JPH02190851A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the degradation in fogging, sensitivity and graininess by irradiation of radiations by specifying the average silver iodide contents of silver halide in all emulsion layers and incorporating a specific compd. into the layers. CONSTITUTION:The average silver iodide contents of the silver halide in all the emulsion layers of a red sensitive silver halide emulsion layer, green sensitive silver halide emulsion layer and blue sensitive silver halide emulsion layer are specified to >=10mol% and the compd. expressed by the formula Q-SM<1> is incorporated therein. In the formula, Q denotes the residual heterocyclic group directly or indirectly combined with one kind selected from the group consisting of -SO3M<2>, -COOM<2>, etc.; M<1>, M<2> independently denote a hydrogen atom, alkaline metal, quaternary ammonium, quaternary phosphonium. The degradation in the fogging, sensitivity and graininess by the irradiation of radiations is prevented in this way.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a color photographic material having a high silver iodide content, improved graininess, and improved desilvering properties. It relates to photographic materials.

(Prior Art) In recent years, demands on photographic light-sensitive materials, especially photographic light-sensitive materials, have become increasingly strict, and light-sensitive materials with high sensitivity and fine grains have been required.

A photographic material containing emulsion grains with a high silver iodide content and a controlled grain structure as a means of fine graining has been proposed, for example, in JP-A-60-143331 and JP-A-5B-181037. Even if these are applied only to one emulsion layer, the grain improvement effect is still insufficient, and as described in JP-A-61-7041, emulsions with a high silver iodide content cannot be processed in the desilvering process. Especially in the fixing process, silver salt and/or
Alternatively, there was a problem that it was difficult to remove silver.

In addition, a photographic material in which the average silver iodide content of silver halide in all emulsion layers in the photographic material is 8 mol% or more is disclosed in Japanese Patent Application Laid-Open No.
No. 128443, the grain quality was particularly improved, but the silver iodide content described in that patent was insufficient in its grain improvement effect, and the resistance to radiation irradiation and desilvering properties were insufficient. There was also a problem.

Furthermore, photosensitive materials containing the compound of the present invention include, for example,
It is described in JP-A No. 62-89952 and JP-A No. 61-282841, etc., but as stated in these patents, combining with an emulsion with a low silver iodide content improves sensitivity and Capri etc. It was considered to be preferable from the viewpoint of properties and processability.

However, when emulsions and light-sensitive materials with low silver iodide content are exposed to environmental radiation or artificial radiation, fog worsens and
It became clear that the sensitivity decreased and the graininess deteriorated significantly, and furthermore, the desilvering property was not so good. Conventionally, as disclosed in JP-A-62-89963, a low silver iodide content was considered essential for shortening the desilvering process.

(Problems to be Solved by the Invention) The purpose of the present invention is firstly to provide a color photographic light-sensitive material with extremely excellent graininess, and secondly, after being exposed to natural environmental radiation or artificial radiation. Another object of the present invention is to provide a color photographic light-sensitive material that exhibits little increase in fog and decrease in sensitivity.A third object is to provide a color photographic light-sensitive material that exhibits a high desilvering speed, particularly a high fixing speed.

(Means for Solving the Problems) These objects of the present invention have been achieved by the following color photographic material.

In a silver halide color photographic light-sensitive material having one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support, the silver halide in all emulsion layers is The average silver iodide content of
1. A silver halide color photographic material containing 0 mol % or more of a compound represented by the following general formula (I).

General formula (I) where Q is -3OffM''-C00M''-OH
and −Nl? 'l? "represents a heterocyclic residue bound directly or indirectly to at least one member selected from the group consisting of ``, where Ml and Mt independently represent a hydrogen atom, an alkali metal,
Represents quaternary ammonium, quaternary phosphonium, R'
, Rχ represents a hydrogen atom or a substituted or unsubstituted alkyl group.

In the present invention, the average silver iodide content of silver halide in all emulsion layers refers to the average silver iodide content of all silver halides (not including metallic silver) present in the light-sensitive material! It is the value obtained by dividing the total iodine content (I) by (Ag .5 to 20.0 mol%, more preferably 11.0 to 15.0 mol%.

In the present invention, it is necessary that each of the red, green, and blue ill-light silver halide emulsion layers have IN or higher, but it is preferable that they each have two or more layers with different sensitivities, and the green-sensitive layer and the red-sensitive silver halide emulsion layer have different sensitivities. More preferably, the layers consist of 3N with different sensitivities.

In the present invention, the average silver iodide content of at least one emulsion layer is preferably 12 mol% or more, more preferably 14 mol% or more.

In the present invention, at least emulsion grains in which silver iodobromide containing 15 to 45 mol % of silver iodide exists with a clear layered structure and the silver iodide content in the entire grain exceeds 10 mol % are treated as It is preferable to include two or more layers.

The emulsion grains will be explained below.

The clear layered structure mentioned here can be determined by an X-ray diffraction method. An example of applying the X-ray diffraction method to silver halide grains is described in H. Hirsch, Journal of Photographic Inc. Science, Vol. 10 (I962), pages 129 onwards. -If the lattice constant is determined by the halogen composition, Black's condition (2dsinθ=nλ)
A diffraction peak occurs at a diffraction angle that satisfies .

