JPS63293536A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PURPOSE:To enable rapid processing with a color developing soln. which does not contain benzyl alcohol by using a silver halide consisting of specific planar particles. CONSTITUTION:A silver halide emulsion layer consisting of the planar particles (A) in which >=50% of the total projection area of the silver halide particles has >=5 average aspect ratio is formed on a reflecting base (e.g., polyethylene coated paper). The particles which contains >=80mol.% silver chloride and is provided with regions having the silver bromide content higher than the average silver bromide content over the entire particle on the surface of said particles are used for the particles A. A color sensitive material formed with the above- mentioned emulsion layer is developed by the color developing soln. contg. substantially no benzyl alcohol after imagewise exposing. The color image having a high color forming density is thereby obtd. with the processing of a short period of time without causing environmental pollution.

Description

[Detailed Description of the Invention] <Industrial Field of Application> The present invention relates to a silver halide color photosensitive material that has excellent storage stability, little fogging, and excellent color reproducibility, and is environmentally friendly. The present invention relates to a color image forming method that enables quick and minimal processing.

<Prior Art> In order to form a color photographic image, photographic couplers of three colors, yellow, magenta and cyan, are contained in a photosensitive layer, and after exposure, the layer is processed with a color developing solution containing a color developing agent. In this process, the oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to form a dye, but in this case, it is desirable to provide as high a color density as possible within the limited development time. .

In order to obtain high color density, it is necessary to use a coupler with a coupling rate as high as possible, to use a silver halide emulsion that is easily developed and has a large amount of developed silver per unit coated amount, or to use color development with a high development rate. It is common practice to use a liquid.

In addition, in order to obtain good color reproducibility with color reflective photosensitive materials, it is necessary that the spectral sensitivities between each photosensitive layer are clearly separated. Separation in the blue region, which is an overlapping region, is an important issue. This problem is usually solved by increasing the silver halide grain size in the blue-sensitive layer compared to other layers to increase sensitivity.
This is achieved by increasing the sensitivity of the blue-sensitive layer relative to the green-sensitive layer and the red-sensitive layer.

In this way, increasing the grain size of silver halide is a commonly used means to improve color reproducibility by increasing the photosensitivity of the blue-sensitive layer in the blue-sensitive region. If it is made larger, there is a drawback that the development speed becomes slower.

On the other hand, since silver chloride does not absorb in the visible light region,
By increasing the silver chloride content of the silver halide grains and color-sensitizing the silver halide grains in the blue-sensitive layer, the sensitivity of the blue-sensitive layer is increased relative to the green-sensitive layer and the red-sensitive layer. Although it is possible to suppress color turbidity and improve color reproducibility, there is a drawback that sensitivity decreases as the silver chloride content increases.

For the purpose of speeding up the development of silver halide emulsions,
It is easy to think of increasing the content of silver chloride. A method of using an emulsion with a high silver chloride content is described, for example, in JP-A-58.
-95345, 59-232342 and 60
19140, however, it is not suitable for practical use because the sensitivity is low, fogging is likely to occur, and the raw storage stability of the photosensitive material is poor.

In addition to increasing the silver chloride content, it is known that the development speed can be increased by making the grain shape tabular. For example, JP-A No. 58-111936 discloses a material having opposing parallel (111) major faces, a thickness of less than 0.3 μm, a diameter of 0.6 μm or more, an average aspect ratio of 7 or more, and a silver chloride content. The use of tabular silver chlorobromide emulsions of up to 40 mole % has been proposed and has been shown to have high development rates as examples in black and white developers. However, there is no description of silver halide grains having a layer mainly composed of silver bromide on the surface of the silver halide grains.

Furthermore, when a tabular silver chlorobromide emulsion containing up to 40 mol% of silver chloride uniformly within the grains is developed using a color developing solution from which benzyl alcohol has been removed and by shortening the development time. , the color density decreases significantly.

For example, in JP-A-58, it has been reported that by localizing a layer mainly composed of silver bromide on the surface of silver chloride grains, fogging of high silver chloride emulsions can be suppressed and the shelf life of photosensitive materials can be improved.
-108533 and JP-A-60-222845.

However, in high-silver chloride emulsions in which 50% or more of the total projected area of silver halide grains are grains with an average aspect ratio of less than 5, the development speed is faster but not sufficient, and a color developer from which benzyl alcohol has been removed is used. However, when development was carried out by shortening the development time, a decrease in color density was observed, making it impractical.

On the other hand, various measures have been conventionally taken regarding color developing solutions to speed up development. Among them, various additives have been investigated to accelerate the penetration of color developing agents into color coupler-dispersed oil droplets and promote color development.In particular, a method of adding benzyl alcohol to a color developer to accelerate color development is currently widely used in the processing of color photographic materials, especially color papers, because of its great color development promoting effect.

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkanolamine, etc. are required as a solvent due to its low water solubility. However, since these compounds, including benzyl alcohol, have high pollution load values such as BOD and COD, it is desired to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Furthermore, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath, which is a post-bath, a leuco form of cyan dye is produced, which causes a decrease in color density.

Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the processed photosensitive material may be adversely affected. Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, color development has generally been processed in 3 to 4 minutes, but with the recent shortening of finishing delivery times and the reduction of laboratory work, there has been a desire to shorten the processing time.

