JPH01167752A - Silver halide color photosensitive material and developing processing method thereof - Google Patents

Abstract

PURPOSE:To provide the title material which has an excellent rapid processing property, is free from unequal fogging and provides an excellent finish by incorporating a specific silver chlorobromide into a photosensitive silver halide emulsion and incorporating the auxiliary particles of silver halide which are not substantially developed into at least one of a photosensitive layer, intermediate layer and protective layer. CONSTITUTION:The silver halide color photosensitive material usually contains at least 3 layers of silver halide emulsion layers and the average silver chloride content of at least 3 layers of the emulsion layer is preferably >=90mol.%. The photosensitive silver halide particles having the locally existing phases where the halogen compsns. vary, more preferably the locally existing phases where the silver bromide content consists of >=15mol.% silver chlorobromide or silver bromide in or on the particles are preferably used. The silver halide particles which are not substantially developed are preferably incorporated into at least one layer of the intermediate layer and protective layer adjacent to the photosensitive layers and the average particle size thereof is preferably <=0.2mum. The photosensitive material which is adaptable to the rapid development processing and yield the finish quality having excellent stability is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photosensitive material suitable for rapid processing and a processing method thereof, and in particular, it relates to a color photosensitive material suitable for rapid processing, and in particular, to a color photosensitive material that is capable of achieving excellent finish quality with excellent stability. The present invention relates to a silver halide color light-sensitive material containing high silver chloride and a developing method thereof.

(Prior Art) Currently commercially available silver halide photographic materials and image forming methods using them are diverse and are used in all fields. The halogen composition of the silver halide emulsions used in many of these light-sensitive materials is mainly silver bromide, silver iodobromide, silver chloroiodobromide, or silver chlorobromide, in order to achieve high sensitivity. There are many cases.

On the other hand, for products used in markets where there is a strong demand for large quantities of prints to be completed in a short period of time, such as light-sensitive materials for color photographic paper, bromide containing virtually no silver iodide is needed due to the need to increase development speed. Silver or silver chlorobromide is used.

In recent years, there has been an increasing demand for improved rapid processing performance of color photographic paper, and much research has been conducted. It is well known that increasing the silver chloride content of the silver halide emulsion used dramatically increases the development speed.

(Problems to be Solved by the Invention) However, silver halide emulsions with a high silver chloride content tend to fog, and it is difficult to obtain high sensitivity with ordinary chemical sensitization. It is generally known that this method has drawbacks such as large changes in sensitivity and all.

Furthermore, when rapidly processing a photosensitive material having a photosensitive layer containing silver halide grains with an extremely high silver chloride content, it is difficult to obtain consistently excellent finishing quality. First, the photosensitive properties of one photosensitive emulsion layer are inhibited as the development of other layers progresses, such as capri being induced in one photosensitive emulsion layer by the development of other adjacent layers. Second, the finish quality changes between the initial stage of development processing and after continuous processing.

Thirdly, the progress of rapid bleach-fixing in the next step is not stable.

In emulsions containing high silver chloride, silver chloride has a lower solubility product than silver bromide and is easily dissolved and deformed, and the adsorbent material is easily desorbed in the developer. Many of the stabilizers that act as a coupler when included in the developer solution.

It is therefore desirable to protect high silver chloride emulsions from other spilled materials.

In addition, when rapidly processing a photosensitive material that has a photosensitive layer containing silver halide grains with an extremely high silver chloride content,
A color developing solution that does not contain a water-soluble bromide having development-inhibiting properties is used, but the above-mentioned problems are particularly severe in a color developing solution that does not substantially contain a water-soluble bromide.

If a water-soluble bromide is added to the replenisher, for example, during color development, the progress of development of the light-sensitive emulsion layer on the surface of the light-sensitive material will be unevenly suppressed. Further, the third problem described above is particularly likely to occur when a bleach-fix solution to which substantially no water-soluble bromide is added is used.

These developments occur in the case of color development and bleach-fixing shorter than 90 seconds, or even 60 seconds, especially 45 seconds.7 The present invention solves the problems of these silver halide emulsions with a high silver chloride content. In particular, it protects high silver chloride grains from becoming easily fogged by themselves or is attacked by other materials, and improves development processing by preventing developer contamination, especially by stabilizing continuous processing. The purpose is to obtain high finishing quality.

On the other hand, Japanese Patent Publication No. 62-32779 discloses that in a multilayer color photographic paper using a silver chlorobromide emulsion with a silver bromide content of 85 to 95 mol%, the photosensitive layer closest to the support or the non-containing layer adjacent thereto is It has been shown that when the photosensitive layer contains low-irritancy silver chlorobromide grains having a silver chloride content of 60% or more, high sensitivity can be obtained and the bromide ion concentration in the developer can be reduced. Also, Japanese Patent Publication No. 62-32779 and U.S. Patent No. 31
No. 52907 discloses that when silver chloride or silver chlorobromide grains with a high silver chloride content are mixed into a silver chlorobromide emulsion, sensitivity and gradation can be increased by strengthening physical development by low-sensitivity fine grains. The technique shown in Japanese Patent Publication No. 62-32779 is a silver chlorobromide photosensitive emulsion with a relatively high silver bromide content, and 0.8 g/l of potassium bromide is added to the developer. It is added to stabilize the process, and does not provide any suggestions for solving the above-mentioned problems when speeding up the layer formation. That is, in the case of a photosensitive emulsion with a high silver chloride content, potassium bromide is captured by the photosensitive emulsion itself, and the effect of achieving the above object of the present invention can be said to be small.

In addition, JP-A-58-95736, JP-A-58-1085
No. 33, JP-A-60-222844, and JP-A-60
No. 222845 states that in order to overcome the drawbacks of silver halide emulsions with a high silver chloride content, it is effective to have various silver halide grain structures having layers with a high silver bromide content. This is disclosed. It is true that the photographic performance of silver halide emulsions with a high silver chloride content changes in various ways by introducing a layer with a high silver bromide content, but even with these techniques, there are problems such as increased sensitivity and reciprocity law failure. The improvement effect was not necessarily satisfactory.

Therefore, the primary object of the present invention is to provide a silver halide color light-sensitive material and a processing method thereof, which are excellent in rapid processing properties and can stably obtain excellent finishing quality without uneven fogging. It is in.

A further object of the present invention is to provide a silver halide color light-sensitive material which has excellent rapid processing properties and is capable of obtaining high-temperature, high-contrast gradation, and a developing processing method thereof.