Regarding the measurement method of X-ray diffraction, please refer to Basic Analytical Chemistry Course 24rX
vA Analysis” (Kyoritsu Shuppan) and “X-ray Diffraction Guide” (Rigaku Denki Co., Ltd.). The standard measurement method is to use Cu as a target and obtain the diffraction curve of the (220) plane of silver halide using β rays as a radiation source (tube voltage 40 kV, tube current 60 mA). In order to increase the resolution of the measuring device, the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed are selected appropriately and the measurement accuracy is confirmed using a standard sample such as silicon. There is a need to.

The clear layered structure in the present invention refers to the curve of diffraction intensity versus diffraction angle of the (220) plane of silver halide using β rays for Cu with a diffraction angle (2θ) in the range of 38° to 42°. At least two diffraction peaks, one corresponding to a high iodine layer containing 15 to 45 mol% silver iodide and the other diffraction peak corresponding to a low iodine layer containing 8 mol% or less silver iodide. A case where there is a maximum and one small peak between them, and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/I of the diffraction intensity of the peak corresponding to the low iodine layer. More preferably, the diffraction intensity ratio is 115 to 3/1,
This is especially the case when the ratio is 1/3 to 3/1.

In the present invention, the emulsion having substantially two distinct layered structures is more preferably one in which the minimum diffraction intensity between the two peaks is one of two or more diffraction maxima (peaks) with a weaker intensity. It is preferably 90% or less.

More preferably 80% or less, particularly preferably 6
It is 0% or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and 4. For example, it is explained in Experimental Physics Course 11 Lattice Defects (Kyoritsu Publishing).

It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentzian function and to analyze it using a curve analyzer manufactured by DOPont.

Even in the case of an emulsion in which two types of grains having different halogen compositions coexist and do not have a clear layered structure, two peaks appear in the X-ray diffraction.

Such emulsions cannot exhibit the excellent photographic performance obtained with the present invention.

In order to judge whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the XvA diffraction method, the EPMA method (
Electron-Probe Micro.

This is possible by using the Analyzer method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and elemental analysis of minute portions can be carried out by X-ray analysis using sit beam excitation by irradiating the sample with an electron beam.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

By confirming the halogen composition of a small number of grains (50 in total) by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention or not.

In the emulsion of the present invention, it is preferable that the iodine content among the grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is preferably 50% or less, more preferably 35% or less.

Another preferred interparticle iodine distribution is one in which the logarithm of particle size and iodine content exhibit a positive correlation. In other words, the iodine content of large size particles is high and the iodine content of small size particles is low. Emulsions exhibiting such a correlation give favorable results in terms of graininess. This correlation coefficient is preferably 40% or more, more preferably 50% or more.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but a higher proportion of silver bromide is preferable, and the silver iodide content is 15 to 45 mol%. Any amount is fine, but preferably 25 to 45 mol%, more preferably 3
It is 0 to 45 mol%. The most preferred silver halide for the core portion is silver iodobromide containing 30 to 45% silver iodide.

The composition of the outermost layer is silver halide containing 8 mol% or less of silver iodide, more preferably silver halide containing 6 mol% or less of silver iodide.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. Particularly preferred for the outermost layer is silver iodobromide or silver bromide containing 0.1 to 6 mol % of silver iodide.

Regarding the halogen composition of the entire grain, it is preferable that the silver iodide content exceeds 10 mol%, more preferably 11 to 20 mol%, and still more preferably 14 to 17 mol%.

The size of the silver halide grains having a clear layered structure of the present invention is 0.10 to 3.0 μm, preferably 0.0 μm.
~2.00 μm, more preferably 0.30-1.7 μm
1 More preferably, it is 0.40 to 1.4 μm.

The average grain size of silver halide grains in the present invention is
T.H. James (T.H.

“The Theory of the Photographic Ink Process” by J awes et al.
or thePhotographic Process
ss) 3rd edition 39 pages, published by Macmillan (I966)
is the geometric mean value of particle size well known in the art as described in . In addition, the particle size is determined by "Introduction to Particle Size Measurement" by Masafumi Marukaku (Powder Engineering Society Journal, Vol. 17, 299-31).
It is expressed in equivalent sphere diameter as described on page 3 (I980), and can be measured by methods such as the Coulter counter method, single particle light scattering method, and laser light scattering method.

The type of silver halide grains having a clear layered structure of the present invention may have a regular crystal shape (normal crystal grain) such as hexahedron, octahedron, dodecahedron, or dodecahedron. It may have an irregular crystal shape such as a spherical shape, a potato shape, or a tabular shape. In particular, the aspect ratio is 1.0 to 10, especially 1.
5 to 8 twinned grains are preferred.

In the case of normal crystal grains, grains having 50% or more (I11) planes are particularly preferred. Even in the case of irregular crystal forms (I11
) Particles having 50% or more planes are particularly preferred. (I11
) surface pressure ratio can be determined by the Kubelka-Munk dye adsorption method. This is because the dye is preferentially adsorbed to either the (I11) plane or the (I00) plane, and the association state of the dye on the (I11) plane and the association state of the dye on the (I00) plane are spectrally different. select. The surface pressure ratio of the (I11) plane can be determined by adding such a dye to an emulsion and examining the spectroscopic spectrum in detail with respect to the amount of the dye added.

The emulsions preferred for use in the present invention can have a broad grain size distribution, but emulsions with a narrow grain size distribution are preferred. In particular, in the case of normal crystal grains, 90% of the total weight or number of silver halide grains in each emulsion
A monodispersed emulsion in which the grain size that accounts for % of the average grain size is within 140% or even within ±30% of the average grain size can also be used.

The effect of the present invention can be best seen in twin grains. It is preferable to contain tabular grains having two or more parallel twin planes in a projected area of 30% or more, preferably 50% or more, more preferably 70% or more.