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color density will be significantly reduced.

In order to solve this problem, various color development accelerators (for example, U.S. Pat. No. 2,950,970, U.S. Pat. No. 2,515.
No. 147, No. 2.496.903, No. 2.304.9
No. 25, No. 4.038.075, No. 4.119.46
2, British Patent No. 1, 430.998, 1.455
．． No. 413, JP-A-53-15831, JP-A No. 5.5-6
No. 2450, No. 55-62451, No. 55-6245
No. 2, No. 55-62453, Special Publication No. 51-12422
Even when the compound described in No. 55-49728 was used in combination, sufficient color density could not be obtained.

Methods of incorporating 3-pyrazolidones (e.g., JP-A-60
No. -26338, No. 60-158444, No. 60-1
The method described in No. 58446) has disadvantages in that sensitivity decreases and fog occurs if the sensitive material is stored raw.

Also, a method of incorporating a color developing agent (for example, U.S. Patent No. 3)
No. 719492, No. 3342559, No. 334259
7, JP-A No. 56-6235, JP-A No. 56-16133, JP-A No. 57-97531, JP-A No. 57-83565, etc.), the disadvantages are that color development is delayed and fog is generated. There is.

As described above, no method has been found for obtaining sufficient color images in a short period of time using a color developing solution that does not substantially contain benzyl alcohol.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that has excellent shelf life, less fogging, and excellent color reproducibility. Another object of the present invention is to provide a color image forming method that processes the silver halide color photographic light-sensitive material in a short time and provides high color density without causing environmental pollution.

[Means for solving problems]

With excellent shelf life, minimal environmental pollution, and quick development processing, you can obtain color prints with improved color reproducibility.
The object of the present invention is to include at least one silver halide emulsion layer on a reflective support, in which at least 50% of the total projected area of silver halide grains in the silver halide emulsion layer have an average aspect ratio of 5 or more. A region that is a tabular grain, the tabular grain contains at least 80 mol% (average value) of silver chloride, and the grain surface has a silver bromide content higher than the average silver bromide content of the entire grain. A silver halide color photographic light-sensitive material characterized by having the following: and a color image forming method characterized by developing this light-sensitive material in a color developing solution substantially free of benzyl alcohol after imagewise exposure. achieved by.

In the present invention, "substantially free of benzyl alcohol" means that the benzyl alcohol concentration in the color developer is 0.
．． This means less than 5 mA/12, preferably not at all.

The silver halide emulsion used in the present invention is one in which 80 mol % or more of the total silver halide constituting the grains consists of silver chloride. Preferably, it is 80 mol% or more and 99.5 mol% or less, more preferably 90 mol% or more and 99 mol% or less. When the silver chloride content is less than 80 mol %, processing with a color developing solution that does not substantially contain benzyl alcohol results in low color density and is not suitable for rapid processing. Furthermore, when the silver chloride content exceeds 99.5 mol%, fog increases and storage stability also decreases significantly.

The silver halide tabular grains of the present invention have regions on their surfaces having a silver bromide content higher than the average silver bromide content of the entire grain. This high silver bromide content region may uniformly cover the entire tabular grain, or may cover only a portion thereof. The difference between the silver bromide content in this region and the average silver bromide content of the entire grain is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. This difference in silver bromide content can be determined by measuring X-ray diffraction before and after annealing the sample (making the halogen distribution uniform by heating at high temperature), and from the peak position on the high silver bromide content side that appears before annealing. It can be determined as the difference between the determined silver bromide content and the silver bromide content determined from the peak position after annealing. In the following, this difference will be referred to as ΔBr.

In the silver halide emulsion used in the present invention, tabular grains having an average aspect ratio of 5 or more occupy at least 50% of the total projected area of the silver halide grains. As used herein, "aspect ratio" refers to the ratio of diameter to thickness of a particle.

The "diameter" of a grain refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion grain is observed under a microscope or an electron microscope. From shaded electron micrographs of emulsion samples, the thickness and diameter of each grain can be measured and the aspect ratio of each tabular grain can be calculated.

The average aspect ratio of the silver halide emulsion used in the present invention is determined as follows. That is, from among all the silver halide grains present in the emulsion, those with a diameter of 0.1 to 10 μ and a thickness of 0.3 μ or less are selected, and from among them, tabular grains with a large aspect ratio are selected. It is sufficient to collect as many particles as necessary to exceed 50%, calculate the average aspect ratio of the particles thus collected, and adjust the value to be 5 or more.

The diameter of the tabular silver halide grains used in the present invention is:
As mentioned above, 0.1 to 10μ, preferably 0.2 to 5μ.
It is 0μ, particularly preferably 0.3 to 2.0μ.

Further, the thickness of the particles is 0.3 μm or less.

Grain thickness is expressed as the distance between two parallel planes constituting a tabular silver halide grain.

In the present invention, more preferred tabular silver halogenide grains have a grain diameter of 0.2 μm or more and 5.0 μm or less,
The particle thickness is 0.3 μm or less, and the aspect ratio (
average diameter/average thickness) is 5 or more and 30 or less. More preferably, in the case of a silver halide photographic emulsion, grains having a grain diameter of 0.3 μm or more and 2.0 μm or less and an aspect ratio of 5 or more and 8 or less occupy 85% or more of the total projected area of all silver halide grains. be. If the aspect ratio exceeds 30, the silver halide becomes too easy to dissolve, which is not preferable.

