JPH02207250A - Color image forming method - Google Patents

Abstract

PURPOSE:To form a color image nearly free from color turbidity and having superior color reproducibility and color developability, and reduced load of pollution by using a specified photosensitive material and a specified color developing soln. CONSTITUTION:A photosensitive material contg. a diffusion resistant compd. developing no color represented by formula I and a color developing soln. contg. 0-1ml/l benzyl alcohol and 0-0.008mol/l sulfite ions are used. In the formula, each of R<11>-R<13> is H, an aliphat. group, etc., R<14> is H, alkyl, etc., G<11> is carbonyl, sulfonyl, etc., and n is 0 or 1. A color image nearly free from color turbidity and having superior color reproducibility and color developability, and reduced load of pollution is formed.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a method for forming a color image using a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a method for forming a color image using a silver halide color photographic light-sensitive material, and more specifically, a method for forming a color image that has improved color clouding, good color development, (Conventional technology) Regarding a color image forming method with a low pollution load of a processing liquid Photographic materials are desired.

In particular, with regard to rapid processing, silver halide rotational photosensitive materials are processed continuously in automatic processing machines installed in each photofinishing laboratory. , it is now required to develop and deliver the prints to the user on the same day that the development is received, and even more recently, it has become necessary to deliver the prints within a few hours from the date of receipt, and the need for this has increased. ing.

Furthermore, the development of rapid processing is urgently needed because shortening of processing time brings about improvements in production efficiency and makes it possible to reduce costs.

In order to achieve rapid processing, approaches have been taken from both the light-sensitive material and the processing solution. Regarding color development processing, attempts have been made to raise the temperature of the processing solution, increase p+-1, and add a color developing agent at a high concentration, and it is also known to add additives such as development accelerators.

As the development accelerator, 1-phenyl-3-pyrazolidone described in British Patent No. 811185, U.S. Patent No. 2,
N-methyl-p-aminephenol described in No. 417.514, N, N, N' described in JP-A-50-15554,
Examples include N'-tetramethyl p-phenylenediamine.

However, these methods often fail to achieve sufficient speed and are accompanied by performance deterioration such as increased fog.

On the other hand, it is known that the shape, size, and composition of halide root grains in silver halide emulsions used in photosensitive materials do not significantly affect development speed, etc.; It has been found that the use of silver halide emulsions containing high silver contents exhibits significantly higher development rates.

On the other hand, in the formation of a dye image in a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent usually reduces the exposed silver halide grains in the silver halide color photographic light-sensitive material. The oxidation process is carried out by coupling this oxidized product with a coupler previously contained in the silver halide color photographic light-sensitive material. Generally, three types of couplers are used, each of which forms three pigments: yellow, magenta, and cyan, in order to perform color reproduction using the subtractive color method.

In order to achieve better color reproduction, a large number of elements need to come together. That is, starting with the spectral sensitivity and interlayer effects of photosensitive materials for photography, in photosensitive materials for printing, the matching of the spectral sensitivity with the coloring dye of the photosensitive material for photography, the overlap of the spectral sensitivities of photosensitive layers with different color sensitivities, and color development. The level of color reproducibility is determined by the spectral absorption characteristics of dyes, color mixing during processing between photosensitive layers containing different coloring dyes (processing color mixing), etc.

In recent years, in response to the above-mentioned demand for rapid processing, processing solutions that use high silver chloride as mentioned above for photosensitive materials and do not use sulfites and benzyl alcohol, which are contained in color development processing solutions for ordinary color paper, have been developed. A new system is being developed and introduced for use in combination with the above-mentioned process color mixture, but this new process has a major drawback from the perspective of process color mixing, as the process color mixture is much greater than that of conventional processes. The problem was discovered.

In particular, it has been found that color mixing during the above-mentioned treatment is particularly likely to occur in 1'' combinations in which a so-called two-equivalent coupler having a leaving group other than a hydrogen atom at the coupling position is used as the coupler.

In the first place, it has been well known that in color image forming methods using silver halide color light-sensitive materials, undesirable color blurring occurs between different coloring layers, and as a means to prevent this, for example, US Pat. No. 2,336. 32
No. 7, No. 4,277553, etc. propose methods using hydroquinone compounds. It is true that these compounds have some effect on preventing color turbidity, but the effect is small, and after exerting their preventive effect, they may produce colored substances or cause changes in photographic performance during the production or storage of photosensitive materials. There were problems such as not being delivered.

Therefore, there has been a desire for a technique that has a greater effect of preventing color turbidity and color fogging than the use of such hydroquinone compounds.

The present inventor has discovered that the color cloudiness that tends to occur when a color sensitive material using a high silver chloride emulsion is processed with a color developing solution that does not substantially contain sulfite or benzyl alcohol is caused by a color sensitive material containing a ballast group. We have discovered that this can be suppressed by using a hydrazine compound, and have completed the present invention.

On the other hand, redox compounds and couplers which release compounds similar to the compounds of the present invention by reaction with oxidized forms of color developing agents have been proposed in US Pat. No. 4,390,618 and the like. However, these compounds differ from the compounds of the present invention in that they have coupler color-forming units and redox units, and their effects and mechanisms for expressing them are also different from those of the present invention. Also, JP-A-62-
No. 27731 proposes the use of a compound similar to the compound of the present invention, but the above patent requires that the compound has diffusivity and acts on the silver halide emulsion, but the present invention In this case, it is necessary to have diffusion resistance, and interaction with the emulsion is not desirable, and the effects thereof are completely different.

Also, JP-A-63-146041 and JP-A No. 6317064
No. 2 discloses that when a sensitive material using a high silver chloride emulsion is processed with a color developing solution that does not substantially contain benzyl alcohol and sulfite ions, a hydrazine compound (a hydrazine compound (for sensitive materials) is added as a preservative to the color developing solution. Although it is described that a compound (compound that diffuses in the medium) is added, there is no mention that this can provide an effect of preventing color mixture, and in fact, such an effect is poor.

(Problems to be Solved by the Present Invention) The first object of the present invention is to form a color image using a high-silver chloride color photographic material with little color turbidity and excellent color reproducibility, and which is suitable for rapid processing. The second object is to provide a color image forming method that has excellent color development and has a low pollution load.

(Means for Solving the Problems) These objects of the present invention have been achieved by the following (1) and (2).

(1) A high silver chloride emulsion layer containing at least one cyan coupler, a high silver chloride emulsion layer containing a magenta coupler, a high silver chloride emulsion layer containing a yellow coupler, and at least one non-containing layer on a support. In a method of forming a color image by treating a silver halide color photographic light-sensitive material having a light-sensitive layer with a color-forming developer, the light-sensitive material is non-color-forming and diffusion-resistant and has the following general formula (
A color image containing the compound represented by A), and characterized in that the color developing solution contains benzyl alcohol from 0 to 1 ml/l and sulfite ion from 0 to o, oos mol/ρ. Formation method.

General formula (A) In the formula, R, R12, and R13 represent a hydrogen atom, an aliphatic group, or an aromatic group, and R14 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group. group, amino group, alkoxycarbonyl group, or carbamoyl group.

G represents a carbonyl group, a sulfonyl group, a sulfinyl group, 0=P-R'' or an iminomethylene group (HN=C), and n is 0 or 1.

(2) The color image forming method according to item (1) above, wherein the non-photosensitive layer contains a compound represented by general formula (A).

Next, the compound represented by general formula (A) will be explained in detail.

The aliphatic group represented by RI1, RI2, and R'3 preferably has 1 to 30 carbon atoms,
Particularly preferred are straight chain, branched or cyclic alkyl groups having 1 to 20 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

Examples of such groups include t-butyl group, n-octyl group, L-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group, tetrahydrofuryl group, and morpholino group.

In the general formula (A), the aromatic group represented by Rl 1, R12, and R13 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphculene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, quinoline ring,
Among the isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc., those containing a benzene ring are preferred. Particularly preferred are aryl groups. The aryl group or unsaturated heterocyclic group of RII and R12R13 may have a substituent. Typical substituents include, for example, alkyl groups, aralkyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, aryl groups, These include an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, and a carboxyl group.