The emulsion of the present invention having a clearly layered structure can be prepared by selecting and combining various methods known in the field of silver halide photographic materials.

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting the soluble root salt and soluble halogen salt can be selected from the one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. As another type of simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (eg, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used.

Silver halide solvents such as ammonia, rhodan salts, thioureas, thioethers, and amines may be selected and used during core preparation.It is desirable that the grain size distribution of the core grains be narrow emulsions.Especially for the monodisperse cores mentioned above. Emulsions are preferred, where the halogen composition, especially the iodine content, of the individual grains is more uniform at the core stage.

Whether the halogen composition of each particle is uniform can be determined by the aforementioned X-ray diffraction method and EPMA method. When the halogen composition of the core particles is more uniform, the diffraction width of X-ray diffraction becomes narrower and sharper peaks are obtained.

After creating a silver iodobromide seed crystal containing a high concentration of silver iodide,
The iodine odor can be reduced by the method of accelerating the addition rate over time as disclosed in Japanese Patent Publication No. 48-36890 by Irie and Lead Powder, or the method of increasing the addition rate over time as disclosed by Saito in U.S. Pat. No. 4,242.445. Uniform silver iodobromide can also be obtained by the method of growing silver iodobromide grains.

These methods give particularly favorable results. Irie et al.'s method involves the production of poorly soluble inorganic crystals for photography by a double decomposition reaction in which two or more inorganic salt aqueous solutions are simultaneously added in approximately equal amounts in the presence of a protective colloid. , to be added at an addition rate Q that is above a certain temperature acceleration and below an addition rate that is proportional to the total surface area of the growing sparingly soluble inorganic salt crystal, that is, at Q = γ or more and Q = αtt + βt + γ or less. It is.

τ'ji Saito's method is a method for producing silver halide crystals in which two or more types of inorganic salt aqueous solutions are simultaneously added in the presence of a protective colloid, and the concentration of the inorganic salt aqueous solution to be reacted is adjusted so that almost no new crystal nuclei are produced during the crystal growth period. It is also possible to increase it to the extent that it never occurs. In preparing silver halide grains having a clear layered structure according to the present invention, shelling may be carried out directly after core grain formation, but it is preferable to carry out shelling after washing the core emulsion with water for desalting.

Shelling can also be prepared by various methods known in the field of silver halide photographic materials, but a simultaneous mixing method is preferred. The aforementioned methods of Irie et al. and Saito's method are preferred as methods for producing emulsions having a clear layered structure.

In the case of fine-grain emulsions, conventional tools are useful for preparing grains with a clear layered structure, but they alone are not sufficient to improve the degree of perfection of the layered structure. First, it is necessary to carefully determine the halogen composition of the high iodine layer. Silver iodide and silver bromide have different thermodynamically stable crystal structures, and it is known that mixed crystals do not form at all composition ratios. The mixed crystal composition ratio depends on the temperature during particle preparation, but is 15~
It is important to select the optimum one from within the range of 45 mol%. Although the stable mixed crystal composition ratio depends on the atmosphere, 30
It is estimated that it exists in ~45 mol%.

The temperature when growing the low iodine layer outside the high iodine layer,
Of course it is important to select pi, pAg, stirring conditions, etc., but it is also important to select the amount of protective colloid when growing a low iodine layer, and to select the amount of halogenated spectral enhancing dye, antifogging agent, stabilizer, etc. It is preferable to take measures such as growing a low iodine layer in the presence of a compound that adsorbs on the silver surface. It is also effective to add fine grain silver halide instead of adding water-soluble root salt and water-soluble alkali metal halide when growing a low iodine layer.

As mentioned above, in the present invention, silver halide grains having a clear layered structure mean that there are two different halogen compositions within the grains.
It has been explained that there are essentially three or more regions, and the center side of the particle is the core part, and the surface side is the shell part.

Substantially, the two are the core part and the third region (other than the shell part).
For example, this means that there may be a layer between the central core portion and the outermost shell portion.

However, even if such a third region exists, when an X-ray diffraction pattern is obtained as described above, two peaks (two peaks corresponding to a high iodine portion and a low iodine portion) are obtained.
This means that it may exist within a range that does not substantially affect the shape of the .

That is, there is a core region with high iodine content, a middle region, and a shell region with low iodine content, and the X-ray diffraction pattern has two peaks and two peaks.
There is one minimum part between the two peaks, and the diffraction intensity corresponding to the high iodine part is 1/10 to 1/10 of that of the low iodine part.
3/1, preferably 1/y to 3/1, especially 1/3 to 3/1
1, and the minimum portion is less than 90%, preferably less than 80%, especially less than 70% of the smaller of the two peaks, then such silver halide grains have substantially two distinct layered structures. They are particles with a structure.

The same applies when the third region exists inside the core portion.

The color light-sensitive material of the present invention preferably has at least two emulsion layers containing the silver halide grains of the present invention, and in the emulsion layer, the grains of the present invention are present in the core layer. It is present in an amount of preferably 50% or more, more preferably 70% or more, particularly preferably 90% or more of the sum of the projected areas of all silver halide grains.

Dyes used when growing the low iodine layer include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, a chain of nuclei commonly used for cyanine dyes can also be applied as a basic heteroartic ring nucleus. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; i.e., indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole Nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be directly converted onto carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heteroartic ring nucleus such as a 4-dione nucleus, a thiosilydine-2,4-dione nucleus, a rhodanine nucleus, a thiobarbyl nucleus, etc. can be applied.

