JPH0243546A - Image forming method - Google Patents

Abstract

PURPOSE:To make it possible to form the picture of a photosensitive material which has high sensitivity, and is improved the generation of a color mixture due to processing the material and is prevented the processing fluctuation of the material by incorporating a specified nitrogen contg. heterocyclic compd. in the photosensitive material comprising a silver halide emulsion having a high silver chloride content, and by developing the photosensitive material with a specified color developer. CONSTITUTION:The photosensitive material provides at least one layer of the silver halide emulsion layers contg. a silver halide emulsion having the silver chloride content of >=80mol.%. the nitrogen contg. heterocyclic ring compd. having the solubility product of silver of <=10<-10> and >=10<-18> is incorporated in the photosensitive material. And, the color developer contains a chlorine ion of 3.5X10<-2>-1.5X10<-1>mol./L. and a bromine ion of 30X10<-5>-1.0X10<-3>mol./L. So that, in the color developer, the effect of preventing the development of the photosensitive material and the effect of preventing the dissolution of a silver halide emulsion particle due to the chlorine and the bromine ions and the nitrogen contg. heterocyclic ring compd., are balanced. Thus, the picture of the photosensitive material which has the high sensitivity and a less tendency for generating the color mixture due to the processing and the processing fluctuation of the material, is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to an image forming method using a silver halide photographic light-sensitive material, and more specifically, it uses a high silver chloride silver halide photographic light-sensitive material, is suitable for rapid processing, and is suitable for high-speed processing. The present invention relates to an image forming method using a silver halide photographic material having high sensitivity and good color reproducibility.

[Prior art]

Generally, a silver halide photographic light-sensitive material consists of a support and a photographic layer coated on the support. The photographic layers herein include a photosensitive silver halide emulsion layer and nine non-photosensitive hydrophilic colloid layers.

In the case of a silver halide color photographic light-sensitive material, three types of silver halide photographic emulsion layers sensitive to blue light, green light and red light are coated on a support. These layers are
When exposed to blue light, green light, and red light, aromatic compounds are removed during development.
They contain couplers that react with the oxidation products of grade amine developing agents to form yellow, magenta, and cyan colors, respectively.

By the way, in recent years, with regard to color hardeners, with improvements in the productivity of photographic printing, shortening of finished delivery times, and reductions in laboratory work, there has been a growing demand for faster development processing and higher sensitivity of photosensitive materials. Countermeasures are being taken to prevent the spread of the virus.

Increasing the temperature and increasing the amount of replenishment are common methods to shorten the time of each processing step, but there are also many other methods (some have been proposed), such as increasing stirring or adding various accelerators. It's here.

Among these, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsions are processed in place of conventionally widely used silver bromide thread emulsions or silver iodobromide emulsions. method is known. For example, W
No. 037-04534 describes a method for rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer substantially free of sulfite ions and indyl alcohol.

However, when developing using the above method, so-called processing color mixing occurs in which magenta coloring is added to areas that should originally be yellow/cyan coloring, which is not preferable from the viewpoint of color reproducibility. Furthermore, it was also found that the maximum concentration fluctuated greatly during continuous processing.

Moreover, it has been found that the degree of these developments deteriorates as the processing temperature is raised to increase the color development speed, and as the silver chloride content of the silver halide emulsion grains is increased.

This rapid processing using a 5K, high-silver chloride color photographic photosensitive side has serious problems such as color mixture during processing and variations in color density, and is not suitable for practical use.

As a method for improving color mixture during processing, it is effective to increase the amount of Hyde-90 quinone derivative in the non-photosensitive layer.
As a result, the sensitivity of the photosensitive material decreases and the drying time becomes longer, so that it cannot be considered a preferable solution from the viewpoint of rapid processing.

It has also been found that variations in maximum density due to processing can be improved by improving the coupler, and for example, using a coupler as shown in WO 38-04793 as a magenta coupler can significantly improve the variation. However, when such a coupler is used, although the variation in the maximum color hardness is reduced, the degree of color mixing during processing is adversely affected, and it has not been possible to obtain a product that satisfies both performances.

Furthermore, in JP-A No. 61-70552, a high silver chloride silver halide color photographic light-sensitive material is used, and during development, a high replenishment amount is added to the developer bath so that no overflow occurs. The method is described in JP-A No. 63-106655.
In order to stabilize processing, a silver halide color photographic light-sensitive material consisting of a silver halide emulsion layer with a high silver chloride content is developed with a color developing solution containing a hydroxylamine compound and chloride at a predetermined concentration or higher. A method of processing is disclosed. However, in these methods, the above-mentioned processing color mixing and variation in maximum density occur, and they are not suitable for practical use.

Chloride ions and bromine ions are known to be good anti-fogging agents, but their effect on improving color mixing during processing is small in Kodoku, and in fact, if they are added to the extent that even a slight improvement effect is recognized, they may delay development. 5. On the contrary, there was an adverse effect of lowering the maximum concentration.

Further, nitrogen-containing heterocyclic compounds are also well known as antifoggants and aging stabilizers. However, when this compound was also used alone, the variation in maximum density was slightly improved, but little improvement in processing color mixing was observed.

Therefore, it was necessary to develop a silver halide color photographic light-sensitive material that is suitable for rapid processing, causes less color mixing during processing, and exhibits small fluctuations in photographic properties (up to 1 degree), and a processing method for the same.

As a result of various studies, the present inventors have found that a light-sensitive material containing a high silver chloride silver halide emulsion consisting of 80 moles or more of silver chloride and a silver salt solubility value of 10 to 10 is found. A silver halide color photographic light-sensitive material containing a nitrogen heterocyclic compound was treated with chlorine ions of 3.5×10 −2 to 1
．． Contains 5810-"% L/L and 3.5% bromide ion.
It has been found that by processing with a color developer containing 0 x 10-5 to 1.0 x 10" mol/L, the processing color mixture is improved and the variation in maximum density is reduced. These facts are unexpected. It was truly surprising.

[Problem to be solved by the invention]

Accordingly, a first object of the present invention is to provide an image forming method which uses a high silver chloride color photographic light-sensitive material, is rapid, has high sensitivity, and has improved color mixing during processing.

A second object of the present invention is to provide a single-plane image forming method in which fluctuations in photographic properties (maximum density) accompanying continuous processing are significantly suppressed using a high-silver chloride color photographic light-sensitive material.

[Means to accomplish the task]

The present inventors have 1. The above-mentioned object is to provide a light-sensitive material with a high silver chloride silver halide emulsion having a small number of silver chloride to silver halide emulsion layers (both of which have a high silver chloride silver halide emulsion consisting of silver chloride of 80 molar or more), and A silver halide color photographic material (containing a nitrogen-containing heterocyclic compound with a solubility product of silver salt of 10 or more and 10-18 or less) is mixed with 3.5 x 10-2 - 1.5 x 10 chloride ions.
-1 mol/L and 3.0x10 bromide ions
This was achieved by processing with a color developer containing ~1.0 x 10'' mol/L.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but the order may be different from this. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the light to which they are exposed - yellow for blue, i-zenta for green, and cyan for red. By incorporating a so-called color coupler to form, subtractive color reproduction can be performed. However, the coloring hue of the photosensitive layer and the coupler may not have the above five correspondences.

As the silver halide emulsion used in the present invention, one which does not substantially contain silver iodide and has a silver chloride content of 80 mole or more based on the total silver halide can be preferably used. Here, the term "substantially free of silver iodide" means that the silver iodide content is 1 mole or less, preferably 0.2 mole or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to have continuous structural changes.

The silver chloride content of these high silver chloride emulsions is preferably 90 mol/l or more, more preferably 95 mol/l/l or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized layer is inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above.The halogen composition of the localized phase is The silver bromide content is preferably at least 10 moles, more preferably more than 20 moles. And these localized j sauces are 1
It can be located inside the grain, on the edge, corner, or surface of the grain surface, but one preferred example is epitaxial growth on a part of the corner of the grain.

On the other hand, even in high silver chloride emulsions with a silver chloride content of 90 molt or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure. This is also preferably done.

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is between 98 mol S and 10
Emulsions of almost pure silver chloride, such as those having 0 molarity, are also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ.

The particle size distribution thereof is preferably so-called monodisperse, with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Further, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The high silver chloride emulsion used in the present invention is P, G1afkides.
Written by Chimie at Ph1aique Ph
otographique (Paul Wanted, 1967), Photo by G. F. Duffin
graphic emulsion chemist
y (FocaxPreets, 1966), V
, L., Zelikman et al. Making
and Coating Photographic
Emulsion (published by Focal Press, 19
64). That is, any method such as a diluted method, a neutral method, an ammonia method, etc. may be used, and methods for reacting a soluble silver salt with a soluble silver salt include a one-sided mixing method, a simultaneous mixing method,
Any method such as or a combination thereof may be used. A method (newly developed back mixing method) in which particles are formed in an atmosphere containing excess silver ions can also be used. As one type of simultaneous mixing method, a method in which PAg in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a /S silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Salts or complex salts of ruthenium, rhodium, radium, osmium, iridium, platinum, etc. can be mentioned. In particular, the above Group Ⅰ elements can be preferably used. The amount of these compounds added can vary widely depending on the purpose. However, it is preferably 10 to 10 mol per 10 silver germide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F', M, and Harmer II H.
eterocyclic compounds-Cya
nine dies and related com
pounds (John Wiley & Sons (Ne
W York, London, 1964). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272 specification on page 22, upper right column to page 38 are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

The nitrogen-containing heterocyclic compound that can be used in the present invention is
Preferably, the solubility product with the silver salt in water at 25°C is from 1()-10 to 1o18. More preferably, 10
It is preferably 10 or less.

This solubility product is determined as follows.

(Definition of solubility product) In a saturated aqueous solution of silver salt at 25°C, the concentrations (mo1/L) of silver ions and heterocyclic compound ions are respectively [
Ag''), [furnace], the solubility product of silver salt (Ksp)
Ha, Ksp=(:Ag”)XI:Xe] ChiLtuf
t6゜The nitrogen-containing heterocyclic compound of the present invention is not particularly limited as long as the solubility product is within the above range, but among those that can be preferably used are triazoles and benzotriazoles (for example, 5-methylbenzotriazole). , 5-nitrobencitriazole, 5-chlorobenzotriazole, 5-promobenzotriazole), benzimidazoles (e.g. 6-nitrobenzimidazole, 6-methylbenzimidazole, 2-methylbenzimidazole, 2-thiazoli Rubenzimidazole, 2
-thiazolylmethyl-benzimidazole), tetraazaindenes and mercaptotetraazaindenes (4-mercapto-6-methyl-1,3,3a).

