JPH0432834A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow the expression of images on a CRT by a difference in hue and a difference in density by constituting the silver halide particles of a silver halide emulsion of a specific silver chloride, spectrally sensitizing the particles with a specific dye and incorporating couplers therein. CONSTITUTION:The silver halide particles of the silver halide emulsion consist of at least >=90mol% silver chloride and are spectrally sensitized with the sensitizing dye expressed by formula I. In addition, the silver halide emulsion layers contain the couplers forming respectively different dye images. In the formula I, R1, R2 denote an alkyl group; A denotes a hydrogen atom, 1 to 3C alkyl group, aryl group; Y1, Y2 denote a sulfur atom, oxygen atom, etc.; Z1, Z2 denote the nonmetallic atom group necessary for forming a benzene nucleus, etc.; X denotes an anion group; (p) denotes 1 or 2. The images on the CRT expressed by green are expressed by the difference in the hue and the difference in the density is executed in this way and the expression of the images by the difference in the hue and density is possible even in X-ray photography.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide color light-sensitive material having a multilayer structure. Specifically, when imagewise exposed using a green light source, the difference in intensity of the light source is converted into a hue. This invention relates to a silver halide color photosensitive material that can be expressed by a density difference.

[Prior art] Green C is used in diagnosis using MEN instruments such as X-ray photography, medical CT (computed tomography), ultrasound diagnosis, R1 (nuclear medicine), and thermography.
Create an image on RT, expose it to black and white photosensitive material,
Very often black and white images are created. Since this image is expressed only by density differences, it is difficult to identify detailed parts. In some cases, computer processing is performed to produce a color image on a color CRT, which is then exposed to a color photosensitive material to obtain a color image. However, this system is highly octavalent. Therefore, since most images obtained from a CT scanner or the like are generally monochromatic images displayed on a green CRT, it is very difficult to read detailed changes from the images.

Furthermore, when used in medical applications, it is strongly required that the development processing time be short. However, when silver halide containing a high bromine content is used, there is a limit to the shortening of the development processing time because the development activity is reduced by the bromine ions eluted from the silver halide.

[Problems to be Solved by the Invention] The first object of the present invention is to be able to represent an image on a CRT expressed in green by a difference in hue and a difference in density, and also to be able to represent an image in Xsim shadow. The object of the present invention is to provide a silver halide color photosensitive material that can be expressed by hue and density difference.

A second object of the present invention is to provide a color photosensitive material that can shorten development time.

[Means for Solving the Problems] An object of the present invention is to provide a silver halide color photosensitive material having at least two or more silver halide emulsion layers containing at least photosensitive silver halide grains and a coupler on a support. , the silver halide grains of the silver halide emulsion are composed of at least 90 mol % or more of silver chloride, are spectrally sensitized with a sensitizing dye represented by the following general formula (I), and the silver halide emulsion layer is This is achieved by using silver halide color light-sensitive materials each containing couplers that form different dye images.

General formula (I) In the formula, R1 and R2 are an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent, and A is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group. group, Yl and Y2 are sulfur atoms, oxygen atoms, selenium atoms, N-R, R3 is an alkyl group having 1 to 3 carbon atoms, Zl and 72 are nonmetals necessary to form a benzene nucleus and a naphthalene nucleus. A group of atoms,
represents an anion group. p represents 1 or 2, and when p is 1, an inner salt is formed.

The halogen composition of the silver halide used in the present invention is 90% of the total silver halide constituting the silver halide grains.
It is preferable that at least mol % is silver chloride and consists of silver chlorobromide containing substantially no silver iodide.

Average grain size of silver halide grains (the grain size is the grain diameter for spherical or approximately spherical grains, and the length of the ridge for cubic grains, expressed as an average based on projected area)
is not particularly limited, but it is preferably 3 μTrL or less.

The particle size distribution U may be narrow or wide.

Silver halide grains may have regular crystal shapes such as cubes and octahedrons, or may have irregular crystal shapes such as spherical or plate shapes, or composites of these crystal shapes. But that's fine. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

It may be a particle in which a latent image is mainly formed on the surface, or it may be a particle in which a latent image is mainly formed inside the particle.