For example, Re5search Disclosure+I
Compounds described in teml 7643, page 23, section 2 (December 1978) or the compounds described in the cited literature can be used.

Typical specific examples include the compounds described in Tokoku 1 Sen No. 63-212932.

Antifoggants and stabilizers are also useful compounds when growing low iodine layers. Re5search D described above
It is possible to select and use the compounds shown in the isclosure.

Silver halides of different compositions may be further bonded to the emulsion of the present invention by epitaxial bonding, or compounds other than silver halide such as rotane or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The total coating silver of the photosensitive material of the present invention! (Including metallic silver) 3.0 to 8.0 g/n (preferably 4.0 to 7.0 g/n)
5g/nf is better than 4.5~7, Og/r
rf is more preferred. If the amount of silver is greater than this, there will be problems with desilvering properties and radiation resistance, and if it is less than this, graininess will deteriorate.

The film thickness of the photosensitive material of the present invention is preferably 13 to 25 μm, more preferably 15 to 23 μm, and 17 to 22 μm.
is even more preferable. If it is thicker than this, the desilvering performance will be poor, and if it is thinner, there will be problems such as insufficient color density and weak film strength.

Next, the compound of general formula (I) will be explained.

-Eye formula (I) In the formula, Q represents a heterocyclic residue directly or indirectly bound to at least one selected from the group consisting of -SO3M2-C0O" -OH and -NR'R", and M'
, M'' independently represent a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium, and R1 and Rt represent a hydrogen atom or a substituted or unsubstituted alkyl group.

It is thought that the compound of general formula (I) is imparted with water solubility or has improved water solubility in the pH atmosphere of the developer, and flows out from the photosensitive material into the developer. In other words, if the compound of general formula (I) is contained in a light-sensitive material, it will dissolve in the developer and contaminate the developer. Despite this, it is truly surprising that the change in development finish characteristics is small and the capri is low. This kind of unpredictable effect is caused by -mathematical [! ] of the compound of
This is thought to be because the effect is significantly different when it is contained in a photosensitive material and when it flows out into the developer, but the details are unknown, and future research will clarify its behavior. There will be.

As a photosensitive material obtained by subjecting the compound of the general formula (I) used in the present invention to the compound of formula (I),
i is -3O, Hl-COOII, -OH.

A silver halide color photosensitive material r1 containing a heterocyclic mercapto compound containing at least one group selected from -Nllffi is disclosed, but such a photosensitive material can be developed with a low developer replenishment amount. There is no mention of whether or not the above-mentioned problems can be solved by processing.

- Specific examples of the heterocyclic residue represented by Q in formula (I) include an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a l-lyazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, and a bentazole ring. , pyrimidine ring, thiasia ring, triazine ring, thiadiazine ring, etc., or rings fused with other carbocycles or heterocycles, such as penduteazole ring, benzotriazole ring, benzydazole ring, benzoxazole ring, benzoselenazole ring, naphthoxazole ring ring, triazaindolizine ring, diazaindolizine ring, tetraazaindolizine ring, etc.

-a Among the mercapto heterocyclic compounds represented by the formula (+), -formulas (Il) and (
Examples include those represented by Il.

General formula (IT) General formula (I) In general formula (IT), Y and Z are independently a nitrogen atom or CR'(R' is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted ) represents an aryl group, R3 is -5O311''-COOM
It is a UQ residue substituted with at least one selected from the group consisting of "-OH and -NR'R", and specifically, it is an alkyl group having 1 to 20 carbon atoms (for example, a methyl group,
ethyl group, propyl group, hexyl group, dodecyl group, octadecyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, etc.), and Ll is -5-
1-〇--N-1-CO-1-SO- and -SO.

represents a linking group selected from the group consisting of, n is O or 1
It is.

In addition to these alkyl groups and aryl groups, halogen atoms (F, Ci!, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), aryloxy groups (phenoxy group, etc.), alkyl 7J (R1 is an aryl group) ), aryl group (I?1 is an alkyl group)
, amide group (acetamido group, benzoylamino group, etc.), carbamoyl group (MffA carbamoyl group, phenylcarbamoyl group, methylcarbamoyl group, etc.), sulfonamide group (methanesulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group ( filA sulfamoyl group, methylcarbamoyl group, phenylsulfamoyl method, etc.), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl group (methylsulfinyl group, phenylsulfinyl group, etc.),
Other groups such as cyano groups, alkoxycarbonyl groups (such as methoxycarbonyl groups), aryloxycarbonyl groups (such as phenoxycarbonyl groups), and nitro groups
It may be WIA'd by the group.

Here, the substituent of R3 -5Ox M, COOM''
When there are two or more -OH and -NR'R'', they may be the same or different.

M 2 ' means the same as that represented by general formula (I).

Next, in formula (III), X represents a sulfur atom, a substituted or unsubstituted alkyl group, or ff1A or an unsubstituted aryl group.

t,' is -CONR'-NR'CO--3o□NR
'-NI'?'SO! OCOC00-
-3--NR' --CO--3O- I-0COO--NR'C0NR'--NR'CO
O-10CONR'- or -NR'SO, NR muff-
In the expressions, R'' and R represent each a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted 1# or an unsubstituted aryl group.

R3, M'' means the same as those represented by the -catalytic formulas (I) and (II), and n represents 0 or 1.