The alkyl group represented by R+4 preferably has 1 to 30 carbon atoms and may be linear, branched, or cyclic. Specifically, methyl, ethyl, butyl, t-butyl,
Examples include cyclohexyl, octyl, dodecyl, octadecyl, etc., and the aralkyl group preferably has 7 to 7 carbon atoms.
30, specifically benzyl, phenethyl, naphthylmethyl, etc. The aryl group preferably has 6 to 30 carbon atoms, specifically phenyl, naphthyl, etc., and the heterocyclic group is preferably has 1 or more carbon atoms
12, specifically imidazolyl, pyridyl, etc., and the alkoxy group preferably has 1 to 30 carbon atoms.
Specific examples include methoxy, ethoxy, octyloxy, dodecyloxy, hensyloxy, cyclohexyloxy, etc. Aryloxy groups preferably have 6 to 30 carbon atoms, and specific examples include phenoxy, naphthyloxy, etc. The amino group preferably has 0 to 30 carbon atoms, and specifically includes an unsubstituted amino group, an alkyl-substituted amino group (e.g., methylamino), an aryl-substituted amino group (e.g., phenylamino), etc. The alkoxycarbonyl group is preferably one having 1 to 30 carbon atoms, such as ethoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, hensyloxycarbonyl, etc., and the alkoxycarbonyl group is Preferably, it has 7 to 30 carbon atoms, such as phenoxycarbonyl, naphthyloxycarbonyl, etc. The carbamoyl group preferably has 1 to 30 carbon atoms, such as carbamoyl group, alkylcarbamoyl group (for example, NN-diethylcarbamoyl). ,
and arylcarbamoyl groups (eg phenylcarbamoyl).

Here, the alkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, amino group, and carbamoyl group represented by R'' may have a substituent, and specifically, RR'', As the substituent for R13, the same ones as mentioned above can be mentioned.

Diffusion resistance is an essential requirement for the compound of general formula (A), but
"Diffusion resistance" refers to a photographic material that has been made diffusion resistant so that the compound is difficult to diffuse.

For example, there are the following methods for diffusion resistance.

First, an aliphatic group having a molecular weight above a certain level,
This is a method in which one or more so-called diffusion-resistant groups containing an aromatic group or a heterocyclic group in the partial structure are introduced into the hydrazine molecule. The total number of carbon atoms constituting the diffusion-resistant group is usually preferably 6 or more, more preferably 12 or more. Two hydrazine molecules may be linked via some diffusion-resistant group or the like.

The molecular weight of these hydrazine compounds is preferably 300 to 2,000, more preferably 400 per N-N-Q.
~1,200, particularly preferably 450-1000, most preferably 500-800.

The second method is to form a polymer using a hydrazine compound as a multimer, and increase the molecular weight to make it resistant to diffusion. The third method is to introduce into the molecule a group that adsorbs to the surface of silver halide grains.

Preferably, the first method (introduction of a diffusion-resistant group) is preferred. When the molecular weight of the hydrazine compound is >N-N and exceeds 2,000 per compound, the film thickness becomes thick, which tends to slow down the processing speed and reduce sharpness, which is not preferable.

Among those represented by general formula (A), preferred are those represented by general formula (B).

General formula (B) R21N N Ge1-R22R23R'' (wherein R21 represents an aliphatic group, aromatic group, or heterocyclic group; R22 is a hydrogen atom, an alkyl group, a 7-ralkyl group, an aryol group, Represents an alkoxy group, an aryoxy group, or an amino group; G21 represents a carbonyl group, a sulfonyl group, a sulfinyl group, ](2Z represents P-1 or an iminomethylene group (HN-C); R23 and Rza are both A hydrogen atom, or one hydrogen atom and the other one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.

However, a hydrazine structure (>N->=C) may be formed by including G'', R23, R'' and hydrazine nitrogen. Further, the groups described above may be substituted with a substituent if possible. ) To explain in more detail, R21 may be substituted with a substituent, specifically, Rl l, R1 in the general formula (A)
2. The same substituents as RI3 and R14 can be mentioned, especially ureido group, alkoxy group, alkyl group,
Acylamino group, substituted amine group, sulfonylamino group,
Urethane groups, aryloxy groups, and hydroxy groups are preferred.

Further, these substituents may be linked to each other to form a ring when possible.

R'' is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl, naphthyl).

Among the groups represented by R22, preferred are a hydrogen atom, an alkyl group (e.g. methyl) or an aralkyl group, (
For example, hydrogen atoms such as hydroxyhenzyl are particularly preferred.

As the substituent for R22, the above-mentioned R11, R12, R13
In addition to the substituents listed for R'', for example, acyl groups, acyloxy groups, alkyl or aryloxycarbonyl groups, alkenyl groups, alkynyl groups and nitro groups can also be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

R21 and Rzz, especially R21, may incorporate a ballast group commonly used in immobile photographic additives such as couplers. The palaste group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group,
It can be selected from alkylphenyl groups, phenoxy groups, alkylphenoxy groups, ether groups, amide groups, ureido groups, urethane groups, sulfonamide groups, thioether groups, etc., and combinations of these groups.

The total number of carbon atoms of R21 and R22 is preferably 13 or more,
More preferably, it has 20 to 60 carbon atoms.

R23 and R24 are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an alkylsulfonyl group (preferably a phenylsulfonyl group or a group substituted such that the sum of Hammett's substituent constants is -0.5 or more) phenylsulfonyl group), an acyl group with a carbon number of 8920 or less (preferably a benzoyl group, or a sum of Hammett's substituent constants -0,
Hendiyl group substituted with 5 or more atoms, or linear, branched, or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups,
Examples include sulfonamide group, carbonamide group, hydroxyl group, carboxy group, and sulfonic acid group.

Hydrogen atoms are most preferred as R23 and R24.

Specifically, what is represented by G"-R" is a formyl group, an acyl group (acetyl, propionyl, trifluoroacedel, chloroacetyl, hendiyl, 4-chlorohendiyl, pyruvoyl, methoxalyl group, methyloxamoyl). , alkylsulfonyl group (methanesulfonyl, 2-chloroethanesulfonyl), arylsulfonyl group (henzensulfonyl), alkylsulfinyl group (methanesulfinyl), arylsulfinyl group (
henzensulfinyl), carbamoyl group (methylcarbamoyl, phenylcarbamoyl), sulfamoyl group (dimethylsulfamoyl), alkoxycarbonyl group (methoxycarbonyl, methoxycarbonyl)
, awaroxycarbonyl group (phenoxycarbonyl), sulfinamoyl group (methylsulfinamoyl),
Alkoxysulfonyl (methoxysulfonyl, ethoxysulfonyl), thioacyl group (methoxysulfonyl)
, represents a thiocarbamoyl group (methylthiocarbamoyl) or a heterocyclic group (pyridyl).

Particularly preferred are formyl group and acyl group.

In general formula (B), c", R", R24, and hydrazine nitrogen are included in the hydrazone structure. In the above, RZ5 does not represent an alkyl group, an aryl group, or a heterocyclic group. R'' represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Specific examples of the compound represented by general formula (A) are described below.

However, the present invention is not limited to the following compounds.

○ C21(S ○ ○ ○ C(H9
-86,829, U.S. Patent No. 4,560.638,
No. 4.4.78, as well as No. 2.563,785, No. 2.588,982, and JP-A-56-67.843.
, U.S. Pat. No. 4,030.925, U.S. Pat. No. 4,080,
No. 207, No. 4.031,127, No. 3,718
．． No. 470, No. 4,269.929, No. 4.27
No. 6364, No. 4,278,748, No. 4385
．． No. 108, No. 4.459.347, No. 4,4.7
No. 8,928, No. 4.560.632, British Patent No. 2
．． No. 011,391B, JP-A-54-74.729,
No. 55-163.533, No. 55-74,536,
No. 60-179゜734, No. 61-236548,
No. 61-270744, patent application No. 61-115,036
No. 62-67.508, No. 62-67.509, No. 62-67.510, No. 62-58,513,
It is described in No. 61-268,249.

The compound represented by the general formula (A>) of the present invention (hereinafter referred to as the compound of the present invention) is non-color-forming and forms a colored or colorless dye by coupling with an oxidized aromatic primary amino developing agent. It does not have any coupler residues.

The compounds of the present invention may be used in combination of two or more.