The silver halide grains may have a layered structure with different layers inside and on the surface, or may be bonded to silver halide grains having different compositions by epitaxial bonding.

In the present invention, the silver halide grains of the silver halide emulsion preferably have localized phases having a silver bromide content of 30 to 60 mol % epitaxially grown on the surfaces of the silver halide grains, particularly at the corners of the grains. . The localized phase is preferably composed of 0.5 to 7% silver based on the amount of gold and silver constituting the silver halide grains. This method for preparing epitaxial silver halide grains is described in European Patent Publication No. 273.
It is described in the specification of No. 430.

The silver halide emulsion used in the present invention is P, Glaf
kids ii Chimie et Ph
ysiquephotograph+que (Pau
l MOnte1, 1967〉, G, F, Duf
finl Photographic Eenuls
ionChemistry (The Focal P
ress, 1966), V.L., 2elik++
HakinQ and coatr by an et al
ngPhotographic Emulsion
(The Focal Press, 1964)
It can be prepared using the method described in et al. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any of the forward flow method, reverse flow method, simultaneous mixing method, and combinations thereof. May be used.

As one of the simultaneous mixing methods, a method of keeping DAg constant in a solution in which silver halide is produced, a so-called Chondral double jet method, can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

During the formation of silver halide grains or during physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be present.

Silver halide emulsions are usually chemically sensitized.

As chemical sensitization, for example, H, Fr1eser @
DieGrundlagender Photogra
phischen prOZesselt S11be
r-halogeniden (Akademisch
eVerlagsgesel 1schaH, 19
68), pp. 675-734, can be used.

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, Reduction sensitization using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal sensitization using member metal compounds (for example, lead salts of metals such as gold, platinum, iridium, and palladium), etc. Or they can be used in combination.

The silver halide emulsion of the present invention is spectrally sensitized with a sensitizing dye represented by general formula (I).

General formula (1) In the formula, R1 and R2 are alkyl groups having 1 to 6 carbon atoms that may have a sulfo group as a substituent (for example, a methyl group,
ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, isohexyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group) , A is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, etc.), an aryl group (e.g., phenyl group, etc.), and Yl and Yl are sulfur atoms. , oxygen atom, selenium atom, N-R, and R3 is an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, n
-propyl group, isopropyl group, etc.). zl and 2
2 is a non-containing compound necessary to form a benzene nucleus or a naphthalene nucleus which may have a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a carbonyl group, an alkoxycarbonyl group, a cyano group, etc.). Represents a group of metal atoms. X represents an anion group (e.g., chloride ion, bromide ion, iodide ion, perchlorate ion, pt-toluenesulfonate ion, ethyl sulfate ion, etc.), p represents 1 or 2, p is 1 When , an inner salt is formed.

Specific examples of the dye represented by general formula (I) are described below.

Margin below (CH2)3S03K Q These sensitizing dyes are used at a concentration of 10-6 to 10-3 mol per mol of silver halide in the silver halide emulsion. Furthermore, when adding such a sensitizing dye to a silver halide emulsion, a method may be used in which the sensitizing dye is directly dispersed in the silver halide emulsion, and an appropriate solvent, for example,
Methyl alcohol, ethyl alcohol, acetone, N,
A method can be applied in which the compound is dissolved in N-dimethylformamide, ethyl acetate, or a mixed solvent thereof, or in a solvent containing a surfactant, and then added to the silver halide emulsion.

These sensitizing dyes can be added to the silver halide emulsion at the time of silver halide grain formation or after physical ripening. Preferably, it is added to the silver halide emulsion during or after chemical ripening. Particularly preferably, it is added after chemical ripening is completed.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (
For example, U.S. Patent No. 2,933.390, U.S. Patent No. 3.6
35.721), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. No. 3.7
43.510), cadmium salts, azaindene compounds, etc.

As a specific example of this silver halide color light-sensitive material, a cyan coupler is contained in a low-sensitivity silver halide emulsion that has been spectrally sensitized with a sensitizing dye represented by the general formula (I>, This is a silver halide color light-sensitive material in which a yellow coupler is contained in a sensitive silver halide emulsion that has been spectrally sensitized with a sensitizing dye represented by I).