The size distribution of the tabular silver halide grains used in the present invention may be narrow or wide, but monodisperse emulsions are preferred, and the grain size distribution, which represents the degree of monodispersity, has a statistical standard deviation ( The ratio (s) of the average particle size (R) to the average particle size (R)
/7) is 0.25 or less, preferably 0.23 or less.

The silver halide emulsion used in the present invention consists of silver chlorobromide and/or silver bromide substantially free of silver iodide. Here, the term "substantially free of silver iodide" means that the content is 2 mol % or less, and preferably it does not contain any silver iodide.

The silver halide grains used in the present invention are composed of two or more types of monodispersed silver halide emulsions with different grain sizes in an emulsion layer having substantially the same color sensitivity in order to satisfy the target gradation of the light-sensitive material. They can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The tabular silver halide emulsion used in the present invention is Cugn
ac, Chateau's report, and Duffin's "Chemistry of Photographic Emulsions J.
ulsion Chemistry) (Focal
Press, New York 1966), pp. 66-72, and A, P., HoTrivelli, V.
4. F, Sm1th edition “Photo Magazine J (Photo
, Journal) 80 (1940) 285
Although it is described in page 1, Japanese Patent Application Laid-Open No. 58-113927,
No. 58-113928, No. 58-127921, No. 58-111935, No. 58-111936, No. 5
It can be easily prepared by referring to the methods described in No. 8-111937 and No. 58-10853.

For example, in the presence of a peptizer containing an adenine and thioether bond while maintaining a low PC1 of P CJ 0.3, NaCj! It is obtained by simultaneously adding a solution and an AgNOs solution to form pure silver chloride tabular grains, and then adding a KBr solution.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and quality of the solvent, the silver salt used during grain growth, the addition rate of the halide, etc.

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of the solvent used is preferably in the range of 10-4 to 1.0% by weight, particularly preferably in the range of 10-3 to 10-1% by weight of the reaction solution. In the present invention, as the amount of solvent used increases, the particle size distribution becomes monodisperse and the growth rate can be accelerated, but the thickness of the particles also tends to increase as the amount of solvent used increases.

In the present invention, known silver halide solvents can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, nioureas, quacyanate salts, thiazolinthiones, and the like. Regarding thioethers, U.S. Pat.
．． No. 271.157, No. 3.574.628, No. 3.790.387, etc. can be referred to. Regarding thioureas, Japanese Patent Application Publication Nos. 53-82408 and 55-77737, and regarding thiocyanate salts, US Patent Nos. 2.222.264 and 2.448.534.
No. 3.320.069, and for thiazolinthiones, reference may be made to JP-A-53-144319, respectively.

In the process of forming or physically ripening silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron acid or iron complex salts, etc. may coexist. .

When producing the tabular silver halide grains used in the present invention, a silver salt solution (for example, A
A method of increasing the addition rate, amount, and concentration of the silver halide solution (eg, KBr aqueous solution) and the silver halide solution (eg, KBr aqueous solution) is preferably used.

These methods are described, for example, in British Patent No. 1,335.
．． No. 925, U.S. Patent No. 3.650.757, U.S. Pat.
, No. 672.900, No. 4.242.445, JP-A-55-142329, and JP-A No. 55-158124.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating. In order to remove soluble silver salts from the emulsion after physical ripening, washing with water, flocnylation precipitation, ultrafiltration, etc. are performed.

The tabular silver halide grains used in the present invention can be chemically sensitized if necessary.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines); reduction sensitization method using noble metal compounds (e.g., total complex salts, Pt, Ir
5Pd.

A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Rh and Fe can be used alone or in combination.

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

Next, a processing step (image forming step) in the present invention will be described.

The color development process in the present invention has a short processing time of 2 minutes and 30 seconds or less. The preferred treatment time is 30 seconds to 1 minute and 30 seconds. The processing time herein refers to the time from when the photosensitive material comes into contact with the color developer to when it comes into contact with the color developer, and includes the transit time.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As the color developing agent, p-phinidine diamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N- Ethyl-N
-β-hydroxylethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
Examples include N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates, p-(t-octyl)benzenesulfonates, and the like.

Examples of aminophenol derivatives include O-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F.A. Mason, Focal Press (1966) (L.F., AoMason.

Photographic Processing C
22 of “hemistry”, FocalPress)
6-229, U.S. Pat. No. 2.193.015, 2.
529.364, JP-A No. 48-64933, etc. may be used. If necessary, two or more color developing agents may be used in combination.

The processing temperature of the color developer in the present invention is 30° to 5°C.
The temperature is preferably 0°C, more preferably 35°C to 45°C.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, U.S. Patent No. 2.648.604, Japanese Patent Publication No. 44-950
3, U.S. Patent No. 3.171.247, various pyrimidylam compounds and other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 1973- 930
No. 4, U.S. Pat. No. 2,533.990, U.S. Pat. No. 2,531.
No. 832, No. 2.950.970, 2, 577, 12
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 7, U.S. Patent No. 3
．． Thioether compounds described in No. 201.242, and other JP-A Nos. 58-156934 and 60-220344
Examples include the compounds described in No.

