JPH03291647A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable processing of a high silver chloride color photographic sensitive material with superior desilverability without causing bleach stain by forming at least three photosensitive layers each contg. a silver chlorobromide emulsion having >=90 mol% average silver chloride content as the silver halide emulsion layers of the sensitive material. CONSTITUTION:At least three photosensitive layers each contg. a silver chlorobromide emulsion having >=90 mol% average silver chloride content are formed as the silver halide emulsion layers of a high silver chloride color photographic sensitive material. At least one of cyan, magenta and yellow couplers is incorporated into each of the photosensitive layers and the total amt. of silver halide in the photosensitive layers is regulated to <=0.70 g/m<2> (expressed in terms of silver). Color development is followed by termination and/or washing and then bleaching, fixing and washing are carried out. Processing of the high silver chloride color photographic sensitive material is enabled with superior desilverability without causing bleach stain.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic materials, and more specifically, the present invention relates to a method for processing silver halide color photographic materials. This invention relates to a method for processing silver color photographic materials.

(Prior Art) Processing methods for silver halide color photographic materials basically consist of color development treatment, desilvering treatment, unnecessary matter removal treatment represented by water washing or rinsing, and/or stabilization treatment. .

Desilvering treatment is usually carried out as a bleaching treatment and a fixing treatment or a bleach-fixing treatment.As an oxidizing agent for bleaching the developed silver generated by zero color development, an organic acid such as an aminopolycarboxylic acid metal complex salt is used. Metal complex salts are often used, and at the time they were introduced, there were 8! This is because acid metal complex salts pose relatively few environmental protection problems and the treatment liquid can be recycled.

However, processing solutions using organic acid metal complex salts generally do not have sufficiently high oxidizing power, so the bleaching speed of developed silver is not necessarily high. In silver color photographic materials,
The drawback is that bleaching or bleach-fixing requires a long time.

Furthermore, even in silver halide color photographic light-sensitive materials where the amount of coated silver or developed silver is not necessarily large, there are cases where the silver component cannot be eliminated.For example, silver halide emulsions containing a high content of silver chloride Such a phenomenon has also been observed in printed photosensitive materials using a small amount of coated silver.

Such so-called desilvering defects often cause problems in color print type silver halide color photographic materials.
In particular, if such a silver component remains in the yellow coloring layer, color turbidity is likely to be noticeable.

In order to improve this defective desilvering, bromide salt is added to the bleach-fix solution.
The effectiveness of the technology of incorporating iodide salts was demonstrated in JP-A-64.
-62642, 64-62643 and 64-63
It is described in No. 960, etc.

According to the technology disclosed herein, although the above-mentioned problems are solved to some extent, the desilvering speed and fixing speed at the initial stage of bleach-fixing processing are reduced, and furthermore, the bleach-fixing solution causes corrosion of the materials used in processing equipment. There was a problem in that it was not always satisfactory because it also worsened sex.

In addition, a technology for immediately bleaching and then fixing a high silver chloride photosensitive material after color development was published in Japanese Patent Application Laid-Open No. 2-331.
It is described in the specification of No. 42.

Although this is a treatment process with excellent desilvering properties, it has the disadvantage that bleaching stains are likely to occur and is not a sufficient technique.

As described above, a technique sufficient to solve the defective desilvering caused by high silver chloride without causing other problems has not yet been found.

(Problems to be Solved by the Present Invention) An object of the present invention is to provide a processing method that does not cause bleaching stain and has excellent desilvering properties using a high silver chloride color photographic light-sensitive material. It is in.

(Means for Solving the Problem) The object of the present invention can be achieved by the following method: (1) A halogenated compound containing a coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine color developing agent. In a method for processing a silver color photographic light-sensitive material, the silver halide emulsion layer is composed of at least three light-sensitive layers containing a silver chlorobromide emulsion having an average silver chloride content of 90 mol% or more, and each light-sensitive layer is cyan. containing at least one of a coupler, a magenta coupler or a yellow coupler,
The total silver halide coating amount of the photosensitive layer is 0.70 g/silver equivalent.
A method for processing a silver halide color photographic light-sensitive material, which is less than or equal to rrr and is characterized by carrying out a color development process followed by a stop and/or a water washing process, followed by a bleaching process, a fixing process, and a further water washing process.

(2) Halogenation according to item (1), wherein the bleaching solution contains 0.02 to 0.1 mol/l of a ferric complex salt of a compound represented by the following general formula (I) Processing method for silver color photographic materials.

General formula (I) In the formula, A1 to A4 may be the same or different, and -
Represents CH20H or 1000M.

M represents a hydrogen atom, sodium, potassium or ammonium; n represents an integer from 3 to 5;

(3) The method for processing a silver halide color photographic light-sensitive material according to item (1) or item (2), wherein the fixing solution does not substantially contain ammonium ions.

(4) The method for processing a silver halide color photographic material according to item (1) or item (2), characterized in that the stop solution contains vinegar vi or sulfuric acid (5) Silver halide emulsion The method for processing a silver halide color photographic light-sensitive material according to items (1) to (4), wherein is silver chlorobromide having a localized silver bromide phase.

The processing steps of the present invention will be explained in detail below.

The color developing solution used in the present invention contains a color developing agent. Preferred are aromatic primary amine color developing agents represented by p-phenylenediamine, and examples of the compounds are shown below.

D-I N, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl-p-phenylenediamine) (β・-hydroxy7tyl)aminoaniline D-52-methyl-4-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline D-7N-(2-amino-5-diethylamino phenylethyl)methanesulfonamide D-8N,N-'; Methyl-P-phenylenediacine D-94-amino-3- Methyl-1N-ethyl-N-methoxydiethylaniline D-104-avino-3-methyl-N-rethiru-N-β
-Methoxyethylaniline D-11,4-amino-3-methyl-N-ethyl-N-
β-Butoxyethylaniline Also, these p-phenylenediamine derivatives include sulfate, hydrochloride, ri sulfate, p-) luenesulfone rJti
The above compounds, which may be salts such as salts, are described in U.S. Pat.
．． 1'93. Ql, No. 5, No. 2,552゜241, No. 2,566.271, No. 2,592.364,
It is described in the same No. 3,65.6,950, the same No. 3゜698.525, etc. Cough aromatic-grade amine! 11 (& The amount of main agent used is about 0.1g to about 20g per 1j of developer solution.
More preferred is a concentration of about 0.5 g to about Log.

As is well known, the color developer of the present invention may contain hydroxylamines. Preferred hydroxyl-7G compounds include compounds of the general formula (I) shown in JP-A No. 63-106655,
The ia fudialkylhydroxylamines described in No. 1 can be mentioned. In addition, as other preservatives, US Pat.
It is also a preferred embodiment to use the hydrazine V' conductor described in No. 801521. Other examples include reethanolamine, catechol disulfonic acid, and catechol trisulfonic acid.

The color developer used in the present invention preferably has a pH of 9
~12, more preferably 9-1! The color developer may contain other known developer component compounds.

For example, alkaline agents and Pd1HIi agents include caustic soda, caustic potash, soda carbonate, potassium carbonate, tertiary sodium phosphate,
Tertiary potassium phosphate, potassium metaborate, borax, etc. are used alone or in combination.

In addition, for the purpose of imparting illumination ability, for convenience in formulation, or to increase ionic strength, it is also possible to add dihydrogen phosphate 17, potassium, potassium dihydrogen phosphate or sodium, sodium bicarbonate or potassium, ;I: Various salts such as acids, alkali nitrates, alkali sulfates, etc. are used.

In addition, various chelating agents can be used in the color developer to prevent the precipitation of calcium and magnesium.
Examples include hydroxylykylidene-1,1-cyphosne-1, phosphoric acids, and the like.

In particular, nitrilo-+', N, N-i, 7-styrenephosphonic acid, hydroxyethyl-monodiacetic acid, ethylenecyamone-tetraacetic acid, diethylenetriamine-pentaacetic acid, L-hydroxyethylidene-1,1-diphosphonic acid, etc. It is preferable to use

Add any development accelerator to the color developer if necessary.
'■Can be done0 For example, U.S. Patent No. 2,648,604, Japanese Patent Publication No. 44-9', 50', U.S. Patent No. 3171.24
No. 7 represents various types of pyridium chloride and others/-unaoni, rinikaratoku, phenosanoranini, ○
neutral salts such as krylam nitrate and potassium nitrate, Japanese Patent Publication No. 44-9304, U.S. Patent No. 2;
533,990 beg 64 (monthly 12゜531.8rII
No. 2. :: , o, No. 97o, 2.577.1
No. 27' self-published (...51 methylene glycol, its 11 conductor, nonionic compounds such as bonotioethers, and thioether compounds described in US Pat. No. 3,201,242 may also be used.