A further object of the present invention is to improve sensitivity by changing exposure illuminance.
An object of the present invention is to provide a silver halide photographic material with little change in gradation and a developing method thereof.

(Means for solving the problem) The above object is to provide a color photosensitive material in which a photosensitive layer containing a color coupler and a photosensitive silver halide emulsion, an intermediate layer, and a protective layer are provided on a support. Silver chloride emulsion The photosensitive silver halide emulsion used in at least one layer of the photosensitive layer contains silver chlorobromide with an average silver chloride content of 90 mol % or more, and further includes the photosensitive layer, an intermediate layer adjacent thereto, and a protective layer. It has been found that this can be achieved by a silver halide color light-sensitive material characterized in that at least one of the layers contains silver halide auxiliary grains that are not substantially developed.

Silver halide color light-sensitive materials usually contain at least three silver halide emulsion layers, and it is preferred that the average silver chloride content of the 3N emulsion layers is at least 90 mol %. Particularly preferred silver halide photosensitive grains have localized phases having different halogen compositions inside or on the grains, preferably localized phases consisting of silver chlorobromide or silver bromide with a silver bromide content of 15 mol % or more. It is better to use one with .

Further, silver halide grains that are not substantially developed are preferably contained in at least one of the intermediate layer and the protective layer adjacent to the photosensitive layer, and the average grain size thereof is 0.
It is preferable that it is 2 μm or less. The silver halide auxiliary grains include silver iodobromide, silver bromide, silver iodochloride, silver iodochlorobromide,
Silver chlorobromide or silver chloride may be used, but silver chloride bromide or silver chloride having a chloride content of 50 mol % or more is particularly preferred.

Furthermore, when using the photosensitive silver halide grains described above, the objects of the present invention can be particularly effectively achieved when a pyrazoloazole type magenta coupler represented by the general formula [M-11] described below is used as a color coupler. can. Other elements used in the present invention will be apparent from the description of the specification.

The halogen composition of the photosensitive silver halide grains according to the present invention is 90% of the total silver halide constituting the silver halide grains.
It is necessary to consist of silver chlorobromide that is substantially free of silver iodide and has a mole % or more of silver chloride.

Here, "substantially free of silver iodide" means that the silver iodide content is 1.0 mol % or less. A preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, in which 95 mol % or more of the total silver halide constituting the silver halide grains is silver chloride.

The silver halide grains according to the present invention preferably have localized phases in the interior or on the surface of the photosensitive grains in which the silver bromide content is significantly different from that of the adjacent substrate in a layered or island-like manner. . A significant difference means a difference of about 5 mol %, depending on the halogen composition ratio of the water-soluble additive in the emulsion formulation or the measurement accuracy of the analytical technique.

More preferably, the silver bromide content is at least 1
It has 5 mol% localized phase. The localized phase with high silver bromide content can be arranged freely depending on the purpose, and may be located inside the silver halide grain, on the surface or subsurface, or between the interior and the surface or subsurface. In addition, the localized phase may have a layered structure surrounding the silver halide grains inside or on the surface, or may have a discontinuously isolated structure. One preferred example of the arrangement of localized phases with a high silver bromide content is a structure in which localized phases with a silver bromide content of at least 15 mol % are discontinuously isolated on the surface of silver halide grains. It has the following.

The silver bromide content of the localized phase should preferably exceed 15 mol%, but if silver halide auxiliary grains are not used or an intermediate layer or protective layer containing the auxiliary grains is not used, If the silver bromide content is too high, it is undesirable for photographic materials, such as causing desensitization when pressure is applied to the material or causing large changes in sensitivity and gradation due to changes in the composition of the processing solution. Characteristics are often assigned. Taking these points into consideration, the silver bromide content of the localized phase is preferably in the range of 20 to 60 mol%, and 30 to 60 mol%.
The most preferred range is 50 mol%.

The silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, described in "Nippon Kagaku Yoshin, New Experimental Chemistry Course 6. Structural Analysis", Maruzen) or the XPS method (for example, "Surface The analysis can be performed using methods such as IMA, Applications of Auger Electron/Photoelectron Spectroscopy, published by Kodansha. Furthermore, when there is a discontinuously isolated localized phase on the surface of the photosensitive particle, especially when there is a localized phase at a part of the corner of the photosensitive particle, EDX (Energy Dis
The silver bromide content can be measured using an EDX spectrometer attached to a transmission electron microscope (described in "Electron Beam Microanalysis" by Hiroyoshi Soejima, published by Nikkan Kogyo Shimbun).

The localized phase accounts for 0.0% of the total silver amount constituting the silver halide grains of the present invention. It is preferably comprised of 1-20% silver, more preferably 0.5-7% silver.

The interface between such a localized phase with a high silver bromide content and other phases may have a clear phase boundary or a short transition region where the halogen composition gradually changes. Also good.

Various methods can be used to form such a localized phase with a high silver bromide content.

For example, a localized phase can be formed by reacting a soluble root salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method. Furthermore, it includes a process of converting already formed silver halide to silver halide with a smaller solubility product,
A localized phase can also be formed using the so-called convergence method. Alternatively, a localized phase can also be formed by recrystallizing the surface of silver chloride particles by adding silver bromide fine particles.

Metal ions can be added to the silver halide grains according to the present invention.

The metal ions used in the present invention are not particularly limited, but are preferably cadmium, lead, copper, zinc, rhodium,
Palladium, iridium, platinum, thallium, iron, etc. are used. These metal ions are preferably used in the form of metal salts or metal complex salts.

The amount added is 10-8 to 1 per mole of silver halide.
0-S mole, and its optimum value is appropriately selected within this range depending on the grain size and crystal habit of the silver halide grains, and also in combination with other additives such as aggravating dyes. Generally 1
If the amount is less than 0-'' mol, the effects of the present invention will not be fully exhibited, and if the amount exceeds 10-'' mol, other photographic properties such as desensitization may be adversely affected.

The metal ions used in the present invention may be added at any stage of the formation, grain growth, or physical ripening of the silver halide grains of the present invention, or may be added in portions. These metal ions are used in the form of metal salts or metal complex salts, and these compounds are added after being dissolved in water or a suitable solvent.

Also, during the formation of the localized phase, metal ions such as iridium can be present and deposited at the same time.