In addition, in short-time development processing as in the present invention,
An important issue is not only a means to accelerate development, but also a technique to prevent development fog. Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.

Examples of organic antifoggants include benzotria 7'-
NoL,,6-nidropenzimitazole/be5-nitroindazobe5-methylbenzotriazole,5
-Nitropenzotriazonobe 5 -Chloropenzotriazonope 2-Thiazolylupenzimidazole Novel 2-
To nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazonopehydroxyazaindolizine and mercapto substitutions such as 1-phenyl-5-mercaptotetrazole, 2-mercaptopenzimidazonope2-mercaptobenzothiazole Terocyclic compounds can be used as well as mercapto-substituted aromatic compounds such as thiosalicylic acid. Particularly preferred are halides. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

In addition, the color developer in the present invention may contain pH buffering agents such as alkali metal carbonates, borates or phosphates: hydroxylamine, triethanolamine, compounds described in OLS No. 2622950. , preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers: competitive couplers: nucleating agents such as Nato IJ ram boron hydride; Auxiliary developer; viscosity imparting agent; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminoniacetic acid, N-hydroxymethylethylenediaminetriacetic acid,
diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids such as the compounds described in JP-A-58-195845, ■-hydroxyethylidene-1,1'-diphosphonic acid, research
Disclosure (Research Discl.
organic phosphonic acid, aminotris (methylene phosphonic acid), ethylenediamine-N, N, N', N'-
Aminophosphonic acids such as methylene phosphonic acid, JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-
No. 4025, No. 55-=126241, No. 55-65
No. 955, No. 55-65956, and Research Disclosure.
re) No. 18170 (May 1979) may contain a chelating agent such as a phosphonocarboxylic acid.

In addition, the color developing bath can be divided into two or more parts as necessary.
Replenish color developer replenisher from the first bath or last bath,
The development time may be shortened or the amount of replenishment may be reduced.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (I), cobalt (■), chromium (■), and copper (n), peracids, quinones, and nitroso compounds. for example,
Ferricyanide, dichromate, organic complex salts of iron(III) or cobalt(II[), amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid Polycarboxylic acids or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates, manganates; nitrosophenols, etc. can be used. Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate (I[), and iron ethylenediaminetetraacetate (I[)]
Particularly useful are II[) ammonium triethylenetetraminepentaacetate iron(I) ammonium persulfate. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Pat.
No. 6, No. 49-26586, JP-A-53-32735
Thiourea-based compounds as shown in JP-A No. 53-36233 and JP-A No. 53-37016;
No. 3-57831, No. 53-32736, No. 53-6
No. 5732, No. 54-52534 and U.S. Patent No. 3,
Thiol compounds as shown in 893.858, etc., or JP-A-49-59644, JP-A-50-
No. 140129, No. 53-28426, No. 53-14
No. 1623, No. 53-104232, No. 54-357
Heterocyclic compounds described in JP-A No. 27, etc.; thioether compounds described in JP-A-52-20832, JP-A-55-25064, and JP-A-55-26506; Compounds such as quaternary amines described in JP-A-48-84440 or thiocarbamoyls described in JP-A-49-42349 may also be used.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and anti-spiking agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. Typical hardeners, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L
, B. West), Photographic Science
and Engineering (Photo, Sci.

and Eng, ), Volume 9, No. 6, (1965
) etc. may be added. The addition of chelating agents and anti-piping agents is particularly effective. In addition, by using a multistage (for example, 2 to 5 stages) countercurrent method in the water washing process,
It is also possible to save water.

Also, after or instead of the water washing process, JP-A-57-
A multi-stage countercurrent stabilization treatment process such as that described in No. 8543 may be performed. In the case of this step, a countercurrent column with 2 to 9 tanks is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers for adjusting membrane pH (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, Polycarboxylic acids, etc.) and formalin can be given. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (Proxe/ni, isothiazolone, 4-thiazolylbenzate, etc.), as needed. (imidazole, halogenated phenol benzotriazoles, etc.), a surfactant, a fluorescent brightener, a hardening agent, etc. may be added.

Furthermore, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can be added as membrane pH adjusting agents after treatment.

The blue-sensitive, green-sensitive and red-sensitive emulsions used in the present invention are spectrally sensitized with methine dyes and other dyes so as to have color sensitivity. The dyes used 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. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei;
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, Sunawati, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, Benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
．． 688.545, 2.977, 229, 3.
No. 397.060, No. 3.522.952, No. 3, 5
No. 27.641, No. 3.617.293, No. 3.62
No. 8.964, No. 3.666, No. 480, No. 3.672
．． No. 898, No. 3.679.428, No. 3.703.
No. 377, No. 3.769.301, No. 3, 814.6
No. 09, No. 3.837.862, No. 4.026.70
7, British Patent No. 1.344.281, British Patent No. 1.507.
No. 803, Special Publication No. 43-4936, No. 53-1237
No. 5, JP-A-52-110618, JP-A No. 52-1099
It is described in No. 25.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