In addition, a sulfite source commonly used as a preservative, such as potassium sulfite, potassium bisulfite, or sodium bisulfite, can be added as necessary.

In the present invention, any anti-cuffing agent can be added to the color developer, if necessary. As antifoggants, alkali halides such as potassium bromide, sodium bromide, potassium iodide, and organic antifoggants can be used.

As an organic anti-grid agent, for example, .= y','
;-Riazole, 6-nidrobenzigokunur, 5-
Ditamine indazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzigodazole, 2-thiazolylmethylbenzimodazole, hydroxyazaindolizine Nitrogen-containing heterocyclic compounds such as and l-phenyl-5-mercaptotetrazole 2-
Mercapto 11A heterocyclic compounds such as mercaptobenzimidazole and 2-mercaptobenzothiazole, as well as aromatic compounds of mercapto IIA such as thiosalicylic acid, can be used. Particularly preferred are nitrogen-containing heterocyclic compounds. These antifogging agents may be eluted from the color photosensitive material during processing and may accumulate in the color printing solution.

Color development 1.Temperature 1. I:'', 0°''-50'
C preferably t'''33°C-・42'Cm-tsunoru
Also, the processing time is 1Oゞ), = 373 C, ¥y, 3.0 seconds to 2 minutes. Also, the replenishment amount is photosensitive material 1; r(''!, ') dOm1 ~350 kiki, preferably 60~20.Od.

In the present invention, it is necessary to stop and/or wash with water after color development to prevent uneven processing, bleach fog, or to promote desilvering.

The stop bath of the present invention generally uses an acidic acid having a pH of 0105 to 6.0. If it is water-soluble and has acidic properties, it is possible to use a substance that is water-soluble; it is preferable to use an inorganic acid. Examples of organic acids include acetic acid, propionic acid, oxalic acid, tartaric acid, benzoic acid, and malonic acid. In addition, examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. In particular, it is preferable to use acetic acid and sulfuric acid from the viewpoint of preventing bleaching blades from blurring11. stomach.

The stop bath time is 5 seconds to 60 seconds, preferably 10 seconds to 30 seconds.
Seconds. Temperature: 25°C to 50°C 1 Replenishment amount is smaller than 7', 30m1-5 per light-sensitive material.
0 b +J1 preferably 1.0 (jml-30,0
It is.

A washing bath can be installed after the stop bath.

The washing time is 5 seconds to 90 seconds, preferably 1.0 seconds to CO seconds. The temperature is J9℃~40℃, the amount of water is 1r of photosensitive abrasive
100+J~·iox per rf.

Original OI'JC)! For the white liquor, a ferric complex salt in a compound represented by the following general formula CI) is used as a bleaching agent.

General formula CI) where Δ1. ~A4 can be hidden/- or different.<
-CH20H or (11-C0Q) M represents a hydrogen atom, sodium, potassium, or ammonium, with hydrogen atoms and ammonium being particularly preferred.
It is preferable to have two or more -COOh/· groups, and it is particularly preferable that all of A1 to A1 are C00M groups.

n represents an integer of 2 to 5, preferably 3 or 4, and most preferably 1 when n is 3.

Further, the ferric complex salt may be prepared by separately adding the compound of general formula CI3 and the ferric salt to the processing solution to form a complex salt in the processing solution 6. It may be added in the form from the beginning.

The amount of the above bleaching agent added is 0.02 to 0.02 o per bleaching solution If.
1 mol, preferably 0.03-0. (18 moles.

If the amount added is less than the above amount, desilvering failure will occur, and if it is more than the above amount, processing unevenness and bleaching blade blur will easily occur.

In the present invention, various other bleaching agents may be used in combination as necessary. Preferred bleaching agents when used in combination include ethylenediaminetetraacetic acid iron (11) salt diethylene + 1 amine, pentaacetic acid iron (■) salt, glycol↓-te,
Examples include iron(I) salts of diaminetetraacetate, hydrogen peroxide, persulfates and bromates.Chlorides, bromides and/or iodides may also be added to the bleaching solution. Particularly preferred is the addition of sodium chloride or ammonium bromide.

Furthermore, a bleach accelerator can be used in the bleach bath or its pre-bath, if necessary. Specific examples of useful accelerators are described in U.S. Patent No. 3. '89
3.85'1, West German patent certificate.

Compounds having a mercapto group or disulfide bond described in JP-A No. 290.812, JP-A-53-95,630, etc., thiazolidine derivatives described in JP-A-50-140,129; U.S. Patent No. 3,706.561 Thiourea derivatives described in West German Patent No. 2.74.8.4 a oi
Polyoxyethylene compound described in Japanese Patent Publication No. 4', '-
Polyamine compounds of No. 8836 can be used.

The pH of the bleaching solution of the present invention is preferably 1 to 1, particularly 1.
0 to 6.0 is preferred. The bleaching bath time is 10 seconds to 2 minutes, preferably 30 seconds to 100 seconds.The treatment temperature is 25°C.
~40℃, the replenishment amount is 30 Irl per liter of photosensitive material.
00-1 is preferably 50-300. In order to reduce the amount of waste liquid, it is preferable that the bleaching liquid of the present invention 11'1 is not recycled. The method of recycling is to remove the overflow from the bleaching process, and once the specified capacity has been accumulated,
Add missing chemicals (generally bleach, halides, acids)
However, the preferred method is to reuse it as a replenisher, but it is not limited to this method. In addition, the tack liquid and stock liquid may be used for =r-alloyment, if necessary.

In the present invention, after the bleaching process, the fixing process U! be done. Further, washing with water may be performed between the bleaching treatment and the fixing treatment, if necessary.

In particular, when the fixer is to be recycled and used, it is a preferred embodiment to carry out the above-mentioned washing with water.

As the fixing agent used in the fixing solution of the present invention, known fixing agents such as thiosulates, thiocyanates, thioether compounds, and thioureas can be used. Further, these fixing agents may be used in combination. In particular, it is preferable to use sodium thiosulfate or thioVtM ammonium.
If there are environmental restrictions on ammonia, the use of sodium thiosulfate is most preferred. The amount of fixative used is il
0.1 mole-2,0 mole, preferably 0.2 mole to 0.8 mole.・As a preservative, sulfite,
1jX! [I! Sulfate, metabisulfite, carbonyl-
Bisulfite adducts, ascorbic acid, etc. can be used b). Furthermore, if necessary, a buffer, a fluorescent whitening agent, a chelating agent, an antifungal agent, etc. may be added.

/ 0 The silver halide emulsion used in the present invention is a silver halide emulsion containing 90 mol % or more of silver chloride in the halogen composition, and is silver chloride or silver chlorobromide containing substantially no silver iodide. If the silver bromide content is high or contains silver iodide, there are fewer color gradation problems to be solved by the present invention, but if the silver bromide content exceeds 10 mol%, the halogen When a light-sensitive material containing a silveride emulsion is run in a processing solution, the concentration of bromide ions that accumulate in the solution in equilibrium as a result of development increases, slowing down the development speed and maintaining rapid processing. There is an inconvenience that it is not possible. It is preferable that the silver iodide content is 1 mol % or less from the viewpoint of eliminating the adverse effects due to processing solution accumulation.Most preferably, no silver iodide is contained, and the silver chloride content is 90 mol %.
Any amount may be used as long as it is above, but it is preferably 95 mol% or more, more preferably 98 mol% or more, and most preferably 99 mol% or more.

However, although a higher silver chloride content is preferable, a silver chloride content of 100 mol % may not be preferable in the present invention due to the adsorption characteristics of the sensitizing dye.

That is, if the silver chloride content is 100 mol % and does not contain any other silver halides such as silver bromide, it may be disadvantageous in terms of the amount of sensitizing dye adsorbed, or the sensitivity of the photosensitive material may deteriorate over time. This is because it may make it easier to make changes.

This is because the adsorption power of sensitizing dyes is generally weak for silver chloride and relatively strong for silver bromide, so containing a small amount of silver bromide strongly adsorbs individual sensitizing dyes. This is thought to be because it is advantageous for immobilization.

Therefore, in the silver halide emulsion of the present invention, it is necessary to avoid pure silver chloride and to contain i amount of silver bromide or silver iodide. It is preferable.