The surface of the photosensitive silver halide grains used in the present invention must be chemically sensitized to a certain extent that the grains are substantially of the surface latent image type. For chemical sensitization, sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas,
Sulfur enhancement method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Metal compounds (e.g. In addition to total complex salts, a noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pt, Ir%Pd, Rh5Fe, etc. can be used alone or in combination. Among these chemical sensitizations, sulfur sensitization is preferably used.

A light-sensitive material composed of silver halide grains preferably prepared in this way has particularly excellent rapid processing properties, high sensitivity, high contrast, and little reciprocity failure, and also has high latent image stability and improved handling properties. Can be done.

The silver halide grains according to the present invention have (100
) surface, (111) surface, or both surfaces,
Furthermore, even those containing higher order planes are preferably used. The shape of the silver halide grains according to the present invention may have a regular crystal shape such as a cube, an octahedron, a dodecahedron, or a dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may also have the following. It is also possible to use tabular grains (
Specifically, the emulsion may be an emulsion in which tabular grains having a length/thickness ratio of 3 or more, especially 8 or more occupy 50% or more of the total projected area of the grains.

The size of the photosensitive silver halide grains according to the present invention may be within a commonly used range, but the average grain size is 0.
The thickness is preferably 1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but monodisperse is preferable.

The particle size distribution, which represents the degree of monodispersity, is defined as the ratio of the statistical standard deviation (s) to the average particle size (τ) (S/(T)
So 0. It is preferably 2 or less, more preferably 0.15 or less.

It is preferable to use a rapid type color developing solution for the color photosensitive material according to the present invention. In particular, since this type of developing solution does not substantially contain water-soluble bromide, the above-mentioned defects when using a silver halide emulsion with a high silver chloride content are noticeable. By mixing the silver halide auxiliary grains of the present invention in an intermediate layer, a protective layer, or an emulsion-sensitive layer, the above-mentioned defects of high silver chloride emulsions can be improved or eliminated. Silver halide auxiliary grains are antifoggants that not only capture bromine ions and very small amounts of iodine ions contained in silver halide photosensitive grains during the color development process, but also adsorb onto silver halide photosensitive grains. and capture stabilizers. Capturing bromine ions prevents contamination of the developing solution with bromine ions, stabilizes development processing, especially continuous processing, and maintains rapid developability.

Furthermore, heterocyclic compounds added in advance as stabilizers, such as azaindene compounds and mercaptoazolates, and in some cases even iodide ions, may cause irregular fogging if they act during the development process. The silver halide auxiliary grains prevent the occurrence of fog, which is characteristic of these high silver chloride-containing silver halides. In addition, the captured bromide ions and mercapto- or thioxoheterocyclic compounds are carried into the subsequent desilvering process, particularly the bleach-fix solution, to promote the desilvering action. In particular, no water-soluble bromide is added or 0. 5
Mol/! This effect appears when using a bleach-fixing solution containing as much as: Presumably, as a result of this, it is possible to eliminate the occurrence of fog caused by the development of other adjacent layers in a certain photosensitive emulsion layer and the inhibition caused by the progress of development, and to achieve a stable and excellent finish quality. Furthermore, it is possible to achieve stabilization of the high silver chloride grains themselves.

Silver halide auxiliary grains can be produced by the methods described for the formation of photosensitive grains or by commonly used methods. In particular, in the case of silver chloride or silver chlorobromide grains having a silver chloride content of 50 mol% or more, for example,
It is preferable to use a physical ripening inhibitor in combination as described on pages 13 to 47 of Specification No. 33020. It is preferably smaller than photosensitive silver halide grains, and further has a grain size of, for example, 0.
Use particles smaller than 2 μm.

The silver halide auxiliary grains may be silver iodobromide or silver bromide, but preferably have a silver chloride content of 50 mol % or more. Depending on the purpose, stabilizers, anti-fogging agents for development, bleaching accelerators, etc. may be adsorbed and allowed to coexist.

The silver halide auxiliary grains have a sensitivity lower than that of the light-sensitive silver halide emulsion used, and are preferably substantially at the foot or halftone of the characteristic curve of the light-sensitive layer (color density 1.0).
(color density is 0) which does not contribute to the formation of developed images (below).
．． 1 or less) are particles that undergo color development. Even if the auxiliary particles according to the invention are not substantially developed themselves, they may develop due to the color development of the adjacent illuminating layer. Preferably, a silver halide emulsion containing only silver halide auxiliary grains is subjected to sensitometry using a practical developer to determine the substantial sensitivity of the silver halide auxiliary grains.

Next, the silver halide grains and emulsion used in the present invention will be explained.

In the process of forming or physically ripening silver halide grains according to the present invention, a cadmium salt, a zinc salt, a thallium salt, a lead salt, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds such as oxadorinthione; azaindenes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a).

7) Tetraazaindene), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides and the like.

Among them, the following general formula (1
), (If) or (I[[) are preferably added. The amount added is 1X10-' to 5X10-2 per mole of halogenated i
Moles are preferred. Furthermore, lXl0-' to lXl0-2 moles are particularly preferred.

- Monna (1) In the formula, R represents an alkyl group, an alkenyl group or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. Alkali metal atoms include, for example, sodium atoms, potassium atoms, etc., and ammonium groups include, for example, tetramethylammonium groups,
Trimethylbenzylammonium group, etc. Further, the precursor refers to a group that can become X=H or an alkali metal under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, and the like.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups.

Substituents for substituted alkyl groups include halogen atoms, nitro groups, cyano groups, hydroxyl groups, alkoxy groups, aryl groups, acylamino groups, alkoxycarbonylamino groups, ureido groups, amino groups, heterocyclic groups, acyl groups, and sulfamoyl groups. , sulfonamide group, thioureido group,
Examples include a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and further a carboxylic acid group, a sulfonic acid group, or salts thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and the substituents of the alkyl group listed above.

- Monna (n) In the formula, L represents a divalent linking group, and RO represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. R
The alkyl group and alkenyl group of o have the same meanings as the alkyl group and alkenyl group of R in -i formula (I), and X has the same meaning as X in general formula (1), respectively.

Specific examples of the divalent linking group represented by the above are: or a combination of these.

n represents 0 or l, and R1, R2 and R3 each represent a hydrogen atom, an alkyl group or an aralkyl group.

General formula (I[[) In the formula, R and X are synonymous with those of general formula (T),
L has the same meaning as that in general formula (n).

R4 has the same meaning as R, and may be the same or different.