The compound of the present invention is contained in at least one layer such as a protective layer, a light-sensitive silver halide emulsion layer, a non-light-sensitive fine-grain silver halide emulsion layer, an intermediate layer, a filter layer, an undercoat layer, and an antihalation layer in a light-sensitive material. However, it is preferable to use it in a light-sensitive emulsion layer and/or an intermediate layer between two light-sensitive emulsion layers (which may have the same or different color sensitivities); is most preferred.

When the compound of the present invention is added to the non-photosensitive layer, the appropriate amount of gelatin applied in the non-photosensitive layer is 0.2 to 2.0 g/M, and 0.3 to 1.2 g/M. It is preferably 0.4 to 1.0 g/n (more preferably 0.4 to 1.0 g/n).

In order to add the compound of the present invention to these materials, it can be added directly to the coating solution, or it can be added to the coating liquid as is, or it can be added to the coating solution using a low-boiling point material such as ethyl acetate or alcohol (such as methyl alcohol) that does not affect the silver halide color photographic light-sensitive material. It can also be added after being dissolved in an organic solvent. Further, it can be dispersed and impregnated into a polymer such as latex, or it can be dissolved in a high boiling point organic solvent as described in detail later as a coupler solvent and emulsified and dispersed in an aqueous solution.

The total amount of the compound of the present invention added to the sensitive material is usually 0.00
1 to 0.8 g/n (and preferably 0°005 to 0
．． 5g/n (, more preferably 0.01~o, 3g/r
It is rr.

High silver chloride contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention includes silver chloride, silver iodochloride, silver iodochlorobromide, or silver chloride containing 80 mol% or more (average value) of silver chloride. It is silver. The silver iodide content is preferably 1 mol% or less. Particularly preferred is silver chlorobromide or silver chloride containing 96 mol % or more (average value) of silver chloride.

The high silver chloride emulsion used in the present invention preferably has a silver bromide localized layer in its silver halide grains in which the silver bromide content is relatively high compared to that of the substrate. Such a silver bromide localized phase may be present inside the silver halide grain, on the grain surface or near the grain surface, or on both. This silver bromide localized phase is a so-called core phase that envelops the entire grain inside or on the grain surface.
It may take the structural form of a shell of a shell type structure, or it may take a localized structure in which part of the structural form of the shell is missing, or a plurality of discontinuous and mutually independent partial structures. A preferable example of such a localized structure is one that has a localized phase on the surface of the silver halide grain or inside the grain near the surface, and in particular has a localized phase on the edge or corner part of the crystal surface of the grain, or a protrusion on the crystal surface. Those having a localized phase are preferred. The halogen composition in the localized phase may be from 10 mol% to 95 mol%, preferably from 15 mol% to 90 mol%, in terms of silver bromide content. Furthermore, it is preferably 20 mol% or more and J: 60 mol% or less, most preferably 30 mol% or more and 60 mol% or less.

The remaining silver halide of the localized phase consists of silver chloride, but preferably also contains trace amounts of silver coated. However, as mentioned above, it is not preferable for the amount to exceed 1 mol % based on the total amount of silver halide.

In addition, these localized phases account for 0.03 mol% or more of the back of the silver halide constituting all the silver halide grains of the emulsion.
It preferably accounts for 5 mol% or less, and more preferably 0.1 mol% or more and 25 mol% or less.

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

To form a localized silver bromide phase as described above, a water-soluble root salt and a water-soluble halide salt containing water-soluble bromide are simultaneously mixed into an emulsion containing silver chloride or high silver chloride grains that has already been formed. by reacting and depositing, or by converting some of the already formed silver chloride or high silver chloride grains into a silver bromide-rich phase using the so-called halogen conversion method, or by converting silver chloride or high silver chloride grains into a silver bromide-rich phase. It can also be formed by adding fine grains of silver bromide or high silver bromide grains or other poorly soluble silver salts and crystallizing them by recrystallization on the surface of silver chloride or high silver chloride grains.

Such a manufacturing method is also described, for example, in European Patent Application No. 0.273,430A2.

The silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, described in "Nippon Kagaku Gold Line, New Experimental Chemistry Course 6, Structural Analysis", Maruzen).
Alternatively, the analysis can be performed using the xps method (for example, described in "Surface analysis, 1MA, application of Auger electron/photoelectron spectroscopy", Kodansha). Furthermore, the silver bromide localized phase was observed by electron microscopy and the aforementioned 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
The effects of the present invention can be better exhibited under various conditions by incorporating transition metal ions of group 1, lead ions of group 1, metal ions of group 1, copper ions, etc.) or their complex ions. preferable. These metal ions or complex ions thereof may be contained in the entire silver halide grains, in the localized silver bromide phase described above, or in other phases.

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 preferred. In particular, it is 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 incorporated into the localized phase of the silver halide grains by physical control of the metal ions or complex ions before, during or after the formation of the silver halide grains. It may be added directly to the reaction vessel during ripening, or it may be added in advance to the water-soluble halogen salt or water-soluble silver salt addition solution. When the localized phase is formed from fine grains of silver bromide or high silver bromide, it is contained in silver bromide or high silver bromide fine grains using the same method as above, and then added to the silver chloride or high silver chloride emulsion. You may. Alternatively, metal ions may be contained while forming a localized phase by adding a relatively highly soluble bromide of metal ions such as those mentioned above in solid or powder form, other than silver salt.

In order to achieve sufficient rapid processability in the present invention, a yellow coupler-containing light-sensitive silver halide emulsion layer, a magenta coupler-containing light-sensitive silver halide emulsion layer, or a cyan coupler-containing light-sensitive silver halide emulsion layer must both have a high silver chloride content. It is necessary to use an emulsion.

The silver halide grains used in the present invention can have the shape of so-called regular grains such as cubes, octahedrons, tetradecahedrons, or dodecahedrons, or irregular grains such as spherical and tabular shapes. It can also take the form of particles.

Further, the particles may have a more complex shape having a combination of these crystal planes, or may even have a higher-order crystal plane. These silver halide grains may be mixed. Preferably used in the present invention is a silver halide emulsion containing 50% or more, more preferably 70% or more, still more preferably 90% or more of silver halide grains having a regular crystalline shape in terms of grain number or weight. In particular, emulsions containing crystal grains having (100) crystal faces are 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. In the case of an emulsion that accounts for a large proportion of 100% of the total amount of polyester, it is particularly advantageous in terms of rapid processability.

The size of the silver halide grains 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 particles is converted into a circle is 0.1~
Preferably, it is 1.7 μm. The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are preferred in terms of photographic properties such as latent image stability and pressure resistance, and processing stability such as developer pH dependence. The value S/d, which is the standard deviation S of the diameter distribution when the projected area of the silver halide grains is converted into a circle divided by the average diameter, is preferably 20% or less, and more preferably 15% or less.

The silver chloride, silver chlorobromide or silver chloroiodobromide emulsion used in the present invention is described in "Chemistry and Physics of Photography" by P. Glafkides (Paul Montell, 1967), G. F. Duffin ( ``Chemistry of Photographic Emulsions'' (Focal Press, 1966), by John Duffin
, V., L., Zelikman
It can be prepared by applying the method described in "Preparation and Coating of Photographic Emulsions" (Focal 1 Less Publishing, 1964), etc. by John 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 because they reduce fog. Further, in order to obtain a silver halide emulsion by reacting a soluble silver salt with a soluble halide salt, any one of the so-called one-sided mixing method, simultaneous mixing method, or a combination thereof may be used. It is also possible to use a so-called back-mixing method in which particles are formed under conditions of excess ions. It is preferable to use a simultaneous mixing method to obtain an emulsion of monodisperse grains preferred for the present invention. As one form of the simultaneous mixing method, it is more preferable to use a method in which the concentration of ions in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondrold double-Jietz I method.

By using this method, it is possible to obtain a silver halide emulsion which is preferred for the present invention and has a regular silver halide crystal shape and a narrow grain size distribution.

In the process of tM imprint formation or physical ripening of silver halide, cadmium salts, zinc salts, lead salts, thallium salts, or the above-mentioned iridium salts or their complex salts, rhodium salts or their complex salts, iron salts Alternatively, a complex salt thereof may be coexisting.