From the above, in the present invention, the silver chloride content is preferably 99.9 mol% or less.

The high silver chloride emulsion used in the present invention preferably has a silver bromide localized phase with a relatively high silver bromide content in its silver halide grains. The localized silver bromide phase may exist inside the silver halide grain, on the grain surface or near the grain surface, or both. It may take the shell structure of a so-called core-shell type structure that envelops the entire particle, or it may have a localized structure in which part of the shell structure is missing, or it has multiple discontinuous and mutually independent substructures. A preferable example of such a localized structure is one having a localized phase on or near the surface of a silver halide grain, particularly at the edge or corner part of the grain's crystal surface. Alternatively, those having a localized phase on the crystal plane are preferable.The halogen composition in the localized phase may be 10 mol% or more and 95 mol% or less in terms of silver bromide content, and 15
It is preferably mol % or more and 90 mol % or less, more preferably 20 mol % or more and 60 mol % or less, and most preferably 30 mol % or more and 60 mol % or less.

3. The remaining silver halide of the localized phase consists of silver chloride, but it is also preferable that it contains a trace amount of silver iodide. However, as mentioned above, it is preferable that the amount exceeds 1 mol % based on the total amount of silver halide. do not have.

In addition, these localized phases account for 0.03 mol% or more of the silver halide constituting all the silver halide grains of the emulsion.
It preferably accounts for mol% or less, and more preferably 0.1 mol% or more and 25 mol% or less.

The localized phase does not need to be limited to a single halogen composition; it may have two or more localized phases with distinctly different silver bromide contents, or it may be mixed with other phases other than the localized phase. The interface may be formed with the halogen composition continuously changing.

In order to form the silver bromide localized phase as described above, a water-soluble silver salt and a water-soluble halide salt containing water-soluble bromide are simultaneously mixed into an emulsion containing already formed silver chloride or high silver chloride grains. Similarly, a part of the already formed silver chloride or high silver chloride grains can be converted into a silver bromide rich phase using the so-called halogen conversion method, or silver chloride or high silver chloride grains can be reacted and deposited. It can also be formed by adding silver bromide or high silver bromide particles having a particle size smaller than that of the grains and crystallizing the silver chloride or high silver chloride particles by recrystallization on the surface of the silver chloride or high silver chloride particles.

Such a production method is also described, for example, in European Patent Application No. 0.273.43OA2.

The silver bromide content of the localized phase can be determined using the X-ray diffraction method (for example, as described in "New Experimental Chemistry Course 6, Structural Analysis, edited by the Chemical Society of Japan", Maruzen).
Alternatively, it can be analyzed using the XPs method (for example, described in "Surface Analysis, - IMA, Applications of Auger Electron/Photoelectron Spectroscopy - J Kodansha," etc.).Also, the silver bromide localized phase can be analyzed by electron microscopy or as described above. European Patent Application Publication No. 0.273,4
It can also be determined by the method described in No. 30A2.

The silver halide grains used in the present invention include metal ions other than silver ions (for example, metal ions of group Ⅰ of the periodic table, metal ions of group
It is preferable to contain transition metal ions of Group 1V, lead ions of Group 1, gold ions and copper ions of Group Ⅰ, or complex ions thereof. It may be the entire silver halide grain, the aforementioned silver bromide localized layer, or another phase.

Among the metal ions or complex ions thereof, those selected from iridium ions, palladium ions, rhodium ions, zinc ions, iron ions, platinum ions, gold ions, copper ions, etc. are particularly useful. Desired photographic properties are often obtained by using these metal ions or complex ions in combination rather than using them alone, and in particular by changing the type and amount of added ions between the localized phase and other parts of the particle. is preferable, and it is particularly preferable that iridium ions and rhodium ions be contained in the localized phase.

In order to incorporate metal ions or complex ions into the localized phase of silver halide grains and/or other parts of the grains, the metal ions or complex ions can be added before, during, or after the formation of silver halide grains. Form a localized phase with fine particles of silver bromide or high silver bromide, which can be added directly to the reaction vessel during physical ripening, or added in advance to the additive solution of water-soluble halide or water-soluble silver salt. In this case, silver bromide or high silver bromide may be contained in fine grains using the same method as above, and then added to silver chloride or high silver chloride emulsion. By adding a relatively sparingly soluble bromide of metal ions such as in solid or powder form, metal ions may be contained while forming a localized phase.

In order to achieve sufficient rapid processability in the present invention, any one of a yellow coupler-containing blue-sensitive silver halide emulsion layer, a magenta coupler-containing green-sensitive silver halide emulsion layer, and a cyan coupler-containing light-sensitive silver halide emulsion layer is required. However, it is preferable to use a high silver chloride emulsion as described above.

The silver halide grains used in the present invention can have the shape of so-called regular grains such as cubes, octahedrons, dodecahedrons, or rhombidodecahedrons, and can also have the shapes of spherical, twinned, tabular, etc. It is also possible to take an irregular particle shape. In addition, silver halide grains such as these, which may be grains with more complex shapes that have a combination of these crystal faces, or even grains with higher-order crystal faces, may be mixed. 0
Silver halide grains having a regular crystal shape are preferably used in the present invention in terms of number of grains or weight.
Silver halide emulsions containing 0% or more, more preferably 70% or more, still more preferably 90% or more, and emulsions containing crystal grains having (100) crystal planes are particularly preferred.

Further, in the emulsion used in the present invention, tabular grains having an average aspect ratio (ratio of circular diameter/grain thickness to the main plane of the grain) of 5 or more, particularly preferably 8 or more account for 50 or more of the total projected area of the grains. If the emulsion is such that it occupies 100% of the total amount of light, it is not only advantageous in terms of rapid processability, but also the effect of the present invention on color gradation is more clearly expressed.

The grain size of the silver halide emulsion used in the present invention is not particularly limited as long as it does not impair rapid processability, but the average diameter when the projected area of the grains is converted into a circle is 0.1 to 1. The size distribution of the silver halide grains, which is preferably 7 μm, may be wide or narrow;
So-called monodisperse emulsions are preferable in terms of photographic properties such as latent image stability and pressure resistance, and processing stability such as developer pH dependence.The standard diameter distribution when the projected area of silver halide grains is converted into a circle. The value S/ which is the deviation S divided by the average diameter d
It is preferable that d is 20% or less, and more preferably 15% or less.

The silver chlorobromide emulsion used in the present invention is P, Glaf-kide.
"The Chemistry and Physics of Photography" by Grafkide (Ball Montell, 1967), by G.

"Chemistry of Photographic Emulsions" by F. Duffin
(Focal Press, 1966), V, L, Z
e 1 i ckman (Zelikman) et al.
"Preparation and Coating of Photographic Emulsions" (Focal Press, 1
It can be prepared by applying the method described in 964) et al. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, but the acidic method and the neutral method are particularly preferred in the present invention in terms of reducing fog. In order to obtain a silver oxide emulsion, either the so-called one-sided mixing method, the simultaneous mixing method, or a combination thereof may be used.The so-called back-mixing method in which grains are formed under conditions of excess silver ions may also be used.The present invention In order to obtain an emulsion with monodispersed grains that are preferred for It is more preferable to use the Chondrald double jet method. By using this method, it is possible to obtain a silver halide emulsion preferred for the present invention having a regular silver halide crystal shape and a narrow grain size distribution.

In the process of grain formation or physical ripening of silver halide, cadmium salt, zinc salt, lead salt, thallium salt, or the above-mentioned iridium salt or its complex salt,
A rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

During or after grain formation, silver halide solvents (for example, known ones include ammonia, thiocyanate, U.S. Pat. No. 3,271,157, JP-A-51-123.
No. 60, JP-A-53-82408, JP-A-53-14
4319, JP-A-54-100717, JP-A-54-155828, etc.) may be used, and when used in combination with the above-mentioned method, the silver halide crystal shape becomes regular. A silver halide emulsion preferred for the present invention having a narrow grain size distribution can be obtained.

In order to remove soluble salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. can be used.

The emulsion used in the present invention is sulfur-sensitized or selenium-sensitized,
Chemical sensitization can be carried out by reduction sensitization, noble metal sensitization, etc. alone or in combination. In other words, active gelatin, a sulfur sensitization method using a compound containing a sulfur compound that can react with silver ions (e.g., thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.), and a sulfur sensitization method using a reducing substance (e.g., primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.), and metal compounds (such as the above-mentioned total complex salts, platinum, iridium, palladium, rhodium, iron, etc.). In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used. It is also preferable to use gold sensitization in combination with these. Furthermore, in these chemical sensitizations, it is preferable to have a hydroxyazaindene compound or a nucleic acid present in order to control sensitivity and gradation.