Below are the general formula (■), -Momona (n) and -Momona (II)
Specific examples of the compound I) will be listed, but the invention is not limited thereto.

(If-1) (n-2) ([
[-1) (I[[-2) The present invention can be applied to a color photosensitive material provided with at least three emulsion photosensitive layers containing a color coupler and silver halide grains. This emulsion-sensitive layer can be composed of at least 2N having similar spectral sensitivities. This multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required.

Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In addition, an antihalation layer, an intermediate layer, a yellow filter layer, a functional bad light layer, a plurality of protective layers, etc. can be used in combination.

As the spectral sensitizing dye, methine dyes such as cyanine dyes and merocyanine dyes commonly used for photography can be used, but cyanine dyes represented by the following formula (IV) are particularly preferred for the present invention. The addition time is preferably during the production process of the silver halide agent, particularly before the water washing process of the emulsion or before chemical sensitization.

General Formula (IV) In the formula, Zll and Zlz each represent an atomic group necessary to form a heterocyclic nucleus.

Examples of the heterocyclic nucleus include a 5- to 6-membered ring nucleus containing a nitrogen atom and other heteroatoms, such as a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom (a fused ring may be further bonded to these rings, Furthermore, a substituent may be bonded) is preferable.

Specific examples of the above-mentioned heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus, benz List the imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyridine nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, penzotelllazole nucleus, naphthotellazole nucleus, etc. Can be done.

Ro and R1! each represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.

These groups and the groups described below are used to include their respective substituted forms. For example, taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched, or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of substituents for substituted alkyl groups include halogen atoms (chlorine, bromine, fluorine, etc.), cyano groups, alkoxy groups, substituted or unsubstituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. One or more of these may be substituted in combination.

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

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

ml1 represents a positive number of 0, 1.2, or 3.

When m+ represents 1, R13 represents a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group.

Specific examples of the aryl group include substituted or unsubstituted phenyl groups.

R14 represents a hydrogen atom. When mlI represents 2 or 3, R13 represents a hydrogen atom, R14 represents a hydrogen atom,
In addition to representing a lower alkyl group or an aralkyl group, it can be linked to R02 to form a 5- to 6-membered ring. Also m+
, represents 2 or 3, and RI4 represents a hydrogen atom, Rts may be combined with another R13 to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- to 6-membered rings. j++, k each represent 0 or 1,
X I I represents an acid anion, and nil represents O or 1.

Among these, red sensitizing dyes in particular have reduction potentials of -1 and 2.
Compounds having a reduction potential of -1, 27 or less are preferred, and compounds having a reduction potential of -1, 27 or more are preferred. As for the chemical structure, a benzothiadicarbocyanine dye in which two methine groups of a pentamethine linking group are linked to each other to form a ring is preferred. It is preferable that an electron-donating group such as an alkyl group or an alkoxy group is bonded to the benzene ring of the benzothiazole nucleus of the dye.

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

In addition, measurement of reduction potential by phase-discriminative second-harmonic AC portammetry using platinum as a working electrode is
of Imaging Science” (Journal
of Imaging 5science), Vol. 30, pp. 27-35 (1986).

Typical examples of red sensitizing dyes that can be used in the present invention are listed below.

Yellow couplers, magenta couplers, and cyan couplers which develop yellow, magenta, and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developing agents are commonly used in color light-sensitive materials.

Among the yellow couplers used in the present invention, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Among them, yellow couplers have the following general formula (Y-
1) and (Y-It) are preferred.

(Y-I) (Y-n) In the formula, Xl represents a hydrogen atom or a coupling-off group.

R21 represents diffusion resistance with a total carbon number of 8 to 32, and R2t
represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, or a diffusion-resistant group having a total of 8 to 32 carbon atoms. R2 represents a hydrogen atom or a substituent. When there are two or more Ro's, they may be the same or different.

For more information on pivaloylacetanilide type yellow couplers, see U.S. Pat. No. 4,622,287, No.
It is described in column 15, line 15 to line 8839, and column 14 (I!!), line 150 to column 19, line 41 of the specification of 4゜623.616.

For details on benzoylacetanilide type yellow couplers, see U.S. Pat.
3.501, 4. 046. No. 575, 4.1
No. 33.958, 4. It is described in No. 401゜752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include the aforementioned US Patent No. 4. Compound examples (Y-1) to (
Y-39), among them (Y-1),
(Y-4), (Y-6).

(Y-7), (Y-15), (Y-21),
(Y-22), (Y-23), (Y-26)
, (Y-35)l (Y-36), (Y-3
7), (Y-38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples (Y-1) to (Y-33) in columns 9 to 23 can be mentioned, among which (Y-2), (Y-7),
(Y-8), (Y-12).

(Y-20), (Y-21), (Y-23).

(Y-29) etc. are preferred.

Other preferred examples include US Pat. No. 3,408.
Typical example (34L) described in column 6 of specification No. 194
Compound examples (16) and (19) described in No. 88 of Specification No. 3,933,501, Example compounds (9) described in Nos. 7 to 8 of Specification No. 4,046,575, 4,133,
Compound example (1) described in columns 5 and 6 of specification No. 958,
Compound Example 1 described in column 5 of the specification of 401.752 and the following compounds Y-a) to Y-g) can be mentioned.

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

Examples of magenta couplers that can be used in the present invention include pyrazoloazole couplers such as phosphorus and pyrazolotriazoles. 5-pyrazolone couplers are 3
A coupler substituted with an arylamino group or an acylamino group at the -position is preferable from the viewpoint of the hue and color density of the coloring dye, and a representative example thereof is U.S. Patent No. 2,311,08
No. 2, No. 2.343,703, No. 2. eoo
, No. 788, No. 2,908,573, No. 3.
No. 062.653, No. 3,152,896, and No. 3,936,015. As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazolone azole coupler, U.S. Patent No. 3
, 369,879, preferably the pyrazolo(5,1-c)(1,2,4)) liazoles described in U.S. Pat. No. 3,725.067, Research Disclosure 24220 (
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Examples include the pyrazolopyrazoles described in June 2003). Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula [M-r]
, [M-II) or [M-Ill].

Here, R31 represents a diffusion-resistant group having a total carbon number of 8 to 32, and R3□ 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 may have a substituent (including a fused ring).

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, US Pat. No. 4,540,654, No. 2.
It is described in column 41st line to 8th column line 27th.