During or after grain formation, a silver halide solvent (for example, known ones such as ammonia, thiosoanate, U.S. Pat.
No. 60, JP-A-51-82408, JP-A-53-14
431.9, JP-A-54-1.00717, JP-A-54-155828, etc.) may be used, and when used in combination with the above-mentioned method, silver halide It is possible to obtain silver halide pores preferable for the present invention which have a regular crystal shape and a narrow grain size distribution.

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

The emulsion used in the present invention can be chemically sensitized by Gz yellow sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc., or chemically sensitized by (JF). That is, it can react with active gelatin or silver ions. Sulfur sensitization method using compounds containing sulfur compounds (e.g. thiosulfates, thiourea compounds, mercapto compounds, rhodanine compounds, etc.) and reducing substances (e.g. soot salts, amines, hydrazine derivatives, formamidine sulfinic acid) , silane compounds, etc.), and noble metals using metal compounds (e.g., salts of metals from group Ⅰ of the periodic table such as kumquat salts, platinum, iridium, palladium, rhodium, iron, etc., or their complex salts, etc.). Sensitization methods and the like can be used alone or in combination.

In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and gold sensitization is preferably used in combination with these.

In addition, during these chemical sensitizations, it is preferable to avoid the presence of a hydroxyazaindene compound or a nucleic acid in order to control the sensitivity and gradation.

The silver halide emulsion and photographic material of the present invention may contain various additives, including those mentioned above, during their preparation or manufacturing process.
losure (Research-Disclo 4 Jar) Volume 176, m17643 (197812
) and Volume 187, No. 1,8716 (197
(September, November), etc. They are specifically described in the following sections.

Additive types Chemical sensitizers Sensitivity enhancers Spectral sensitizers Super sensitizers Brighteners Antifoggants and stabilizers Light absorbers and filters Dyes and ultraviolet absorbers Anti-stain agents Dye image stabilizers RD 17643 RD 187] , 623 pages
Page 648 right column 223-24 Page 648 right column - 649 right column 24 pages 24-25 @ 649 right column 25-26 Page 649 right column - 650 Left column 25 pages right column 650 page left column 〜Right column page 25 Hardener page 26 Page 651 Left column binder page 26 ``Two plasticizers and
Page 27 Page 650 Right Column Lubricant Coating Aid and Pages 26-27 ``Disurfactant Static Preventing Agent'' Page 27 Same The color photographic light-sensitive material of the Joshi invention contains an oxidized product of an aromatic amine color developer and Coupled with yellow, magenta,
Yellow couplers, magenta couplers, and cyan couplers that develop a cyan color are used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention are those shown by the following general 2(r), (Hn), (1), (TV) and (V).

General formula (1) %formula% General formula (V) ll3 Y.

[However, in general formulas (J) and (H), R1, R
2 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, R5 and R6 represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R3 together with R2 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring. Yl,
Y2 represents a hydrogen atom or a group that leaves during the coupling reaction with the oxidized product of the developing agent. ] R5 in general formula (U) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pesotadecyl group, tθrt-butyl group, cyclohexyl group. Examples include cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxyethyl group.

Preferred examples of the cyan coupler represented by the general formula (1) or (IT) are as follows.

In general formula (1), R1 is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, or a sulfamide group. More preferably, it is an aryl group substituted with a group, an oxycarbonyl group, or a cyano group.

In general formula (1), when R3 and R2 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted alkyl group, and R3 is preferably a hydrogen atom.

In general formula (II), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably an alkyl group substituted with a substituted aryloxy group.

In general formula (II), R5 preferably has 2 to 15 carbon atoms.
It is a methyl group having an alkyl group and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (IT), R7 is more preferably an alkyl group having 2 to 5 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (II), R5 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y in general formulas (I) and (II)
l and Y2 are each a hydrogen atom, a halogen atom, an alkoxy group, an aryoloxy group, an acyloxy group, or a sulfonamide group.

In the general formula (DI), R7 and R7 represent an aryl group, R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y
3 does not represent a hydrogen atom or a leaving group. The substituents allowed for the aryl group (preferably the phenyl group) of R7 and R9 are the same as the substituents allowed for the substituted gR,
When there are two or more substituents, they may be the same or different. RB is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferred Y3 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. 351.897 and WO38104795.

In general formula (IV), R+o represents a hydrogen atom or a substituent. Y4 represents a hydrogen atom or a leaving group, and is particularly preferably a halogen atom or an arylthio group. Za, Zb
and Zc is methine, substituted methine -N- or -NH
- represents a Za-Zb bond and a Zb-Zc bond, one of which is a double bond and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where Rlo or Y4 forms a multimer of type 2 or more, and when Za, Zb or Zc is a substituted methine, the case where a multimer of 2N or more is formed with the substituted methine.

Among the pyrazoloazole couplers represented by the general formula (■), imidazo(1,2-b)virazole is described in U.S. Pat. are preferred, and U.S. Patent No. 4. ．． Pyrazolo (1,5-
b)(1,24] triazoles are particularly preferred.

Others, JP-A-61. A pyrazolotriazole coupler in which a branched alkyl group is directly connected to the 2,3 or 6 position of the pyrazolotriazole ring as described in JP-A-65245, and a sulfonamide in the molecule as described in JP-A-61652.16. pyrazoloazole couplers containing groups, such as pyrazoloazole couplers having an alkoxyphenylsulfonamide halas 1-group as described in JP-A-61-147254 and as described in European Patent Publication No. 226,849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position.

In general formula (V), R1+ represents a halogen atom or an alkoxy group, and R12 represents a hydrogen atom, a halogen atom or an alkoxy group. A is N HCORl 3, N HS 02 Rl :l
, S 02 N HRl:l, -C○0R33, SO2
Represents N R13. However, DI3 and R14 each represent an alkyl group. Y does not represent a leaving group. R12 and R
1ff, the substituent for R14 is the same as the substituent allowed for R1, and is a leaving group Y.

is preferably a type in which either an oxygen atom or a nitrogen atom is eliminated, and a nitrogen atom elimination type is particularly preferred.

Specific examples of couplers represented by general formulas (1) to (V) are listed below.

(C (C (C (C (C C2H1 C4II.

(C (C (C (C (C (C (C (C (C (M (M e 7I C21'(S p (C (M (M Cρ H3 (M CH.

H3 (Y ■) (Y (Y (Y (Y (Y (Y 0.1 to 1.0 mol per mol, preferably 0.
It is contained in an amount of 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-ice dispersion method known as the oil protection method, and 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-ice droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low boiling point a solvent may be removed by a method such as distillation, noodle washing or ultrafiltration, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the dielectric constant (25°c
) It is preferable to use a high boiling point solvent and/or a water-insoluble polymer compound having a refractive index (25°C) of 1.3 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) W w2-o-p=.

○ General formula (B) W, -COO-W2 General formula (C) W -CON2 W.

General formula (D) \ / General formula (E) WI OW2 (wherein WI, W2 and W3 each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W4 is W, ,
represents OW or S-W, n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other, and in the general formula (E), W and W2 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
Compounds that are immiscible with water at temperatures above 0°C and are good solvents for couplers can be used. The melting point of the high boiling point organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.
It is above °C.

For details on these high boiling point organic solvents, please refer to JP-A-61
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

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 polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The photosensitive material produced using the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. in addition to the compound of the general formula (A) of the present invention as a color fogging inhibitor or color mixing inhibitor. May be contained.

Among hydroquinone derivatives, the most representative are alkylhydroquinones, which are disclosed in U.S. Patent No. 2360.290.
No. 2.4.19,613, No. 2.728,6
No. 59, same No. 2. 732. No. 300, No. 3,96
No. 0.570, No. 3,700.453, etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxyhenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and argylated. Typical examples include ether or ester derivatives. Metal complexes such as (biszaritylaldoximato)nickel complex and (bis-N,N dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hytocoquinones are U.S. Patent No. 2,360.290,
2.418,613, 2,700.453, 2,701.197, 2,728,659
No. 2. 732. No. 300, No. 2,735,
No. 765, No. 3.982.944, No. 4. /13
0.425, British Patent No. 1.363.921, U.S. Patent No. 2,710.801, U.S. Patent No. 2.816,028
G~hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3432.
No. 300, No. 3,573.050, No. 3.574
．． No. 627, same No. 3. 698. No. 909, same No. 3.
No. 764.337, Japanese Unexamined Patent Publication No. 52152225, etc.
Spiroindanes are described in U.S. Patent No. 4.360.589, and p-alkoxyphenols are described in U.S. Patent No. 2.735.
, 765, British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 59-1.0539, and Japanese Patent Publication No. 57-19765, hindered phenols are described in US Patent No. 3.700.
No. 455, JP-A-52-72224, U.S. Patent No. 4.
No. 228.235, Japanese Patent Publication No. 526623, etc., and gallic acid derivatives, methylenedioxyhenzenes, and aminophenols are disclosed in US Pat.
Hindered amines are disclosed in U.S. Patent No. 4,332.886, Japanese Patent Publication No. 56-21144, etc.;
32. No. 889, same No. 1. 354. 313, L 410.84.6, Special Publication No. 511420,
JP 58-114036, JP 59-53846,
No. 51-78344, etc., metal complexes are described in U.S. Patent No. 4
, No. 050.938, No. 4,241,155, and British Patent No. 2.027731 (A).