In the present invention, the total coating amount of the silver halide emulsion thus prepared is 0.70 g/rrf or less, preferably 0.64 g/rrr or less, in terms of silver. Furthermore, the coating amount of silver halide emulsion for each of the cyan, magenta, and yellow coloring layers is 0.10 to 0.35 g in terms of silver.
It is preferably less than /r/.

2. In the present invention, the use of spectral sensitizing dyes is important. As the spectral sensitizing dyes used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes are used. As the cyanine dye, simple cyanine dyes and carbocyanine dyes are preferably used. These cyanine dyes can be represented by the following general formula (I).

General formula (I) (X)m In the formula, L represents a methine group or a substituted methine group, and R1
and Rut each represents an alkyl group or a substituted alkyl group, Zl and Z2 each represent an atomic group forming a nitrogen-containing 5- or 6R heterocyclic nucleus, and X
represents an anion.

n represents a numerical value of 1.3 or 5, nl and R2 are each O or 1, and when n=5, nl and R2
is also O, and when n=3, either nl or R2 is 0. 9m does not represent O or 1, but is O when forming an inner salt. Further, when n is 5, L may be linked to each other to form a substituted or unsubstituted 5- or 6-membered ring.

The cyanine dye represented by general formula (I) will be explained in detail below.

Representative substituents of the substituted methine group include lower alkyl groups (eg, methyl group, ethyl group, etc.) and aralkyl groups (eg, benzyl group, phenethyl group, etc.).

The alkyl group represented by R1 and R2 may be linear, branched, or cyclic, and there is no limit to the number of carbon atoms, but preferably 1 to 8 carbon atoms, and among them 1 to 4 carbon atoms.
is particularly preferable, and examples of substituents for substituted alkyl groups include sulfonic acid groups, carboxylic acid groups, hydroxyl groups, alkoxy groups, acyloxy groups, and aryl groups (eg, phenyl groups, substituted phenyl groups, etc.). These 3 groups may be bonded to an alkyl group singly or in combination of two or more, and the sulfonic acid group and carboxylic acid group may form a salt with an alkali metal ion. A combination of the above includes the case where each of these groups is independently bonded to an alkyl group. Examples of the latter include sulfoalkoxyalkyl group, sulfoalkoxyalkoxyalkyl group, carboxyalkoxyalkyl group, and sulfophenylalkyl group. be able to.

Specific examples of R1 and R2 are methyl group, ethyl group, n-propyl group, n-butyl group, vinylmethyl group,
2-hydroxyethyl group, 4-hydroxybutyl group, 2
-acetoxyethyl group, 3-acetoxypropyl group, 2
-methoxyethyl group, 4-methoxybutyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-(2
-carboxyethoxy)ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-(3-sulfopropoxy)ethyl group , 2-acetoxy-3-sulfopropyl group, 3-
methoxy-2-(3-sulfopropoxy)propyl group,
2-(2-(3-sulfopropoxy)ethoxyethyl group, 2-hydroxy-3-(3-sulfopropoxy)propyl group, etc.).

Specific examples of the nitrogen-containing heterocyclic nucleus formed by Zl or Zl include oxazole nucleus, thiazole nucleus 1, selenazole nucleus, imidazole nucleus, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, selenazoline nucleus, imidacilline nucleus, and Examples include fused benzene rings, naphthalene rings, or other saturated or unsaturated hydrocarbon rings, and these nitrogen-containing heterocycles may further contain substituents (for example, alkyl groups, trifluoromethyl groups, alkoxycarbonyl groups). The anion represented by ，
Examples include 5O4-, NO3-, ClO4-, and the like.

6 The silver halide emulsion of the present invention is suitable not only for spectral sensitization in the visible region but also for spectral sensitization in the red to infrared region. The sensitizing dye can be selected from the following formulas (I[), (III) and (■).

These spectral sensitizing dyes are characterized in that they are relatively strongly adsorbed to the surface of silver halide grains and are difficult to desorb even when a coupler is present in a color light-sensitive material or the like.

In the present invention, -i formula (I), (I[[) and (
At least one compound can be selected from the compounds represented by IV) and spectral sensitized to have a spectral sensitization peak at 720 nm or more. In the color photosensitive material, at least one photosensitive layer has the general formula (I), (
Although it may be spectrally sensitized with a compound selected from the compounds represented by DI) and (IV) to have a spectral sensitization peak at 720 nm or more, preferably two or more photosensitive layers are made of these compounds. Spectrally sensitized with different compounds selected from

The compounds represented by general formulas (I), (I[[) and (IV) have 720n
It includes compounds that are spectrally sensitized so as to have a spectral sensitization peak at m or more, but also compounds that are spectral sensitized so that they have a spectral sensitization peak at 720 nm or less.

Therefore, as long as at least one photosensitive layer is spectrally sensitized to have a spectral sensitization peak above 720 nm, other photosensitive layers having a spectral sensitization peak below 720 nm are included in these formulas. It may be spectrally sensitized with a compound, or it may be spectrally sensitized with a compound not included in these formulas, such as a compound represented by formula (I).

The sensitizing dyes represented by the general formulas (II), (I[[) and (rV)] are detailed below.

- Formula (II) In the formula, Zll and Z12 each represent an atomic group necessary to form a heterocycle.

The heterocyclic nucleus includes 5 to 5 atoms containing nitrogen, sulfur, oxygen, selenium, or tellurium atoms in addition to carbon atoms.
A 6-membered ring nucleus is preferred, and a condensed ring may be further bonded to these rings, or a substituent may be further bonded to these rings.

Examples of the above-mentioned heterocyclic nuclei include thiazole ring nucleus, benzothiazole ring nucleus, naphthothiazole ring nucleus, selenazole ring nucleus, benzoselenazole ring nucleus, naphthoselenazole ring nucleus, oxazole ring nucleus, benzoxazole ring nucleus, naphtho ring nucleus. Oxazole ring nucleus, imidazole ring nucleus, benzimidazole ring nucleus, naphthoimidazole ring nucleus, 2-quinoline ring nucleus, 4-quinoline ring nucleus, pyrroline ring nucleus, pyridine ring nucleus,
Examples include a tetrazole ring nucleus, an indolenine ring nucleus, a benzindolenine ring nucleus, an indole ring nucleus, a tetrazole ring nucleus, a penzotelllazole ring nucleus, a naphthotellazole ring nucleus, and the like.

R11 and R12 each represent an alkyl group, an alkyl group, an alkynyl group, or an aralkyl group. These groups and the groups described below may each contain a substituent. For example, for an alkyl group, teeth,
The alkyl group includes an unsubstituted alkyl group and a substituted alkyl group, and the alkyl group itself may be linear, branched, or cyclic. The alkyl group preferably has 1 to 8 carbon atoms. Specific examples of substituents for substituted alkyl groups include halogen atoms (chlorine, bromine, fluorine, etc.), cyano groups, alkoxy groups,
Substituted or unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. can be mentioned, and even one of these groups,
Alternatively, a combination of two or more may be substituted.

A specific example of the alknyl group is a vinylmethyl group.

Specific examples of the aralkyl group include benzyl group and phenethyl group.

m11 represents an integer of 1.2 or 3.

R13 represents a hydrogen atom, and R14 represents a hydrogen atom, a lower alkyl group, or an aralkyl group, and can also be linked to R012 to form a 5- or 6-membered ring. Further, when R14 represents a hydrogen atom, R13 may be linked with another R13 to form a hydrocarbon ring or a heterocycle, and these rings are preferably 5- to 6-membered rings.
ll and kll represent O or 1, xll represents an acid anion, and n11 represents O or 1.

General formula (III) In the formula, z21 and Z22 have the same meanings as the above-mentioned Zll or Z12. R21 and R22 have the same meaning as R11 or R12, R23 represents an alkyl group, an alkenyl group, an alkynyl group, or an aryl group (for example, a substituted or unsubstituted phenyl group, etc.); 0m21 represents 1.2 or 3;
In addition to R24 representing a hydrogen atom, a lower alkyl group, or an aryl group, R24 and another R24 may be linked to form a hydrocarbon ring or a heterocycle, and these rings are preferably 5- or 6-membered rings. .

Q21 is a sulfur atom, an oxygen atom, a selenium atom or >N-
It represents R25, and R25 has the same meaning as R23.

j21, R21, x21 and n21 are respectively jll
, is synonymous with 11, xll and n11.