Among pyrazoloazole couplers, U.S. Pat.
The imidazo(1,2-b)pyrazoles described in U.S. Pat. Particularly preferred.

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, and as described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent Publication No. 226,849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No.

The pyrazoloazole coupler represented by the general hole CM-DI) has the above-mentioned excellent advantages.

However, pyrazoloazole couplers have the property that their color developability is inhibited by interaction with silver ions. Therefore, when used with a silver chloride-rich silver chloride-containing silver chloride-sensitive emulsion or a silver chloride-sensitive emulsion, the color developability becomes lower than that of a silver iodobromide-sensitive emulsion. However, when used in conjunction with the auxiliary particles according to the invention, this defect is ameliorated. In this case, it is particularly advantageous if the auxiliary grains are silver bromide or silver chlorobromide.

Specific examples of these couplers are listed below.

The most typical cyan couplers are phenolic cyan couplers and naphthol cyan couplers.

As a phenolic cyan coupler, US patents 2 and 3
No. 69.929, No. 4,518,687, No. 4,51
1.647 and 3. 772. 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, such as those described in Canadian Patent No. 62.
Coupler of Example 2 described in No. 5,822, U.S. Pat.
Compound (1) described in , No. 772.002, No. 4,56
Compounds (I-4) and (I-5) described in No. 4.590,
Compounds (1) and (2) described in JP-A-61-39045
), (3) and (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772, 162, 2. 895. 826, No. 4,334.011, No. 4.500゜653, and JP-A-59-164555, there are 2,5-diacylaminophenol couplers. The compound described in Patent No. 2゜895.826 (
■), the compound (17) described in No. 4゜557.999
, Compound (2) and (1) described in 4°565.777.
2), the compound (4) described in No. 4,124,396,
Compound (I-19) described in No. 4,613.564 and the like can be mentioned.

Examples of phenolic cyan couplers include U.S. Pat. No. 4,327.173 and U.S. Pat. 564゜586, No. 4,430,423, JP-A No. 61-390441, and Japanese Patent Application No. 100222-1987, there are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus. Specific examples of couplers particularly useful in the present invention include couplers (1) and (3) described in U.S. Pat. No. 4,327,173.
), the compound (3) described in No. 4,564,586, and (
16), the compound (1) described in No. 4,430,423
(3), and the following compounds are listed as other phenolic cyan couplers, as disclosed in U.S. Patent No. 4,333.9.
No. 99, No. 4,451゜559, No. 4,444.87
No. 2, No. 4,427.767, No. 4,579.813
There are ureido couplers described in European Patent (EP) No. 067.689B1, etc.;
7), coupler (1) described in No. 4,451,559
, the coupler (14) described in No. 4,444,872,
Coupler (3) described in No. 4,427,767, No. 4
, 609.619, couplers (6) and (24) described in
, No. 4,579,813, coupler (1) and (
11), couplers (45) and (50) described in European Patent No. (EP) No. 067.689B1, JP-A-61-426
Examples include coupler (3) described in No. 58.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2,313,586);
Those having an alkylcarbamoyl group at the 2-position (e.g., U.S. Pat. No. 2,474,293, U.S. Pat. No. 4,282.312)
, those having an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523-1983), those having a carbonamide or sulfonamide group at the 5-position (e.g., JP-A No. 60-23)
No. 7448, No. 61-145557, No. 61-153
No. 640), those with an aryloxy leaving group (e.g., U.S. Pat. No. 3,476,563), those with a substituted alkoxy leaving group (e.g., U.S. Pat. No. 4,296,199), and those with a glycolic acid leaving group. (For example, special public service in 1986
-39217).

When the color light-sensitive material used in the present invention is a color negative light-sensitive material for photography, the colored coupler for correcting unnecessary absorption of the coloring dye is research disclosure No. ,6
No. 70, Special Publication No. 57-39413, U.S. Patent No. 4,0
Preferred are those described in British Patent No. 04,929, British Patent No. 4.138.258 and British Patent No. 1,146.368.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

As the coupler from which the coloring dye is eluted from the additive layer, those described in JP-A-59-171955 and JP-A-61-20037 are used.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , multi-equivalent couplers described in JP-A No. 4,310.618, etc., DIR redox compound releasing couplers described in JP-A-60-185950, etc., and recoloring after separation described in European Patent No. 1'73,302A. Examples include couplers that release dyes.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Patent No. 4. 199°363,
It is described in West German Patent Application (OLS) No. 2.541.274 and OLS No. 2.541.230.

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

In addition, as a dye image stabilizer, for example, JP-A-59-
Catechol derivatives described in JP-A-60-262159 and the like can also be used.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat. Nos. 3,314,794 and 3.352°681) ), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat.
5.805, as described in 3,707,375)
, butadiene compounds (e.g. U.S. Pat. No. 4,045.22)
No. 9), or benzoxidol compounds (such as those described in US Pat. No. 3,100,455) can be used. UV-absorbing coupler (
For example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

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 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 The Macromolecular Chemistry of Gelatin, written by Arthur Weiss (Academic Press, published in 1964).

The supports used in the present invention are usually cellulose nitrace films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, which are used in photographic materials. In addition, there are laminates of these materials, thin glass films, paper, etc. Baryta or α-olefin polymers, especially polyethylene,
Paper coated or laminated with a polymer of α-olefin having 2 to 10 carbon atoms, such as polypropylene or ethylene-butene copolymer, vinyl chloride resin containing a reflective material such as TiO□, surfaces as shown in Japanese Patent Publication No. 47-19068 Supports such as plastic films whose surfaces are roughened to improve adhesion to other polymeric substances also give good results. Further, an ultraviolet curable resin can also be used.

These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it colored and transparent. ' Opaque supports include those that are inherently opaque such as paper, transparent films with pigments such as dyes and titanium oxide added, or those that have been surface-treated by the method shown in Japanese Patent Publication No. 19068/1983. This also includes plastic films etc. The support is usually provided with an undercoat layer. In order to further improve the adhesion, the surface of the support may be subjected to a preparation treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The color light-sensitive material applicable to the production of color photographs of the present invention is suitable for ordinary color light-sensitive materials, particularly color light-sensitive materials for printing and rapid processing color negative light-sensitive materials.