Furthermore, when using a silver halide emulsion spectrally sensitized with a sensitizing dye represented by the general formula (I) as a low-speed emulsion, a medium-speed emulsion, or a high-speed emulsion, a magenta cobbler, This is a silver halide color photographic material containing a cyan coupler in a medium-opening emulsion and a yellow coupler in a high-sensitivity emulsion. The silver halide sensitivity is set so that the silver halide emulsion layer with lower sensitivity begins to increase in density at the exposure amount that reaches the density called the shoulder of the characteristic curve in the silver halide emulsion layer with higher sensitivity. It is preferable.

The present invention can be applied to various multilayer silver halide color photosensitive materials. For example, it is applied to color photosensitive materials for printing, typical examples of which include color vapor, color reversal paper, color positive film, and back-illuminated large color prints.

The silver halide color light-sensitive material of the present invention can be used as an image-forming material in MEII instruments such as X-ray photography, medical CT (computed tomography), ultrasonic diagnosis, R1 (nuclear chemistry), and thermography.

A variety of couplers can be used with the present invention.

Here, the coupler refers to a compound that can react with an oxidized product of an aromatic primary amine herbal medicine to form a dye. Useful couplers can include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of cyan, magenta and yellow couplers that can be used in the present invention are
Disclosure 17, 643 (December 1978
18°717 (November 1979). Preferably, these couplers have ballast groups or are polymerized and diffusion resistant. The coupling position is preferably substituted with an lI[ll1l group rather than a hydrogen atom. Couplers in which the coloring dye has suitable diffusivity can also be used.

Yellow couplers that can be used in the present invention include oil-protected acylacetamide couplers.

Specific examples thereof are described in specifications such as U.S. Pat. No. 2,407,210, U.S. Pat.

In the present invention, it is preferred to use a 2-equivalent yellow coupler, U.S. Patent No. 3.408.194;
47.928, 3.933.501, and 4.401.752, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4 No. 022.620, No. 4゜32
6.024, Research Disclosure 18.053 (April 1979), British Patent No. 1.
No. 425.020, West German Published Patent No. 2.219.9
No. 17, No. 2.261.361, No. 2.329.
Examples include nitrogen atom separation type yellow couplers described in various specifications such as No. 587 and No. 2.433.812. α-pivaloylacetanilide couplers are characterized by the fastness of color-forming dyes, while α-benzoylacetanilide couplers are characterized by good color-forming properties.

Examples of magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is
Those in which the 3-position is substituted with a 7-arylamino group or an acylamino group are preferable from the viewpoint of the hue of the coloring dye and the speed of coloring. Specific examples include U.S. Pat.
No. 2, No. 2.343.703, No. 2,600.7
No. 88, No. 2.908,573, No. 3.062.
No. 653, No. 3,152,896 and No. 3.9
Couplers described in various specifications such as No. 36.015 can be mentioned. Two equivalents of 5-pyrazolone couplers are particularly preferred, as leaving groups, as described in U.S. Patent No. 4.310.
．． Examples include the nitrogen atom leaving group described in US Pat. No. 4,351,897 and the arylthio group described in US Pat. No. 4,351,897. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 has high color reactivity and is a preferred coupler.