- Formula (IV) In the formula, Z31 represents an atomic group necessary to form a heterocycle. Examples of this heterocycle include the thiazolidine ring, thiazoline ring, benzothiazoline ring, and naphthothiazoline ring described for Zll and Z12. ring, selenazolidine ring,
Examples include a selenazoline ring, a benzoselenazoline ring, a naphthoselenazoline ring, a benzoxazoline ring, a naphthoxazoline ring, a dihydropyridine ring, a dihydroquinoline ring, a benzimidacilline ring, and a naphthoimidacyline ring.

Q31a has the same meaning as Q21. R31 is synonymous with R11 or R12, and R32 is synonymous with R23.0m3
1 represents 2 or 3; R33 has the same meaning as R24; R33 and another R33 may be linked to form a hydrocarbon ring or a heterocycle; j31 has the same meaning as jll.

In general formula (If), Zll and/or Z12
Sensitizing dyes in which the heterocyclic nucleus has a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a naphthimidazole ring, or a 4-quinoline ring are particularly preferred.

- Z21 and/or Z2 in i formula (Iff')
The same applies to Z31 in 2-Formula (IV). Further, a sensitizing dye in which the methine chain forms a hydrocarbon ring or a heterocycle is preferable.

Infrared sensitization generally uses M-band sensitization of a sensitizing dye, so the spectral sensitivity distribution is usually broader than in J-band sensitization.

Therefore, in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer,
It is preferable to provide a colored layer containing a dye or the like to adjust the spectral sensitivity distribution.This colored layer is effective in preventing color mixing due to its filter effect.

As the red-sensitive or infrared-sensitive sensitizing dye, compounds having a reduction potential of -1.
A sensitizing dye having this characteristic, preferably a compound having a value of 10 or more, is advantageous for increasing sensitivity, particularly for stabilizing sensitivity and stabilizing latent images.

The reduction potential can be measured using phase-discriminative second harmonic AC polarography using a mercury dropping electrode as the working electrode, a saturated force Romero electrode as the reference electrode, and a platinum electrode as the counter electrode.

In addition, the measurement of the reduction potential by phase-discriminative second harmonic AC portammetry used at the working electrode is described in the Journal of Imaging Science.
f Imaging 5science), Volume 30,
27-35 (1986).

Furthermore, a compound selected from the group of compounds represented by the letter formulas CIV), (V), CVl) and [■] shown in the specification of Japanese Patent Application No. 63-310211, or - formula [■-a] ], [■-b], [■-
It is preferable to use a compound selected from formaldehyde condensates of the compound represented by C).

Specific examples of the sensitizing dyes represented by general formulas (II), (I[l) and (IV) are shown below.

(V-3) (V-4) (V-5) χN% -1% (V-6) (V-7) (V-8) 7 (V-12) (V-13) (V, -14) 9 (V-9) (V-10) (V-11) 8 (V-15) (V-16) (V-17) 0 (V-18) (V-19) (V-20) 1 (V-24) (V-25) (V-26) 3 (V-21) (V-22) (V-23) 2 (V-27) 4 (V=30) (V-31) (V-32) 5 (V-36) (V-37) (V-38) 7 (V-33) (V-34) (V-35) 6 (V-40) (V-41) (V-42) 8 (V-43) (V-44) (V-45) 9 (V-49) − (V-50) (V-51) − 1 (V-46) (V-47) (V-48) 0 (■ 52) (V-53) (■ 54) (V 55) (CH,), 30. H-NEt.

(V 56〉 (V-57) (V 58) So- (V 59) 3 (V 65〉 (V-66) (■ 67) 5 (V 60) (OH,), So, HINET.

(V-61) (■ 62) (C)l,)3So3K (Shin2) s8υi l”l’ N b’U 14 (V-68) (V-69) (V-70) (V 71) A (V-72) (V-76) (V-73) (C:H,), 50. H−Nεh (V-74) (V-78) (CH,) 4So, H-NET,.

(V 75) (v-79) (CH,)4So, H-NBt.

7 8 (V-80) (v-84) (V-85) (V-81) (V-86) (V-82) (V-83) (V 87) 9 452- 0 (V-88) (V-89) 1 (V 92) (V-93) 2 4 /I+', "2-" The sensitizing dye used in the present invention is 5.5% per mole of silver halide.
X10-'mol to 5x10 lmol, preferably IX
It is contained in the halogenated radiographic emulsion in a proportion of 10-'mol-1X10-'xio-' mol to 5X10-' mol.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion. Alternatively, these are first dissolved in a suitable vehicle, such as methyl 7-ol, ethyl alcohol, methyl serosonol, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. You can also. Ultrasonic waves can also be used for dissolution. In addition, as a method for adding this infrared sensitizing dye, as described in US Pat. A method of dispersing water-insoluble dyes and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., involves dissolving water-insoluble dyes in a water-soluble solvent for 11 minutes without dissolving them. and this amount 1i, -; 'z 91, method of adding to the agent, US Pat. No. 3. 82'2, 135, surface activity 5, as described in Patent No. 3,822,135! , a method of dissolving a dye in a surfactant and adding the solution into an emulsion; a method of dissolving the dye using a red-shifting compound as described in JP-A-51-14624; and adding the dye solution into the emulsion. A method such as that described in JP-A-50-80826, in which substantially water is mixed with an N-free acid, and the resulting solution is added to an emulsion, is used. others,
For addition to emulsions, U.S. Pat.
The method described in No. 3,429,835 is also used. The infrared sensitizing dye may also be uniformly dispersed in a silver halide emulsion before being coated on a suitable support. It is also preferable to add it before chemical sensitization or in the latter half of silver halide grain formation.

In order to make it compatible with rapid color development processing, the halogen other line color light-sensitive material according to the present invention preferably contains a coupler having a high molar ratio of the color forming coupler to the developed halogen line, This makes it possible to reduce the amount of photosensitive halogenated radiation used. Especially Iwa Vl
Z+ 2-equivalent couplers are preferably used. Furthermore, it is possible to combine the use of a so-called 1-equivalent coupler, in which the quinone-containing compound of the aromatic amine of the color developing agent is coupled with the color coupler, and the oxidative coloring process is carried out with an oxidizing agent other than the halogenated beam. Good too.

Normally, color photosensitive materials use a color photosensitive material so that the static water color density is 3 or more in transmission density and 2 or more in reflection density.In the image forming method using the exposure unit of the present invention, the Since color gradation conversion processing is performed in conjunction with color correction processing by the processing equipment, the maximum color reflection density is approximately 1
, 2, and preferably about 1.6 to 2.0, an excellent color image can be obtained. Therefore, the amount of color coupler and photosensitive silver halide used can be reduced.

The amounts of the yellow coupler, magenta coupler and cyan coupler used in the color photosensitive material used in the present invention, particularly the reflective color photosensitive material, are 2.5 to 10XIO-
'． 1.5-8X10-' and 1.5-7XIO
-'mol/m riru.

Couplers that are compatible with color sensitive materials according to the invention will now be described.

The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention have the following formulas (C-1), (C-11), CM-1), (M-It
) and (Y).

General formula (C-I) H 1 General formula (C-n) H - Mathematical formula CM-1) Mathematical formula CM-TI) General formula (Y) In the general formulas (C-1 and (C-11), R+ ,
Rt and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, Rs and R1 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or azilamino group, R3 together with R1 Y3 may represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring
, Y represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized product of a developing agent, and n represents 0 or 1.

R5 in -If1 formula (C-11) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, ter
Examples include a t-methyl group, a cyclohexyl group, a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a putana-sensate methyl group, and a methoxymethyl group.

Preferred examples of the cyan coupler represented by formula (C-1) or (C-11) are as follows.

-a In formula (C-1), R3 is preferably an aryl group,
A heterocyclic group, including a silogen atom, an alkyl group, an alkoxy group, an aryloxy group, an azilamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and a cyano group. More preferably, it is an aryl group substituted with .

- In formula (C-I) fV, when Ra and R1 do not form a ring, R3 is preferably a W-substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted acyloxy-substituted alkyl group. , R2 is preferably a hydrogen atom.

In the general formula (C-It), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted -ruoxy-substituted alkyl group.

In general formula (C-11), R3 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups and a substituent having 1 or more carbon atoms, and the substituted IA groups include an arylthio group, an alkylthio group, an azilamino group, a 71-noroxy group,
Alkyloxy groups are preferred.