Furthermore, as the 1tlA group of the alkyl group, °, and aryl group represented by R4, R6, R&, and R7, R3
The same ones mentioned as the WIA group can be mentioned.

In the general formula, R3 is -3O:l M'' and C0
0M2 is particularly preferred.

Specific examples of preferred compounds represented by general formula (I) used in the present invention are shown below.

CHIGH20H 0OH CHvCHtCHtSOsN& CH,CHtSO3Na -N The compounds represented by the general formula (or) are known and can be synthesized by methods described in the following literature.

U.S. Patent No. 2,585.388, 2.54L, 9
No. 24, Special Publication No. 42-21,842, Japanese Patent Publication No. 53-5
No. 0.169, British Patent No. 1,275,701, D. A. Berginis et al., 1 Journal of Heterocyclic Chemistry'' (D. A. Berge
set, al,, ”Journal of 1l
eterocyclic Chemist, ry') Volume 15, No. 981 (No. I978), “The Chemistry of Heterocyclic Chemistry” Imidazole
and Derivatives, Part 1 (“The
Chea+1stry of l1terocycle
ic ChemistryImidazole and
Derivatives part I), 3
pp. 36-9, Chemical Abstracts
tract), AE, No. 7921 (I963), 39
4 pages, Bogarth, “Journal Op Chemical.
Society (I!,, Iloggarth “Jo”
urnal of Chemical Society
”) L pages 160-1 (I949), and S, R
, Saladler, W, Kawa, 'Organic Functional Group Prevalence', 7;
ro,”Organic Functional G
roupPreparation” Acaden+
lc Press) page 312A'5, M, Chaffldon, et al.
, Bulletin de la 5ociete
Chi+m1que daFrance), 723
(I954), D.A., Shirley, D.W., Alley, Journal of the American Chemical
Society (D, A, 5hirley
, D, W, 8l1ey, -1, Ame
r.

Chem, Soc, ), 1 Lord, 4922 (I95
4) A. Ball, W., Marchwald, Belichte (A.

Wohl, W., March%4ald, Ber.
) (Journal of the German Chemical Society), vol. 22, p. 568 (I8
89) Journal of the American Chemical Society (J, Amer, Chem, Soc,), 44
U.S. Patent No. 3,017,270, British Patent No. 940.
No. 169, Japanese Patent Publication No. 8.334/1983, Japanese Patent Publication No. 55/1983
No. 9,463, Advanced In Heterocyclic Chemistry
ic Chemistry), 9.165-209 (
I96B) West German Patent No. 2.716.707, The Chemistry of Heterocyclic Compounders, Imidazole & Derivatives (The
Chemistry of Heterocycle
c CompoundsIn+1dazole and
Derivatives), Vol L, 38
4 pages.

Organi 7li Synthesis (Org, 5ynLh,
) r'/, .

Berichte ([ler,), 9.465 (I97
6), Journal of the American Chemical Society (J, 8mer, Chem, Soc,)
, 45.2390 JP-A-50-89,034, 5
No. 3-28,426, No. 55-21.007, and Special Publication No. 40-28.496.

The compound represented by the general formula (I) is contained in the silver halide emulsion layer and the hydrophilic colloid N (intermediate layer, surface protective layer, yellow filter layer, antihalation layer, etc.).

It is preferable to contain it in a silver halide emulsion layer or a layer adjacent thereto.

In addition, the amount added is lXl0-'~lXl0-'mo
l/m", preferably 5X10-' to lXl0
-'mol/m'', more preferably lXl0-' ~3
X10"mol/m".

In the light-sensitive material of the present invention, it is sufficient that at least IN of each of the silver halide emulsion layers of the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer is provided on the support. There are no particular restrictions on the number or order of the non-light-sensitive layers; a typical example is a support that includes a plurality of silver halide emulsion layers with substantially the same color sensitivity but different photointensities. A silver halide photographic material having at least one blue-sensitive, green-sensitive, and red-sensitive photosensitive layer consisting of -i
The unit photosensitive layers are arranged in order from the support side: a red-sensitive layer,
The green-sensitive layer is installed in that order, followed by the blue-sensitive layer.

However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61,20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the halogen emulsion so that the intensity of light decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
II2751, II62-200350, II62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (B)l) / high-sensitivity green-sensitivity 1 (G)l) / low-sensitivity green Photosensitivity i (G
L)/high-sensitivity red-sensitive layer (R) I>/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH
/RL order or Bl(/BL/G)l/GL/I?
They can be installed in the order of L/R11, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer is arranged in the order of blue-sensitive layer/GL/RL/'Gl(/R)I from the side farthest from the support. You can also.

Furthermore, as described in Japanese Patent Publication No. 49-15495, the earth and stone are used as a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
The same layer may be arranged in the order of medium sensitivity emulsion layer/high sensitivity emulsion N/low anger emulsion layer from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The silver halide other than the above-mentioned silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodo containing about 30 mol% or less of silver iodide. It is silver bromide.

Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Halogenation in photographic emulsions! ! Particles are cubic, octahedral,
It may have a regular crystal shape such as a tetradecahedron, an irregular crystal shape such as a spherical shape or a plate shape, a crystal defect such as a twin plane, or a composite shape thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) k17643 (
December 1978), pp. 22-23 1"■, Emulsion Production (
Emulsion preparation and
types)”, and Nα18716 (I9
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafki
des, Chemie et Physique P
photograph-4que, Paul Mont
e, I+ 1967), by Duffin [Photographic Emulsion Chemistry],
Published by Focal Press (G, F, Duffin.