Examples of pyrazoloazole couplers include pyrazolo[1,
5-bl [1,2,41 triazoles, pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,897, Research Disclosure 2
4°220 (June 1984), and Research Disclosure 24.
230 (June 1984). Japanese Patent Publication No. 59-1625
The imidazopyrazoles and pyrazolo[1,5-bl[1,2,411-riazoles] described in Japanese Patent No. 48 are preferable because they have little yellow side absorption of coloring dyes and high light fastness.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, and US Pat.
Naphthol couplers described in No. 4,293;
Preferably, U.S. Pat.
Examples include highly active 2-equivalent naphthol couplers of the oxygen atom elimination type described in the specifications of No. 146.396, No. 4.228.233 and No. 4.296.200. As phenolic couplers, U.S. Patent No. 2.369.929 and U.S. Patent No. 2.423,730
No. 2,772,162, No. 2.801゜17
Couplers described in various specifications such as No. 1 and No. 2,895,826 can be mentioned. Cyan couplers that are robust to humidity and temperature are preferred, such as the phenolic cyan couplers described in U.S. Pat. No. 3,772,022, U.S. Pat.
No. 72.162, No. 3.758.308, No. 4.
No. 126.396, No. 4.334, No. 4,327.
2,5-diacylamino substituted phenolic couplers described in the specifications of No. 173 and JP-A-59-166956, etc., U.S. Pat. No. 3.446.622 and U.S. Pat. No. 4,333.999 , No. 4,451゜559
has a 7-enylureido group at the 2-position and is described in the specifications of No. 4.427.767 and the like, and
It is a phenolic coupler having an acylamino group at the - position.

In the present invention, two or more types of couplers can be used together in the same layer in order to satisfy the characteristics required of a color photosensitive material.

The coupler used in the present invention can be introduced into the silver halide emulsion by various dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. can be mentioned. In the oil-in-water dispersion method, a high-boiling point organic solvent with a boiling point of 175°C or higher and a low-boiling point auxiliary solvent are dissolved in either a single solution or a mixture of both, and water or an aqueous gelatin solution is used in the presence of a surfactant. finely dispersed in aqueous media such as As a high boiling point II solvent, US Patent No. 2.32
2.027 specification etc. Dispersion may be accompanied by phase inversion, and if necessary, co-solvents may be distilled,
It can be used for application after being removed or reduced by noodle washing or ultrafiltration.

Specific examples of high-boiling organic solvents include phthalate esters (
esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl bosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl p- hydroxybenzoate, etc.), amides (diethyldodecaneamide, N
-tetradecylbi〇lidone, etc.), alcohol or phenol (stearyl alcohol, 2,4-di-te
rt-amylphenol, etc.), 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, those having a boiling point of about 30°C to about 160°C can be used, and specific examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, Dimethylformamide and the like can be mentioned.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat.
It is described in various specifications such as No. 41.230.

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 alone or together with gelatin.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles, e.g.
Benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
phenyl-5-mercaptotetrazole), mercaptopyrimidones, mercaptotriazines, thioketone compounds, azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-1,
Compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. can.

In the photographic emulsion layer of the light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary It may also contain ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic material used in the present invention may contain a dispersion of a water-insoluble or haze-soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability or the like.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic material of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,2,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5 -1-riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The photosensitive material of the present invention contains hydroquinone derivatives, aminophenol station conductors, gallic acid, etc. as color fog preventive agents. Derivative, ascorbine 1all? It may also contain a conductor or the like.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent Box 3.533
, 794, the specifications of 4,236.013, Japanese Patent Publication No. 51-6540, and European Patent No. 5
Aryl-substituted benzotriazoles described in No. 7.160, etc., U.S. Patent Box 4,195.9
Butadines described in No. 99, U.S. Patent Box 3
．． 705.805 and 3.707.375, U.S. Patent Box 3.
215.530 and British Patent No. 1.321,355
Benzophenones described in the specifications of U.S. Patent Nos. 3,761,272 and 4,431.726
Polymer compounds having ultraviolet absorbing residues described in each specification of the above can be used. US Patent Box 3.499.
The ultraviolet absorbing optical brighteners described in No. 762 and No. 3,700,455 may also be used. Specific examples of ultraviolet absorbers are described in Research Disclosure 24.239 (June 1984).

The photosensitive 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. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

In the light-sensitive material of the present invention, an anti-fading agent can be used, and one or more kinds of anti-fading agents can be used. As the anti-fading agent, for example, JP-A-59-12
Phenol or phenyl ether compounds described in JP-A No. 5732, metal complexes described in JP-A-60-97353, hindered amines or hindered phenol compounds described in JP-A-62-115157, JP-A-62-115157; Examples include metal complexes described in Publication No. 61-140941.