The purpose of these compounds can be achieved by co-emulsifying them with the corresponding color couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight. 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 on both sides adjacent to it.

As ultraviolet absorbers, hensitriazole compounds substituted with an oryl group (for example, U.S. Pat. No. 3,533,794) are used.
4-thiazolidone compounds (e.g. those described in U.S. Pat. ), cinnamate ester compounds (e.g., U.S. Pat. Nos. 3,705,805 and 370)
No. 7.375), butadiene compounds (such as those described in U.S. Pat. No. 4,045,229), or hendioxidol compounds (such as those described in U.S. Pat.
700.455) can be used. An ultraviolet absorbing coupler (for example, an α-naphl-based cyan dye-forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, the above-mentioned aryl-substituted hensitriazole compounds are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, the use of a compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or alone, for example, for storage after processing. This is preferable in order to prevent staining and other side effects caused by the reaction of the coupler with the color developing agent remaining in the film or its oxidized product and the coupler.

Preferable compounds (F) have a second-order reaction rate constant kz with p-anisidine (trioctylphosphate-1 to 80'c) of 1. OA/mol ・see～lXl
It is a compound that reacts in the range of 0-5β/mol·sec. Note that the second-order reaction rate constant is based on JP-A-63-1585.
It can be measured by the method described in No. 4.5.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range iJ, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (Fl) or (FII).

General formula (Fl) R+ = (A) n-x General formula (Fn) R2-C=Y In the formula, R-8R2 does not each represent an aliphatic group, an aromatic group, or a heterocyclic group. n does not represent 1 or O. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (FII) represents a group that Here R1, X, Y
and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the remaining aromatic amine developing agent, typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (FT) and (Fll), see JP-A-63-1.5854.5 and JP-A-63-1.5854.5;
Preferred are those described in specifications such as No. 283338, Japanese Patent Application No. 62-158342, and European Patent Publication No. 277589.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (GT ).

General formula (C1) -Z In the formula, R does not represent an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (Gl), Z is Pearson's nucleophilic 'CH8T value (
R.G., Pearson, et al. Am
, Chem, Soc, ,90. 319 (196
8) A group in which ) is 5 or more, or a group derived therefrom is preferred.

For specific examples of compounds represented by general formula (CI), see European Patent Publication No. 255722,
No. 48, No. 62-229145, Patent Application 1986-1.3
No. 6724, No. 61-21468, No. 62-158
Preferably, those described in No. 34.2 and European Patent Publication No. 277589 are preferred.

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

The photosensitive material prepared according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and ab dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

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

In the present invention, the gelatin may be either lime-treated or acid-treated. The details of the method for producing gelatin are described in The Macromolecular Chemistry 1-1 of Gelatin, written by Arlie Weiss (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nylon I/lace film and polyethylene terephthalate I/reflective supports which are normally used in photographic materials can be used. For the purposes of the present invention, it is more preferable to use a reflective support, and the "reflective support" used in the present invention is one that enhances the reflectivity and sharpens the dye image formed in the silver halide emulsion layer. This type of reflective support includes a support coated with a hydrophobic resin containing dispersed light reflective substances such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc. This includes those using the hydrophobic resin contained therein as a support. For example, Halique paper, polyethylene coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyesters such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate. There are films, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins, etc., and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use chimono treated with tetrahydric alcohol.

The area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (R4) of the fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of R1 to the average value (R) of R1. The number of target unit areas (n) is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the two particles can be said to be "substantially uniform."

In the processing of the photosensitive material in the present invention, for example, search,
Disclosure (Research Disclosure)
ure) No. 17643, pages 28-30 (RD-17
Any of the known methods and known treatment liquids as described in 64, 3) can be applied. This photographic processing may be a photographic process that forms a silver image if a color image is finally obtained, or a photographic process that directly forms a dye image. The treatment temperature is usually between 18°C and 5°C, preferably 18°C.
The temperature may be lower than C or higher than 50C.

There are no particular restrictions on the color photo processing method, and various methods can be applied. For example, a typical example is
A method in which color development and bleach-fixing are performed after exposure, followed by washing and stabilization as necessary.A method in which color development, bleaching and fixing are performed separately after exposure, and further washing and stabilization are carried out as necessary. After exposure, the film is developed with a developer containing a black and white developing agent, and then exposed to -like light.
Development 1Q Color development, bleach-fixing, and if necessary further washing with water and stabilization. After exposure, development with a developer containing a black and white developing agent, followed by a fogging agent (e.g. sodium borohydride). There is a method in which the image is developed with a color developing solution containing , and then subjected to bleach-fixing treatment, followed by further washing with water and stabilization treatment as required.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developing agents include aminophenol and p-phenylenediamine derivatives. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

Z-1,N,N-diethyl-p-phenylenediamine Z-22-amino-5-diethylamine toluene Z-32-amino-5-(N-ethyl-N-laurylamino)toluene 4-[N-ethyl- N-(β-hydroxyethyl)aminocyaniline 2-methyl-4-[N-ethyl-N [β-hydroxyethyl)aminocyaniline 3-methyl-4-amino-N-ethylN-(β-methanesulfone amidoethyl)aniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide Z-8N, N-dimethyl-p-
Phenyldiamine 4-amino-3-methyl-N-ethyl N-methoxyethylaniline Z-104-amino-3-methyl-N=ethyl N-β-
Ethoxyethylaniline Z-114-amino-3-methyl-N-ethyl N-β-
Butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The above compound is disclosed in U.S. Patent No. 2,193
, No. 015, No. 2.552241, No. 2,566, 2
No. 71, No. 2,592, No. 364, No. 3,656,95
No. 0, No. 3, No. 698, No. 525, etc. The amount of the aromatic primary amine color developing agent used is 1 p of the developer.
from about 0.1 g to about 20 g, more preferably about 0.

5g to about Log.

The color developer used in the present invention may contain hydroxylamines.

Hydroxylamines can be used in the form of free amines in color developers, but may also be used in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and others. Hydroxylamines may be substituted or unsubstituted, but those in which the nitrogen atom of the hydroxylamines is substituted with an alkyl group, such as N. N-diethylhydroxylamine, etc.) are particularly preferably used in the present invention, which uses a silver halide emulsion with a high silver chloride content.

The amount of hydroxylamine added is 1 per 11 of the coloring atomic liquid.
It is preferably 0 g or less, more preferably 5 g or less. If the stability of the color developing solution is to be maintained, it is preferable that the amount added be small.

In addition, as a preservative, it improves preservability by containing sulfites such as sodium sulfite, potassium sulfite, thorium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. However, when using a high silver chloride emulsion like the one of the present invention, it is preferable to use as little as possible, and the effects of the present invention are particularly greatly exhibited in such a liquid. In the present invention, the amount of these sulfites added is 0.008 mol or less, preferably 0.004 mol or less, and more preferably 0.002 mol or less (including 0) per 1β of the color developer.
It is.