Photographic Emulsion Che
mistry (Focal Press+1966)
), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikmanet
al,, Making and Coating P
photographic Emul-sion, Fo
Cal Press+ 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic5ci).
ence and Engineering), Vol. 14, pp. 248-257 (I970); U.S. Patent No. 4
, 434,226, 4.414.310, 4.
433,048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver halide or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and K 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Meng ■Star 1! 1 Chemical sensitizer, page 23, page 648, right paddle 2 Sensitivity increasing agent Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Strong stimulants
Page 649 right column (capital) 4 Brightener Page 24 5 Anti-fogging IP1 Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, Page 650 left column Ultraviolet rays Absorbent 7 Anti-stain agent Page 25, right column, page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 2G page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 12 Coating aid, pages 26-27 Page 650 Right paddle surfactant 13 Scratch 7 page 27 Same as above Patch Also, photograph with formaldehyde gas In order to prevent performance deterioration, US Patent No. 4,411,987 and US Pat.
It is preferable to add a compound capable of reacting with formaldehyde and immobilizing it to the photoluminescent material, as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. 17643, described in the patent described in ■-C-C.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4.022,620, No. 4.3
No. 26.024, No. 4,401,752, No. 4.
No. 248.961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476.760, U.S. Patent No. 3,973,968, No. 4.314,
No. 023, No. 4.511.649, European Patent No. 24
9.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3゜725,064, Research Disclosure Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure Nα24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4.500, 630, No. 4,540,654
No. 4,556,630, WO (PC?) 88
Particularly preferred are those described in No. 104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4,052.212.
No. 4.146.396, No. 4,228.23
No. 3, No. 4,296.200, No. 2,369.9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2.895.826, No. 3,772
．． No. 002, No. 3.758,308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
A, No. 249°453A, U.S. Patent No. 3.446
, No. 622, No. 4,333,999, No. 4,77
No. 5,616, No. 4,451,559, No. 4.4
No. 27,767, No. 4,690,889, No. 4,
Preferably, those described in No. 254°212, No. 4,296,199, and JP-A-61-42658 are preferred.

Colored couplers for correcting unnecessary absorption of color pigments are available from Research Disclosure Koji 17643.
- Section G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138,258, British Patent No. 1.146.
No. 368 is preferred, and also U.S. Pat.
, 774.181, which corrects unnecessary absorption of coloring dyes by means of fluorescent dyes released during coupling, and couplers that react with developing agents to form dyes, as described in U.S. Pat. No. 4,777.120 It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, No. 570, European Patent No. 96,570, West German Patent (
The one described in Japanese Publication No. 3,234,533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DIR coupler emitting the development inhibiting side is the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248.96
No. 2, No. 4°782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound emitting couplers, DIR coupler emitting couplers described in JP-A-60-185950, JP-A-62-24252, etc.,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
Couplers that release dyes that undergo aftercoloring after separation, R, D, described in No. 02A, R, D, 11449, 24241, JP-A-61
-201247 etc. bleach accelerator releasing couplers,
Ligand-releasing couplers described in U.S. Pat. No. 4,553,477, leuco dye-releasing couplers described in JP-A-63-75747, U.S. Pat. No. 4,774,1
Examples include couplers that emit fluorescent dyes as described in No. 81.

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.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(I,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexylphenyl phosphonate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amide M (N, N-diethyl dodecanamide,) LN-diethyl lauryl amide, N-tetradecyl pyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4
-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-
butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30"C or more, preferably 50°C or more and about 160°C or less, can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The present invention can be applied to various colored fluorescent materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643, and pages 647, right column to page 648, left column of Doibei 18716.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate TI/l is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate TI/O can be measured according to a method known in the art.
For example, Photographic Science and Engineering (Photogr, Sci, Eng,) + vol. 19 by A. Green et al.
2, pp. 124-129 (
The TI7□ can be measured by using a swollen film), and the saturated film thickness is 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30°C for 13 minutes and 15 seconds.
Defined as the time it takes to reach a film thickness of .

The membrane swelling rate TI/l can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above, using the formula: (maximum swollen film thickness -
It can be calculated according to (film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention can be developed by the usual method described in the above-mentioned RD, pages 28 to 29 of Magnetics 17643, and pages 615 of Nα1B716, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidinediamine compounds are preferably used, representative examples of which include 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-N, ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH slowing agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (I,4-diazabicyclo(2,2,2)octane), etc. various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, caplacing agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolymer Various chelating agents such as phosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyethylidene −
1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N, H,N,
Representative examples include N-tetramethylene lenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they 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 being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to reduce the area of contact with the air in the processing tank to prevent liquid build-up and air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