To spectrally sensitize silver halide emulsions with these sensitizing dyes, generally well-known methods may be used. That is, the sensitizing dye is dissolved in a suitable solvent (methanol, ethanone ethyl acetate, etc.) to obtain a solution with a suitable concentration, and the solution is added to a silver halide emulsion. The above solution is added at any step during the preparation of the silver halide emulsion. For example, the addition of stabilizers and antifoggants may be carried out at any step during or after the formation of silver halide emulsion grains, before chemical ripening, during chemical ripening, after the completion of chemical ripening, before preparing a coating liquid, or during the preparation of a coating liquid. Although the order does not matter, it is preferable to do this before preparing the coating solution. In particular, when a plurality of emulsions having substantially the same color sensitivity are used as a blend, it is preferable that the additive be added before blending these emulsions.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
7.210, 2.875.057 and 3
．． 265.506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
3.933.501 and 4.022.62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401.752, No. 4.326.024, R'D
18053 (April 1979), British Patent No. 1.42
No. 5.020, West German Application No. 2.219.917,
Typical examples thereof include the nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2.261.361, 2.329.587, and 2.433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-
Benzoylacetonitride couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrozolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. 2.3 of the same
No. 43.703, No. 2.600.788, No. 2.
No. 908.573, No. 3, No. 062.653, No. 3
．． No. 152.896 and No. 3, No. 936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351
．． The aIJ-ruthio group described in No. 897 is preferred.

Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, US Patent No. 13.
369.879, preferably pyrazolo[5,1-CI (:1.2.4E) as described in U.S. Pat. No. 3.725.067.
Triazoles, Research Disclosure 242
20 (June 1984) and Research Disclosure 24230
(June 1984). Imidazo C1,2-bE pyrazoles described in European Patent No. 119.741 are preferable from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and pyrazolo (1 , 5-b)
(1,2,4)triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2.474.293, preferably U.S. Pat.
．． No. 212, No. 4.146.396, No. 4, 22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8.233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
No. 01.171, No. 2.772.162, No. 2,
895.826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,772.
．． Phenolic cyan coupler having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 002, US Pat.
No. 8.308, No. 4.126.396, No. 4, 3
No. 34.011, No. 4.327.173, West German Patent Publication No. 3.329.729 and Patent Application No. 1983-426
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 71 and U.S. Pat.
No. 2, No. 4.333.999, No. 4.451.5
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 59 and No. 4.427.767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570; .234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3.451.82.
No. 0 and No. 4.080.211. Specific examples of polymerized magenta couplers are given in British Patent No. 2.102.173 and U.S. Pat. No. 4,367,2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil droplet dispersion method in ice, the boiling point is 1
After dissolving in either a high boiling point organic solvent of 75°C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion (and, if necessary, co-solvents may be removed or reduced by distillation, noodle washing or ultrafiltration before use for coating).

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, etc.) ,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecyl pyrrolidone, etc.), alcohols or phenols (instearyl alcohol 2,4-di-tert-amylphenol) ), aliphatic carboxylic acid esters (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 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used. Typical examples include ethyl acetate, butyl acetate, ethinobemethyl ethyl ketone propionate, cyclohexanone, 2-ethoxy Examples include ethyl acetate and dimethylformamide.

Specific examples of the latex dispersion process, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0 for magenta coupler, 0 OB to 0.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

The light-sensitive material of the present invention may contain hydroquinone derivatives, aminephenol derivatives, amine phenols, gallic acid derivatives, catechol derivatives,
It may also contain ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychroman i, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols,
Typical examples include gallic acid derivatives, methylene dioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of azephtha dye images, especially deterioration caused by light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of infrared absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing in the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, usually preferably I x 10-'
mol/m"~2 X 10-' mol/ml, especially 5
X 10-' mol/ml-1,5X10-3 mol/
It is set in the range of mH.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of 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 or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. .

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

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

For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein, etc.;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Substances can be used.

In addition to lime-processed gelatin, acid-processed gelatin, Bull, Sci, Phot, Japan, and No.
, p. 16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (197
(November 6).

(Example) Next, the present invention will be explained in more detail based on examples.

The emulsion used in the present invention was prepared as follows.

Add INH2S to 1000CC of 2.5% gelatin aqueous solution.
18.7cc of O4, 1g of 2,4-thiazolidinone, and Na
22.0 g of Cβ was added. This solution was kept warm at 50 °C, and under strong stirring, 320 °C of 37.5% AgNO3 aqueous solution was added.
c and 320 CC of 12.9% NaCII aqueous solution were added over 45 minutes by double jet method. During this time, the amount of sodium chloride aqueous solution added was adjusted so that the initial PAg was maintained. Then 100cc of 1.68% KBr aqueous solution
was added to the above emulsion over a period of 10 minutes.

Furthermore, after removing soluble salts by a sedimentation method, gelatin was added to redisperse the mixture, and sodium thiosulfate was added to perform optimal chemical sensitization.

The emulsion thus obtained is referred to as Emulsion A. In emulsion A, 80% of the total projected area of the silver halide grains contained therein is occupied by tabular grains, and the average thickness of the tabular grains is 0.
．． The 19 μm 1 average aspect ratio was 7. Furthermore, the average particle size was measured using a Coulter Counter Model TA-II manufactured by Coulter Electronics, and was found to be 0.
It was 80 μm. Moreover, as a result of measuring the X-ray diffraction of this grain before and after annealing, the average silver bromide content of the entire grain was 98 mol%, and ΔBr was 24 mol%.