7-tetraazaindene), mercaptotriazoles (e.g. 1-ethyl-2-mercapto-5-amino-1
, 3,4-triazole, 2-mercapto-5-amino-1,3,4-)riazole, 2-mercapto-5-acetamyt, 3,4-triazole, 1-methyl-
2-mercapto-5-acetamido-1,3,4-lyazole), tetrazoles, mercaptotetrazoles (e.g. 1-)uni-5-mercaptotetrazole, 1-(5-methylureidophenyl)-5-mercaptotetrazole, 1-ethyl-5-mercapto-1,2
, 3°4-tetrazole), mercaptothiadiazoles (e.g. 2-mercapto-5-amino-1,3,4-
thiadiazole), mercaptobenzimidazoles,
Mercaptobenzothiazoles, mercaptothiazolines, pyrimidines (e.g. 2-mercapto-4-methyl-6,6'-dimethylpyrimidine), indazoles (
Examples include M (5-nitroisoindazole), hybiloxyazinte 9-lysine, adenine, and the like. For details on how to calculate the solubility product and the values of individual compounds, see 1-The Theory of the Photog.
rapic Process, 4thEd JJam
eslFi (1977) pages 7-10.

The nitrogen-containing heterocyclic compound that can be used in the present invention is
It can be used by adding it to a silver halide photosensitive layer or a non-photosensitive layer. In this case, only the silver halide photosensitive layer
Alternatively, it may be contained only in the non-photosensitive layer, or it may be contained in both layers at the same time. Furthermore, multiple types of nitrogen-containing heterocyclic compounds may be used, and the combination may be changed in each photosensitive layer and non-photosensitive layer. Preferably, the effect of the present invention is further improved by containing it in the photosensitive layer.

There are no particular restrictions on the timing of addition of the nitrogen-containing heterocyclic compound of the present invention. In other words, when adding to the silver halide emulsion layer, it can be added at the time of silver halide emulsion grain preparation (at the time of grain formation, before chemical sensitization, during chemical sensitization, after chemical sensitization) or at the time of coating solution preparation. can. Preferably, a portion is added during emulsion grain formation and the remaining amount is added during preparation of the coating solution.

The amount added varies depending on the size of the solubility product of the silver salt of the nitrogen-containing heterocyclic compound, but it is approximately 1 part silver halide.
Preferably 1×lθ to 5810 mol per mol,
More preferably, it is 1X10 to 1X10"" moles.

When a plurality of nitrogen-containing heterocyclic compounds are used, it is preferable that the total thereof falls within the above range.

The coating silver amount of the silver halide photosensitive material of the present invention is 0.90 (
The amount of coated silver is 0.90 fi/r, preferably 17 m" or less, and particularly preferably 0.751/m2 or less
If the number is greater than n2, photographic fluctuations (maximum density fluctuations) due to continuous processing will be large, and the object of the present invention will not be achieved.

In the present invention, chlorine ions are added to the color developer by 3.5X.
10-" to 1.5X10"' is required to contain 1/L. Preferably 4x1O-2 to 1x10-1
Mol/L. Chlorine ion concentration is 1.5 x 10-
If it is more than 1 mol/L, it has the disadvantage of delaying development and lowering sensitivity, making it impossible to achieve the object of the present invention. Further, if the chloride ion concentration is less than 3.5×10''-2 mol/L, color mixture during processing increases, making it impossible to achieve the object of the present invention.

In the present invention, three bromine ions are simultaneously added to the color developer.
．． OX 10' ~1. It is necessary to contain 10-3 mol/L of OX. Preferably 5X10-'~5
X 10-'mol/L. Bromine ion? If the degree of III is more than 3 mol/L, development will be delayed, sensitivity will be low, and the maximum density will be lowered, making it impossible to achieve the object of the present invention. Also, the bromine ion concentration is 3. If OX 10'' is less than 5 mol/L, color mixture during processing will increase, making it impossible to achieve the object of the present invention.

In the present invention, both the chloride ion concentration and the bromide ion concentration must be within the concentration ranges mentioned above, and if either one falls outside this range, the purpose of the present invention will not be achieved. This is achieved by successfully balancing the development inhibitory effects of chlorine ions, bromide ions, and chlorine-containing heterocyclic compounds and the dissolution inhibitory effects of silver halide emulsion grains, resulting in fast development speed and high sensitivity. It is thought that the fluctuations in processing color mixture and color density were suppressed while maintaining the same.

Here, the chlorine ions and bromine ions may be directly added to the developer (or may be eluted from the photosensitive material in the developer).

When added directly to a color developer, chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and chloride. Preferred among these are sodium chloride and potassium chloride. It may also be supplied from a fluorescent brightener added to the developer. Bromine ion supply materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide,
Examples include thallium bromide and cerium bromide, of which potassium bromide and sodium bromide are preferred.

When eluting from the light-sensitive material in the developer, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from a source other than the emulsion.

In color light-sensitive materials, a yellow-cuffler-magenta coupler and a shea/coupler, which develop yellow-magenta and cyan colors respectively when pulled with an oxidized product of an aromatic amine color developer, are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide (In) conductors such as benzoylacetanilide and bivaloylacetanilide are preferred.

Among them, yellow couplers have the following general formula (Y-
Those represented by 1) and (Y-2) are preferred.

(Y-1) (Y-2) In the formula, X represents a hydrogen atom or a pulling-off group.

R21 represents diffusion resistance with a total carbon number of 8 to 32, and R22
is a hydrogen atom, one or more...rogen atoms, a lower alkyl group, a lower alkoxy group, or a total carbon number of 8 to 32
R23 represents a hydrogen atom or a substituent. When there are two or more R23's, they may be the same or different.

For more information on pivaloylacetanilide yellow couplers, see U.S. Pat. No. 4,622,287, No.
It is described in column 15, line 15 to column 8, line 39, and in column 14, line 50 to column 19, line 41 of the specification of 4,623,616.

For details on penzoylacetanili P-type yellow couplers, see U.S. Pat. No. 3,408,194;
No. 3,501, No. 4.846.575, No. 4,133
, No. 958, No. 4,401,752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include compound examples (Y-1) to (Y
-39), among which (Y-1)
, (Y-4), (Y-6), (Y-7),
(Y-15), (Y-21), (Y-22), (Y-
23).

(Y-26), (Y-35), (Y-36), (Y-3
7).

(Y-38), (Y-39), etc. are preferred.

Also, the first specification of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples (Y-1) to (Y-33) in columns 9 to 24 can be mentioned, among which (Y-2) and (Y-7).

(Y-8), (Y-12), (Y-20), (Y-21
).

(Y-23), (Y-29), etc. are preferred.

Other preferred examples include U.S. Patent No. 3.408,
Typical specific example (34) described in column 6 of specification No. 194
, Compound examples (16) and (19) described in column 8 of the same specification No. 3,933,501, and compound examples (9) described in columns 7 to 8 of the same specification No. 4,046,575 , 4.133
Compound example (1) described in columns 5 and 6 of the specification of No. 958
Compound Example 1 described in Column 5 of , No. 4,401,752. and the following compounds a) to h).

Among the above-mentioned couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

The magenta couplers used in the present invention include oil-protected couplers of indacylon type or cyanoacetyl type, preferably 5-pyrozolone type and pyrazoloazole type couplers such as pyrazotetratriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. Same 2nd.
No. 343,703, No. 2,600,788, No. 2
．． No. 908,573, No. 3,062,653, No. 3.152,896, No. 3,936.015, and the like. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
Preferred is the orio-ruthio group described in No. 1,897.

Further, the 5-pyrazolone coupler having two last groups, described in European Patent No. 73,636, provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 2,
Pyrazolobenzimidazoles described in No. 369,879, preferably pyrazolo(5,1-c)(1,2,4)) liazoles described in Mokukuni Patent No. 3,725,067, Research Disclosure 24220 (19
Pyrazolotetrazoles described in June 1984) and Research Disclosure 24230 (June 1984)
Examples include the pyrazolopyrazoles described in K. Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula (M-1)
, (M-2) or (M-3).

Here, R31 represents a diffusion-resistant group having a total carbon number of 8 to 32, and R32 represents a phenyl group or a substituted phenyl group. R33 represents a hydrogen atom or a substituent. Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring has a substituent (
fused rings) may also be useful.

x2 represents a hydrogen atom or a leaving group. For details of the substituents of R33 and the substituents of the azole ring, see, for example, U.S. Pat. No. 4,540,654, column 2, No. 4.
It is described in the 1st line to the 8th column, 27th line.

Among pyrazoloazole couplers, U.S. Pat.
The imidazo(1°2-b)pyrazoles described in US Pat. preferable.

In addition, pyrazolotriazole couplers 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 No. 61-65245, as described in JP-A-61-65246, A pyrazoloazole coupler containing a sulfonamide group in the molecule, JP-A-61-147254, a pyrazoloazole coupler with a wonderful alkoxyphenylsulfonamide parast group and a European patent (published)! Preference is given to using pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position as described in No. 226.849.

Specific examples of these couplers are listed below.

In the present invention, when using a 5-pyrazolone magenta coupler, more preferable results can be obtained by using a coupler having a leaving group represented by the following formula (I). By using this coupler within the scope of the present invention, it is possible to form an image with less color mixing during processing and less variation in maximum density.

(However, Ll and L2 represent methylene and ethylene groups.

1 and m represent O or 1. R1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R2 represents a group connected to A through a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. A represents a carbon atom or a sulfur atom. n represents 1 when A is a carbon atom, and represents 1 or 2 when A is a sulfur atom. B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. X represents an atomic group necessary to form a ring. R1 and R2 may be combined with each other to form a ring. When B is a carbon atom or a nitrogen atom, B and R2 may be bonded to each other to form a ring.

) Each substituent in general formula (1) will be explained in detail below.