The flexible support used in the photosensitive material of the present invention includes a film made of synthetic polymers such as cellulose acetate, polystyrene, polyethylene terephthalate, and polycarbonate, a baryta layer, or an α-olefin polymer (e.g.
Paper coated or laminated with polyethylene, polypropylene, etc. The support may be colored using dyes or pigments.

When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Examples include zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, white silica, white alumina, and titanium phosphate. Particularly useful are titanium dioxide, iiim barium, and zinc oxide.

The surfaces of these supports are subbed-treated to improve adhesion with photographic emulsions and the like within the film.

The surface of the support may be subjected to treatments such as corona discharge and ultraviolet irradiation before or after the subbing treatment.

When these supports are used for reflective materials, a hydrophilic colloid layer containing a high density of white pigment is further provided between the support and the emulsion layer to improve the whiteness and sharpness of the photographic image. I can do it.

In the light-sensitive material of the present invention, when a synthetic resin film kneaded with a white pigment is used, photographic images with improved smoothness, gloss, and sharpness as well as excellent saturation and depiction of dark areas can be obtained. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as the synthetic resin film, and barium sulfate and titanium oxide are particularly useful as the white pigment.

In addition to the above, various photographic additives such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc. can be added to the photographic material of the present invention as necessary. , an example of which is Research Disclosure v-17,643
(December 1978).

In some cases, substantially non-photosensitive fine-grain silver halide emulsions (e.g., silver chloride, silver bromide, salts with an average grain size of 0.20 μm or less) are included in the silver halide emulsion layer or other hydrophilic colloid layer. Silver bromide emulsion) may also be added.

The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Color developing agents include 4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N.

N-diethylaniline, 4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
Examples include 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline and 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline.

The color developing solution is charcoal m salt, hou jl! pHW buffering agents such as salts and phosphates, antifoggants such as bromides, iodides, and organic antifoggants, and the like can be included. In addition, if necessary, water softeners, alkali metal sulfites, preservatives such as hydroxylamine and diethylhydroxylamine, development accelerators such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts, and amines, Dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydrite, 1-
Auxiliary ring imaging agents such as 7enyl-3=pyrazolidone, viscosity imparting agents, polycarboxylic acid chelating agents described in U.S. Pat. No. 4.082.723, West German Published Patent Application No. 2.6
It may also contain antioxidants such as those described in 22,950.

Color photosensitive materials are subjected to color development, usually bleaching. Bleaching treatment may be performed simultaneously with fixing treatment,
May be performed separately.

Examples of bleaching agents include iron (■), cobalt (■),
Compounds of polyvalent metals such as chromium (■) and copper (I[), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron(I[) or cobalt(II[)], such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-
Aminopolycarboxylic acids such as propatooltetraacetic acid, complex salts of organic acids such as citric acid, tartaric acid, and malic acid, persulfates, manganates, nitrosophenols, and the like can be used. Among these, potassium ferricyanide,
Sodium ethylenediaminetetraacetate iron (I[[) and ammonium ethylenediaminetetraacetate II (m) are particularly useful. Ethylenediaminetetraacetic acid iron (III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

A water washing treatment may be performed after color development or bleach-fixing treatment. Color development can be carried out at any temperature between 18°C and 55°C. Preferably, the temperature is 30°C or higher, particularly preferably 35°C or higher. The on-site time ranges from about 3 minutes and 30 seconds to about 10 seconds, and the shorter the better. For continuous development processing, liquid replenishment is preferred, with a concentration of 100 - or more per square meter of processing area, preferably 160 - 330 -
- Replenish the solution. The benzyl alcohol in the developer is 5
d/j or less is preferable. Bleach fixing is from 18℃ to 50℃
Although it can be carried out at any temperature, 30°C or higher is preferable.

When the temperature is 35°C or higher, the processing time can be reduced to less than 1 minute, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and washing can be done within 1 minute using a stabilizing bath.

Colored pigments not only deteriorate due to light, heat, or temperature, but also deteriorate and fade due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of antifungal agents are disclosed in JP-A-57-1572.
Examples include 2-thiazolylbenzimidazoles described in Japanese Patent No. 44. The antifungal agent may be built into the photosensitive material, or may be added from the outside during the development process, or may be added at any step if it coexists with the processed photosensitive material.