-a In formula (C-11), Rs is more preferably an alkyl group having 2 to 15 carbon atoms, and carbon T: 2 to 15 carbon atoms.
Particularly preferred is an alkyl group of No. 4.

- In the formula (C-n), hydrogen atoms and halogen atoms are preferred, with chlorine atoms and fluorine atoms being particularly preferred 1.), - In the formulas (CI) and (C-n), preferred Yl and Y are They are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

-i In formula (M-1), R1 and R1 represent an aryl group, R1 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group...Allowable substitutions f for the aryl group (preferably phenyl group) of R7 and R9
Is the A group acceptable for substituent R1? ! It is the same as the m group and may be the same or different when there are two or more 1tAa, R1 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. .

Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
Particularly preferred are sulfur atom dissociative types such as those described in No. 51,897 and International Publication No. W08B104795.

-a In formula (M-11), R8 represents a hydrogen atom or a tA group, Y4 represents a hydrogen atom or a leaving group,
Particularly preferred are halogen atoms and arylthio groups, Za%
zb and Zc are methine, fiA methine 1, N- or -
11) Represent 1- and form the Za -Zb bond Zb -Zc
One of the bonds is a double bond and the other is a single bond.

When the Zb-Zc bond is a carbon-carbon double bond, R8° or Y, including when it is part of an aromatic ring.

When forming a multimer of 2iL or more, Za.

When zb or Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

-a Among the pyrazoloazole couplers represented by formula (M-11), Imo-dashi (described in U.S. Pat. No. 4,500°630) is preferred in terms of low yellow sub-absorption of the coloring dye and light fastness. 1,2-b) pyrazoles are preferred;
Pyrazolo (1
,5-b)(1,2,4)) riazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide parast group as described in JP-A-61-147254, and European Patent Publication No. 226. It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position, such as those described in No. 849 and No. 294.785.

In the general formula (Y), R1 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, R1□ represents a hydrogen atom, a halogen atom, or an alexoxy group, and A represents -t(HCOR+, 3 4 , provided that Rat and Ro are each an alkyl group,
Represents an aryl group or an acyl group, Ys represents a leaving group *a, , and Rat, as xtai of RI4, R
The substitution fA group allowed for 1 is the same as that for 1, and the leaving group is preferably either an oxygen atom or a nitrogen atom for 1
il! It is of the type that escapes, and nitrogen atoms 81. The m type is particularly preferred.

General formula (C-1), (C-11), CM-1), CM-
Specific examples of couplers represented by n) and (Y) are listed below.

(C-1) (C"-4) 5 6 (C-6) (C-7) (C-8) (C-13) (C-14) (C-15) (C-16) 7 9 (C-9) (c-io) (C-12) (C-17) (C-18) (C-1!]) IJ 8 0 (C-20) (C-21) (C-22) CM-4) (M-6) 1 3 CM-1) CM-3) CM-7) (M-8) C 2 4 7 98 99 (Y-1) (Y-2) 00 (Y-3) (Y-4) (Y-7) (Y-8) (Y-9) 03 (Y-5) (Y-6) (Y-10) (Y-11) 04 06 Above - Formula (C-1 ) to (Y) are couplers represented by
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol per mol of silver halide, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, in order to add the above-mentioned coupler to the photosensitive layer, various known techniques can be applied. Usually, the oil-in-water dispersion method known as the Olp-Rotect method,
After being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
By methods such as distillation, noodle washing or ultrafiltration, it has a low boiling point of 11il! After removing the t6 medium, it may be mixed with a photographic emulsion.

As a dispersion medium for such couplers, dielectric constant (25”C
) 2 to 20 and a high boiling point mt8 medium having a refractive index (25° C.) of 1.5 to 1.7 and/or a water-insoluble polymer compound.

As the high boiling point solvent, the following general formula (A
) to (E) are used.

General formula (A) General formula CB) L　COO’At General formula (E) Hl O-ga.

07 (In the formula, Hl, 11! and H2 each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, H4 is W,
represents OR, or S-W+, where n is an integer from 1 to 5, and when n is 2 or more (s) may be the same or different from each other;
may form a fused ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 14
Any compound that is immiscible with water at 0'C or higher and is a good solvent for the coupler can be used. The melting point of the high boiling point organic solvent is preferably 80°C or lower. High boiling point* The boiling point of the solvent is
Preferably 160'C or higher, more preferably 17
The temperature is 0°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, bottom right (closed ~ 1
It is written on the upper right side of page 44.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W08B100723 are used, and the use of acrylamide-based polymers is particularly preferred from the viewpoint of color image stabilization.

The photosensitive material made using the present invention has 1.・May contain hydroquinone derivatives, aminophenol derivatives, gallic acid conductors, ascorbic acid derivatives, etc.

Various anti-fading agents can be used in the photosensitive material of the invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, P-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid salt conductors, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkyl Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic anti-fading agents can be found in the patent specifications below! ! a
It is listed.

Hydrokino 91M is U.S. Patent No. 2,360,290, U.S. Patent No. 2,418,613, U.S. Patent No. 2+700153, U.S. Patent No. 2,701.197, U.S. Patent No. 2,728,659.
No. 2,732,300, No. 2,735.76
No. 5, No. 3,982,944, No. 4,430.4
No. 25, British Patent No. 1,363,921, U.S. Patent No. 2.71Q, No. 801, No. 2.816. (6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are listed in U.S. Patent No. 3,432,3).
No. 00, No. 3,573,050, No. 3,574,
No. 627, No. 3,698゜909, No. 3,764
．． No. 337, Japanese Unexamined Patent Publication No. 52. -152225, etc., and spiroindanes are described in U.S. Patent No. 4.360.589, etc.
p-Alkoxyphenols are U.S. Patent No. 2,735,
No. 765, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 5
No. 9-10539, Special Publication No. 57-19765, etc.
Hindered phenols are US patent 3.700.45
No. 5, JP-A-52-72224, U.S. Patent No. 4,228
．． Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3.457.079, U.S. Pat. No. 21144, etc., the hinder door upper cheek is disclosed in U.S. Patent No. 3,336,13.
No. 5, No. 4,268.593, British Patent No. 1,32
No. 6,889, No. 1,354,313, No. 1.4
No. 10,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1983
-114036, 59-53846, 59
-78344 etc., metal complexes are disclosed in U.S. Patent No. 4.05.
No. 0,938, No. 4.241°155, British Patent No. 2,027.731(A), etc., respectively. The purpose of these compounds can be achieved by adding them to the photosensitive layer by co-emulsifying them with the respective color couplers, usually in an amount of 5 to 100 fEI%. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers adjacent to it on both sides.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compound 91 (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352)
．． 681), benzo, phenone compounds (
For example, in Japanese Patent Application Laid-open No. 46-2784, iil! listed)
Cinnamate ester compounds (e.g. U.S. Pat. No. 3,70
5°805, iil in the same No. 3,707.395! ), butadiene compounds (U.S. Patent No. 4,045,
It! in issue 229! ), or benzoxazole compounds (e.g., US Pat.
) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyanophore-forming coupler) or an ultraviolet absorbing polymer may be used, and these ultraviolet absorbers may be mordanted in a specific layer.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

12 In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds, particularly in combination with pyrazoliazole couplers.

That is, chemically bonded with the aromatic amine developing agent remaining after the color development process, resulting in a chemically inert and substantially colorless compound CF) and/or remaining after the color development process. For example, a compound (CG) which chemically bonds with the aromatic amine-based oxidant after color development treatment to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, after the treatment. This is preferable in order to prevent the occurrence of staining and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent remaining in the film or its oxidized product and the coupler during storage.

A preferred compound (F) has a second-order reaction rate constant kt (in trioctyl phosphate at 80'C) with P-aningine of 1. Oj! /mol-sec ~I
It is a compound that reacts in the range of X10-'fg/mol·sac.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

On 11'J 14! If ko is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose, causing a 1° error. On the other hand, if ko is smaller than this range, the remaining aromatic amine developing agent and The reaction is slow, and as a result, it may not be possible to prevent side effects of the remaining aromatic amine developing agent.

A more preferable compound (F) can be represented by the following formula (F1.) or (Fll).

General formula (Fl) R, +-(A)R-X General formula (Fn) Rt -C= Y In the formula, R1 and R8 each represent an aliphatic group, an aromatic group, or a heterocyclic group, n represents 1 or 0.