A black and white developer and/or a color developer is used for the development of the photosensitive material of the present invention. In the case of color reversal development processing, a black and white developer is also used. The color developing solution used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, and a typical example is 3-methyl-4-amino-N
, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Examples include N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, and p-)luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds, and the like. Common. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acid 11,) lyethylenediamine (1゜4-
Various preservatives such as diazabicyclo[2,2,2]octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, and dye formation. couplers, competitive couplers, coupling agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids Various chelating agents such as ethylenediaminetetraacetic acid,
Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N, N', N'
-tetramethylenephosphonic acid, ethylene diamine di(
(0-hydroxyphenylacetic acid) and their salts are representative examples.

The rapid color developing solution of the present invention does not substantially contain water-soluble bromide. Here, “substantially no content” means “
or no more than 3.3XIO-' moles of bromide.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer may contain known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virasolidone such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methifle p-aminophenol, alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
ml or less, preferably 250mj! You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), copper (old),
Peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic LJ of iron (Ill) or cobalt (fir).
, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. ;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(III) complexes and persulfates, including ethylenediaminetetraacetic acid iron(I[) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059°988, JP-A-53-32.736, No. 53-57,831, No. 5
No. 3-37.418, No. 53-72,623, No. 53
-95,630, 53-95,631, 53-
No. 10.4232, No. 53-124,424, No. 53
-141.623, 53-28,426, Research Disclosure No. 17,129 (197
Compounds having a mercapto group or disulfide group as described in JP-A No. 1982-140.129; thiazolidine derivatives described in JP-A No. 8,506-1982, JP-A No. 52-20.832 No. 53-32,735
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
- Iodide described in No. 16゜235; West German Patent No. 966,
410, polyoxyethylene compounds described in 2,748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; others, JP-A No. 49-42.434,
No. 49-59.644, No. 53-94.927, No. 54-35,727, No. 55-26,506, No. 5
Compounds described in No. B-163,940; bromide ions, etc. can be used.

Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of having a large promoting effect, and in particular, US Pat.
No. 2, JP-A No. 53-95.630 is preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred; these bleach accelerators may be added to the sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but as long as thiosulfates are commonly used, ammonium thiosulfates are particularly preferred. Most widely used. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Televisi
on Engineers Volume 64, P, 248-
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, all the known methods described in JP-A-57-8,543, JP-A-58-14-834, and JP-A-60-220.345 can be used.

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

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,597
Indoaniline compounds described in the same No. 3,342.5
No. 99, Schiff base type compounds described in Research Disclosure No. 14,850 and Research Disclosure No. 15.159, Research Disclosure No. 1
3.924, the aldol compounds described in U.S. Pat.
Metal salt complex described in No. 719.492, JP-A-53-13
Examples include urethane compounds described in No. 5.628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64,339 and JP-A-57-14.4547.
No. 58-115.438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2.226.770 or US Pat. No. 3.6T4.499 may be carried out.

In order to fully exhibit the excellent features of the silver halide photographic light-sensitive material of the present invention, the silver halide color photographic light-sensitive material of the present invention must be substantially free of benzyl alcohol and contain 0.002 mol/It. It is preferable to process with the following color developing solution containing or not containing bromine ions for a developing time of 90 seconds or less.

“Substantially free of benzyl alcohol” as stated above
What is Color Developer II! , meaning 2 ml or less per unit, preferably 0. 5mj! Hereinafter, it most preferably means that it is not contained at all.

(Example) Next, an example of the present invention will be shown. However, it is not limited to this.

Example-1 Preparation of silver halide emulsion Blue-sensitive silver halide emulsion: 32 g of lime-treated gelatin was added to 10,100 O of distilled water and dissolved at 40°C, then 5.8 g of sodium chloride was added and the temperature was raised to 75°C. raised.

Add this solution N,N'-dimethylimidazolidine-2-thione (1% aqueous solution) to 3. 8mj! Added.

Next, add 6.4 g of silver nitrate to 180 mj of distilled water! A solution obtained by dissolving 2.2 g of sodium chloride in 180 m 2 of distilled water was added to and mixed with the above solution over a period of 1° while maintaining the temperature at 75°C. Furthermore, 153.6 g of silver nitrate and 410 mj of distilled water! solution and 52.8g of sodium chloride
was dissolved in 410 ml of distilled water, and the mixture was added and mixed over 35 minutes while maintaining the temperature at 75°C. After the addition of the silver nitrate aqueous solution and the sodium chloride aqueous solution was completed, the mixture was kept at 75°C for 15 minutes and then lowered to 40°C, followed by desalting and washing with water. Furthermore, lime-processed gelatin and 3-(2-[5-chloro-3-(3-sulfonatopropyl)benzothiazolin-2-ylidenemethyl]-3-naphtho-[1,2-d
172.8 mg of triethylene ammonium salt (1thiazolio)propanesulfonic acid (S-1) was added to form an emulsion (B).

Using this emulsion (B), triethylthiourea was added to optimally chemically sensitize the emulsion (B-1), 0.05μ
Silver bromide fine grain emulsion (1) was added to emulsion (B) at a ratio of 0.
Emulsion (B-2) is obtained by adding triethylthiourea at a ratio of 6 mol % and chemically sensitizing it optimally.

Furthermore, the silver bromide fine grain emulsion used in (B-2) was chemically sensitized optimally using emulsion (2) containing 2.5X10-' mol of iridium per 1 mol of silver.
).

In each of emulsions (B-1), (B-2), and CB-3), 90 mg of the following compound was added per mole of emulsion as a stabilizer.

Green-sensitive silver halide emulsion: 32 g of lime-treated gelatin was added to 10,100 O of distilled water and dissolved at 40°C, then 3.3 g of sodium chloride was added and the temperature was raised to 52°C.

3. Add this solution N,N'-dimethylimidacylin-2-thione (1% aqueous solution). 2mj! Added. Subsequently, a solution in which 32.0 g of silver nitrate was dissolved in 200 rrl of distilled water and a solution in which 11.0 g of sodium chloride was dissolved in 200 mA of distilled water were added to and mixed with the above solution over 14 minutes while maintaining the temperature at 52°C. Furthermore, 111,128.0 g of nitric acid and 560 mj of distilled water! solution and sodium chloride 44.0
A solution prepared by dissolving 560 ml of distilled water was added and mixed over 20 minutes while maintaining the temperature at 52°C. One minute after the addition of silver nitrate aqueous solution and sodium chloride aqueous solution was completed, 2-(
5-phenyl-2-(2-[5-phenyl-3-(2-
sulfonatoethyl)benzoxazolin-2-ylidenemethyl]-1-butenyl)-3-penzooxazolio]
Ethanesulfonic acid pyridinium salt (S-2) 286.7
mg was added. After being kept at 52°C for 15 minutes, the temperature was lowered to 40'C, and desalination and water washing were performed. Furthermore, lime-treated gelatin is added to prepare a chemically sensitized emulsion, which is then converted into an emulsion (G
).

