.958.995, JP-A-55-142339,
JP-A-54-126.027, JP-A-54-155.
No. 835, JP-A-53-30328, JP-A-54-9
Water-dispersed latex described in U.S. Pat. No. 2274; polyvinylpyridinium salts described in U.S. Pat. and the water-insoluble ammonium salt polymers described in US Pat. No. 3,898,088.

A preferred anion conversion polymer has the following general formula: % where A represents an ethylenically unsaturated 7-unit. R,
is a hydrogen atom or a lower alkyl group having 1 to about 6 carbon atoms,
L represents a divalent radical having 1 to about 12 carbon atoms.

Rt, R3 and R4 are each the same or different 1-
an alkyl group having about 20 carbon atoms, or from 7 to
It represents an aralkyl group or a hydrogen atom having about 20 carbon atoms, and Rz, R's and R4 may be interconnected to form a cyclic structure with Q. Preferably, from the viewpoint of residual color, only one of R, R, and R4 is a hydrogen atom. Q is N or P, and XO represents an anion other than an iodine ion. x is O to about 90 mol%, y is about 1
It is 0 to 100 mol%.

Examples of the ethylenically unsaturated heptamers of A include olefins (e.g., ethylene, propylene, 1-
butene, vinyl chloride, vinylidene chloride, isobutyne, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chloroprene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, allyl acetate, esters of ethylenically unsaturated acids (e.g. methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate 1, benzyl methacrylate,
Phenyl methacrylate, octyl methacrylate, amyl acrylate, 2-ethylhexyl acrylate,
Benzyl acrylate, maleic acid dibutyl ester,
diethyl fumarate, ethyl crotonate, dibutyl methylene malonate, etc.), styrenes (e.g., styrene, α-methylstyrene, vinyltoluene, chloromethylstyrene, chlorstyrene, dichlorostyrene, bromstyrene, etc.), There are saturated nitriles (eg acrylonitrile, methacrylatetrile, allyl dianide, crotonitrile, etc.). Among these, styrenes and methacrylic acid esters are particularly preferred from the viewpoint of emulsion polymerizability, hydrophobicity, and the like. A is 2 of the above monomers
It may contain more than one species.

R1 is preferably a hydrogen atom or a methyl group from the viewpoint of polymerization reactivity.

h h In the Yukigami formula, R1 represents alkylene (for example, methylene, ethylene, trimethylene, tetramethylene, etc.), annelene, aralkylene (for example, alkylene having a child), and R6 represents a hydrogen atom or R2. n is an integer of 1 or 2.

Q is preferably N in view of the toxicity of the raw material.

XO is an anion other than iodide ion, such as halogen ion (e.g. chloride ion, bromide ion, etc.),
Alkyl sulfate ions (e.g. methyl sulfate ion, ethyl sulfate ion, etc.), alkyl or aryl sulfonate ions (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), nitrate ion, acetate ion, sulfuric acid ions, etc.

Among these, chloride ions, alkyl sulfate ions, arylsulfonate ions, and sulfate ions are particularly preferred.

The alkyl groups and aralkyl groups of R2, R3 and R4 include substituted alkyl groups and substituted aralkyl groups.

Examples of alkyl groups include unsubstituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, t-butyl, hexyl, cyclohexyl, 2-ethylhexyl, and dodecyl groups; substituted alkyl groups, such as alkoxyalkyl groups; (e.g., methoxymethyl group, methoxybutyl group, ethoxyethyl group, butoxyethyl group, vinyloxyethyl group, etc.), cyanoalkyl group (e.g., 2-cyanoethyl group, 3-cyanopropyl group, etc.)
, halogenated alkyl group (e.g., 2-fluoroethyl group, 2-chloroethyl group, perfluoropropyl group, etc.), alkoxycarbonylalkyl group (e.g., ethoxycarbonylmethyl group, etc.), allyl group, 2-butenyl group, propargyl group and so on.

Examples of the aralkyl group include unsubstituted aralkyl groups, such as benzyl, phenethyl, diphenylmethyl, and naphthylmethyl groups; substituted aralkyl groups, such as alkylaralkyl groups (such as 4-methylbenzyl,
2.5-dimethylbenzyl group, 4-isopropylbenzyl group, 4-octylbenzyl group, etc.), alkoxyaralkyl group (e.g., 4-methoxybenzyl group, 4-pentafluoropropenyloxybenzyl group, 4-ethoxybenzyl group, etc.) , cyanoaralkyl group (e.g. 4-
cyanobenzyl group, 4-(4-cyanophenyl)benzyl group, etc.), halogenated aralkyl group (e.g., 4-
chlorobenzyl group, 3-chlorobenzyl group, 4-bromobenzyl group, 4-(4-chlorophenyl)benzyl group, etc.).

The alkyl group preferably has 1 to 12 carbon atoms, and the aralkyl group preferably has 7 to 14 carbon atoms.

Examples of Rz, Rz and R4 interconnecting to form a cyclic structure with Q include the following.

An example of an aliphatic heterocycle (representing an atomic group necessary to form a bare ring) is, for example, R4. (n is an integer of 2 to 12) and R7° each represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms.

).