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 (bleach-fixing process). Furthermore, in order to speed up the process, it is also possible to carry out a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as [I), chromium (IV), and 1(n), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic 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) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron (I[1 ) if salts are particularly useful in both bleach and bleach-fix solutions. The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (II You can also do it.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, 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 No. 53-32736, No. 53-5783L, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure N [No. 117129 (July 1978), etc.; Thiazolidine derivatives described in Japanese Patent Publication No. 140129; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735, U.S. Patent No. 3,706.56
Thiourea derivatives described in No. 1; West German Patent No. 1.127,
No. 715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748.43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-42.434, No. 49-59,644, No. 53
-94,927, 54-35,727, 55-
Compounds described in No. 26,506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, compounds having a mercapto group or a disulfide group are preferred, and are particularly preferred as described in US Pat.
No. 8, West Patent No. 1゜290.812, JP-A-53-9
Preferred are the compounds described in US Pat. No. 5.630, and also preferred are the compounds described in US Pat. No. 4,552.834.
These bleach accelerators may be added to the photosensitive 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 thiosulfates are commonly used, and ammonium thiosulfate is the most commonly used in poetry. Can be used widely. 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
urn-al of the 5ociety of
Motion Picture and Te1e-v
fsion Engineers Volume 64, P, 24
8-253 (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 T$ particles will adhere to the photosensitive material. As a solution to such problems in processing the color photosensitive material of the present invention, the method for reducing calcium ions and magnesium ions described in JP-A No. 62-2BB, No. 838 has been proposed. It can be used very effectively. Also, JP-A-57-8, 54
Chlorine-based disinfectants such as isothiazolone compounds and cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in No. 2, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, and "Microorganisms" edited by Sanitation Technology Association. It is also possible to use disinfectants described in sterilization, sterilization, and anti-mildew technology J, "Encyclopedia of antibacterial and antifungal agents" published by the Japanese Society of Antibacterial and Antifungal Agents.

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 also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 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, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 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 resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in 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 the processing.In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

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-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

In addition, West German Patent No. 2.226.7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Margin below) The present invention will be further explained below with reference to Examples.

Example 1 (Preparation of emulsion) An aqueous solution of 20 g of inert gelatin, 2.4 g of potassium bromide, and 2.05 g of potassium iodide dissolved in 800I117 of distilled water was stirred at 58°C, and nitric acid vA5. og
150 cc of an aqueous solution dissolved in the above was added instantly, excess potassium bromide was further added, and the mixture was physically aged for 20 minutes. Further, a 0.2 mol/1.0.67 mol/l, 2 mol/1 silver nitrate and potassium halide aqueous solution (potassium bromide 58 mol% 42 mol% of potassium iodide) was added at a flow rate of 10 cc/min.
Mol% silver iodobromide grains were grown. The emulsion was washed with water for desalination to prepare emulsion a. The finished amount of emulsion a was 900 g. The grain size of emulsion a is 0.69 μm.

Take 200 g of Emulsion A, add 850 cc of distilled water and 30 cc of 10% potassium bromide, heat to 70°C, stir, and mix together 300 cc of an aqueous solution containing 33 g of silver nitrate and 320 cc of an aqueous solution containing 25 g of potassium bromide for 30 minutes. 80 g of an aqueous solution in which 100 g of silver nitrate was added.
Aqueous solution of 0cc and 75g of potassium bromide 860
silver iodide 1 by simultaneously adding cc for 60 minutes.
A 110 mol % 1.09 μm silver iodobromide emulsion was prepared.

Emulsion 1 is twinned with an aspect ratio of 2.3, and its (I1
1) The surface pressure ratio was 85%. According to this method, Table 1
Emulsions A-G were prepared as listed below.

Sample 101, which is a multilayer color light-sensitive material, was prepared by coating each layer having the composition shown below in a multilayer manner on a cellulose triacetate support produced by the production method described in JP-A-62-115035.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rd unit, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the halogen in the same layer The coating amount per mole of silveride is shown in mole units.

(Sample 101) 1st layer; antihalation layer black colloidal silver...110.18
Gelatin...1.40 Second layer: Intermediate layer 2.5-di-t-pentadecylhydroquinone...0,18EX-1
...0.20 EX-3・0.09 U-1...0.06 U-2...0.08 U-3...0.10 HBS-1...0.10 HBS -2...0.02 Gelatin...1.04 Third layer (first red-light emulsion layer) Emulsion A ・! II 0,
20 Emulsion B...Silver 0.2
0 sensitizing dye■...6.9×10-'
Sensitizing dye H Sensitizing dye ■ EX-2 EX-3 EX-10 EX-15 Gelatin 4N (second red-sensitive emulsion layer) Emulsion C Enhancing dye ■ Sensitizing dye ■ Enhancing dye ■ EX-2 EX-3 EX -14 EX-10 Gelatin 5th layer (3rd red-sensitive emulsion layer) Emulsion aggravating dye ■...1.8X10-'...3. lX10-'...0.335...0.025...0.020...0.015...0.87 Silver...i, o.

...5. lX10-'...1.4X10-'...2.3X10-' ...0.400 ...0.025 ...0.030 ...0.015 ...1.30 Silver・・・1.40 ・・・5.4X10-' Sensitizing dye■ Sensitizing dye■ EX-3 EX-4 EX-2 SB-1 B5-2 Gelatin 6th layer (Hakuma-taki) EX-5 BS -1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Enhancing dye ■ EX-6 EX-1 ...1.4X10-' ...2.4X10- ' ...0.007 ...0.080 ...0.095 ...0.22 ...0. l O...1.63...0.060...0.040...0.70 Silver...0.15 2 rods...0, 15...3.0X10-'・...1.0X10-'...3.8X10-' ...0.260 ...0.012 EX-7 EX-8 EX-15 B5-1 B5-4 Gelatin 8th layer (second green Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 B5-1 B5-4 Gelatin 9th layer (third green emulsion N) Emulsion sensitizing dye ■ ...0°...0°...0°...O8 ...O8 ...0° Silver...1.00 ...2.1X10-' ...7.0XIO- '...2.6XIQ-'...0.094...0.018...0,026...0.160...o,oos...0.50 Silver...1 .20...3.5X10-' Sensitizing dye■...8.0X10-'Sensitizing dye■...3.0X10-'EX
-13...0.01S EX-11...o, io.