Ll and L2 represent substituted or unsubstituted methylene or ethylene groups. Examples of substituents include halogen atoms, fluorine, chlorine, and alkyl groups (e.g., straight-chain and branched alkyls having 1 to 22 carbon atoms, aralkyl, alkenyl, alkynyl, cycloalkyl, and cycloalkenyl), and aryl groups (e.g., phenyl). , naphthyl), heterocyclic groups (e.g. 2-furyl, 3-pyridyl), alkoxy groups (e.g. methoxy, ethoxy, cyclohexyloxy), aryloxy groups (e.g. phenoxy, p-methoxyphenoxy, p-methylphenoxy), alkylamino groups (e.g. ethylamino, dimethylamino), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), carbamoyl groups (e.g. N,N-dimethylcarbamoyl), anisino groups (e.g. phenylamino, N-
ethylanilino), sulfamoyl group (e.g. N, N-
/j-tylsulfamoyl), alkylsulfonyl group (e.g. Id methylsulfonyl), arylsulfonyl group (e.g. tolylsulfonyl), alkylthio group (e.g. methylthio, octylthio), aIJ, -ruthio group (
For example, phenylthio, 1-naphthylthio), acyl group (
(e.g. acetyl, benzoyl), acylamino groups (e.g. acetamide, benzamide e), imide groups (e.g. cono-phosphoric acid imide, phthalic acid imide), ureido groups (
e.g. phenylureido, N,N-U butylureide)
, sulfamoylamino group (e.g. N,N-dipropylsulfamoylamino), alkoxycarbonylamino group (e.g. methoxycarbonylamino), sulfo/amide 9 group (e.g. methanesulfonamide 9, etc.), hydroxyl group, cyano group, etc. may have. Preferred are unsubstituted methylene and ethylene groups. 1 and m&maO or 1
, preferably 0.

R1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Specifically, hydrogen atoms, straight chain and branched alkyl groups having 1 to 22 carbon atoms, alkyl groups such as alkenyl groups and cycloalkyl groups, aryl groups such as phenyl groups and naphthyl groups, or 2-furyl, 2-thienyl, Represents a heterocyclic group such as 2-pyrimidinyl and 4-pyridyl group. These may further have substituents defined in Ll and Ll. Preferably R1 is a hydrogen atom or an alkyl group.

R2 represents a group connected to A through a carbon atom, oxygen atom, nitrogen atom or sulfur atom. Specifically, groups linked via carbon atoms such as alkyl groups, aryl groups, heterocyclic groups (linked at carbon atoms), acyl groups, alkoxycarbonyl groups, and carnoflexyl groups; alkoxy, aryloxy, etc. Groups linked via an oxygen atom; groups linked via a nitrogen atom such as an alkylamino group, anilino group, acylamino group, ureido group, sulfamoylamine group, alkoxycarbonylamino group, sulponamide group; and an alkylthio group, arylthio group, etc. Represents a group linked by a sulfur atom. Similar to R1, these may further have substituents defined in Ll and Ll. Preferably R2 is an alkyl group, an aryl group, an alkylamino group and an anilino group.

A represents a carbon atom or a sulfur atom, preferably a carbon atom.

n represents 1 when A is a carbon atom, and represents 1 or 2 when A is a sulfur atom.

B represents a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom, preferably a carbon atom or a nitrogen atom,
More preferably, it represents a carbon atom.

X represents an atomic group necessary to form a ring.

Preferably, it represents an atomic group composed of atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, or sulfur atoms necessary to form a saturated or unsaturated 5-, 6-, or 7-membered ring. More preferably, it represents an atomic group composed of atoms selected from carbon atoms, oxygen atoms, and nitrogen atoms necessary to form an unsaturated 5- or 6-membered ring. This ring may further have a fit substituent defined for Ll and Ll described above, or another ring may be fused to the ring containing X.

R1 and R2 may be bonded to each other to form a ring, preferably a 5- or 6-membered saturated or unsaturated ring. In addition, these frostings further have substituents defined in Ll and Ll.

When B is a carbon atom or a nitrogen atom, B and R-V4↓ may be combined with each other to form a ring (preferably 5 or 6
A saturated or unsaturated membered ring may be formed. More preferably, a 5- or 6-membered saturated ring may be formed. Further, on these rings, substituents defined in Ll and Ll may be added.

A first preferred pyrazolo/coupler can be represented by the following general formula.

In this hole, Yl represents Ra or ZXRb.

Ra represents a substituted or unsubstituted aryl or a substituent having a Re heterocyclic group and a Re secondary or tertiary group represented by -(CHz)z-C-Ra; 1 is O or 1;
represents.

Zl represents an oxygen atom, a sulfur atom or NRf.

Rb represents a substituted or unsubstituted alkyl, aryl or heterocyclic group. Re, Ra is a halogen atom, Rb
and Z2Rg. Re represents a hydrogen atom or a group defined by RO, R (l,
Rf represents a hydrogen atom and a group defined by Rb. z
2 represents an oxygen atom, a sulfur atom, or NRh. Rg represents the group defined by Rf.

Rh represents a group defined by Rf. Re may be combined with at least one of Ra and Re to form one or two carbocycles or heterocycles (which may further have a substituent, R1, X and B are the above-mentioned substituents of,
Synonymous with atomic group and atom.

R3 is an anilino group, an acylamino group, or a ureido group.

carnomimoyl group, alkoxy group, aIJ /I/ odP? , /fulvonyl group, alkoxycarbonyl group or N-heterocyclic group, preferably these groups contain an oil-solubilizing group. R4 is a substituted or unsubstituted aryl group, preferably a substituted phenyl group, and more preferably a 2,4,6-dolychlorophenyl group.

A more preferred pyrazolone coupler of this type can be represented by the following general formula.

In this hole, R1, R3, R4, Rc, Ra,
Re, X and B have the same meanings as the above substituents. 1 is O
Or represents 1.

A second preferred pyrazolone coupler can be represented by the following general formula.

Nine NHR.

In this crest, R5 represents a substituted or ii-substituted alkyl, aryl or heterocyclic group. R1, R3,
R4, X and B have the same meanings as the substituent atomic groups and atoms described above. Preferably, R3 is a group represented by -NH-Y2, and R4 is a 2,4,6-dolychlorophenyl group. Y2 represents a substituted or unsubstituted aryl, arylcarbonyl or arylaminocarbonyl group.

A third preferred pyrazolone coupler can be represented by the following general formula.

In this pattern, R1, R3, R4 and X have the same meanings as the substituents and atomic groups described above. Y3 represents a substituted or unsubstituted methylene, ethylene group or \/NRf. Preferred pyrazolone couplers (in this general formula in which Rf has the same meaning as the substituent described above) can be represented by the following general formula.

In this pattern, R1, R3 and R4 have the same meanings as the substituent groups described above. R6 and R7 represent an alkyl group and an aryl group, and R8 represents a substituent defined for L1 and R2 above. D represents a methylene group oxygen atom, nitrogen atom or sulfur atom. n' represents an integer from O to 2 in the case of a methylene group, but represents 1 in other cases. p represents an integer from 0 to 3.

In the following, the term "coupler part" refers to the part excluding the pull-off group, and the term "coupler" refers to the whole including both the coupler part and the pull-off group.

"Coupler moieties" are pyrazolone couplers well known and used in the photographic industry that react with oxidized color developing agents to form dyes, particularly magenta dyes. Examples of preferred pyrazolone carab moieties include, for example, US Pat. No. 4,413,054.

4.443,536, 4,522,915, 4,336.325, 4.199.361, 4
, No. 351,897, No. 4.385,111, JP-A-60-170854, No. 60-194452, No. 6
No. 0-194451, U.S. Patent No. 4,407,936,
No. 3,419,391, No. 3,311,476, British Patent No. 1.357,372, US Patent No. 2,6 Q O
, No. 788, No. 2.908,573, No. 3,062,
No. 653, No. 3,519,429, No. 3,152,8
No. 96, No. 2,311,082, No. 2,343,70
3 and 2,369,489 or the inventions cited in these patents. In these patents, when a pyrazolone coupler is partially substituted with a pulling-off group, they can be replaced by a pulling-off group represented by the general formula (I) of the present invention. The pyrazolone couplers of the present invention can also be used in combination with other pyrazolone couplers such as those described in the above-referenced patents.

An example of a preferred "coupler moiety" can be represented by the following general formula.

RIO In this emblem, Q represents a pull-off group of the invention. R9 represents anilino, acylamino, ureido, carbamoyl, alkoxy, allyloxycarbonyl, alkoxycarbonyl or N-heterocyclic group. R.I.
O is a substituted or unsubstituted aryl group, preferably having at least one substituent selected from the group consisting of no-rogen atom, alkyl, alkoxy, alkoxycarbonyl, acylamino, sulfamide 9, sulfonamide 9, and cyano group. It is a phenyl group. The carbon atoms and nitrogen atoms of these substituents may be unsubstituted or substituted with groups that do not reduce the effect of the coupler. R9 is.

Preferably it is an anilino group, more preferably an anilino group represented by the following general formula.

In this pattern, R11 is an alkoxy group having 1 to 30 carbon atoms, an aryloxy group, or a halogen atom (preferably a chlorine atom).

R12 and R13 are a hydrogen atom and a hydrogen atom (
For example, chlorine atom, A atom, fluorine atom), alkyl group (e.g. alkyl group having 1 to 30 carbon atoms), alkoxy group (e.g. alkoxy group having 1 to 30 carbon atoms), acylamino group, sulfonamide group, sulfamoyl group group, sulfamyl-"M, carbamoyl group, diacylamino group, aryloxycarbonyl group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group,
It represents an alkanesulfonyl group, an arenesulfonyl group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a purkyl group, an acyl group, a nitro group, and a carboxy group. For example, R12 and R13 may each be a hydrogen atom or a ballast group.

RlQ is preferably a substituted phenyl group. Examples of substituents include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), alkyl groups having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, propyl group, t-butyl group, tetradecyl group), and 1 to 22 carbon atoms. -22 alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy), carbon number 1-2
3, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tetradecyloxycarbonyl group), an acylamino group (for example, an α-[3-pentadecylphenoxybutyramide group) and/or a cyano group. RIO is more preferably 2.4.6-)
! J is a dichloroenyl group.