"Wz represents an atomic group required to form a benzene ring), t and R2. When two R2's, they may be the same or different."

Among these ring structures, R, , R, , R, , Q and XO in the above example have the same meanings as in general formula (1).

Of course, the y component may be a mixture of two or more components.

X is preferably 20 to 60 mol%, and y is preferably 40 to 80 mol%.

Furthermore, at least two (preferably 2 to 4
It is particularly preferable to copolymerize monomers having the following properties to form a crosslinked aqueous polymer latex.

The crosslinked aqueous polymer latex preferably has a structure represented by the following general formula (n).

(n) R8 ■ R1 In the formula, A, R+, R2, Ra, R4, and LSX have the same meanings as in general formula (1). y in general formula (n) is 10 to 99.9 mol%, preferably 10
~95 mol%.

Z is 0.1 to 50 mol%, preferably 1 to 20 mol%.

B is a structural unit obtained by copolymerizing a copolymerizable monomer having at least two ethylenically unsaturated groups. Examples of B include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate. Acrylate, tetramethylene glycol diacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl phthalate, methylenebisacrylamide, methylenebismethacrylamide, trivinylcyclohexane, divinylbenzene,
N.

N-bis(vinylbenzyl)-N,N-dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxyethyl)-N-(vinylbenzyl)ammonium chloride, N,N,N'.

N'-tetraethyl-N,N'-bis(vinylbenzyl)-p-xylylene diammonium dichloride, N,N
'-Bis(vinylbenzyl)-triethylenediammonium dichloride, N,N.

Examples include N', N'-tetrabutyl-N, N'-bis(vinylbenzyl)-ethylenediammonium dichloride. Among these, divinylbenzene and trivinylcyclohexane are particularly preferred from the viewpoint of hydrophobicity, alkali resistance, and the like.

Compound example x:y:2=47.5:47.5:5
II) + CHz CH+-r-+CHz
CH lever - 1,000 CHx CH+ 2 菟CH2 III) +CH, CH±y---→C
Hz CH CH.

y:z=95:5 rV) -+c Ht CHMo1,000CHx CH+-
v→c Hz CH) 2 Hs x : y:z-45:45:10 y:z-90: 10 ■) +CH2CH+-r-+CH! CH+-v-
CH.

x:y=50:50 (2) As the polymer providing +CH2CH+- cation sites, one or more of the above polymers can be used. The molecular weight of the polymer is arbitrary, but the molecular weight is 1000 to 1
0,000,000, preferably soo'o to 200,000.

The amount of polymer that provides cation sites is as follows:
The number of cation sites per mole of total iodine in the light-sensitive material is 0.1 or more, preferably 0.3 to 100, more preferably 0.5 to 30.

The polymer that provides cation sites can be added to both the photosensitive layer and the non-photosensitive layer, but the non-photosensitive layer provided between the photosensitive layer and the support or the opposite side of the photosensitive layer across the support. Among polymers that provide cation sites that are preferably added to a certain non-photosensitive layer, those that have a high ability to capture iodide ions are preferred.

The photosensitive material to be processed in the present invention is characterized by having an emulsion layer containing the above-mentioned silver iodide and containing a polymer having a cation site, but other configurations will be described below.

Milk Jμ Processing and General Additives The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral enhancement. Additives used in such processes are described in Research Disclosure Vol. 176, m 17643 (December 1978) and Research Disclosure Vol. They are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

1 Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer Pages 23-24 Page 648 Right column ~ 4 Supersensitizer Page 649 Right column 5 Brightener
24 page 7 Coupler 25 page 8 Organic solvent 25 page 10 Ultraviolet absorber 11 Stain inhibitor 25 page right 1KA650 page left to right column 12 Dye image stabilizer 25 page 13 Hardener page 26 651 page left column 14 Binder 26 page Same as above 15
Plasticizers, Lubricants Page 27 650 Right Column Prevention Color Coupler 1 Color couplers can be contained in the light-sensitive material to be processed in the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 17643 (December 1978) ■=D
1B717 (November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler whose coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon the campling reaction can also be used.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. 2.3 of the same
No. 43,703, No. 2,600,788, No. 2.
No. 908.573, No. 3,062,653, No. 3
, 152, 89.6 and 3.936,015. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4.310.619 or U.S. Pat.
The arylthio group described in No. 1897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, US Patent No. 3.
369,879, preferably the pyrazolo[5°1-c)(1,2,4)) liazoles described in U.S. Pat. (
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Examples include pyrazolopyrazoles described in June 2013).

Imidazo (1,
2-b) Pyrazoles are preferred, as described in European Patent No. 119,
Pyrazolo (1,5〒b) (1,2,4
)) Riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol and phenolic couplers, preferably the naphthol couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat.
, No. 212, No. 4.146.396, No. 4,22
Typical examples include the oxygen atom elimination type naphthol couplers described in No. 8,233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
No. 01.171, No. 2.772,162, No. 2,
No. 895,826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772.
．． Phenolic cyan coupler having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 002, US Pat.
No. 8,308, No. 4,126,396, No. 4.3
No. 34.011, No. 4,327,173, West German Patent Publication No. 3,329.729 and.