A represents a group that reacts with an aromatic amine developing agent to form a chemical bond, X represents a group that reacts with an aromatic amine developing agent and leaves, B represents a hydrogen atom, an aliphatic group, an aromatic group group, hetero yi group, acyl group, or sulfonyl group, Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (FII), where R
+ and X, Y and R2, or p)- may be bonded to each other to form a cyclic structure.

Among the methods for chemically bonding residual aromatic amine-based developers to drugs, substitution reactions and addition reactions are typical.

For specific examples of compounds represented by the general formula (Fl)λ (FI[), see JP-A-63-158545 and JP-A-63-158545;
i11! Preferably something that is being fought.

On the other hand, more preferable compounds (CG) that chemically bond with the oxidized aromatic amine developing agent remaining after color development to produce a chemically inert and colorless compound are as follows - Tsuzuriyo (Gl ) is expressed as C.

General formula (GI)-2 In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and 2 is a nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. Compounds represented by -glyph (Gl), which represent a group, have Z as Pearson's nucleophile "CHxlit"
i (31, G, Pearsonlat al, *'
J, please.

Chew, Soc, 319 (196B)
) is preferably 5 or more, or a group derived from it.

-Specific examples of compounds represented by CHI include European Patent Publication No. 255722 and JP-A-62-143.
No. 048, No. 62-229145, Patent Application No. 63-13
No. 6724, No. 62-214681, European Patent Publication 2
Those described in No. 98321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound CF) are described in European Patent Publication No. 277589.

The photosensitive material made using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. ), 4-thiazolidone compounds, (e.g. U.S. Pat. No. 3,314.79)
4, No. 3,352,681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705.805, JP-A-46-2784), No. 3,707.375), butadiene compounds (e.g., those described in U.S. Pat. No. 4.0
No. 45,229) or benzoxazole compounds (g, 1, e.g., those described in U.S. Pat. No. 3,700,45);
5) can be used. UV & % absorbing couplers (e.g. α-naphthol-based cyan dye-forming Kavlar) and UV-kIA absorbing polymers may also be used; these UV-VA absorbers are mordanted in specific layers. It's okay.

In the color photographic light-sensitive material of the present invention, colloidal daughters and dyes are used to prevent irradiation and halide radiation, and especially to ensure the spectral sensitivity distribution of each photosensitive layer is 8M and the safety TII against safelight in the visible wavelength range. It will be done. Such dyes include oxonol dyes, hemooxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these, 1K I sonol dyes, short oxonol dyes, and merocyanine dyes are useful, and indolenine dyes are particularly useful.

Especially for dyes for red end or infrared, for example, JP-A-62-32
No. 50, No. 62-181381, No. 62-12345
4, No. 63-197947, etc., as well as dyes for back layers and JP-A-62-39682, JP-A-62-123192, JP-A-62-158779, JP-A-62-174741, etc. The dye described above or the same dye can be used by introducing a water-soluble group that can flow out during processing.The infrared dye used in the present invention has substantially no light absorption in the yt wavelength range. It may be colorless.

When the infrared dye used in the present invention is mixed into a spectrally sensitized silver halide emulsion in the end-red to infrared wavelength region, it causes desensitization and fogging, and in some cases, the dye itself adsorbs to the silver halide grains. There are problems such as weak and broad spectral sensitization. Preferably, it is preferable to substantially contain the dye only in the colloid layer other than the photosensitive layer.For this purpose, it is preferable to contain the dye in a predetermined colored layer in a diffusion-resistant state.Firstly, the dye is contained in the ballast layer. It is to add a group and make it resistant to expansion t1. However, the second method is to mordant anionic dyes with polymers or polymer latexes that provide cationic sites, which tend to cause residual color and processing stains. The third method is to use a dye that is insoluble in water with a pH of 7 or less and is decolored and eluted during the treatment process in fine particle dispersion.

For this purpose, it is used by dissolving it in a low boiling point a solvent or solubilizing it in a surfactant and dispersing it in an aqueous solution of a hydrophilic protective colloid such as gelatin. Preferably, the solid dye is used by kneading it with an aqueous surfactant solution and mechanically turning it into fine particles in an agar and dispersing it in an aqueous solution of a hydrophilic colloid such as gelatin.

As the binder or protective colloid that can be used in the photosensitive layer of the photosensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated.Details of the gelatin manufacturing method can be found in Arthur Vuis, "The Macromolecules Research Book 19.・Of Gelatin” (Academic Press, 19
(published in 1964).

The color photosensitive material according to the present invention includes known photographic additives,
In particular, materials used in commercially available color papers using high silver chloride (particle average silver chloride content of 96 mol % or more) can be selected and used. You can select and use the additives and materials listed in Research Disclosure below.

Sensitivity enhancer 4 Super sensitizer 5 Brightener 7 Coupler 8 Yes 1t8 medium 20 Same as above, same as above, page 24, page 25, same as above, same as above, same as above, same as above \ Ultraviolet absorber, stain inhibitor, dye image stabilizer, hardener, binder, plasticizer , lubricant coating aid, surfactant Same as above, page 25, right page, page 26, page 26, page 27, pages 26-27, page 650, left to right, page 651, left (fund), page 650, right, page 21, 22 Example 1 A paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was applied, and various photographic #f layers were applied to form the following layers: A multilayer color photographic paper with the following structure was prepared. Apply the coating liquid as follows.
Manufactured.

19.1 g of yellow coupler (BXY) manufactured by FJi, 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cp
d-7) 27.2 cc of ethyl acetate and 4 each of solvent (Solv-3) and (Solv-7) to 0.7 g
．． 1 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0
．． Large size emulsion A of 8871111 and 0.70I11n
3-near mixture (silver molar ratio) with small size emulsion A. The coefficient of variation of particle size distribution is 0.08 and 0.10, respectively.
Emulsions of each size contained 0.3 mol % of silver bromide locally on a part of the grain surface. This emulsion contains blue-sensitive sensitizing dye A shown below.

B is added per mole of silver to the large emulsion A at 2.0 x 10 -' mol, and to the small emulsion layer at 2.5 x 10 -' mol, respectively. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above-mentioned emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution as shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. ■-Oxy-3,5-dichloro-5-)riazine sodium salt was used as the gelatin hardening agent for each layer.

Further, Cpd-10 and Cpd-11 were added to each layer so that the total amounts were 25.0 mg/m' and 50.0 mg/m', respectively.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

23 Sensitizing dye A for blue-sensitive emulsion layer 24 (per mole of silver halide, 4.(IXIO-' mole for large size emulsion B, 5.6X10-' mole for small size emulsion B) and a sensitizing dye for the green-sensitive emulsion layer and a sensitizing dye B for the blue-sensitive emulsion layer (per mole of silver halide, 2. Sensitizing dye C for the green-sensitive emulsion layer (2.5 X 10-' mol each for large size emulsion B) (7.0 X 10-' mol per mol of silver halide for large size emulsion B, and 7.0 X 10-' mol for small size emulsion) Sensitizing dye E for the red-sensitive emulsion layer (per mole of silver halide, 0°9X10-' mole for large emulsion C, and 0. For the red-sensitive emulsion layer, the following compounds were added to the halogenated t
2.6xlO-'mol was added per mole of a.

(10g/m") In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, edge-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide, respectively.
．． 5 X 10-' mol, 7.7 X 10-' mol, 2
．． 5 X 10-' moles were added.

Also, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,? -tetrazaindene per mole of silver halide, respectively, lX1O-'
mol and 2X10-' mol were added.

In addition, the following dyes (coating amounts are shown in parentheses) were added to the emulsion layer to prevent irradiation.