More specifically, R12 and R13 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), straight chain or branched alkyl groups having 1 to 30 carbon atoms (e.g. methyl group, Fluoromethyl group, ethyl group, t-butyl group, tetradecyl group), carbon number 1-3
0 alkoxy groups (e.g. methoxy group, ethoxy group, 2
-ethylhexyloxy group, tetradecyloxy group),
Acylamino groups (e.g. 3 acetamide groups, 9 benzamide groups, butyramide groups, 9 tetradecanamide groups, α
-(2,4-di-t-pentylphenoxy)acetamide group, α-(2,4-di-t-tylphenoxy)butyramide group), α-(4-hydroxy-3-t-butylphenoxy)tetradecane amide 9 groups, 2-oxo-
pyrrolidin-1-yl group, 2-oxy-5-tetradecyl-pyrrolin-1-yl group, N-methyltetradecanamide group, t-butylcarbonamide group), sulfonamide group (e.g. methanesulfonamide group, -zenesulfone Amido group, p-) Luenesulfonamide group, p-)
"Decylbenzenesulfonamide 9 groups, N-methyltetradecylsulfonamide 9 groups, hexadecane sulfonamide group), sulfamoyl-d (e.g., ttfN-methylsulfamoyl group, N-hexadecylsulfamoyl group, N, N -dimethylsulfamoyl group, N-[3-
()'7' syloxy)furobyl]sulfamoyl group,
N-[4-(2,4-di-t-pentylphenoxy)phthyl]sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, N-)"7'silsulfamoyl group), sulfamide group (e.g. N-methylsulfamide group, N-octadecylsulfamide group), carbamoyl group (e.g. N-methylcarbamoyl group, N-octadecylcarbamoyl group, N-C4-(2,4-:)-t - is methylphenoxy)butyl]carbamoyl group, N-meth
Leu N-tetradecylcarbamoyl, l,N.

N-dioctyl moyl group), diacylamino group (e.g. N-succinimide group, N-phthalimide group,
2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, N-acetyl-N-)Fdecylamino group), aryloxycarbonyl group (e.g. phenoquinecarbonyl group, p-) "decyloxyphenoxycarbonyl group), carbon a2-30
alkoxycarbonyl groups (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, dodecyloxycarboel group), alkoxysulfonyl groups having 4 to 30 carbon atoms (e.g. methoxysulfonyl group, octyloxysulfonyl group) group, tetradecyloxysulfonyl group, 2-ethylhexyloxysulfonyl group), aryloxysulfonyl group (e.g. evaphenoxysulfonyl group, 2.4-
di-t-pentylphenoxysulfonyl group), carbon number 1
-3o alkanesulfonyl group (e.g. evamethanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexadecanesulfonyl group), arenesulfonyl group (e.g. hahenzenesulfonyl group, 4-nonylbenzenesulfonyl group, p-) luenesulfonyl g), alkylthio group having carbon a1 to 22 (e.g. ethylthio group,
octylthio group, benzylthio group, tetradecylthio group, 2-(2゜4-di-t-pentylphenoxy)ethylthio group), arylthio group (e.g. phenylthio group,
p-tolylthio group), alkoxycarbonylamino group (
For example, ethoxycarbonylamino group, indyloxycarbonylamino group, hexadecyloxycarbonylamino group), alkyl fret group (for example, N-methylureido group, N,N-dimethylureido group, N-methyl-
N-dodecylureido 9 groups, N-hexadecylureide P
group, N,N-dioctadecylureido group, N,N-dioctyl-N'-ethylureido group), acyl group (e.g. acetyl group, penzoyl group, octadecanoyl group, p
-r decanamide 9bency group, cyclohexanecarbonyl group), nitro group, cyan group, and carboxy group.

More specifically about the alkoxy group and aryloxy group of R11, the alkoxy group includes methoxy group, ethoxy group, propoxy group, butoxy group, 2-methoxyethoxy group, filtrate-butoxy group, hexyloxy group, and 2-ethylhexyloxy group. , I, 2-(2゜4--)-t-pentylphenoxy)ethoxy group, 2-dodecyloxyethoxy group, aryloxy group is phenoxy group, α or β-
These are naphthyloxy group and 4-tolyloxy group.

- A monomer containing a pyrazolone coupler having a leaving group (I) is co-polymerized with an oxidation product of an aromatic-grade amine developer and a non-pulling non-chromogenic ethylene-like monomer. You may also make

Acrylic acid, α
-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid) and esters or amides derived from these acrylic acids) J (e.g. acrylamide, n-butylacrylamide 9, t-butylacrylamide 9, diacetone acrylamide 1) , methacrylamide 1, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate.

t-butyl acrylate, 1θ0-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide , vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its x-conductor, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid , citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. buerethyl ether), maleic acid, m-water maleia #maleate, N-bu, L/-2-pyrrolidone, N-vinylpyridine, and Examples include 2- and 4-vinylpyridine. Two or more types of the non-color-forming ethylene-like uncelled monomers used here can also be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide 9, etc.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers are based on the physical and/or chemical properties of the copolymer formed. For example, solubility, photographic colloid)
* The binder of the composition can be selected such that its compatibility with, for example, gelatin, its flexibility, thermal stability, etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler ditex is particularly preferred.

For a long time, the compound represented by the general formula (I) and pulling'#degrouping (
Specific examples of Q) will be shown, but the invention is not limited to these.

Q-2) Q-3) Q-29) C4H0(t+ NH302C16H33(nl (n) ext(2s UM3) Next, specific examples of the coupler of the present invention will be shown, but the coupler is not limited thereto.

This (M-1) H3 Q-56) Q-57) Q-58) (M-3) H3 (M-5) (M-6) (M-7') (M-12) (M-13 ) H3 C/ H3 l H3 C/ H3 J (M-8) (M-16) H3 Shig (M-17) (M-23) 2H5 (M-20) (M-21) (M-22) (M-26) (M-27) (M-28) C/ (Je Shig lI H3 2H5 (M-32) (M-38) (M-40) H3 l (M-42) (M- 43) C/ (M-44) (M-46) CH3 H3 (M-53) (M-59) (M-62) H3 l (M-63) 6g (M-64) C,1 of the present invention The magenta coupler usually has IX 10=mol to 1 mol per mol of silver halide, preferably lXl
It can be used in the range of 0 mol to 8X10 mol. The coupler of the present invention can also be used in combination with other magenta couplers.

The magenta coupler addition layer of the present invention may be any silver halide emulsion layer, but is preferably a green-sensitive silver halide emulsion layer. The silver filtration rate used in this green-sensitive silver halide emulsion MK is preferably 0.1-0.31/m.

The magenta coupler of the present invention is certified as International Publication 4i (PCT).
It can be synthesized by the method described in WO88104795 or according to it.

As cyan couplers, phenolic cyan couplers and naphthol cyan couplers are the most popular.

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518,687, No. 4.51
As described in No. 1,647 and No. 3,772,002, etc.
There are compounds (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position; typical examples include Canadian Patent No. 625,
Coupler of Example 2 as described in '822, U.S. Pat. No. 3,7
Compound (1) described in No. 72,002, No. 4,564,
Compounds (1-4) and (1-5) described in No. 590, compounds (1) and (2) described in JP-A-61-39045,
(3) and c! i, Compound (C-2) described in 62-70846-1tK.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772,162, No. 2,895,826, No. 4.
No. 334,011, No. 4,500,653 and JP-A-5
The 2,5-diacylaminophenol coupler described in U.S. Pat. Compound αη, 4.56
Compound (2) and α-ri described in No. 5,777, No. 4.12
Compound (4) described in No. 4,396, No. 4,613,5
Examples include the compound (1-19) described in No. 64.

As a phenolic cyan coupler, U.S. Pat.
, No. 372,173, No. 4,564,586, No. 4.
430,423, Japanese Patent Application Laid-open No. 61-390441, and Japanese Patent Application No. 61-100222, there are compounds in which a nitrogen-containing heterocycle is condensed with a phenol nucleus. , 327,173, the compound (3) and α9 described in 4,564,586, and the compound (Riya (3)) described in 4,430,423. , and the following compounds.

l 6t11a (nl In addition to the above-mentioned cyan couplers, diphenylimidazole cyan couplers described in European Patent Application Publication EP O, 249,453A 2 can also be used. Other phenolic cyan couplers include those described in U.S. Patent No. 4 ,3
No. 33,999-, No. 4,451,559, No. 4.4
No. 44,872, A, No. 427,767, No. 4,57
9.813Ishi8, European Patent (EP) 067,689
There are ureide couplers such as B1, etc., and typical examples include U.S. Patent No. 4,333,
Coupler (7) described in No. 999, No. 4,451,55
Coupler (1) described in No. 9, coupler a described in No. 4,444,872, coupler (3) described in No. 4,427,767, coupler described in No. 4,609,619. (6) and Coupler (1) and αυ described in 4.579,813, European Patent No. (EP) 067,
Lord Kapler and 6I described in 689 B 1, JP-A-6
Examples include coupler (3) described in No. 1-42658.

Examples of naphthol-based uncoupler include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2.3t3.5s6).
, those having an alkylcarbamoyl group at the 2-position (e.g., U.S. Pat. Nos. 2,474,293 and 4,282,312), those having an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523-1983), Those having a carbonamyl or sulfonamide group at the 5-position (e.g., JP-A-60-2
No. 37448, No. 61-145557, No. 61-15
No. 3,640), those with aryloxy leaving groups (e.g., U.S. Pat. No. 3,476,563), and those with substituted alkoxy leaving groups (e.g., U.S. Pat. No. 4,296,199).
No.), those with a glycolic acid leaving group (e.g.
〇-39m No. 17).

These couplers can be contained in the dispersed emulsion layer in the presence of at least one type of high-boiling organic solvent. Preferably, a high-boiling organic solvent represented by the following formula (At or Di) is used.

Formula (A) Wl Formula (B1 wl-coo-w2 Formula (Q Wl and W2 may form a fused ring).

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification No. 137, lower right column ~ 14
It is written in the upper right column of page 4. Other types of high boiling organic solvents that may be usefully used in the couplers of the present invention include N,N-dialkylaniline derivatives. Among these, those in which an alkoxy group is bonded to the ortho position of the nuclear N,N-dialkylamino group are preferred. Specific examples include the following compounds.