2゜5-diacylamino substituted phenolic couplers described in Japanese Patent Application No. 58-42671, etc., and U.S. Pat. No. 3,446,622, U.S. Pat.
4,451.559 and 4,427.76
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 7.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are given in U.S. Pat. , 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4.367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It is also possible to introduce more than one.

Typical usage amounts for color couplers range from o,ooi to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.00 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-ice dispersion method is U.S. Patent No. 2.322.02.
It is stated in issue 7 etc.

Further, the process, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat. It is written in the number etc.

Support The photographic light-sensitive material to be processed in the present invention can be a commonly used plastic film, (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. applied. For details on the support and coating method, please refer to R.
ESEARCHDrSCLOSURE Volume 176, I
tem 17643XV term (p, 27)X■ term (p, 2
8) (December 1978 issue).

Typical examples of the light-sensitive materials of the present invention include color negative films for general use or movies, color reversal films for non-slip screens or televisions, color papers, color positive films, color reversal vapors, black-and-white films, and black-and-white barbers. be able to.

In the processing method of the present invention, the amount of replenishment of the processing liquid having fixing ability is 300 ml per 1 m of the photosensitive material to be processed.
Hereinafter, preferably 50 to 250n+42, particularly preferably 50 to 200mj2 is used. Here, the term "bath having fixing ability" means a fixing solution and a bleach-fixing solution, and the replenishment amount of these processing solutions is set within the above-mentioned range.

The processing method of the present invention includes combinations of various processing steps, specifically: (i) development - bleaching, fixing - washing - drying (ii) - p - ~ - - stabilization - Drying (1!
f) ' - # -// - Stabilization - Drying (iv
)〃 - Bleach fixing, washing, drying (v) # -〃 -
Stabilization-drying (vi) -” -Water washing-stabilization-drying (V)I
) Development - bleaching - bleach-fixing - washing - drying (vii) s
-s -~ -〃 -Stabilization-Drying (ix)
Examples of treatment methods include -s - -stabilization-drying. Here, washing with water may be provided between development and bleaching or bleach-fixing, or between bleaching and fixing. The treatment bath may be of any type, such as a single tank, a multi-stage countercurrent system, or a multi-stage parallel current system. Note that the above-mentioned development step can include a reversal color development step consisting of black and white development, water washing, reversal, and one color development.

The color developing solution used in the development of the photosensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-)luenesulfonates, etc. Can be mentioned. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it contains agents such as agents. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, various preservatives such as those described in Japanese Patent Application No. 61-280792, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, and development accelerators such as class ammonium salts, amines, dye-forming couplers, competitive couplers, couplers such as sodium boron hydride -1-phenyl-
Auxiliary developers such as 3-pyrazolidone, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, West German Patent Application (OL S) No. 2,622
．． Antioxidants such as those described in No. 950 may be added to the color developer.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black and white developers such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The amount of replenishment of these color developing solutions and black and white developing solutions depends on the color photographic light-sensitive materials to be processed, but is generally 31 or less per square meter of light-sensitive material, but the concentration of bromide ions in the replenisher should be reduced. It can also be reduced to 500n11 or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the opening area of the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

bleaching, fixing After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Further, a fixing treatment can be carried out before the bleach-fixing treatment, or a bleaching treatment can be carried out after the bleach-fixing treatment depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I[
Compounds of polyvalent metals such as I), chromium (■), and copper (n), peracids, quinones, and nitrone compounds are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobal (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates; bromates; manganates; nitrosophels, etc. can be used. can. Among these, aminopolycarboxylic acid iron (III) salts and persulfates, including ethylenediaminetetraacetic acid iron (I[[) salt, are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, aminopolycarboxylic acid iron(I[I) complex salts can also be used in independent bleaching solutions.
- Also particularly useful in bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators include compounds containing mercapto or disulfide groups; thiazolidine derivatives; thiourea derivatives; iodides; polyethylene oxides; polyamine compounds; and iodine and bromide ions. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Patent No. 3.893.858 and West German Patent No. 1.290.
．． Compounds described in No. 812 and JP-A No. 53-95630 are preferred.

Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. When bleaching and fixing color photosensitive materials for photography,
These bleach accelerators are particularly effective.

Examples of fixing agents include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfuric acid sulfate is commonly used, and ammonium thiosulfate is the most widely used. Can be used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

Among the processing solutions for the above-mentioned desilvering step, the replenishment amount of the processing solution having fixing ability is preferably 300 mJ or more, particularly preferably 300 mf or more and 1000 ml or less per 1 m 2 of the light-sensitive material. In addition, when processing with a bleach solution, the replenishment amount is preferably 50 mβ or more,
In particular, it is preferably 100ml1 or more and 500ml1 or less.