EX-1...0.025 HBS-1...0.25 HBS-2...0.10 Gelatin...1.54 No. 10
Layer (yellow filter layer) Yellow colloidal silver Silver...0.05EX-
5-0,08 HBS-1...0.03 Gelatin...0.95 No. 11
N (first blue-sensitive emulsion N) Emulsion A 1! ...0.08 Emulsion B Silver...0.07 Emulsion C Silver...0.15 Sensitizing dye■ ...3.5X10-'E
X-9...0.721 EX-8...0.042 HBS-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion C Sensitizing dye■ X-9 X-10 B5-1 Gelatin layer 13th layer (third blue-sensitizing emulsion layer) Emulsion sensitizing dye ■ X-9 B5-1 Gelatin 14th layer (first protective layer) ) (BS-1 Gelatin...0.28...1. 10 Silver...0.70...2.lX1(I'...0.154...0.007...0.05...0.78 Silver...0.80...・2.2xlO-' ...0.20 ...0.07 ...0.69 ...0°...0°...0°...1°15th layer (2nd Protective layer) Polymethyl acrylate particles (diameter approx. 1.5 μm) = 0.54 emulsion G
...0.10H-1...0.
38O 3-1...0.2O 3-2...0.05 Gelatin...1.20 In addition to the above ingredients, each layer contains a surfactant and 4-chloro-3,5-
Dimethylphenol was added.

(Samples 102 to 104) Samples 102 to 104 were prepared by replacing the emulsions in Sample 101 as shown in Table 2.

(Samples 105-108) 5th layer, 9th layer, and 13th Ji of samples 101-104
2X 10-6 of the compound (I7) of the present invention, respectively.
Samples 105 to 108 were prepared by adding mol/rd.

These light-sensitive materials were sensitometrically exposed and subjected to the following color development process. In addition, the sample was uniformly irradiated with xvA (I20KV, 2 seconds) and color developed to 'c line L' same 4p.

The obtained photographic performance results are expressed as RMS value (4
The values are shown in Table 3 along with the values for an 8μ diameter aperture).

Further, the degree of desilvering failure when the fixing time of the following treatment was set to 1 minute and 30 seconds was expressed by the density at a cyan density of 2.0 obtained at 6 minutes and 30 seconds.

The development process used here was carried out at 38°C under the following conditions.

1. Color development...3 minutes 15 seconds 2. Bleaching...6 minutes 30 seconds 3. Washing...
3 minutes 15 seconds 4, settled...6 minutes 30 seconds 5,
Washing with water...3 minutes 15 seconds 6, stable...
...3 minutes 15 seconds The treatment components used in each step are as follows.

Color developer Sodium nitrilotriacetate Sodium sulfite Sodium carbonate Potassium bromide Hydroxylamine sulfate 4-(N-Ethyl-N-β Roquinethylamino) Add thyl-aniline sulfate water and bleach solution Ammonium bromide Aqueous ammonia (28 %) Human 2-meethylenediamine-tetraacetic acid sodium trilam salt 160°25°Q@f 30g Rice vinegar M 14aZ Add water 11 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175 .0@j Sodium bisulfite 4.6g Add water 11 Stabilized liquid formalin 8.0d Add water 12 From Table 3, the sample of the present invention has good graininess and desilvering property in the unirradiated sample. Not only is it superior, but it is clear that increases in fog, decreases in sensitivity, and deterioration of graininess due to radiation irradiation are significantly less.

(Example 2) Instead of the compound (I7) of the present invention added to the 5th layer, 9th N, and 13th layer of sample 107, equimolar amount of compound 11!1 (I8) and 0.4 times mol of compound 11! Samples replaced with compounds (I1) and (I2), as well as compound (I7)
sample in which compound (I1) was added in half and 0.2 times the mole of compound (I1) was added. Both samples showed almost the same performance in terms of relative fogging, graininess, and desilvering properties before and after XvA irradiation, and when the compound of the present invention was added. The performance was clearly superior to that of Sample 103, which was not tested.

Example 1. Structural formula of the compound used in 2 %formula% X X X-10 X-11 H CthlI+3(n) X-8 X-12 X-13 H EX-14 OH EX CI+□ OHff -f-CI+.

C-)7 -(-CH2-C-)y CO-0-C1h )IBS-1 tricresyl nonacid B5-2 dibutyl phthalate n, c-c-co3 OH3 OH H3C-C-Clli 1ls H, C-C-CH.

OH3 B5-3 H3C-C-CH3 OH1 Hs Sensitizing dye■ 3O,Na (CHz+5SO3- (CHz+isO3Na Exacerbating pigment V Exacerbating pigment■ CHI-CH3 Hz CH2 SOL CHI.

Sensitizing dye■ CHI.

0 Ja (CL).

(CHz)4 OJa Sensitizing dye■ Procedural amendment (issued by I) 1゜ Display of incidents Heisei z year special application 1/nige issue 2゜ name of invention Silver halide color photographic material 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support, The average silver iodide content of silver halide in the emulsion layer is 1
A silver halide color photographic light-sensitive material, characterized in that it contains 0 mol% or more of a compound represented by the following general formula (I). General formula (I) Q-SM^1 In the formula, Q is -SO_3M^2, -COOM^2, -OH
and -NR^1R^2 represents a heterocyclic residue directly or indirectly bonded to at least one selected from the group consisting of , represents quaternary phosphonium, R^
1, R^2 represents a hydrogen atom or a substituted or unsubstituted alkyl group.