When d is the diameter of a circle having an area equal to the projected area when the silver halide grains of emulsion A are dispersed on a flat surface, the standard deviation S of d is divided by the mean value of d, which is 100.
The value multiplied by (this is called the coefficient of variation) was 20%.

In the formulation of emulsion A, the temperature of the solution, the amount of adenine sulfate added, and the AgN0. Emulsion B was obtained by appropriately changing the addition time of the aqueous solution. Emulsion B had a similar profile to Emulsion A except that the average tabular grain thickness was 0.13 .mu.m and the average grain size by Coulter Counter was 0.45 .mu.m.

In the formulation of emulsion A, AgN0. The amount of aqueous solution added is 314
Changed to cc. Furthermore, 5.4 cc of a 37.5% 8 g NO aqueous solution was added at the same time as the second-stage KBr aqueous solution to obtain an emulsion C. Emulsion C had a similar profile to Emulsion A except that ΔBr was 28 mol%.

An emulsion was obtained by appropriately changing the temperature of the solution and the amount of chemicals added in the formulation of Emulsion C.

The emulsion had the same profile as Emulsion B except that ΔBr was 28 mol%.

In the formulation of emulsion C, the NaCβ aqueous solution added in the first stage is added to 100OCC of NaCj! 129gKBr1
Emulsion E was obtained by changing to an aqueous alkali halide solution containing 4.82 g. Emulsion E had a similar profile to Emulsion C except that the average silver bromide content across the grains was 20 mole percent. .

Emulsion F was obtained by appropriately changing the temperature of the solution and the amount of chemicals added in the formulation of Emulsion E.

Emulsion F had a similar profile to Emulsion A except that the average silver bromide content of the entire grain was 20 mol %.

Next, a method for preparing a comparative emulsion will be described.

In the formulation of emulsion A, AgN0. KB after addition of aqueous solution
Emulsion G was obtained by omitting the step of adding an aqueous solution.

Emulsion G had a similar profile to Emulsion A, except that it had pure silver chloride grains.

In the formulation of emulsion B, KB after addition of AgNO3 aqueous solution
Emulsion H was obtained by omitting the step of adding an aqueous solution. Emulsion H had a similar profile to Emulsion B except that it had pure silver chloride grains.

In the formulation of emulsion G, the NaCl aqueous solution added is
Mail during 100OCC! 129 g, KBrl
Emulsion I was obtained by changing to an aqueous alkali halide solution containing 68 g of . Emulsion I had the same profile as Emulsion G except that 2 mol% of AgBr was uniformly contained within the grains.

IN)12 in 1000cc of 2.5% gelatin solution
S0゜18.7cc and NaCji! 6.8 g was added. This solution was kept at 62°C and heated to a concentration of 19.2% under strong stirring.
130 cc of NohegNo. aqueous solution and 130 cc of 6.6% NaCl aqueous solution were added over 60 minutes using a double jet method. After 10 minutes, 35.1% AgN0. 285 cc of an aqueous solution and 285 cc of a 12.1% NaCβ aqueous solution were added over 25 minutes by a double jet method. Subsequently, an aqueous solution containing 75 g of KBrl was added to the above emulsion over 10 minutes. After precipitation and redispersion, this emulsion was optimally chemically sensitized with sodium thiosulfate. This emulsion is referred to as Emulsion J. The shape of Emulsion J was cubic, the average grain size by Coulter Counter was 0.80 μm, and the coefficient of variation was 12%. The average silver bromide content of the entire grain was 2 mol%, and ΔBr was 38 mol%.

In the formulation of Emulsion J, the temperature of the solution was lowered to 56°C, and AgN0. Emulsion K was obtained by changing the addition times of the aqueous solution and the NaCβ aqueous solution. For the emulsion, coulter
The profile was similar to that of Emulsion J except that the average grain size by counter was 0.45 μm.

In the formulation of Emulsion J, the NaCβ aqueous solution added in the first stage was changed to an alkali halide aqueous solution 1300C containing 0.27% KBr and 6.5% NaCl, and the NaCJ2 aqueous solution in the second stage was changed to 0.49% NaCJ2 aqueous solution. KBr and 11.83%
285cc of aqueous alkali halide solution containing NaCβ
changed to Furthermore, an emulsion was obtained by removing the step of adding the KBr aqueous solution after adding the AgNO3 aqueous solution. Emulsion E had the same profile as Emulsion J except that ΔBr was 0.

In the emulsion formulation, the temperature of the solution was changed to 75°C.

Furthermore, emulsion M was obtained by changing the amounts of KBr and NaCβ in the alkali halide solution so that the molar ratio was 70:30, and by appropriately changing the molar ratio of silver added in the first and second stages. Emulsion M has an average silver bromide content of 70 throughout the grains.
The profile was similar to that of the emulsion except that the coefficient of variation was 10%.

Emulsion N was obtained by lowering the temperature of the solution to 56° C. and appropriately changing the addition times of the alkali halide aqueous solution and AgNO3 aqueous solution in the formulation of Emulsion M. Emulsion N had a similar profile to Emulsion M, except that the average grain size by Coulter Counter was 0.46 .mu.m.