Water Washing and Stabilization The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of theSociety of Mo
tion Picture and Televisi
onEngineers Vol. 64, P, 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. Can be done. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use the disinfectants described in ``Sterilization, sterilization, and anti-mildew technology of microorganisms'', Hygiene Technology Extra Section, and ``Encyclopedia of Antibacterial and Antifungal Agents'', Japan Antibacterial and Anti-Mold Science Extra Section.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 25
A range of 30 seconds to 5 minutes at -40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
All known methods described in No. 4, No. 60-220345, etc. can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifouling agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.
For this purpose, it is preferable to use various precursors of color developing agents. For example, U.S. Patent No. 3,342.
Indoaniline compounds described in No. 597, No. 3.34 of the same
2.599, Research Disclosure 14,8
Schiff base-type compounds described in No. 50 and No. 15,159, aldol compounds described in No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 3-135628.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate the processing and shorten the processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, West German Patent No. 2,226.770 or US Patent No. 3.
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

〔Example〕

Example 1 A color photosensitive material (sample 101) was prepared by coating each layer having the composition shown below on a cellulose triacetate support.

1st layer: Red-sensitive emulsion layer Silver iodobromide emulsion (Ag I, 3 mol%, internal high Agl type sphere equivalent diameter 1.0μ, coefficient of variation of sphere equivalent diameter 20%, grain, diameter/thickness ratio 3) coating Silver amount 2.5g/m gelatin 3.3g1rd sensitizing dye I
3X10-' moles of sensitizing dye II per mole of silver
#lXl0-'molar coupler E
X-11.4g/rd Solvent 1 0.5g/
n? Container 2
0.5g/r+? 2nd layer: 1st protective layer gelatin 1.8 g/n
? The types and amounts of cationic polymers are shown in Table-1.

Ultraviolet absorber UV-10, 1g/m # UV-20, 2g/m Solvent 1 0.01 g/
rrr solvent 2 0.01g
/m Third layer: second protective layer gelatin 1.5g/m polymethyl methacrylate 0.2g/m particles (diameter 1
．． 5μ) In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

The following compounds were used as the above compounds.

Sensitizing dye I Sensitizing dye■ Color Ex-1 H (i) CJJCNH Solvent-Technical solvent-2 CHz = CH5OzCHzCONH-CI□CHt-
CHSOzCHzCONH-CHz The silver iodobromide emulsion used in Sample 101 above was prepared as follows.

Ammoniacal silver nitrate and alkali halide aqueous solution were added to a reaction vessel containing gelatin aqueous solution to which potassium bromide and potassium iodide had been added in advance, and kept at 60'C.
was added over 40 minutes while maintaining the pH at 8.7, and after washing with demineralized water, gelatin was added to obtain an emulsion with pAg of 8.0 and pH of 6.2. Furthermore, sodium thiosulfate, chloroauric acid, and rotane potassium were added, chemically aged at 58°C for 60 minutes, and 4-hydroxy-6-methyl-1,3,3a,7-titraazaindene was added. A silver iodobromide emulsion was obtained.

Next, by changing the composition of the alkali halide, emulsions were prepared by changing the silver iodide mol%, and these emulsions were used to prepare samples 102 to 1 having the compositions shown in Table 1.
29 was created.

The sample prepared in this manner was exposed to light so that the amount of developed silver produced in the color development step was 2±0.05 g/m', and then developed according to the following steps. The amount of residual silver in the photographic material after processing was measured by fluorescent X-ray analysis and is shown in Table 1 along with the graininess and sensitivity.

The amount of cationized polymer added in the table is expressed as the amount of cation sites per 1 mole of total iodine in the photosensitive material (
same as below).

Using the above-mentioned samples, development processing was carried out by varying the amount of bleach-fixing solution replenished. Incidentally, the amount of replenishment from now on will be expressed in ml per 1 m'' of photosensitive material.

Color development 2°30” 38°C 640ml
Bleach fixing 1'OO" 〃 Washing with water as shown in Table-1 ■ 30'" 〃 〃 ■ 30" 4860m1 Stable
30 ”〃570n+ 1 Wash with water■,
■ was a countercurrent replenishment method from tank ■ to tank ■. The composition of the treatment liquid is shown below.

Mother liquor (g) Diethylenetriaminepentaacetic acid 2.01-Hydroxyethylidene-1,3,01-diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide
1.5■Hydroxylamine sulfate 2.4 4-[N-ethyl-N-(β-hydroxyethyl)amino]-2-methylaniline sulfate was added to 11 pH 10
, 05 Hoshi Watarui Melon Mother liquor (unit: g) Ethylenediaminetetraacetic acid ferric SO,O ammonium dihydrate Ethylenediaminetetraacetic acid 5. 〇 Disodium salt Sodium sulfite 12.0 Ammonium thiosulfate 260.0 ml aqueous solution (
70χ) Acetic acid (98χ) 5.0mj
! Bleach accelerator Add 0.01 mol of water to 1N pH 6.0. Add H-type strongly acidic cation exchange resin (Mitsubishi Kasei Corporation) to H-type strong acidic cation exchange resin (Mitsubishi Kasei Corporation).
Diaion 5K-IB) and OH-type strongly basic anion exchange resin (Diaion 5A-IOA) were passed through a heated bed column to obtain the following water quality. After that, isocyanuric dichloride was added as a disinfectant. Sodium acid 20/1
was added.