Formula (D) Wl-〇-W2 (where Wl, W2 and W3 each represent an h-substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W4 is Wl,
represents OWl or 5-Wl, n is an integer from 0 to 5, and when n is 2 or more, W4 may be the same or different from each other, - In Monana ■, this type of high boiling point organic solvent is (Processing color print on white background over time)
It is also useful for preventing the occurrence of magentastin and also for preventing capri due to development. This usage is generally 10 mol% to 500 mol% per coupler,
Preferably, it is in the range of 20 mol % to 300 mol %.

These couplers can also be synthesized with rhodapul latex polymers (
For example, the hydrophilic colloid can be emulsified and dispersed in a water bath by impregnating it with a water bath (eg, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are used, and the use of acrylamide 0-based IJ polymers is sometimes preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

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
-Hindered phenols, mainly human 90-oxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols,
Typical examples include gallic acid derivatives, methylene dioxybenzenes, amine phenols, hindered amines, and monoter or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)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:

Hyde-90quinones are disclosed in U.S. Patent Nos. 2,360,290, 2,418,613, and 2,700,453.
No. 2,701,197, No. 2,728,65
No. 9, No. 2,732,300, No. 2,735,7
No. 65, No. 3,982,944, No. 4,430,
No. 425, British Patent No. 1,363,921, U.S. Patent No. 2,710,801, U.S. Patent No. 2,816,028, 6-human 90-oxychromans, 5-human 90-oxycoumarans, spirochromans. is U.S. Patent No. 3.432
, No. 300, No. 3,573,050, No. 3.57
No. 4,627, No. 3,698,909, No. 3.7
No. 64,337, JP-A-52-152225, etc.
Spiroindans are disclosed in U.S. Patent No. 4,360,589K.
, p-alkoxyphenols are disclosed in U.S. Patent No. 2.735.
, 765, British Patent No. 2,066,975, JP-A-59-10539, JP-A-57-19765, etc., and Hifdatephenols are disclosed in U.S. Patent No. 3,700,4.
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,2
No. 28,235 and Japanese Patent Publication No. 52-6623, etc., and gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent Nos. 3,457,079 and 4,332,886, respectively. Special Public Service No. 56-21144
Hindered amines are disclosed in U.S. Patent No. 3,336.
, No. 135, No. 4.268,593, British Patent No. 1
．． 32 889, 1,354,313, 1
, No. 410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-114.036, Japanese Patent Publication No. 59-53846.

No. 59-78344, etc., and ether and ester derivatives of phenolic hydroxyl groups are disclosed in U.S. Patent No. 4.155,76.
No. 5, No. 4,174,220, No. 4.254,2
No. 16, No. 4,264,720, Japanese Unexamined Patent Publication No. 54-14
No. 5530, No. 55-6321, No. 58-10514
No. 7, No. 59-10539, Special Publication No. 57-37856
No., U.S. Patent No. 4,279,990, Special Publication No. 1973-3
No. 263, etc., and metal complexes are disclosed in U.S. Patent No. 4.050,9.
No. 38, No. 4,241,155, British Patent No. 2,0
27,731 (Respectively described in No. At, etc.) These compounds can be used to achieve the desired purpose by co-emulsifying the corresponding color coupler with the coupler and adding it to the photosensitive layer in an amount of usually 5 to 100% by weight. In order to prevent deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the above antifading agents, spiroindanes, hindered amines, and the like are particularly preferred.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers.

That is, compounds that chemically combine with aromatic amine developing agents remaining after color development processing to produce chemically inert and substantially colorless compounds and/or aromatic amines remaining after color development processing. Using Compound 0, which chemically combines with the oxidized form of a color developing agent to produce a chemically inert and substantially colorless compound, simultaneously or singly can reduce residual color development in the film during storage after processing, for example. This is preferable in order to prevent the generation of stain and other side effects due to the formation of colored pigments due to the reaction between the developing agent or its oxidized product and Kab2-.

A preferred compound has a second-order reaction rate constant with p-anisidine of 2 (in trioctyl phosphate at 80°C) and 1. OA'/mo〕+sec IX 1O-5
It is a compound that reacts in the range of J/mol/sec. Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

If k2 is greater than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow (as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention. .

A more preferable compound (g) can be represented by the following general formula (FI) or (Fn).

General formula (FI) R1-(A)n-X General formula (FII) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 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,
Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn). Here R1
and 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 residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (FI) and (Fn), see JP-A-63-158545 and JP-A-62-28.
No. 3338, Patent Application No. 158342-1982, Patent Application No. 1983
It is described in specifications such as No.-18439.

On the other hand, more preferable compounds ρ) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are as follows: ).

General formula (GI) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. 2 represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. - Compounds represented by GI) have Z of Pcarson's nucleophilicity n0H3I value (
R.G., Pcarson, et al., ,J.
Am.

Chem, Soc, 90, 319 (1968))
is preferably 5 or more, or a group derived therefrom.

- For specific examples of compounds represented by Monka (CI), see European Patent Publication No. 255722, JP-A-62-1430.
No. 48, No. 62-229145, patent application No. 63-184
No. 39, No. 63-136724, No. 62-21468
No. 1, No. 62-158342, etc.

Further, details of the combination with the above-mentioned compound O) and compound (F') are described in Japanese Patent Application No. 18439/1983.

Similarly, it is preferable to use an amine compound in order to prevent the occurrence of staining and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film during storage after processing and the coupler. A particularly preferred amine compound can be represented by the following symbol (FG).

- Monana (FC) ROOROI \N/ O2 In the formula, ROO is a water-based atom, hydroxy group, alkoxy group, acyloxy group, sulfonyloxy group, substituted or unsubstituted amino group, alkoxy group, aryloxy group, heterocyclic oxy group , represents an aliphatic group, an aromatic group, an aromatic group and a heterocyclic group. ROI represents a hydrogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. RO2 represents an aliphatic group, an aromatic group and a heterocyclic group. Here Roo, R
Both OI and RO2 groups may be bonded to each other to form a monocyclic or multicyclic heterocycle.

- For specific examples of compounds represented by FG, see U.S. Patent No. 4,483,918 and U.S. Pat.
No. 79, No. 4,585,728, JP-A-58-10
No. 2231, No. 59-229557, etc.

The photosensitive material produced 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 azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid 9 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 also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Weiss, The Macromolecule Chemistry of Gelatin (Academic Press, 1964) K.

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For the purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example: lighter paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with reflective layers or reflective materials, such as glass plates, polyesters such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate. Films, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins, etc. are used, and these supports can be appropriately selected depending on the purpose of use.

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

The occupied area ratio (ch) 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 dividing the fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (Rx). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation θ of R1 to the average value (R) of R1. The number of target unit areas (,) is preferably 6 or more. Therefore, the coefficient of variation a/R can be determined.

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

The color developer used in the present invention will be explained in detail.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "substantially free" means that the concentration of benzyl alcohol is preferably 2 ml/l or less, more preferably 0.5 ml/l or less, and most preferably, it does not contain any benzyl alcohol. .

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and also has the effect of dissolving K, silver halide, and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of 3.0 x 10 mol/l or less, and most preferably no sulfite ion at all.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain human 90-xylamine. this is,
This is because human 90xylamine functions as a preservative for the developing solution and at the same time has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The term "substantially free of hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10 mol/l or less, and most preferably no human 90 xylamine at all.

The developer used in the present invention preferably contains an organic preservative in place of the human-90xylamine and sulfite ions, from the standpoint of suppressing fluctuations in photographic properties and color mixing during continuous processing.

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. In other words, it is an organic compound that has the function of preventing the oxidation of color developing agents by air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine (the same applies hereinafter)), hydroxamic acids, human 9 radines, and hydrazides 9 , phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines Particularly effective organic preservatives include the following:
No. 61-165621, No. 61-188619, No. 61-197760, No. 61-186561, No. 6
No. 1-198987, No. 61-201861, No. 61
-186559, 61-170756, 61-
It is disclosed in US Pat. No. 188742, US Pat. No. 61-188741, US Pat. No. 3,615,503, US Pat.

Regarding the preferred organic preservative, its general formula and specific compounds are listed below, but the present invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
5 mol/l to 0.5 mol/l, preferably 0.03 mol/l to 0.1 mol/l! It is desirable to add it to a concentration of .

Particularly preferred is the addition of hydroxylamine derivatives and/or hirazine derivatives.

The hydroxylamine derivative is preferably one represented by the following general formula (I).

General Formula (I) R11-N Hf2 In the formula, R11 and R12 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. Hfl and R12 do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with a nitrogen atom. , the ring structure of the heterocycle is a 5- to 6-membered ring, a carbon atom, a hydrogen atom, a halogen atom, an oxygen atom,
It is composed of nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R11 and R12 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly 1 to
5 is preferred. The nitrogen-containing heterocycle formed by connecting R11 and R12 includes a piperidyl group, a pyrolisilyl group,
Examples include N-alkylpiperazyl group, morpholyl group, indolinyl group, and benztriazole group.

Preferred substituents for Hil and R12 are hydroxy, alkoxy, alkyl or arylsulfonyl, amide, carboxy, cyano, sulfo, nitro and amine groups.

Compound examples C2H6-N -C2H5 OH ■-2 OH3QC2H, -N -C2H, -OCH3OH C2H5QC2H, -N -0H2-OH= OH2H to HOH Human 9 radins and human rats:) The following are preferable as the humans. .

General formula (II) In the formula, R31, R32, and R33 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R34 represents a human 90x group, a hydroxyamino group,
Substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group,
Represents an amine group. The heterocyclic group may be a 5- to 6-membered ring composed of A, G, Hlo, N, S, and a halogen atom, and may be either saturated or unsaturated. X31 is -c
o--5o2-O or 1. Especially at n-00, R3
4 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R33 and R34 may jointly form a petero ring.

In the general formula (I[), R31, R32, ) (33 is preferably a hydrogen atom or an alkyl group of 01 to C'IO, and most preferably R31 and R32 are hydrogen atoms.

- In Monka (II), R34 is an alkyl group, an aryl group,
7/L/koxy group, carbamoyl group, and amino group are preferred. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl group here include a carboxyl group, a sulfo group, a nitro group, an amine group, a phosphono group, and the like. X31 is preferably -Co- or -502-, most preferably -.