It is more preferable that the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions described above.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. That is, organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-Hydroxyketones, α-aminoketones, I
J! Particularly effective organic preservatives include monoamines, diamines, polyamines, quaternary ammonium salts, di-1-logisyl radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. These are JP-A-63-4235, JP-A-63-30845, and JP-A-63-30845.
3-2164.7, 63-44655, 63-
No. 53551, No. 63-43140, No. 63-566
No. 5.1, No. 63-58346, No. 63-43138
No. 63-146041, No. 63-44657,
No. 63-4.4656, U.S. Patent Section 3,6], 5.5
No. 03, No. 2,494.903, JP-A-52-143
020, Japanese Patent Publication No. 4B-30496, etc.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
．． Polyethyleneimines described in No. 34.9, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, etc. may be contained as necessary. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
It is described in No. 5270, No. 61-9713, No. 63-9714, No. 63-11300, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in Japanese Patent Application No. 61-265149 and Japanese Patent Application No. 61-273.
Amines such as those described in No. 751 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 6311300.

The pH of the color developer used in the present invention is preferably 9 to 12, more preferably 9 to 11, and the color developer may contain other known developer component compounds. can.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2
-Methyl 1,3-propanediol salt, valine salt, proline salt, trishydroxyamitumecun salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have a high solubility and pl (9,0
It has the advantages of excellent buffering capacity in the above high p T-I SM region, no adverse effect on photographic processing performance (occurrence of fog) even when added to color developing solution, and low cost. Preferably, a buffer is used.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sulfur/lium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, and sodium borate. , potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2-hydroxybenzoate (5- Examples include sodium sulfosalicylate), potassium 5-sulfo-2hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, it is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol/β or more, particularly 0.1 mol/12 to 0.
．． Particularly preferred is 4 mol/β.

In addition, it is preferable to use various clearing agents in the color developing solution as anti-settling agents for calcium and magnesium, or to improve the stability of the color developing solution.

As the clearing agent, organic acid compounds are preferable, such as aminopolycarphonic acids described in Japanese Patent Publication Nos. 48-030496 and 4430232, and JP-A-56-9734.
No. 7, Special Publication No. 56-39359 and West German Patent No. 2,
Organic phosphonic acids described in No. 227.639, JP-A-52
-102726, 53-, 12730, 54-
Phosphonocarboxylic acids described in No. 1.21.127, No. 55-126241, No. 5565956, etc., and other JP-A-58-195845, No. 58-20344
Examples thereof include compounds described in Japanese Patent Publication No. 0 and Japanese Patent Publication No. 5]-40900. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethylenetriamineoxacetic acid ・Ethylenediaminetetraacetic acid ・TriethylenetheI-laminhexaacetic acid ・NNN-1-rimethylenephosphonic acid ・Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・13-diamino- 2-Pl-cobanol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid-12-diaminopropanetetraacetic acid, human I-koxyethyliminodiacetic acid, glycoletherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthohydroxy Phenylacetic acid/2-phosphonobutane-1,2,4-1~ricarboxylic acid/1-hydroxyethane-1,1-diphosphonic acid/N,
N'-bis(2-hydroxyhensyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example] O per liter,] g/1. It is about Og.

Any development accelerator can be added to the color developing solution if necessary.

Although benzyl alcohol is known as a typical color development accelerator, benzyl alcohol is not substantially used in the present invention. Benzyl alcohol has a pollution burden (BO
D, C0D) is large, so it is preferable not to use it. 1 cc or less, more preferably 0.1 cc per p of color developer.
It should not contain more than 5 cc, most preferably not at all.

Such a color developing solution is preferable because the effects of the present invention are greatly exhibited.

Other development accelerators include Japanese Patent Publication No. 37-16088;
No. 37-5987, No. 38-7826, No. 44-1
No. 2380, No. 45-9019 and U.S. Patent No. 3.
813.247, etc.; p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-1.5554;
Quaternary ammonium salts described in Japanese Patent Publication No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-13429; U.S. Patent No. 2,610.1
p-aminophenols described in U.S. Pat. No. 22 and U.S. Pat. No. 4,119,462; U.S. Pat.
．． 128.182, 4230.796, 3.2
53,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2.482546, U.S. Pat. No. 42-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431,
No. 41-23883 and U.S. Patent No. 3,532,5
Polyalkylene oxide described in No. 01 etc., and others 1
-Phenyl-3-pyrazolidones, hydrazines, meso ion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-virapritones.

In the present invention, any antifoggant can be added to the color developing solution if necessary. As antifoggants, alkali metal halides such as potassium bromide, thorium bromide, potassium iodide, and organic antifoggants can be used. In the present invention, high silver chloride is used to improve rapid processing properties, and to take advantage of this property, it is preferable to keep the amount of bromine ions as low as possible. In fact, sometimes it's convenient.

In the present invention, chlorine ions are added to the color developer by 3.5X.
It is preferable to contain 10 −2 to 1.5×10 −′ mol/β. Particularly preferably 4X10-2 to IX10
-'mol/7! It is. Chlorine ion concentration is 1.5X10
If the amount is more than -'mol/β, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density.

Also, 3.5X10-2 mol/7! If it is less than that, it is not preferable in terms of preventing fogging.

In the present invention, 3.0% bromine ion is added to the color developer.
It is preferable to contain X10-5 mole/β-1,0X10-' mole/ρ. More preferably 5.0 x 10-5
˜5×10 −′ mol/ρ. Bromine ion concentration is 1×
If it is more than 10-3 mol/l, development will be delayed, maximum density and sensitivity will be reduced, and 3°0xlO-5 mol/l! If it is less than that, fogging cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are thorium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, 1-lithium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, odor Among these, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during development processing, both chloride ions and bromine ions may be supplied from silver halide, or may be supplied from sources other than silver halide.

Examples of organic antifoggants include benzotri]05atur, 6-nitrobenzimitazur, 52l-rosoindadur, 5-methylhenzotriadur, 5-
Nitrohencitriazole, 5-chloro-benzo1-riazole, 2-thiazurylbenzimidazole, 2-
Nitrogen-containing heterocyclic compounds such as thiazurylmethyl-benzimidazole, hydroxyazaindolizine, and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazolzimidazole, 2-mercap I-hendithiazole, adenine, Additionally, mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants may be eluted from the silver halide color photographic light-sensitive material during processing and may accumulate in the color developing solution, but from the viewpoint of reducing the amount of emissions, it is preferable that the amount of these accumulated is small. .

The color developing solution of the present invention preferably contains a fluorescent whitening agent. As the optical brightener, 4,4'diamino-2,
2'-disulfostylhene compounds are preferred. The amount added is 0-5gzJ! Preferably it is 0.1 g to 2 g/β.

Furthermore, various surfactants such as alkylbosphonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution in the present invention is 30 to 50°
C is preferable, and 33 to 42 are more preferable. The replenishment amount is 30 to 1500 cc per 1% of the photosensitive material, preferably 30 to 600 cc, and more preferably 30 to 3 cc.
00 cc. From the viewpoint of reducing the amount of waste fluid, it is preferable that the amount of these replenishments be small.

Following color development, the photosensitive material may be processed with a solution having fixing and bleaching functions.

Ferric ion complex salts are generally used as the bleaching agent in the bleach solution or bleach-fix solution used in the present invention.

The ferric ion complex salt is preferably a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. The aminopolycarboxylic acid salt or aminopolyphosphonate is preferably a salt of aminopolycarboxylic acid or aminopolybosphonic acid with an alkali metal, ammonium, or water-soluble amine. Examples of alkali metals include soot, lium, potassium, and lithium, and examples of water-soluble amines include alkyl amines such as methylamine, diethylamine, triethylamine, and butylamine, alicyclic amines such as cyclohexylamine, aniline, and m-toluidine. Mention may be made of arylamines and heterocyclic amines such as pyridine, morpholine and piperidine.

Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosponic acids or salts thereof include: ・Ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenethiaminthi-1- Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid I, disodium salt, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid pentasodium salt, ethylenediamine-N -(β-oxyethyl)N,N
',N'-1-lyacetic acid/ethylenediamine-N-(β-oxyethyl)N,N
',N'-) trina-1helium acetate/ethylenediamine-N-(β-oxyethyl)N,N
',N'-)triammonium salt of acetate, propylenediaminetetraacetic acid, propylenediaminetetraacetic acid (cinnamonium salt), nitrilotriacetic acid, trisodium nitrilotriacetate, cyclohexanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, Iminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, Φethylenediaminetetrapropionic acid, phenylenethiaminth I,
Acetic acid/1,3-diaminopropanol-N,N,N'N'-
TeI・ramethylenephosphonic acid・ethylenediamine-N,N,N',N'-tetramethylenebosphonic acid・1,3-propylenediamine-N,N,N'N'-
Examples include tetramethylenephosphonic acid, but the compound is not limited to these compounds.