Calcium ion 1.1■/1 Magnesium ion 0.5■/1pH6,9 Wataru Gensada Mother liquor (unit g) Formalin (3
7χ) 2.0mf polyoxyethylene-p -0,3 Monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid Add 0.05 disodium salt water 11p8
5.0 to 8.0 As is clear from Table 1, it can be seen that the amount of residual silver increases as the amount of replenishment of the bleach-fixing solution is reduced. However, when a polymer providing cation sites is used in combination, the amount of residual silver is significantly reduced, and it is clear that the present invention has excellent effects. In Table 1, the graininess is expressed as RMS granularity at a density of 1.0, and the relative sensitivity is calculated as the logarithm of the reciprocal of the exposure amount that gives a density of 1.0.
With the sensitivity of 1.0, the sensitivity of other samples is sample 103
The difference in sensitivity between sample 103 and sample 103 was added to the sensitivity and expressed as a relative value.

Example 2 On the triacetate base, the following layers 1 to 14
Sample 301 was prepared by creating a color photographic material coated with
And so.

Noko” Volume 11 Below are the ingredients and g/rr? Indicates the coating amount in units.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (antihalation layer) Black colloidal 8-doped silver ・・・・・・・・・
0.30 Gelatin ・・・・・・・・・
・2.50 ultraviolet absorber (Cpd-1, 2, 3)
・・・・・・・・・ 0.20 UV absorber solvent (So
lv-1) ・・・・・・・・・ 0.10 2nd layer (
(middle layer) Gelatin ・・・・・・・・・ 0.
50 3rd N (low sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dye (ExS-1, 2) (silver iodide 4.0 mol%, average grain size 0.3
5μ) ・・・・・・・・・ 0.50 Gelatin ・・・・・・・・・ 0.
80 cyan coupler (ExC-1, 2)...
...0.25 coupler solvent (Solv-2)
・・・・・・・・・ 0.10 4th layer (medium red sensitivity N) Silver iodobromide (silver iodide 2. 5 mol%, average particle size 0.4
5μ) ・・・・・・・・・ 0.50 Gelatin ・・・・・・・・・ 1.
00 cyan coupler (ExC-1, 2)...
...0.50 coupler solvent (Solv-2)
......0.20 5th layer (high sensitivity red sensitive layer) Silver iodobromide (silver iodide 2.5) spectrally sensitized with red sensitizing dye (ExS-1,2) Mol%, average particle size 0.6
0μ) ・・・・・・・・・ 0.30 Gelatin ・・・・・・・・・ 0.
70 cyan coupler (ExC-1, 2)...
...0.30 coupler solvent (Solv-2)
・・・・・・・・・ 0.12 6th layer (middle layer) Gelatin ・・・・・・・・・ 1.0
Color mixing prevention agent (Cpd-4) ・・・・・・・・・
・0.1 color mixing inhibitor solvent (Solv-1, 2, 3)・
・・・・・・・・・ 0.25 polymer latex (Cp
d-5)・・・・・・・・・ 0.25 7th layer (low-range green-sensitive layer) Silver iodobromide (iodobromide) spectrally sensitized with green sensitizing dye (ExS-3, 4) Silveride 3.0 mol%, average grain size 0.3
μ) ・・・・・・・・・ 0.65 Gelatin ・・・・・・・・・ 1.
50 magenta coupler (ExM-1, 2)...
... 0.35 coupler solvent (Solv-2)
......0.30 8th layer (high sensitivity green sensitive layer) Silver iodobromide (silver iodide 2.5) spectrally sensitized with green sensitizing dye (ExS-3,4) Mol%, average particle size 0.8
μ) ・・・・・・・・・ 0.70 Gelatin ・・・・・・・・・ 1.
00 magenta coupler (ExM-3) ・・・・・・
... 0.25 anti-fading agent (Cpd-6,7)
・・・・・・・・・ 0.15 Anti-fading agent solvent (So
lv-2) ・・・・・・・・・ 0.05 9th layer (middle layer) Gelatin ・・・・・・・・・ 0.
50 10th layer (yellow filter single layer) Yellow colloid II ・------・-0
,10 Gelatin ・・・・・・・・・
1.00 Color mixing prevention agent (Cpd-4)...
・・・・・・ 0.05 color mixing inhibitor solvent (Solv-1
, 2) ・・・・・・・・・ 0.10 Polymer latex (Cpd-5) ・・・・・・・・・ 0.10 11th layer (low sensitivity blue sensitive layer) Blue sensitizing dye ( Silver iodobromide (silver iodide 2.5 mol%, average grain size 0.7μ) spectrally sensitized with ExS-5) ・・・・・・・・・ 0.55 Gelatin ・・・・・・... 0.
90 yellow coupler (ExY-1) ・・・・・・
... 0.50 coupler solvent (Solv-2)
・・・・・・・・・ 0.10 12th layer (high sensitivity blue sensitive layer) Silver iodobromide (silver iodide 2.5 mol%) spectrally sensitized with blue sensitizing dye (ExS-5) , average particle size 1.5...
・・・・・・・・・ 1.00 Gelatin ・・・・・・・・・ 2.
00 Yellow coupler (ExY-1) ・・・・・・
... 1, OO coupler solvent (Solv-2)
・・・・・・・・・ 0.20 13th layer (ultraviolet absorption layer) Gelatin ・・・・・・・・・ 1.
50 UV absorber (Cpd-1, 2, 3, 8)...
・・・・・・ 0.40 Ultraviolet absorber solvent, medium (Sol Sea 1) ・・・・・・・・・ 0.30 Irradiation prevention dye (Cpd-9) ・・・・・・・・・ 0, 10 14th layer (protection N) Fine grain silver iodobromide (silver iodide 1 mol%, average grain size 0.05 μ) ・・・・・・・・・ 0.1
0 Gelatin ・・・・・・・・・ 2
．． OO gelatin hardening agent (Ll) ・・・・・・・・・
・・ 0.30E, S −2 502-SO, M E, 5-4 E, S −5 +・ N(Czlls)s pd-1 r σ (t) C4Hv pd-2 CH (t) Callq pd- 3 il CHCHa CH,C1h pd-4 CH Cρd-5 Polyethyl acrylate pd-6 CH CHs pd-7 CH CH pd-8 pd-9 0sNa Ex C-2 EXM I CJ 21M-2 E, M-3 C11゜Sol Sea 1; dibutyl phthalate 5olv 2; tricresyl phosphate 5ol
v-3; trinonyl phosphate H-1i1.2
-Bis(vinylsulfonylacetamido)ethane (A)
In sample 301, silver iodobromide (silver iodide 2.5 mol%) in the fifth layer was mixed with silver iodobromide (silver iodide 2.5 mol%) in the emulsion of silver iodobromide (silver iodide 115 mol%), and silver iodobromide (silver iodide 2 Silver iodobromide (silver iodide 2 mol%) is added to the twelfth layer of silver iodobromide (silver iodide 2
．． Sample 302 was prepared by replacing silver iodobromide (5 mol %) with an emulsion of silver iodobromide (5 mol % silver iodide).