Using this emulsion (G), triethylthiourea was added to optimally chemically sensitize the emulsion (G-1), 0.05μ
Silver bromide fine grain emulsion (1) was added to the emulsion ((1,) at a ratio of 1 mol %, and triethylthiourea was further added to optimally chemically sensitize the emulsion (G-2). shall be.

Further, the silver bromide fine grain emulsion used in CG-2) contained lXl0-' mol of iridium per mol of silver, and was chemically sensitized optimally (C,-3).
shall be.

In each of emulsions (G-1), (G-2), and (G-3), 125 mg of the following compound was added per mole of emulsion as a stabilizer.

Red-sensitive silver halide emulsions: 2-[5-phenyl-2-(2-[5-phenyl-3) in green-sensitive emulsions (G-1), (G-2), CG-3)
-(2-sulfonatoethyl)benzoxazoline-2-
ylidenemethyl]-1-butenyl)3-penzooxazolio]ethanesulfonic acid pyridinium salt 286.7mg
Instead of iodide 2-[2,4-(2,2-dimethyl-1°3-propano)-5-(6-methyl-3-pentylbenzothiazolin-2-ylidene)-1,3-penta 60.0 mg of diethyl]-3-ethyl-6-methylbenzothiazolium (S-3) was added and chemically sensitized optimally to form red-sensitive emulsions (R-1) and (R-
2), (R-3), and stabilizers (G-1) to (
It was added in the same manner as G-3).

For the silver halide emulsion thus prepared, the grain shape, grain size, and grain size distribution were determined from electron micrographs. All the silver halide grains contained in the emulsion were cubic. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particles, and the particle size distribution was calculated using the value obtained by dividing the standard deviation of the particle diameter by the average particle size.

Next, X-ray diffraction method was used to determine the halogen composition of the localized phase of the particle, and X-ray diffraction method was used to determine the average halogen composition of the surface.
Each was measured using the PS method.

The results are shown in Table 1.

(Preparation of sample of color photosensitive material) Preparation of coupler emulsion used in the present invention: 19.1 g of yellow coupler (ExY) and color image stabilizer (Cpd-1)
27.2 cc of ethyl acetate and solvent (Sol
v-1) 7.7 cc was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8 cc.
% gelatin aqueous solution (185 cc).

In the same manner, other emulsions for magenta, cyan, a protective layer, and an intermediate layer were prepared.

A multilayer color photosensitive material A having the layer structure shown below was obtained on a paper support laminated on both sides with polyethylene (1st N
The leftover ethylene contained a white pigment (TiOx) and a bluish dye (ulmarine).

The numbers represent the coating amount (g/rrf), and the silver halide amount represents the coating amount in terms of silver.

Dye-R (n=o, n5=1 and n-2
) is mixed and added gelatin (1.0 g/po) is coated to prevent Halley silane, an undercoat layer is provided, and the first
1i! Layers i to 7 were provided as follows.

No.-M (blue feeling N) Silver halide emulsion 0.25 stabilizer (
Stab-1) lXl0-'gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd-1)
o, 19 solvent (Solv-1)
0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.31 Stabilizer (
Stab-1) 0.5X10-' gelatin
1.24 magenta coupler (E
xM-1) 0.31 color image stabilizer (Cpd-3)
0.25 color image stabilizer (Cpd-4)
0.12 Solvent, medium (Solv-2) 0
．． 42 Fourth layer (UV absorption N) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.62 Color mixing prevention agent (
CPd-5) 0.05 Solvent (Solv-3
) 0.24 Fifth layer (red sensitive layer) Silver halide emulsion 0.21 Super sensitizer (S-4) 2.6X10-'' stabilizer (St
ab-1) lXl0-' gelatin
1.34 cyan coupler (E x
Blend of C1 and C2゜1:1) 0.
34 color image stabilizer (Cpd-6) 0.17 polymer (Cpd-7) 0.40 solvent (
Solv-4) 0.23 Sixth layer (UV absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.21 Solvent (Solv
-3) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 As a hardening agent for each layer, 1-oxy -3,5-dichloro-8-triazine sodium salt was used.

The compounds used are shown below.

Stab-1 Stab-2 Stab-3 CHl xY-1 ExM-1 C1 ExM-3 l ExM-5 xCI xC4 Ca 6b C CaHw(t) 'Cpd-7 (polymer) →CH, -CHh- C0NHC,H* (t) Average molecular weight 80.000 UV-1 (ultraviolet absorber) Cpd-6a:6b:6c=2:9:8 mixture (weight ratio) Solv-1 (solvent) Solv-2 0=P(O- CsH+t(iso))solv-3 0=P(O-C1H+q(iso))zFor each sample, a 10 and 1150 second exposure was applied through an optical wedge and each blue, green or red filter, followed by color development after 8 minutes, respectively. did. In addition, each sample obtained by performing continuous processing (running test) using substantially the same type of color photosensitive material until twice the capacity of the color developer tank was replenished, and then exposure for 10 seconds as described above. was developed.

A sensitometer (Model FWH, manufactured by Fuji Film Co., Ltd., light source color temperature: 3200°K) was used for the 10-second exposure. The exposure amount is approximately 250
It was LMS.

The concentration of each sample strip obtained was measured using a Macbeth densitometer. Each blue (B), green (G) or red (R)
Measure the filter density, its minimum density (Dmin),
The stability of each characteristic was evaluated by comparing the maximum density (Dmax) and each gradation with sample strips obtained after 8 minutes of exposure.

The results are shown in Table 3.

The development process and processing solution used were as follows.

Temperature u 1m! LJL fl Long-term color development 38℃ 45 seconds 200m
A! 84! Bleach fixing 30-36℃ 45
Seconds 161mI! , 84! Rinse 0 30~
37℃ 20 seconds -42 rinse 0 30~37℃
20 seconds 41 Rinse ■ 30
～37℃ 20 seconds 41 Rinse ■
30~37°C 30 seconds 200mj! 4
I! .