(Compound example) [-2 NH2NH-fCH2-3-5o3H NH2NH÷OHz+20H ■-4 [-6 NH2NH3O3H3 [-7 NH2NHC:○OC2H5 ]l-12 NH2NH3O3H ■-13 NH NHNHC:NH2 ■-14 NHNH C:0CONHNH2 [ -15 NH2NHCH20H2CH2So3H ■-16 -1O NH1tHCONH2 ■-11 ■-17 NH2NH3HCOOH C4H9 (nl l-18 NH2NHCH20H2COOH ■-19 ■-20 Su ■-22 The above - Compound shown by Monna (I) or (ID) and the following −
It is more preferable to use amines represented by In or IV in combination in terms of improving the stability of the color developer and, more particularly, improving the stability during continuous processing.

General formula (III) R71+ N -R73 In the formula, R71, R72, and R73 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group. Here, R and R, R71 and R73, or R72 and R73 may be linked to form a nitrogen-containing heterocycle.

Here, R71, R72 and R73 may have a substituent. R71, R72, and R73 are particularly preferably a hydrogen atom or an alkyl group. Further, examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nido tetragroup, an amino group, and the like.

(Compound example) 1l-1 N÷CH2CH20H)3 1l-2 H2NCH2CH2oH 1l-3 HN% 0H20H20H) 2H C7H1,N(OH2CHCH20H) 2[1-6 III-7 -1l HN+CH2C○0H)2 HooccH,aH 2cHcooH H2 1[-13 H2NCH2CH2SO2NH2 ■-14 [11-9 ■-10 (HOCH2CH2+2NCH2CH2SO2CH3H
2N-C+CH20H)2 ■-16 HOCH2CHCOOH H2 In-17 CH3 ■-18 Among general formulas (IV), particularly preferred ones are general formulas (I
V-a), (IV-1)').

■-19 ll-20 General formula (IV) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and R and R represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group. .

Here, R1 and R2 may be the same or different.

In the formula, Xl represents 〉N or )OH. R1 and R2 are defined in the same way as in general formula (tV), and R3 is R1,
Represents the same group as R2 or -CH.8-.

In general formula (IV-a), Xi is preferably N. The number of carbon atoms in R1, R2, and R3 is preferably 6 or less, more preferably 3 or less, and most preferably 2.

Preferably, R1, R2, and R3 are an alkylene group or an arylene group.

In the formula, R1 and R2 are defined as in general formula (IV).

In general formula (IV-b), the number of carbon atoms in R1 and R2 is preferably 6 or less. R1 and R2 are preferably an alkylene group or an arylene group, most preferably an alkylene group.

Among the compounds of the general formulas (IV-I!L) and (IV-1)), the compound represented by -Monken (IV--) is particularly preferred.

■-1 ■-5 ■-6 ■-7 IV-2 IV-8 IV-3 IV-9 IV-4 ■-10 IV-15 ■-11 H ■-12 ■-16 ■-17 ■-13 ■ -18 ■-14 The organic preservatives mentioned above can be obtained as commercially available products.
It can also be synthesized by the method described in No. 74 and the like.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

A preferred example is p-phenylenediamine derivative Teary, and representative examples are shown below, but the invention is not limited thereto.

D-1N, N-diethyl-p-7 22-diamine D-
22-amino-5-diethylaminotoluene D-32-
Amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl-N-(β-hydroxyethyl)aminecoaniline D-52-methyl-4-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N-[β
-(methanesulfonamide 9)ethylcouaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide 9 D-13N,N-)methyl-p-phenyl diamine D
-94-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-, N-[β-
(methanesulfonamido)ethylcouaniline (exemplified compound D-6).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, salivary sulfate, and p-)luenesulfone salt. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 to about 20.9.
More preferably about 0. i to about 10.9.

The color developer used in the present invention preferably has a pH of 9
-12, preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate/hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, quanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, charcoal W1 salt, phosphate, tetraborate, and human 90-xybenzoate have a low solubility and a pH of 9.
These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or higher, having no adverse effect on photographic performance (such as capri) when added to color developers, and being inexpensive. It is particularly preferable.

Specific examples of these buffers include carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate ( sodium salicylate), potassium 0-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Examples include sodium sulfosalicylate), potassium 5-sulfo-2-human 90-xybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/l.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, 1,2 -diaminopronoξnetetraacetic acid, glycol ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylene diamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-) 1) Carboxylic acid, 1-hydroxyethylide 7-1. 1-diphosphonic acid, N,N/-bis(2-hydroxyamino/L/)ethylenediamine-N,N/-diacetic acid Two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient to sequester metal ions in the color developer. For example, IE
Hit 0. The IJ is about 109.

Any development accelerator may be added to the color developer, if necessary. However, it is preferable that the color developer of the present invention does not substantially contain glycerin alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that the developer contains less than 2, preferably no at all, per liter of developer.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3.
813,247, etc., p-7-nylene diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, and JP-B-Sho 44-30074. , JP-A-56'-156826 and JP-A-52-43429, etc., quaternary ammonium salts, U.S. Pat.
, No. 494,903, No. 3,128,182, No. 4.
No. 230,796, No. 3,253,919, Special Publication No. 4
No. 1-11431, U.S. Patent No. 2,482,546,
Amine compounds described in 2.596,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3,128,183
Polyalkylene oxides shown in Japanese Patent Publication No. 11431/1983, Japanese Patent Publication No. 42-23883, and U.S. Pat. It can be added accordingly.

In the present invention, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, 6-nitroin intasole, 5-nitroin intasole,
5-methylincitriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-(zuimidazole, 2-thiazolylmethyl-
Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, human 30-xiazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4.4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 fi/l, preferably 0. LIA
It is 41/l.

Moreover, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20-50'C, preferably 30-40'C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but the amount of replenishment is 20 to 600WLt (1rrL2 equivalent of photosensitive material)
is suitable, preferably from 50 to 300. More preferably 60TrLl to 200Tnl, most preferably 60-150WLl.

Next, the desilvering step in the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained below.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular, an organic complex salt of iron Preferred are acids, complex salts of aminopolyphosphonic acids, phosphonocarboxylic acids, organic phosphonic acids, etc.) or organic acids such as citric acid, tartaric acid, malic acid; overflow #1 base salts; hydrogen oxide, etc.

Among these, organic complex salts of iron@) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, organic phosphonic acids, or salts thereof useful for forming organic complex salts of iron(2) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1°3-diaminopronoacetic acid, etc. tetraacetic acid,
Propylenediaminetetraacetic acid, nitrilotriacetic acid, Schifftetrahexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid.

Glycol ether diamine tetraacetic acid, etc. can be mentioned. These compounds include sodium, potassium,
Either thirium or ammonium salt may be used. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
, 3-diaminopronocenetetraacetic acid, and methyliminodiacetic acid complex salts are preferred because they have a high bleaching edge. These ferric ion complex salts may be used in the form of complex salts, or as ferric ion complex salts.
Iron salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, phosphorus r! A ferric ion complex salt may be formed in a solution using R ferric or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form a ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is preferably 0.01 to 1.0 mol/l,
(C is 0.05 to 0.50 mol/l.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 5630, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea compounds described in No. 35, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalogenating agent such as ammonium iodide) or an iodide (eg, ammonium iodide) can be included.

If necessary, one or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. It is possible to add isoic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, ie, a thiosulfate salt such as sodium thiosulfate or ammonium thiosulfate.

Thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid,
Thioether compounds such as 3,6-cythia-1,8-octanediol and water-soluble silver halide solubilizers such as thioureas can be used alone or in combination of 281 or more. Also, JP-A-55-1
A special bleach-fixing solution consisting of a combination of the fixing agent described in No. 55354 and a large amount of a halide such as potassium iodide can also be used. In the present invention,
Preferably, the ammonium thiosulfate salt is used for %thiosulfate. The amount of fixing agent per gram is preferably 0.3 to 2 moles, more preferably 0.5 to 1.0 moles. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. potassium, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, followed by washing with water and/or stabilizing treatment.

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 (the number of stages), the complementary method such as countercurrent or forward flow, and various other conditions. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Picture and Television Engineers (Journal
Alofthe 5ociety of Motion
Picture and Television En
cineers) Volume 64, P, 248-253 (19
You can request it using the method described in the May 1955 issue. Normally, the number of stages in the multistage countercurrent system is preferably 2 to 6.
Particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, 0.51 to 11 or less per 1rrL2 of the photosensitive material. As the residence time increases, problems arise such as bacteria propagating and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method of reducing calcium and magnesium described in %M No. 131632/1982 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazole described in JP-A No. 57-8542, chlorinated sodium incyanurate described in JP-A No. 61-120145, and Japanese Patent Application No. 60-105
Benzotriazole, copper ion, etc. described in No. 487, ``Chemistry of antibacterial and antifungal agents'' by Hiroshi Horiguchi, ``Sterilization of microorganisms, sterilization, and antifungal technology'' by the Sanitation Technology White Group, and ``Bacterial and Antifungal Technology'' by the Japan Antibacterial and Antifungal Science White Group. It is also possible to use bactericidal agents described in "Encyclopedia of Bacterial and Antifungal Agents".

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

It is also possible to directly process with a stabilizing solution following the above water washing step (or without going through the water washing step). A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin. and membrane p suitable for dye stabilization.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the light-sensitive material of the present invention, stabilization does not require a water washing step (if stabilization is carried out directly, JP-A No.
No. 8543, No. 58-14834, No. 60-220345
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 l-hydroxyethylidene-1,1-diphospho/acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

In the present invention, a so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering process.

The pH of the water washing step or stabilization step of the present invention is 4 to 10, preferably 5 to 8. Temperature depends on the use of photosensitive materials.
Although it can be set depending on the characteristics etc., it is generally 15 to 45°C, preferably 20 to 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 to 1 minute 3
It is 0 seconds. The smaller the amount of replenishment, the lower the running cost.
Preferable from the viewpoints of reduced emissions, ease of handling, etc.

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, it is 11 or less, preferably 500rnl or less per 1rrL2 of the photosensitive material. 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 wash water that has disappeared in a multi-stage countercurrent system into the bleach-fix bath, which is the previous bath, and replenish the bleach-fix bath with concentrated liquid to reduce the amount of waste liquid. .

The total process time of the desilvering process, water washing and stabilization process of the present invention is 2 minutes or less, preferably 30 seconds to 1 minute 30 seconds.