(B) In sample 301, the fifth layer of silver iodobromide (silver iodide 2.5 mol%) was added to the silver iodobromide (silver ninetate 7 mol%) emulsion, and the eighth layer was silver iodobromide. (silver iodide 2.5 mol%) to silver iodobromide (silver iodide 7 mol%)
A twelfth layer of silver iodobromide (silver iodide 2.
Sample 303 was prepared by replacing silver iodobromide (7 mol% silver iodide) with an emulsion of silver iodobromide (7 mol% silver iodide).

(C) In sample 301, 5N silver iodobromide (silver iodide 2.5 mol%) was added to an emulsion of silver iodobromide (silver iodide 10 mol%) to form the eighth layer of silver iodobromide (silver iodobromide (silver iodide 10 mol%)). Silver iodobromide (silver iodide 2.5 mol %) to an emulsion of silver iodobromide (silver iodide 10 mol %) to iodobromide the 12th layer! ! (silver iodide 2.5 mol%) to silver iodobromide (silver iodide 10 mol%)
Sample 308 was prepared by replacing the emulsion with the above emulsion.

(D) Next, the second layer of samples 303 and 304, a sample in which the cationic polymer of the present invention was added to No. 9N, and a gelatin layer on the side opposite to the emulsion side (hereinafter referred to as the back side) in the same manner as in Example 2. A support to which the cationic polymer of the present invention was added was prepared in advance, and samples were prepared as shown in Table 4.

After exposing the silver halide color photographic materials 301 to 304 prepared as described above, the cumulative replenishment amount of the coloring solution is tripled to the tank capacity using an automatic developing machine using the method described below. Processed up to.

几 1 King [j Crystal Office Kunku 6th Supplement - Development
6 minutes 38℃ 1212 2200m1! /m”
First water wash 45 seconds 38〃2〃2200〃Reverse
45〃38〃2〃1100〃Color development 6 minutes
38〃12〃2200〃Bleaching 2〃 38〃
4〃 200 〃Bleach fixing 4〃 38〃
8〃 250 〃Second washing (1) 1//
38// 2// --Second washing (2)
1〃38〃2〃1100〃Stable 1〃25〃2〃
1100 Dryness 1 65 ----
Here, to replenish the second water wash, the replenisher is introduced into the second water wash (2), and the overflow liquid from the second water wash (2) is transferred to the second water wash (1).
), a so-called countercurrent replenishment method was adopted.

The composition of each treatment liquid was as follows.

First developer sodium sulfite -30g
30g potassium carbonate 33
g 33g potassium bromide
2.5g 1.4g Potassium thiocyanate
1.2g 1.2g potassium iodide 2.0mg ---- 1000mj!
1000m j! pH 9,609,60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Disodium phosphate 5.0g Add water 1000m 1p
H7.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Stannous chloride dihydrate 1. Ogp-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid
15m j! say
1000 ml' pH 6,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Sodium sulfite 7.0g7.0
g Trisodium phosphate 12 hydrate 36g 3
6g potassium bromide 1.0.
----- Potassium iodide 90
mg ---- Sodium hydroxide
3.0g 3.0g Citrazic acid
1.5g Add 1.5g water
1000m 12100001 (1pH
11,8012,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Ammonium bromide 100g Ammonium nitrate 10g Bleach accelerator
o, oos mole 9H6,20 pH was adjusted with hydrochloric acid or aqueous ammonia.