Drying: 70 to 80°C for 60 seconds per batch of photosensitive material (4 tank countercurrent flow method from rinsing ■ to ■) The composition of each processing solution is as follows.

Left standing two developing waves A ffl liquid replenisher water
800mj! 800ml! .

Ethylenediamine-N,N,N,N-tetramethylenephosphonic acid 3. Og 6.0g diethylhydroxylamine 5. Og 7.0g Sodium chloride 1.8g - Potassium carbonate
25g 25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 11. 0g triethanolamine 10g 10g optical brightener (
4,4' Add monodiaminostyl water 100100O10100O! pH
(25°c) 10.05 10.45 Temperature liquid (tank liquid and refill liquid are the same) water
400mf ammonium thiosulfate (7
0%) 100m4 Sodium sulfite
17g Iron(III) ethylenediaminetetraacetate Ammonium 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water
1000mlpH (25°C)
5.40 yu 2 prison fluid (tank fluid and refill fluid are the same) Ion exchange water (calcium, magnesium each 3 ppm
(below) The sensitometry is processed at the start and end of the run, and the minimum concentration (Dmin) and maximum concentration (Dm
ax) and sensitivity (fogE value representing density 0.5) due to continuous processing were measured using a Macbeth densitometer, and the results are shown in Table 3. In the sensitivity change, + indicates the direction of increasing sensitivity, and - indicates the direction of decreasing sensitivity.

The color light-sensitive material using the silver halide emulsion having a halogen composition according to the present invention shows that an image with sufficient color density can be obtained by color development for 45 seconds, and in particular B
-2, G-2, and R-2 improve the sensitivity and high illuminance failure, and particularly suppress fog (Dmin), indicating that the sensitivity is relatively high. In particular, the use of silver halide auxiliary grains improves the stability of continuous processing.

In particular, B-3, which has a localized phase and uses different metal ions,
It has been shown that when G-3 and R-3 are used together with silver halide auxiliary grains in the intermediate layer or photosensitive layer, stability in continuous processing, sensitivity, and dependence on exposure conditions are improved. In particular, if an antifoggant or the like is adsorbed onto silver halide auxiliary grains and used in the intermediate layer, it is possible to prevent an increase in fog during continuous processing without reducing sensitivity. It is also shown that the stability of continuous processing is improved when a pyrazoloazole type magenta coupler is used as the color coupler.

Example 2 In Example 1, each sample was exposed in the same manner, and then 0.5 g (4xlO-'mol)/! of potassium bromide was added to the color developer A in Example 1. Development was carried out in the same manner using the added color developer B.

When developed at 38°C for 45 seconds, the color density was extremely low;
Color development in less than 0 seconds is no longer possible. However, if a 100 second development process is performed using the above-mentioned replenisher, it becomes extremely unstable. If 0.3 g KBr/f is added to the replenisher and continuous processing is performed, for example, the difference between sample A and sample 101 becomes smaller. However, the sensitivity difference, Dmax, was better, and the difference in Dmin disappeared.

The results are shown in Table 4.

Table 4 Next, samples A, D, 101, 105, 106, and 107 were exposed in the same manner, and then 0.2 g (1.7 x 10-'' mole)/2 potassium bromide was added to color developer A. Developer C (The replenisher contains 0.0% potassium bromide.
15 g/l added) for 60 seconds at 38°C, and then processed in the same manner. The results obtained are shown in Table 5.

Table 5 Color photosensitive materials using silver halide auxiliary grains are as follows:
This shows that the stability of continuous processing is better than that without using it.

Similarly, similar effects can be observed by replacing ExM-4 with the above-mentioned exemplary compounds M-11 to M-16 and replacing ExM-5 with the above-mentioned exemplary compounds M-1 to M-10. Furthermore, similar effects can be observed even if the support is changed to a transparent support.

(Effects of the Invention) According to the present invention, in a silver halide color light-sensitive material containing an emulsion containing high silver chloride-containing silver halide grains suitable for rapid processing, it is possible to overcome the ease of fogging and Stable and excellent finish quality can be obtained during processing, especially during continuous processing.

Claims (7)

[Claims] (1) In a color photosensitive material in which a photosensitive layer, an intermediate layer, and a protective layer containing a color coupler and a photosensitive silver halide emulsion are provided on a support, at least one of the silver halide emulsion photosensitive layers is provided. The photosensitive silver halide emulsion used in the layer contains silver chlorobromide with an average silver chloride content of 90 mol% or more,
A silver halide color photosensitive material further comprising silver halide auxiliary grains that are not substantially developed in at least one of the photosensitive layer, an intermediate layer adjacent to the photosensitive layer, and a protective layer. (2) The silver halide color according to claim (1), wherein the silver halide auxiliary grains are silver chloride of 0.2 μm or less or silver chlorobromide with a silver chloride content of 50 mol% or more. photosensitive material. (3) The silver halide color according to claim (1) or (2), in which the photosensitive silver halide emulsion has localized phases with different halogen compositions inside or on the surface of its grains. photosensitive material. (4) A photosensitive silver halide emulsion has a discontinuous isolated localized phase on the surface of its grains, and its silver bromide content is 15
Claims (1) to (3) that are mol% or more
The silver halide color light-sensitive material according to any one of the above items. (5) The silver halide color photosensitive material according to any one of claims (1) to (4), which contains a pyrazoloazole magenta coupler represented by the following general formula [M-III]. material. General formula [M-III] ▲ Numerical formulas, chemical formulas, tables, etc. (The azole ring has a substituent including a fused ring. X_2 represents a leaving group.) (6) A color photosensitive material having a photosensitive layer containing a color coupler and a photosensitive silver halide emulsion, an intermediate layer and a protective layer provided on a support, and at least one aromatic primary amine derivative. In a method of development using a color developing solution as a color developing agent, the average silver chloride content of the photosensitive silver halide emulsion used in at least one of the silver halide emulsion photosensitive layers is 90 mol% or more. , at least one of the photosensitive layer, the intermediate layer and the protective layer adjacent to the photosensitive layer contains silver halide auxiliary grains that are not substantially developed, and further uses a color developing solution that does not substantially contain water-soluble bromide. A method for developing a silver halide color light-sensitive material, characterized in that color development is carried out in a time of 90 seconds or less. (7) The development processing method according to claim (6), wherein the amount of replenishment of the color developing solution is 250 ml or less per 1 m^2 of the silver halide color light-sensitive material.