The ferric ion complex salt may be used in the form of a complex salt, or as a ferric ion complex salt.
Iron salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc., and aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc. - Ferric ion 1 in solution using I.
11 salts may be formed. When used in the form of a complex salt, one type of 211 salt may be used, or two or more types of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a Kill-I agent, one or more types of ferric salts may be used. Furthermore, one or more types of chelating agents may be used.

In any case, the ferric ion complex salt may be formed by using an excess amount of the ferric ion complex.

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01~], Omol/r, preferably 0.05~0.50mol%ρ.

Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Pat. No. 5
No. 3-37418, No. 53-65732, No. 53-7
No. 2623, No. 53-95630, No. 53-9563
No. 1, No. 53-104.232, No. 53-12442
No. 4, No. 53-141.623, No. 53-28426
No. 17129, Research Disclosure Floor (1,
Compounds having mercap 1-4 or disulfide bonds described in JP-A-1401.2-1978 (July 1978) and others;
Thiazolidine derivatives described in No. 9; Japanese Patent Publication No. 4.5-85
No. 06, JP 5220832, JP 53-32735
1,000 urea derivatives described in U.S. Pat. Polyethylene oxides described in National Patent Nos. 966.410 and 2.748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others in Japanese Patent Publication No. 49-42434
No. 49-596/14, No. 53-94927,
Compounds described in No. 54-35727, No. 55-26506 and No. 58-1639.10 and iodine, bromide ions, etc. can be mentioned. 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. Pat.
The compound described in No. 0 is preferred.

In addition, the bleach or bleach-fix solution of the present invention may contain bromides (e.g. potassium bromide, lium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, lium chloride).
It is preferable to include a rehalogenating agent such as lithium, ammonium chloride) or an iodide (eg ammonium iodide). If necessary, use of boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium chloride carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. pH! One or more inorganic acids, organic acids and their alkali metal or ammonium salts having yi-enhancing ability, as well as corrosion inhibitors such as ammonium nitrate and guanidine, can be added.

The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixing agents, i.e. thiosulfates such as thorium thiosulfate and ammonium thiosulfate; lithium thiocyanate;
These are water-soluble silver halide solubilizers such as thiocyanates such as ammonium thiocyanate, thioether compounds such as ethylene bisthioglycolic acid, 3,6-cythia-1,8-octanediol, and thioureas.
A species or a mixture of two or more kinds can be used. It is also possible to use a special bleach-fix solution, which is made of a combination of a fixing agent and a large amount of a halide such as potassium iodide, as described in JP-A-55-155354. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates.

The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

p )-1eM of the bleach-fix solution or fixer solution in the present invention
The range is preferably 3 to 10, more preferably 4 to 9. If the pH is lower than this, the desilvering performance will be improved, but the storage stability of the solution may deteriorate and the leucoization of the cyan dye during processing may be promoted. On the other hand, if p J-1 is higher than this, desilvering is delayed and staining is likely to occur.

To adjust the pH, add hydrochloric acid, sulfuric acid,
Nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, potassium hydroxide, thorium hydroxide, sulfur/lium carbonate, potassium carbonate, etc. can be added.

The bleach-fix solution may also contain various other optical brighteners, antifoaming agents, surfactants, polyvinylpyridine 1':1 ridone, and organic solvents such as methanol.

The bleach-fix solution and fixer of the present invention contain sulfites (e.g., thorium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (e.g., potassium metabisulfite, thorium metabisulfite, ammonyl metabisulfite J, etc.). It is preferable that these compounds contain about 0.02 to 0.05 mol/ρ gold in terms of sulfite ion, more preferably (1
,0,i~O,40 mol/l.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite, carbonyl compound, etc. may also be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

After fixing or desilvering treatment such as GJ bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture Ant Television Engineers.
a1 of the 5ociety of M
otion r'1ture and Telev
ion Engineers) Volume 64, P, 24
8-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multistage countercurrent method, the amount of water used for washing can be greatly reduced, for example, from 0.5 to 17 per 1.7 of the photosensitive material! The following is possible, and the effects of the present invention are remarkable; however, due to the increased residence time of water in the tank, problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material may occur. As a solution to this problem, Japanese Patent Application Laid-Open No. 62-288838
The method for reducing calcium and magnesium described in the above issue can be used very effectively. Also, JP-A-5
78542, chlorine-based disinfectants such as chlorinated isocyanuric acid I.lium described in 61-1.20145, JP-A No. 6], -26776] Henzotriadur, copper ions and others described in Hiroshi Horiguchi's "Chemistry of antibacterial and anti-mildew J"
1,986) Tool Publishing, Hygiene Technology Gold Wire "Sterilization of Microorganisms, Disinfection, and Anti-Mold Technology" (1982) Industrial Technology Association, Japan Antibacterial and Anti-Mold Science Gold Wire "Encyclopedia of Antibacterial and Antifungal Agents J (1, 986) can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent such as EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffers used to prepare H.H. and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the solution and to impart anti-mold properties to the photographic material after processing, the various bactericidal agents and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners may be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, 6 (1220345
Any of the known methods described in No. 1, etc. can be used.

In addition, it is also a preferred embodiment to use chelating agents such as 1-hydroxyethylidene-1,1 diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

The pH of the water washing step or stabilization step is preferably 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45
°C Preferably 20-40 °C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds
seconds to 1 minute and 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running cost I, reduction in emissions, ease of handling, and the like.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or 1β or less per 1% of photosensitive material, preferably 500rrl! It is as follows. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water, which has been reduced by a multi-stage countercurrent system, into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid.

Example 1 Silver halide color photographic materials as shown in Table 1 were prepared. This sample was designated as 1.

The silver halide emulsions shown below were used in each layer.

Emulsion for red sensitive layer: Add 30 g of lime-treated gelatin to distilled water], dissolve at 40°C, adjust the pH to 3°8 with sulfuric acid, add 5.5 g of 1-lium chloride and N, 0.02 g of N'dimethylimidazolidine-2-thione was added and the temperature was raised to 52.5°C. Nitric acid] 20 Add and mix a solution of 62.5 g of silver dissolved in 750 ml of distilled water and a solution of 21.5 g of sodium chloride dissolved in 500 ml of distilled water for 40 minutes while maintaining the temperature at 52.5°C. did. Furthermore, add 62.5 g of silver nitrate to 500 m of distilled water.
1 and 21.5 g of sodium chloride in distilled water 3
00ml of the solution at 52.5°C for 20 minutes.
Add and mix for a minute.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 46 μm and a coefficient of variation of grain size distribution of 0.09.

After washing this emulsion with desalinated water, 0.2 g of nucleic acid and compound (V
-1,) I .6 mol% was added, chemically sensitized with 2 x 10-6 mol of triethylthiourea, 1 mol of Ag, and compound (■1) was added 7X], O-' mol of 1 mol of Ag compound (F1). 5 x 1.0-3 mol 1 mol Ag
Added.

Emulsion for green-sensitive layer: Add 30 g of lime-treated gelatin to 10,100 O distilled water, dissolve at 40°C, and add 5.5 g of sodium chloride and N,
0.02 g of N'-dimethylimidazolidine-2thione was added and the temperature was raised to 50°C. silver nitrate 62.5
A solution obtained by dissolving 21.5 g of thorium chloride in 750 ml of distilled water and a solution obtained by dissolving 21.5 g of thorium chloride in 500 ml of distilled water were heated at 50°.
The mixture was added to the above solution and mixed for 40 minutes while maintaining the temperature. Furthermore, a solution of 62.5 g of silver nitrate dissolved in 500 ml of distilled water and 2.5 g of sodium chloride were added. ]、、5g in 300 m of water
, ] were added and mixed under the condition of 50°C for 20 minutes.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 44μ and a coefficient of variation of grain size distribution of 0.08.

After washing this emulsion with desalinated water, 0.2 g of nucleic acid and compound (V
-2) 5 x 10-' mol 1 mol Ag, (V3)7
X] O-5 mol 1 mol A (H1 average particle size 0.05
A monodisperse silver bromide emulsion of μ (containing 2.5 x 10-5 mol of silver dipotassium hexachloride and 1 mol of Ag) was added in an amount equivalent to 0.4 mol% of silver halide, and approximately 2.5 x 10-6 mol of triethylthiourea was added. Chemical sensitization was performed with 1 mol of Ag, and compound (Il) was further added to 1. 1×10 −3 mol 1 mol Ag was added.