Ethylenediaminetetraacetic acid・Fe() 50g Same as mother liquor・Ammonium・sodium thiosulfate dihydrate 80g Same as mother liquor Sodium sulfite 12.0g
1000m j
! pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Both the mother solution and the replenisher are tap water, and a hot bed filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, and then 20 mg/β of sodium incyanurate dichloride and 1.5 g/l of sodium sulfate were added. The pH of this solution is 6.5-7
．． It is in the range of 5.

Formalin (37%) 5.0m!
The amount of residual silver, graininess, and relative sensitivity of the photosensitive material treated in the same manner as the mother liquor were measured, and the results are summarized in Table 4 along with the structure of the photosensitive material.

As is clear from the positions in Table 4, it can be seen that the present invention provides a color photosensitive material with excellent desilvering properties and photographic properties.

1. Indication of the incident 1988 Patent Application No. 92372 2
, Title of the invention Method for processing silver halide photosensitive materials 3.
Relationship with the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 6, Subject of amendment Detailed explanation of the invention in the specification 1, page 77 of the specification, Table 4 Later, Example 3 below will be added.

“Example 3 On a subbed cellulose triacetate film support,
Samples 401 to 405, which are multilayer color photosensitive materials each having each layer having the composition shown below, were prepared.

(Composition of the amount of light applied) For silver halide and colloidal silver, the coating amount is expressed in g/d of silver, and for couplers, additives and gelatin, it is expressed in g/n? The total is expressed in units, and the sensitizing dye is expressed in moles per mole of silver halide in the same layer.

1st N (Anti-halation N) Black colloidal silver...0.2 Gelatin...1.3 Power puller ExM
-9...0.06 Ultraviolet absorber UV-1...0.03 〃 UV-2...0.06 〃 UV-3...0.06 Dispersion oil So Iv-1-...0 .15〃S
Ol v-2・ ・ ・0.15〃 Sol v
-3・・・0.05′ 2nd layer (intermediate layer) Gelatin...1.0 Ultraviolet absorber UV-1...0.03 Coupler ExC-4-...0.02 Compound ExF-1・...0.004 Dispersion oil 5O1v-1...0.1 〃5olv-2...0.1 Third layer (low-range red-light emulsion M) Silver iodobromide emulsion (AgI 4 mol%, uniform -Agl type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount: Bow, 2 Silver iodobromide emulsion (Agl 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount ...0.6 Gelatin ・・・1.0 sensitizing dye ExS-1・・-4X10-'〃 ExS-2・・
・ 5×10-S coupler ExC-1-・・0.05 〃 ExC-2・ ・・0.50 〃 ExC-3・ ・・0.03 〃 ExC-4・ ・・0.12 〃 ExC-5・ ・ ・0.01 Fourth polishing (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio l:1
(Agl type internal cylinder, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter/thickness ratio 5.0) Coated silver amount ・・・0.7 Gelatin ・・・1.0 Sensitizing dye ExS-1...3X10-'〃ExS-2...2.
3X10-' Coupler ExC-6...0.11 ExC-7--0.05 ExC-4...0.05 Dispersion oil So Iv-1...0.05 Dispersion oil S
o 1 v-3...0.05 5th layer (middle layer) Gelatin...0.5 Compound
Cpd-1...0.1 Dispersion oil So 1v-1...0.05 No. 61 (Low-range green emulsion N) Silver iodobromide emulsion (Ag1 4 mol%, core-shell ratio 1:1
Surface height Agl type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter/thickness ratio 4.0) Coated silver amount...-0,35 Silver iodobromide Emulsion (AgI 3 mol%, uniform-Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter/thickness ratio 1.0) Coated silver ■...0. 2
0 Gelatin...1.0 Sensitizing dye ExS-3...5X10-'s ExS-4...
3X10-' // ExS-5= lXl0°4 force puller ExM
-8・-・0.4 Coupler ExM-9...0.07 〃 ExM-10・ ・ ・0.02〃 ExY-
11. .0.03 dispersion oil So IV-1..
・0.3" So 1v-4...0.05 7th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, core shell ratio l:3
internal high Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 5.0) Application: 1 year old ・ ・ ・ ・ ・ ・ 0.8 aggravating dye ExS-3...5X10-'# ExS-4
...3X10-' 〃 ExS-5... 1x10-4 Force puller ExM-8...0.1 〃 ExM-9...0.02 〃Ex'/ -11' ---0 ,03〃ExC-2・
...0.03 〃ExN1-14...0.01 Dispersion oil So 1v-1...0.2 Dispersion oil 5o
lv-4...0.01 8th layer (middle N) Gelatin...0.5 compound
Cpd-1...0.05 Dispersion oil So 1 v-1...0.02 9th layer (donor layer for multilayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag
1 2 mol%, internal high Agl type with a core-shell ratio of 2:1,
Equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 15%, (reverse-shaped particles, diameter/thickness ratio 6.0) Coated silver amount...0.35 Method (IJm emulsion (Agl 2 mol) %, internal high AgI type with a core-shell ratio of 1:1, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 6.0) Coated silver amount... 0,20 Gelatin...0.5 Exacerbating dye ExS-3...-8X10-'Coupler ExY-13...
...0911" ExM-12...0.03 Force puller ExM-14...0.10 Dispersion oil 5olv-1...o, 2° 10th layer (yellow filter N) Yellow colloidal silver... 0.05 gelatin...0.5 compound Cp
d-2-...0.13 N Cpd-1...0.10 11th layer (low-temperature blue-sensitive emulsion N) Silver iodobromide emulsion (Agl 4.5 mol%, uniform-Agl type, spherical Equivalent diameter 0.7 μ, coefficient of variation of sphere equivalent diameter 15%, spherical particles, diameter/thickness ratio 7.0) Coated silver amount ・・・・・・0
．． 3 Silver iodobromide emulsion (Ag1 3 mol%, uniform-Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains,
Diameter/thickness ratio 7.0) Coated silver amount...0.15 Gelatin...1.6 Exacerbating dye ExS-6...2X10-'Coupler ExC-16.
・・0.05 ” ExC-2・-・0.10 Coupler ExC-3・・0.02 〃ExY-13・・−0,01 〃 ExY-15・・・0.5 〃 ExC-17・・ ・1.0 Dispersion oil So 1v-1...0.20 12th M (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high AgI type, equivalent sphere diameter 1.0μ, Coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Application 1 L1 ・ ・ ・ ・ ・ 0.5 Gelatin ・・・0.5 Exacerbating dye E
xS-6...1. Xl0-'Coupler ExY-15
...0.20〃ExY-13...0. Ol Dispersion oil So 1 v-1...0.10 13th layer (
First protection i! ! layer) Gelatin...0.8 Ultraviolet absorber UV-4...0.1 〃 UV-5...0.15 Dispersion oil So Iv-1...0.01〃 S
o l v-2・・・0.01 cationic polymer
The types and amounts are shown in Table-5.