NaCIi of the initial gelatin solution in the formulation of Emulsion M
The amount was changed to 29.3 g, and the temperature was further changed to 60°C. In addition, while maintaining the condition of a large excess of chlorine ions, the second stage AgNO3 aqueous solution and alkali halide aqueous solution were added in 64 minutes by accelerated addition so that the final flow rate was three times the initial flow rate. Emulsion O was obtained by changing. Emulsion O had the same profile as Emulsion A, except that the average content of the entire grain was 70 mol%, ΔBr was 0 mol%, and the coefficient of variation was 21%.

Emulsion P was obtained by changing the solution temperature and addition acceleration method in the formulation of Emulsion O. Emulsion P is Coulter
The profile was similar to that of Emulsion 0, except that the average grain size by counter was 0.45 μm.

In the formulation of Emulsion C, ΔBr is 3 mol% and 8 mol%, respectively, by adding an appropriate amount of NaCIt to the 1- and 2-role hegNOs aqueous solutions and the second-stage alkali halide aqueous solution. Emulsions Q and R having the same profile as Emulsion A were obtained except for this.

In the preparation of the above emulsions A-P, AgN0. AgNO3 in aqueous solution
21. is added to the aqueous alkali halide solution so that the amount is 1X10-' mol % based on the number of moles of . Contains Cβ6.

The profiles of emulsions A-H are summarized in Table 1.

Table 1 Example 1 A front plate was placed on a paper support laminated on both sides with polyethylene.
A sample coated with a blue-sensitive emulsion layer and a protective layer as shown in 2 was prepared. The emulsions include A, C1E, G, 1. , J.L.
Spectral sensitization was performed using SM, 0, Q, and R using the following spectral sensitizer.

A blue-sensitive emulsion layer coating solution was prepared as follows. Yellow coupler (a)
Add 27.2 mA of ethyl acetate and 7.9 mfl of solvent (C) to 4.4 g of color image stabilizer, etc., and dissolve this solution. % gelatin aqueous solution 185mβ
It was emulsified and dispersed.

The emulsion dispersion and emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 2 to prepare a blue-sensitive emulsion layer coating solution. However, as emulsions, spectrally sensitized Δ, C, and E
, G, I, J, L, M, 0, Q, and R were used. A protective group coating solution was also prepared in the same manner. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-8-triazine sodium salt was used.

(a) Yellow coupler CC) A photosensitive needle (manufactured by Fuji Photo Film Co., Ltd.,
Gradation exposure and light for sensitometry were provided through a blue filter using a FWH type (light source color temperature: 3200°K). The exposure at this time was 250 CMS with an exposure time of 0.5 seconds.
The exposure amount was set to .

Thereafter, treatments A and B consisting of the steps of color development, bleach-fixing, and washing with water were performed. The contents of processes A and B are as follows.

(Processing A) Processing process Temperature Time development
Bleach fixing at 33℃ for 3.5 minutes
33℃ 185 minutes water washing 28
~35℃ 3.0 minutes Developer diethylene triamine pentaacetic acid 1.0 g Benzyl alcohol 15 mf Diethylene glycol 10 ml Na2S O32, Og KBr O,
5g hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-Cβ-(methanesulfonamide) ethyl]-p-phenyl diamine sulfate 5.0g Na2CO
s (monohydrate) 30g Fluorescent brightener (stilbene type) 1.0g Add water to make 1 liter (pH 10,1) Bleach-fix ammonium thiosulfate (54wt%) 150+
njl! Na25Oa 1
5 gNH4[Fe(EDTA)) 5
5 gEDTA2・2Na 4
g Add water to make 1 liter (pH 6,9) (Processing B) Processing process Temperature Time Development
Bleach fixing at 35℃ for 45 seconds
35℃ 45 seconds water washing 28~3
5°C 1.5 minutes Developer diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2g N,N-diethylhydroxylamine 4.2g Potassium bromide
0.01g sodium chloride
1.5g triethanolamine
8.0g potassium carbonate
30 g N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescent brightener (stilbene type) 2.0 g Add water to 1β
(pH 10,05 in KOH) bleach-fix solution EDTAF e (III) NHs” 2H20
60gE DTA 2 Na ・2H204, Og Ammonium thiosulfate (70%> 120ml Sodium sulfite 16g Acetaldehyde sulfite adduct 10g Glacial acetic acid
Add 7 g of water to make up to 1 liter (pH 5,50) The results obtained are shown in Table 3. Table 3
The relative sensitivity at the processing date of emulsions ASC, E, G, I
S.J.

It is a relative value when the sensitivity in processing A of each sample using L, M, OlQ, and R is set to 100. Sensitivity was expressed as a relative value of the reciprocal of the exposure amount required to provide the minimum density plus 0.5. Further, as a measure of the degree of decrease in color density when Process B is performed, the color density obtained when Process B is performed at an exposure amount that gives a density of 1.5 when Process A is performed is taken. Therefore, it can be said that the closer the density is to 1.5, the more efficient color development the photosensitive material exhibits.

Furthermore, the fog value when Processing B was performed is shown together with the fog value when Processing A was performed.

In the sample of the present invention, even without benzyl alcohol in Processing B, the photographic performance was close to that of Processing A with benzyl alcohol, and a sufficiently high color density was obtained even in a short processing time, and a low fog value was obtained. . On the other hand, none of the comparative samples satisfied these two properties at the same time.