(10 mg/m2) (Layer composition) The composition of each layer is shown below. The numbers represent the coating amount (g/m'). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.30 gelatin 1 .86 Yellow coupler (8XY) ' 0.82 Color image stabilizer (Cpd-1) 0.19
Solvent (Solv-3) 0
．． 18 solvent (Solv-7>
0.18 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpcl-5) 0.08
Solvent (SOIV-1)'
0.16 solvent (Solv-4)
0.08 third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion B with an average grain size of 0.55-I and small size emulsion B with an average grain size of 0.39 IB)
:3 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.10 and 0.08, respectively, for each size emulsion.
0.8 mol% of Br was locally contained in a part of the particle surface)
0.12 gelatin
1.24 magenta coupler (BXM)
0.23 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
, 0.16 color image stabilizer (Cpd-
4) 0.02 color image stabilizer (Cp
d-9) 0.02 solvent (Sol
v-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5), 0.0
5 solvent (Sol v-5)
0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.5hm and small size emulsion C with 0.451M)
= 4 mixture (Ag molar ratio). The coefficient of variation of particle size distribution is 0.09 and 0.11, each size emulsion is AgBrO
, 6 mol% was locally contained in a part of the particle surface)
0.23 gelatin
1.34 cyan coupler (8xC)
0.32 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-4
) 0.02 color image stabilizer (Cpd
-6) 0.18 color image stabilizer (C
pd-7) 0.40 color image stabilizer (Cpd-8) 0.05 solvent (
Solv-6) 0.14
Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent (Cpd-5) 0.02
Solvent (Solv-5) 0.
08 Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol Modification degree 17%> Liquid paraffin (RxY) 1:1 mixture with yellow coupler (molar ratio) 1.33 0.17 0.03 ( BxM) Magenta coupler 31 (Cpd-1) Color image stabilizer 32 (BXC) Cyan coupler (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer 33 Yu 34 (Cpd-5) Color mixture inhibitor H rI (Cpd-6) 2:4:4 mixture (weight ratio) of color image stabilizer (Cpcl-7) Color image stabilizer -(C1, -C1l) -- (IIV -1) 4:2:4 mixture (weight ratio) of UV absorber (Solv-1) Solvent (Solv-2) Solvent 37 (Cpd-8) 1=l mixture (weight ratio) with color image stabilizer (Cpd-9) Color image stabilizer (Cpd-10) Preservative (Cpd-11) 1=l mixture with preservative (volume ratio) (Solv-3) Solvent (Solv-4) Solvent (Solv-5) Solvent CO port C, II.

(CHz)- COOCwH+ t (Solv-6) Solvent Yu38 80:20 mixture with GO- (Solv-7) Solvent (volume ratio) C-11+, c) ICI ((C)I-) tCOOC-
1(-\/ Port 39 Water ethylenediamine-N, N.

N,N-tetramethylene phosphonic acid potassium bromide triethanolamine sodium chloride potassium carbonate N-ethyl-N-(β-methyl Tansulfonamidoethyl )-3-methyl-4- Aminoaniline sulfate N, N-bis(carboxy Methyl)hydrazine N,N-di(sulfoethyl) Hydroxylamine/INa Optical brightener (1'1) IIT [lX 4B.

800ml! 800 i! l, 5 g 2.0 g O, 015 g 8.0 g 12.0 g 1.4 g 25 g 25 g 5.0 g 7.0 g 4.0 g 5.0 g 4.0 g 5.0 g Add water and adjust pH (25 ℃) 1000mf 1000d 10,05 10,45 First, a photosensitive needle (manufactured by Fuji Photo Film Co., Ltd.,
A FWH type (light source color temperature: 3200°K) was used to provide gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was carried out so that the exposure time was 0.1 seconds and the exposure amount was 200 CMS.

The exposed sample was subjected to continuous processing (running test) using a paper processing machine using the following processing steps and processing solution composition until twice the capacity of the color development tank was refilled.

Processing process Temperature Time Replenisher tank capacity Color development 35°C 45 seconds 161d 17 J Bleach-fixing 30-35°C 45 seconds 215mf! 17
f Rinse■ 30-35℃ 20 seconds □ 101
Rinse■ 30-35℃ 20 seconds □ 10Il rinse■ 30-35℃ 20 seconds 350d 10
1. Drying at 70 to 80 DEG C. for 60 seconds.The amount of replenishment was per 1 m'' of photosensitive material (3-tank countercurrent flow system from rinsing ■ to ■).The composition of each processing solution was as follows.

Color developer Tank solution Replenisher 40 Bleach fixer (tank solution and replenisher are the same) Water
' 400 ml ammonium thiosulfate (70%>'' 100 ffL
i! Sodium sulfite 17 g
Iron(I) ethylenediaminetetraacetate Ammonium 55 g Disodium ethylenediaminetetraacetate 5g Add water
1ooo mj! pH (25℃)
6.0 Rinse solution (tank solution and replenishment solution are the same) Ion exchange water (3 p each for calcium and magnesium
pm or less) Furthermore, a process (Process B) was performed in which the process after color development was changed as follows.

In this process, as in the case of the above-mentioned process (referred to as process A), continuous running process was carried out until the cumulative amount of color development reached twice the amount of liquid in the color developing bath tank.

As the final washing water, the same rinsing liquid as in Process A was used.

Process Time Temperature ('C) Color development
45 seconds 35 Washing with water 15 seconds 24-34 Bleaching 60 seconds 38 Water 151! 45 seconds 24-34 fixed
45 seconds 38 Water delta 90 seconds 24~34 Dry
The composition of each treatment bath used for 60 seconds at 70 to 9 degrees is as follows.

Add the same potassium bromide nitric acid 4g g water to H 000- 5,0. Sodium thiosulfate Sodium sulfite EDTA 2Na 00Tn1 00g 5g g We experimented with each.

Water-bleached 1,3-propanediaminetetraacetic acid 600+J @1 see table g Add water to H Measured using a concentration system.゛Also, the amount of residual silver in the maximum measurement area (11'OCMS) was measured using fluorescent X-rays. The results are shown in Table 1.

Table 1 The contents of the abbreviations in Table 1 are shown below.

EDTA: ethylenediaminetetraacetate iron(III) ammonium DTPA diethylenetriaminepentaacetate iron(III) ammonium PDTA: 1,3-propanediaminetetraacetate iron(I)
II) Ammonium ratio: Comparative example Book: Present invention Treatment BIO, B12. B14
It is understood that only in the case of , D min is low, that is, the occurrence of staining is suppressed to a low level, and the amount of residual silver is also small and the desilvering property is also excellent.

Table 2 Example 2 For the multilayer color photographic paper (sample a), the amount of silver halide emulsion applied in the second layer was 0.34 g/rr in terms of silver.
, the coating amount of silver halide emulsion in the third layer was 0.14 in terms of silver.
g/ffr, the coating amount of silver halide 1L agent in the fifth layer was 0.26 g/% in terms of silver, and a sample was prepared. The sample A was also treated in the same way as sample a.
compared. The results are shown in Table 2.

I couldn't get it.

Comparing the results of the present invention shown in Table 1 of Example 1 with the results of Example 2, it can be seen that in both cases, the results of Example 2 show inferior performance in terms of Dmin or residual silver amount. I understand.

Example 3 Sample C was prepared in the same manner as Sample a of Example 1 using a silver chlorobromide emulsion with a silver bromide content of 30 mol %.

Although sample C has slightly better desilvering properties than sample a, it is not suitable for rapid processing like processing A or processing B, and has a sufficient developing density among processing B used in Example 4 and Example 1. , Processing B2. B
Wash with water immediately after color development of 4,86-B14 with 20 m of 18N sulfuric acid per 11 parts of water! Process step C (C2, C4, C6 to C
14), the same test as in Example 1 was conducted, but D++
Almost the same results as Process B were obtained, except that in was slightly less and the amount of residual silver was slightly larger.

(Effects of the Invention) According to the present invention, it is possible to provide a method for processing a silver halide color photographic material, which suppresses the occurrence of staining, has excellent desilvering properties, and allows rapid processing.

Claims (5)

[Claims] (1) In a method for processing a silver halide color photographic material containing a coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine color developing agent,
The silver halide emulsion layer has an average silver chloride content of 90 mol%.
It consists of at least three photosensitive layers containing the above-mentioned silver chlorobromide emulsion, each photosensitive layer containing at least one of cyan coupler, magenta coupler, or yellow coupler, and the total silver halide coating amount of the photosensitive layer is 0 in terms of silver.
70 g/m^2 or less, and is characterized in that it is subjected to a color development process followed by a stop and/or water washing process, followed by a bleaching process, a fixing process, and a further water washing process. Processing method. (2) The halogen according to claim (1), wherein the bleaching solution contains 0.02 to 0.1 mol/l of a ferric complex salt of a compound represented by the following general formula (I). Processing method for silver chemical color photographic materials. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A1 to A4 may be the same or different, and -
Represents CH_2OH or -COOM. M represents a hydrogen atom, sodium, potassium or ammonium. n represents an integer of 3 to 5. (3) The method for processing a silver halide color photographic light-sensitive material according to claim (1) or (2), wherein the fixing solution does not substantially contain ammonium ions. (4) The method for processing a silver halide color photographic material according to claim (1) or (2), wherein the stop solution contains acetic acid or sulfuric acid. (5) Patent claims (1) to (4) characterized in that the silver halide emulsion is silver chlorobromide having a localized silver bromide phase.
A method for processing a silver halide color photographic light-sensitive material as described in .