14th layer (second protective layer) Fine grain silver bromide emulsion (Agr 2 mol%, uniform Agl type, equivalent sphere diameter 0.0
7μ) ...0.5 gelatin
...0.45 Polymethyl methacrylate particle diameter 1.5μ...0.2 Hardener H-1...0.4 Compound Cpd-3...0.5 Cpd-4. ...0.5 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3 (
0,04g/rrF) Surfactant Cpd-4 (0,0
2 g/m) was added as a coating aid. Other subliminal compounds Cpd-5 (0.5g/n() ~ Cpd-6(0
, 5g/me) was added.

UV-1 + UV-2 same as Cpd-1 of Example 2: UV-5 same as Cpd-2 of Example 2: Cpd- of Example 2
Same as 8 So1v-1 tricresyl phosphate 5olv-27 dibutyl talate olv-4 Cpd-1 Cpd=2 Cpd-3Cpd-4 Cpt1-5 Cpd-6Exc-
2: Same as color Ex-1 of Example 1 ExC-3 0H Ht lh ■ C(C0s)i ExC-7 H xM-8 m'=25 mol, wL, about 20,000 xM-9 ExY-11 C11゜ExY-13 ExY-14 ExY-15 xC-16 ExY-17 xS-1 ExS-2 ExS-3 ExS-4 ExS-5 xF-1 2H5L+2115 To the samples 401 to 405 prepared as above , the amount of developed silver produced in the color development process ±0.05g/month
am'', and continuous processing was carried out according to the same processing steps as in Example 1 until the cumulative replenishment amount of the color developing solution reached three times the tank capacity.Furthermore, the bleach-fix solution was refilled. Continuous treatment was carried out by changing the amount.The tank capacity of each treatment bath was as follows.

1st process - 9 Otogakikii - 1 color development 5It Bleach fixing 2! Washing ■ 1! Wash with water ■ 17! Stable 1β After the continuous treatment, the residual 1ffiffl of the obtained sample was measured and the results are shown in Table 5.

Table 5 Graininess was measured for the above samples 401 to 405, but sample 401 had a large amount of residual silver, resulting in extremely poor reproducibility. In contrast, sample 402 of the present invention
-405, similar to Example 1, good results were obtained in all cases. ”

Claims (4)

[Claims] (1) After color development of the exposed silver halide photosensitive material,
In a method of processing with a processing solution having fixing ability, the silver halide photosensitive material has at least one light-sensitive silver halide emulsion layer on a support, and at least one of the layers contains 1 mol % of silver iodide. The photosensitive material is formed from a silver halide emulsion containing the above, and the photosensitive material contains a polymer that provides cation sites, and the replenishment amount of the processing liquid having fixing ability is 300 ml per 1 m^2 of the photosensitive material.
A method for processing a silver halide photosensitive material, which is characterized by the following. (2) Replenishment amount of processing liquid with fixing ability is 1 m^ of photosensitive material
2. The method according to claim 1, wherein the amount is 50 to 250 ml/2. (3) The polymer providing cation sites is contained in a non-light-sensitive silver halide emulsion layer formed on the opposite side of the light-sensitive material to which the silver halide emulsion layer is coated. The method described in section. (4) The method according to claim 1, wherein the silver iodide is at least one selected from the group of silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.