Emulsion for blue-sensitive layer: 30 g of lime-treated gelatin was added to 10,100 O distilled water, dissolved at 40°C, and the pH was adjusted to 3°8 with sulfuric acid.
5.5 g of sodium chloride and 0.03 g of N,N'dimethylimidazolidine-2-thione were added and the temperature was raised to 75<0>C. Dissolve 12.5 g of silver nitrate in 150 ml of distilled water and 4.3 g of thorium chloride in 100 ml of distilled water.
was added to and mixed with the above solution for 30 minutes while maintaining the temperature at 75°C. Furthermore, a solution of 112.5 g of silver nitrate dissolved in 1100 ml of distilled water and 38.5 g of sodium chloride were added.
A solution obtained by dissolving 7 g in 650 ml of distilled water was added and mixed at 75° C. over 40 minutes.

When the obtained emulsion was observed under an electron microscope, it was found to be about 0.
The emulsion consisted of cubic grains with an average side length of 82μ and a coefficient of variation of grain size distribution of 0.11.

After washing this emulsion with desalinated water, 0.2 g of nucleic acid, compound (v
-4) 2xlO-3 mol 1 mol Ag, (V5) 2X10
-' Monodisperse silver bromide emulsion with 1 mol of Ag and an average grain size of 0.05μ (iridium dipotassium hexachloride
-'1 mole of Ag (containing 1 mole of Ag) was added in silver halide equivalent to 0.3 mole%, and l.ethylthiourea was approximately 1.2X
Chemical sensitization was carried out with 10-6 mol 1 mol Ag, and further compound N-1) was added in an amount of 9×10-' 1 mol Ag.

These samples contained compounds (Dl) and (D-2) to prevent irradiation and improve image sharpness.
), (1)-3), and (D~4), 0.006g each
/n(,0,007g/%,0.003g/n(,0,
It was coated at a weight of 0.012 g/m.

Further, the following three types of compounds were used as a hardening agent for gelatin in a molar ratio of 3:2:1.

Table 1 CH2NHCOCH2SO2CH=CH7CH2Nl-
lCOCH2soz CJ(=CILOCH2S 0
2 CH= CT42CH25O7CH= CH2 Among the additives in Table 1, the symbols for cyan, magenta and yellow couplers refer to those listed above as specific examples, and the other additives are shown below.

(CH2)4 (CH2)4 S○3H-NEt.

SO3H-NEt3 H (F (V C, +( ■ C2■]5 (■ (■ (C1-h)4　Sυ311 1jt3 (D ■) (D (D (D (E (H (H ]31 H H (X C7! (A ■) ICH7 CONIIC4H7(t) Molecular weight approximately 60,000 ○l-1 (S C2H,.

C00CHz CHCa J (9 (CH2).

000CJ(2CHC4H9 2H5 (S c, H,7CH-(, +((CH2)7coocII
H. Created.

Each of these samples was exposed to white light for 0.1 seconds through a blue filter and an optical wedge, and then subjected to the following color development treatment.

Processing process: Color development 38°C Bleach-fixing 30-36°C Rinse 1 30-37°C Rinse 2 30-37°C Rinse 3 30-37"C Drying 70-80°C 45 seconds 45 seconds 30 seconds 30 seconds 30 seconds 60 seconds Color development V Ethylenediamine-N,N,N N-tetramethylenephosphonic acid 3.0g
NN-di(carboxymethyl)hydrazine 4.5gNN-diethylhydroxylamine oxalate 2.0g1-liethanolamine 8.5gSodium sulfite 0.14g Potassium chloride
1.6 g potassium bromide
O, O], g potassium carbonate
25.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3 methyl-4-aminoaniline sulfate 5. OgWITEX
-4 (manufactured by Sumitomo Chemical) 1. ．． Add 4g water
Adjust to 100100O+-110,05 1 sheep U 1 meal Ammonium thiosulfate (55w Lχ) 100m
1 Sodium sulfite 17.0g Iron (I) ethylenediaminetetraacetate Ammonium 55.0g Disodium ethylenediaminetetraacetate 5. Og ammonium bromide Add 40.0g glacial acetic acid water and adjust to 5.80 H 9,0g 000ml Rinse with ion-exchanged water (under calcium ion appmJu, magnesium ion 2pl) m) Yellow density of the obtained treated sample 1.0 and 1.
The density of the mazenk color component at 75 (DY=1
．． 0 and -=1.75) were measured using an XRITE310 reflection densitometer, and the values obtained are shown in Table 3.

Table 3 In Table 3, the magenta density of the yellow dye itself at yellow density of 1.0 and 175 is about 0.0.
26-0.27 - about 0.39-0.40, it is interpreted that samples exhibiting this value have almost no color turbidity. Comparing Samples 3 to 6 according to the present invention with 1 to 2, they are superior in comparison to Samples I and 3.5 coated with an equimolar amount of color mixing prevention agent, and Sample 2.4 coated with an equimolar amount of coating with a large amount. It is understood that .6 is also excellent.

Example 2 Color developer used in Example 1 (this is referred to as CD-1)
In contrast, color developing solutions CI)-2 to G in which the added amounts of sodium sulfite and benzyl alcohol were changed as shown in Table 4.
was prepared, and the same samples as in Example 1 were conducted using Samples 1 to 6. The same procedure as in Example 1 was performed except for the bleach-fix solution.

Table 4 The magenta density component of the obtained processed sample at a yellow density of 1.75 was measured, and the results are shown in Table 5. However, in the treatment using CD-2 and CD-4, the color does not develop until the yellow density is 1.75, so the yellow density is 1.00.
It is expressed as a magenta density component.

When using CD-2 and CD-4 in Table 5, there was little color turbidity, but the color development was insufficient to begin with, and no difference in the color mixture prevention agent was observed.

Furthermore, when CD-5 and CD-6 are used, although the color is less cloudy, they contain benzyl alcohol, which is a problem in terms of pollution.

When CD-3 is used, there are no disadvantages such as color development or pollution, which shows the advantage of the present invention in terms of cloudy eyes.

Example 3 Samples 7 to 7 in which the color mixing inhibitor ()(-1,') in the fourth and sixth layers of Samples 1 to 6 prepared in Example 1 were replaced with equimolar amounts of Compound 4 of the present invention A sample No. 8 was prepared and subjected to the same exposure and color development treatment as in Example 1 using red light. When the concentration of the magenta component in the cyan coloring part of the obtained colored sample was evaluated by removing the magenta concentration component of the cyan dye itself, it was found that the sample using the compound of the present invention did not contain benzyl alcohol and sulfite ions. Alternatively, only the case of processing with a color developing solution containing almost no color was found to be excellent, with less color turbidity.

(Effects of the Invention) According to the present invention, it is possible to provide a color image forming method with less color turbidity, excellent color reproducibility and color development, and less pollution load.

Claims (2)

[Claims] (1) A high silver chloride emulsion layer containing at least one cyan coupler, a high silver chloride emulsion layer containing a magenta coupler, a high silver chloride emulsion layer containing a yellow coupler, and at least one non-containing layer on a support. In a method of forming a color image by treating a silver halide color photographic light-sensitive material having a light-sensitive layer with a color developing solution, the light-sensitive material is non-color-forming and diffusion-resistant and has the following general formula (A). 1. A method for forming a color image, comprising the compound represented by the formula, and the color developing solution containing 0 to 1 ml/l of benzyl alcohol and 0 to 0.008 mol/l of sulfite ion. General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1^1, R^1^2, R^1^3 are hydrogen atoms,
Represents an aliphatic group or an aromatic group, R^1^4 is a hydrogen atom,
Alkyl group, aralkyl group, aryl group, heterocyclic group,
Represents an alkoxy group, aryloxy group, amino group, alkoxycarbonyl group, or carbamoyl group. G^1^1 represents a carbonyl group, sulfonyl group, sulfinyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or iminomethylene group (HN=C■), and n is 0 or 1
It is. (2) The color image forming method according to claim (1), wherein the non-photosensitive layer contains a compound represented by general formula (A).