The total time here refers to the time from when the silver halide color photographic light-sensitive material comes into contact with the first bath in the desilvering process until it comes out of the last bath in the water washing or stabilization process. Air time for is included.

Here, "the sum of the processing time of desilvering treatment, water washing treatment, and stabilization treatment is 2 minutes or less" means the treatment performed before the desilvering treatment and drying step (specifically, the treatment time of water washing and/or stabilization treatment is less than 2 minutes). For example, the sum of the processing times such as (desilvering → water washing) ■desilvering → stabilization (desilvering → water washing → stabilization) is less than 2 minutes.

Example 1) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene (Sample A). The coating solution was prepared as follows. Preparation of coating solution for the first layer: x, o --) y sol -(EXY) 19.
I 9 color image stabilizer (cpa-1) 4.49 and color image stabilizer (cpa-7) 0.7.9 with acetic acid x chik 2
7.2 CC and Solvent (Solv-3) 8.21
Add and dissolve this solution, and add 1 aqueous solution of 10 thigelatin containing 8 cc of sodium 10 tidecylinzenesulfonate.
It was emulsified and dispersed in 85CC. On the other hand, a silver chlorobromide emulsion (cubic grain size of 0.85μ, coefficient of variation of 0.07, containing 1 mol of silver bromide as a proportion of the whole grain in a localized part of the grain surface) contains the following two types. 2. each of blue-sensitive sensitizing dyes per mole of silver. A sulfur sensitized product was prepared after adding 10" mol of OX. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (2.0×10 each of the above two types per mol of silver halide)
'Mo/L/) Green-sensitive emulsion layer (t per mole of silver halide, :, D 4.OXl 0
'mole) and (# per mole of silver halide)7. OX 10'-' mole) red-sensitive emulsion layer and (b0.9X 10-' mole per mole of silver halide)
For the red-sensitive emulsion layer, the following compounds were used per mole of silver halide. bz, 6xxo-3 moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer configuration) The composition of each layer is shown below, and the numbers represent the coating amount (,9/m). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 gelatin yellow coupler ( EXY) Color image stabilizer (Cpa-x) Color image stabilizer (Cpd-7) Solvent (Solv-3) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (cpct-sun solvent (Solv-1) Solvent (Solv-4) Third layer (green-sensitive layer) Silver chlorobromide emulsion (grain size 0.40μ) Coefficient of variation 0.0
9 cubes and contains 1 mole of silver bromide localized on a part of the grain surface as a proportion of the whole grain) Gelatin magenta coupler (ExM) Color image stabilizer (cpa-3) Color image stabilizer (cpa-4) ) Color image stabilizer (cpa-s) Solvent (Solv-2) 1.86 0.82 0.19 0.03 0.35 Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-1) Color mixing prevention Agent (Cpd-5) Solvent (Solv-5) Fifth layer 0.99 O,0S O916 0,08 0,36 1,24 0,31 0,12 0,06 0,09 0,42 Silver chlorobromide Emulsion (grain size 0.36μ, coefficient of variation 0.1
Gelatin cyan coupler (Ext) Color image stabilizer (Cpd-6) Color image stabilizer (Cpa) -7) Color image stabilizer (Cpa-9) Solvent (Solv-4) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (cpa-s) Solvent (Solv-5) 1.58 0.47 O,OS 0.24 0.21 1.34 0.34 0.17 0.34 0.04 0.37 0.53 0.16 0.02 0.08 Seventh layer (protection Layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (denaturation degree 17) Fluid rough-in (EXY) Yellow coupler 1.33 0.17 0.03 (Ext) Cyan coupler g R=H, C2H,, O , H9's l:3:6 mixture (weight ratio) (Cpa-1) Color image stabilizer (EXM) Magenta coupler (Cpa-3) Color image stabilizer H3 M3 (Cpa-4) Color image stabilizer (Gpd -5) Color mixing inhibitor CH CH (cpa-6) 2:4:4 mixture of color image stabilizer (weight ratio) (Solv-1) Solvent (Solv-2) 1:1 mixture of solvent (volume ratio) ( Solv-3) Solvent (Soxv-4) Solvent (Soxv-5) Solvent cooc, H17 (CH2)8 cooc8H17 (Solv-6) Solvent medium (cpa-'y) Color image stabilizer 1+OH2-CH-piece C0NHC4H3( t) Average molecule J160,000 (Cpd-8) Color image stabilizer C) (30H3 (Cpd-9) Color image stabilizer CH (UV-1) 4:2:4 mixture of ultraviolet absorber?l (weight ratio ) In the same manner as Sample A, except that 1-(5-methylureidophenyl)-5-mercaptotetrazo-k (Ks
p = 10-16" 2) Sample B - 1,1-ethyl-2-mercapto-
5-amino-1,3,4-)riacy/I/ (Ks
A sample containing 5X 10-' moles of p = 1014.7) per silver halide cell was prepared as B++2.
．． =) methyldithiocarbamate (Ks p = 1
0"-19") /' 5 per mole of silver halide
Sample C24
-Hydroxy-6-methyl-1゜3.3α-7-tetraazaindene (Ksp = 10-9°7) was added in 5.01X10-' mol per mol of silver halide as sample D, and five types were prepared. I created a sample.

In order to examine the photographic properties of these coated samples, the following experiments were conducted.

First, a coated sample is separated into three colors of B, G, and R light using a photosensitive needle (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of the light source is 3200 K) and subjected to gradation exposure for sensitometry. gave. The exposure at this time was carried out so that the exposure time was 1/10 second and the exposure amount was 2500 MS.

The above sample was treated with the following treatment composition and the following treatment composition. However, the composition of the color developer was changed as shown in Table 1.

Processing process Temperature Time Color development 38℃ 45 seconds bleach fixing 3
0~36℃ 45 seconds/s ■ 30~37℃
Rinse for 30 seconds■ 30-37℃ 3
Rinse for 0 seconds ■ Dry for 30 seconds at 30-37℃
70-80°C for 60 seconds The composition of each treatment solution is as follows.

Color developer water 80
0rnl Ethylenediamine-N,N,N,N- Tetramethylenephosphonic acid 3.0 F Organic preservative A (I-1) 0.0
3 mol potassium carbonate 5 F N-ethyl-N-(β-methanesulfonamide 9-ethyl)-3-methyl-4-amine aniline sulfate triethanolamine fluorescent brightener (4,4'-u aminostilbene series) Add water to pH (25°C) Bleach-fix water Ammonium thiosulfate (70%) Sodium sulfite Ethylenediaminetetraacetic acid Iron (fil) Ammonium Ethylenediaminetetraacetic acid Disodium Ammonium Bromide Glacial acetic acid Add water to pH (25°C) 5 .0 g 10.0.9 2.0y 1000rrL1 10.05 400r+1 00d 17, F 5g 000ml 5.40 Rinse liquid ion exchange water (3 ppm each of calcium and magnesium
(below) After performing sensitometry on the developer immediately after preparing the above solution, the yellow color density was 2. The extent to which magenta was developed was measured at an acceptable amount of blue light, and this value (DG) was used as a measure of color mixture during processing.

Also, the density of magenta coloring obtained by exposure to green light is 0.
The relative ratio of the logarithm of the exposure amount that gives the value 5, when O is the logarithm of the highest exposure amount used in this experiment, was determined. The larger the negative logarithm of the exposure amount, the higher the sensitivity. This value ΔxogE was used as a measure of sensitivity.

Next, running treatment was performed using the treatment liquid shown in Table 1. During running, the chloride ion concentration and bromide ion concentration in the replenisher and the replenishment amount were adjusted so that the chloride ion concentration and bromide ion concentration shown in Table 1 were kept constant during the running.

During this run, 507FL2 photosensitive material was processed using 21 tanks. At this time, the difference (Dm) between the maximum density (Dm) of magenta coloring obtained by exposure to green light at the start (at the beginning of the development process) and at the end of the running
-Dm(Ftt)) was defined as ΔD and was used as a measure of processing variation.

From the above results, when a sensitive material using a nitrogen-containing heterocyclic compound whose silver salt solubility product is within the range of the present invention is processed with a processing solution containing the chloride ion concentration and bromide ion concentration of the present invention, It can be seen that images can be formed with high sensitivity, small processing fluctuations, and little processing color mixture.

Example 2) Sample E was prepared by changing the third layer (green-sensitive layer) from Sample A of Example 1 as follows.

Third layer (green sensitive layer) (ExM') (Cpd-4') Color image stabilizer silver chlorobromide emulsion (grain size 0.40μ, coefficient of variation 0.0
Gelatin mazen coupler (ExM') Color image stabilizer (Gpa-3) Color image stabilizer ( Cpa-4') Solvent (Solv-2') Solvent (Soxv-7) (Soxv-2') Solvent 0.20 1.24 0.29 0.09 0.06 0.32 0.16 3-nea mixture (Capacity ratio) (Solv-7) GgH17 (tl Same as sample E, except that 1-(5-methylureidophenyl)-5-mercapto was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer. Tetrazole (Kapm
lO-”°2) per mole of silver halide, respectively
．． 5 X 10-5 mol, 7.7 X 10-' mol,
The sample to which 2.5XIF'mol was added was designated as sample F. In addition, in samples E and F, the magenta coupler was changed to the following, and samples were changed to samples G and H, respectively.
And so.

(Magenta coupler) (M-1) These four samples were treated in the same manner as in Example 1, and the results obtained are shown in Table 2.

From the above results, it is clear that when a sensitive material using a nitrogen-containing heterocyclic compound whose silver salt solubility product is within the scope of the present invention is processed with the processing solution of the present invention having a chloride ion concentration and a bromide ion concentration, the sensitivity is specifically high ( , and the processing variation is small (it is clear that images can be formed with less processing color mixture. Furthermore, samples G and H
When using a magenta coupler like the one used in the present invention, the processing color mixture will be thicker than that of other couplers when processed with a processing solution other than the one used in the present invention. It can be seen that the processing color mixture is improved more than other couplers, and the processing variation is small (combined with the high sensitivity), making it the most preferable.

Example 3) Sample E was prepared by changing the third layer (green-sensitive layer) from Sample A of Example 1) as follows.

Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, with average grain size of 0.55μ and 0.39μ mixed at 1:3 (A1 molar ratio),
The coefficient of variation of particle size distribution is 0.10 and 0.0, respectively.
8. Each contains 0.8 mole of A and aBr localized on the particle surface as a proportion of the whole particle) Gelatin magenta coupler (EXM//) Color image stabilizer (Cpd-3) Color image stabilizer (CpcL- 8) Color image stabilizer (cpa-9) Solvent (So'1v-2") 0.12 1.24 0.27 0.15 0.02 0.03 0.54 (ExM") Magenta coupler C3H17 ( t) (Cpd-8) Color image stabilizer C3H11(t) (Gp6-9) Color image stabilizer (Solv-2”) Solvent Same as sample A except that blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer were added. For the emulsion layer, 8.5x 10-s mol of 1-(5-methylureido-9-phenyl)-5-mercaptotetrazole per mol of silver halide, respectively;
The sample containing 7.7 x 10-' moles and 2.5 x 10-4% Y was designated as sample J. This sample 2111 was treated in the same manner as in Example 1. The results obtained likewise satisfied the objectives of the invention in the embodiments of the invention.

Example 4) A multilayer color photographic paper SAMP/I/K having the layer structure shown below was exploded on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

150% ethyl acetate in 60°0g8 of splitting yellow coupler (EXY) and 28.0Ji' of anti-fading agent (Cpd-1).
cc and solvent (Solv-3) 1.0CC and solvent (
Solv-4) 3.0 CC was added and dissolved, and this solution was diluted with 10% sodium dodecylbenzenesulfonate.
After adding it to 450 cc of gelatin aqueous solution, it was dispersed with an ultrasonic homogenizer, and the resulting dispersion was converted into a silver chlorobromide emulsion (silver bromide 0.7 mol%) containing the following blue-sensitive sensitizing dye.
A first layer coating solution was prepared by mixing and dissolving in 420F. Coating solutions for the second layer to the upper layer were also prepared in the same manner as the coating solution for the first layer. 1,2-bis(hinylsulfonyl)furopane was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer;
3'-Disulfoethylthiacyanine human 90 oxide 9 Green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-0 sulfo-actyl oxacarbocyanine human 90 oxide 9 Red-sensitive emulsion layer ;3,3'-diethyl-5-methoxy-9
, 9'-(2,2'-dimethyl-1,3-pro2))thiacarbocyanine iosito0 The following was used as an irradiation-preventing dye.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-oquino-1-(2,5-:)sulfonatophenyl)-2-pyrazolin-4-ylidene)-X-
2,5-lysulfonate disodium salt Nt''-(4,s-
:)Hydroxy-9,1O-dioxo-3,7-cisulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt [3-cyano-5-human90x-4-(3 -(3-cyano-5-oxo-1-(4-sulfonatophenyl)-
2-pyrazolin-4-ylidene)-1-intanyl)-
1-pyrazolyl]henzeno-4-sulfonato sodium salt (layer structure) The composition of each layer is shown below. The numbers are painted it (!i'/
m ). Silver halide emulsions represent coating amounts in terms of silver.

Support Paper support laminated on both sides with polyethylene First layer (blue sensitive layer) Silver halide emulsion (AJBr: 0.7 molt cube, grain size 0.9μ) Gelatin yellow coupler (EXY) Antifading agent (cpa-x) ) 0.29 1.80 0.60 0.28 Solvent (Solv-3) Solvent (Solv-4) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpa-2) Solvent (Soxv-1) Solvent ( Solv-2) Third layer (green-sensitive layer) 0.01 0.03 0.80 0.055 0.03 0.015 Silver halide emulsion (AgBr: 07 molty cubic,
Particle size 0.45μ) Gelatin magenta coupler (ExM) Anti-fading agent (Cpa-3) Anti-fading agent (Gpd-4) Solvent (Solv-1) Solvent (Solv-2) Fourth layer (color mixing prevention layer) Gelatin color mixing Inhibitor (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) 0.305 1.40 0.67 0.23 0.11 0.20 0.02 1.70 0.065 0.45 0.23 Solvent (Solv-1) Solvent (Solv-2) Fifth layer (red-sensitive layer) 0.05 0.05 Silver halide emulsion (AJBr': 4 molten cubic grain size 0.5μ) Gelatin Cyan coupler (ExC-1) Cyan coupler (ExC-2) Anti-fading agent (cpa-t) Solvent (Soxv-1) Solvent (Solv-2) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1 ) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (Soxv-2) Seventh layer (protective layer) Gelatin 0.21 1.80 0.26 0.12 0.20 0.16 0.09 0.70 0.26 0.07 0.30 0.09 1.07 (KXY) Yellow coupler (Cpd-3) Antifading agent α-Vivalyl α-(3-benzyl-1-hydantoynyl)-2-chloro- 5[β-(Kdecylsulfonyl)butyramide]acetanilide (EXM) magenta coupler 1-(2,4,6-)lichlorophenyl)-3[:2-
Chloro-5(3-octadecenylsuccinimito) anilino-5-pyrazolone (EXC-1) Cyan coupler 2-pentafluorobenzamyl-4-ri ao-5(
2-(2,4-di-tert-amylphenoxy)-3
-Methylbutyramidophenol (F,xC-2) cyan coupler 2.4-:)chloro-3-methyl-6-[α-(2,4
-di-tert-amylphenoxy)butylamibi]phenol (Cpa-x) Antifading agent 2,5-di-tart-amylphenyl-3,5-di-tert-butyloxybenzoate (Cpa-2
) Color mixing inhibitor 2.5-di-tart-octylhydride 0-quinone 1.
4-di-tert-amyl-2,5-dioctyloxybenzene (Cpd-4) Antifading agent 2.2'-methylenebis(4-methyl-6-tert-
butylphenol) (UV-1) Ultraviolet absorber 2-(2-hydroxy-3,5-di-tart-amylphenyl)benzotriazole (UV-2) Ultraviolet absorber 2-(2-hydroxy-3,5-di- tert-Butylphenyl) benzotriazole (Solv-1) Solvent di(2-ethylhexyl) phthalate (Solv-2) Solvent dibutyl phthalate (Cpd-5) p-(p-)Luenesulfonami)")-phenyl 0
Decane (Solv-3) Solvent di(1nonyl)7talate (Solv-4) Solvent N, N--; Ethylcarbonamidomethoxy-2,4-
Same as for the di-t-amylbenzene sample, except that 1-(2-acetamino'phenyl)-5-mercaptotetrazole was added to the blue-, green-, and red-sensitive emulsion layers, respectively. - Phenyl-5-mercaptotetrazole mixed in a molar ratio of 7:1 (pKts p: 16.4
) per mole of silver halide') 7. OX 10-'
The sample to which No. 1 was added was designated as Sample L. These two types of samples were subjected to the following treatments and evaluated in the same manner as in Example 1.

The results obtained likewise satisfied the objectives of the invention in the embodiments of the invention.

After the above-mentioned light-sensitive material was exposed to light through an optical film, it was processed in the following steps.

Processing process Temperature Time Color development
Bleach and fix at 35°C for 45 seconds 30
~36℃ Stable for 45 seconds ■ 30~37℃
Stable for 20 seconds■ 30-37℃ 2
Stable for 0 seconds■ 30-37℃ Stable for 20 seconds
■ Dry at 30-37℃ for 30 seconds
70 to 85°C for 60 seconds (stable 4-tank countercurrent flow from ■ to ■) The composition of each treatment solution is as follows.

Color developer water 80
04 Ethylenediaminetetraacetic acid 2.0g
Triethanolamine s, o y
Charcoal potassium 25! ! N-ethyl-N-(β-methanesulfonamyl ethyl)
-3-Methyl-4-aminoaniline sulfate N, 8-diethylhydroxylamine 5,6-dihytooxybenzene-1,2,4-trisulfonic acid fluorescent brightener System) Add water to pH (25℃) Bleach-fix solution Water Thiosulfur Ammonium C70To> Sodium sulfite Iron ethylenediaminetetraacetate (■) Disodium ethylenediaminetetraacetate Add glacial acetic acid water to pH (25℃) 5.0g Stabilized liquid formalin (37y) Formalin-sulfite adduct 0, II 0.7y 4.21! 5-chloro-2-methyl-4-inthiazolin-3-one 0.02#0
．． 3 N 2.0g 000m 10.10 2-Methyl-4-isothiazoline-3-oni70.01 F Copper sulfate 0.005.9 Add water 1000mJP10
00°C) 4.0001L1 8g y 1000WL1 5.5 Example 5) Using sample B-1 in Example IK, Table 3 was used to further confirm the dependence of the chlorine ion concentration and bromide ion concentration in the developer. Evaluations similar to those in Example 1) were conducted using a developer having the composition shown in .

The results are shown in Table 3.

Example 6) Same as Sample E of Example 2 except that (M-2) and (M-3) described in the text were used as magenta couplers.
, (M-49), (M-56), and (M-60) were created, and samples M, N, 0, P, and
I named it Q. In these five types of samples, 1-(5-methylclaybiphenyl)-5-mercaptotetrazole (Ksp = l o-16°2) was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, respectively. 8.5 x 10-5 moles per mole of silver halide, 7.7
:X 10 mol and 2.5X 10 mol added samples were respectively sample R, S, T, U, V.
And so.

When these 10 types of samples were processed in the same manner as in Example 1, samples R,
The results showed that S, T, U, and V satisfied the present invention.

1. Indication of the case Patent Application No. 193671 of 1985 2. Name of the invention Image forming method 3. Person making the amendment Relationship with the case: Patent applicant Address 1210M Naka, Minamiashigara City, Kanagawa Prefecture 5. Subject of amendment: Engraving of the specification Patent applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1゜2゜3゜ Person amending the name of the indicated invention in the case Showa J year patent application No. 1 347/Image Relationship with the formation method incident

Claims (1)

[Claims] (1) At least one of the silver halide emulsion layers has a high silver chloride silver halide emulsion containing 80 mol% or more of silver chloride, and the solubility product of the silver salt in the light-sensitive material is 10^-^1^
A silver halide color photographic light-sensitive material containing a nitrogen-containing heterocyclic compound of 0 or more and 10^-^1^8 or less is mixed with 3.5 x 10^-^2 - 1.5 x 10^-^1 of chlorine ions. Contains mol/L and bromine ion from 3.0×10^-^5
An image forming method characterized by processing with a color developer containing 1.0×10^-^3 mol/L.