Example 2 Using the same sample as in Example 1, the raw storage stability of the photosensitive material under high temperature and high humidity conditions was investigated. After being left under conditions of 40°C and 80% humidity for 2 days, exposure was performed in the same manner as in Example 1,
After processing B, the sensitivity and fog value were measured. The results are shown in Table 4. The relative sensitivity after storage is a relative value with the sensitivity before storage as 100.

It can be seen that the emulsion ASCSE of the present invention shows little change in performance even after storage under high temperature and high humidity conditions, and is comparable in performance to that of a high silver bromide emulsion.

□Nyo□□□-Nini■ Example 3 A multilayer color photographic paper having the layer structure shown in Table 5 was prepared in the same manner as in Example 1. The emulsion was changed as shown in Table 6.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (addition of 7 x 10-' moles per mole of silver halide)
Green-sensitive emulsion layer (4 x 10-' mol m added per 1 mol of silver halide) Red-sensitive emulsion layer SO,- (2 x 1 O-' mol added per 1 mol of silver halide) Irradiation of each emulsion layer The following dyes were used as the preventive dyes.

Green-sensitive emulsion layer: SO, K SO3, red-sensitive emulsion layer: STo, SO, coupler, etc. The structural formulas of the compounds used in this example are as follows.

(d) Color mixing inhibitor H (e) Magenta coupler (f) Color image stabilizer (odor) 2:1 mixture of solvent (weight ratio) Co., Ltd. 1:5:3 mixture of ultraviolet absorber (mole ratio) (i ) Color mixing inhibitor ○H (J) Solvent (iso C, H,,0srP=0 (Foundation) 1:1 mixture (molar ratio) of cyan coupler Shi2 Shi2 (k2) <p> Color image stabilizer A 1:3:3 mixture (molar ratio) (e) Samples (a) to (c) prepared by changing the solvent emulsions were subjected to the same test as in Example 1. However, three types of blue, green, and red were used. Post-processing B was performed by exposing the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer through a felter.The photographic properties of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer were evaluated. Since color development was insufficient after treatment for 45 seconds, treatment was performed for 2 minutes.

In this example, in order to see the effect of improving color reproducibility, the difference in sensitivity between the blue sensitive layer, green sensitive layer, and red sensitive layer when exposed through a blue filter was used as an evaluation measure of color reproducibility. It means that the larger the sensitivity difference, the better the color reproducibility.

The sensitivity difference was calculated by correcting the sensitivity of each layer during processing so that the difference in the logarithm of the exposure amount that gave an optical density of 1.0 when exposed to a blue filter was calculated to reproduce gray when exposed to white for each sample. Shown in hours.

The results are shown in Table 6.

Table 6 shows that the combination of the present invention provides lower fog and higher color density when used in each BSGSR layer or in all layers. It can be seen that particularly when used in all layers, good color reproducibility is exhibited.

The use of particles with a higher silver chloride content showed better color reproducibility and higher color development. However, high silver chloride cubic grains have insufficient coloring properties, and pure silver chloride tabular grains have high fog values (both of which are of no practical use).

(Effects of the Present Invention) According to the present invention, it is possible to obtain a color photographic material which has excellent shelf life, less fogging, and improved brown color reproducibility. Furthermore, this color photographic material develops sufficient color even when processed for a short time with a color developer substantially free of benzyl alcohol, and is excellent in rapid processing.

Furthermore, since benzyl alcohol is not substantially used, the pollution load can be significantly reduced, and the liquid preparation work can be reduced.

Procedural Amendment 63.8.26 Showa Year Month Day 1, Case Description 1988 Patent Application No. 128896
No. 3. Relationship with the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent 5, Date of amendment order Voluntary (13 Specification 1g, page 17, line 10, “Quocyanate salt”) Correct as “thiocyanate salt”.

(2) "'KBr" on page 18, line 8 of the same book is r Na0
Correct it to 2 J.

(3) Insert the following statement next to page 62, line 20 of the same book.

“The tabular grains of the present invention were prepared using JEM-20 manufactured by JEOL Ltd.
When observed using 00FX at a voltage of 200 KV and liquid nitrogen temperature, a large number of dislocations were observed, with 1 dislocation per particle.
The number of tabular grains containing 0 or more dislocations accounted for 50% or more of the total number of tabular grains.

The sample of the present invention has high absolute sensitivity, low pressure fluctuation,
It also had excellent performance with little low-light failure.

”

Claims (2)

[Claims] (1) In a silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer on a reflective support, at least 50% of the total projected area of silver halide grains in the silver halide emulsion layer has an average aspect ratio. 5 or more tabular grains, and the tabular grains contain at least 80 mol%
1. A silver halide color photographic light-sensitive material, which contains (average value) of silver chloride and has a region on the grain surface having a silver bromide content higher than the average silver bromide content of the entire grain. (2) In a silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer on a reflective support, at least 50% of the total projected area of silver halide grains in the silver halide emulsion layer has an average aspect ratio. 5 or more tabular grains, and the tabular grains contain at least 80 mol%
A silver halide color photographic light-sensitive material, which contains (average value) of silver chloride and has a region on the grain surface having a silver bromide content higher than the average silver bromide content of the entire grain. . A method for forming a color image, which comprises, after imagewise exposure, developing with a color developer substantially free of benzyl alcohol.