Margin below [Example] Example 1 A silver halide emulsion was v411 according to the following recipe.

1 part deionized water 1.000 m Sodium chloride 4.09 Inert gelatin
30 9 Citric acid 2.4g ■Liquid 1.3-
Dimethyl-2-imidazolidinethione (1% aqueous solution)
2-m solution Ionized water 200 m Sodium chloride ag Potassium bromide bg Hexachloroiridium 12 potassium salt (0,001%
Aqueous solution) 2 - (1) Solution V (2) Solution Deionized water Silver nitrate Deionized water Sodium chloride Potassium bromide Deionized water Silver nitrate 0 g Water and gelatin were added and redissolved, and the pH was adjusted to 6.0. Next, the temperature was raised to 55°C, sodium thiosulfate was added, and after optimal chemical ripening, the temperature was cooled to 40°C. and added. After standing for 20 minutes, 4-hydroxy-6-methyl-1,3,38,7-titrazaindene was added as a stabilizer in an amount of 50 μm per mole of silver halide.

Note that the values of ad are shown in Table-1.

Below, after dissolving solution (2) at 55°C, solution (2) was added to solution (2), and after 1 minute, solutions (2) and (2) were added simultaneously as shown in Table-1. After aging for 10 minutes, Solution V and Solution (2) were added simultaneously for 30 minutes, and then aged for 10 minutes. Each emulsion is
After the physical ripening was completed, excess salts were removed by the method described in Example 1 of US Pat. No. 2,613.928. Each of the emulsions obtained in this way was simultaneously coated with the first layer (bottom layer) to seventh layer (top layer) as shown in Table 3 on the front polyester film, and then the sample was prepared as shown in Table 4. 1 to 4 were produced.

Immediately before coating, 1.degree. 2-bis-(.alpha.-vinylsulfonylacetamido)ethane was added to each layer as a hardening agent in an amount of 15y per gram of gelatin.

The following margin coupler Y-1: α-pivaloyl-α-(1-benzyl-5-ethoxy-3-hydantoinyl) 2-ri 0-5
-[α-(2,4-di-tert-amylphenoxy)butyramide]acetanilide coupler C-1: 4-chloro-2-(2-chlorobenzamide) -5-[2-(4-tert-amyl-2-chloro phenoxy)octylamide]phenol coupler C-2: 2-[1-(2,4-di-tert
-amylphenoxy)hexanamide]4,6-dichloro-5-ethylphenol*1: bis(4-hydroxy-3,5-di-tert-butylbenzyl)-bis-[(N-vinylcarbonyl-2,2, 6,6-tetramethylbiveridin-4-yl)-oxycarbonylcomethane*2 Nidicheptyl phthalate*3: 2.5-di-tert-octylhydroquinone*4 Nidibutyl phthalate*5: 2.5-di( 4-heptyloxycarbonyl-1,1-dimethylbutyl)hydroquinone*6: 3.3.3-. 3--Tetramethyl 5 5"
, 6.6-tetrapropyloxy1.1'-spiroindane*7: 2-butoxy-5-tert-octyl-N,
N-dibutylaniline *8 Nitricresyl phosphate *9: 4.4" (1-propen-1-yl 3-ylidene)-bis-N-<4-sulfophenyl)-3-carboxy-2-pyrazoline 5- Onco-tetrapotassium salt*10:2-[3-tert-butyl-2-hydroxy-5-(2-octyloxyca!levonylethyl)phenyl]benzotriazole*11:2-(3,5-di-tert-amyl 2-Hydroxyphenyl)-benzotriazole*12:4.4” (1,3-pendadien 1-yl-
5-ylidene)-bis-H-(4sulfophenyl)-3
-■ Toxicity: 2-pyrazolin-5-one] dipotassium salt table -4 The sample thus prepared was tested using a sensitometric sensitometer (
In order to approximate the spectral distribution of a green CRT to a light source color temperature of 3200K>, a green filter was applied and the film was exposed through an optical wedge, processed by the following color development, bleach-fixing and water washing, and dried. The optical wedge image thus obtained was measured using a Macbeth densitometer using a blue filter and a green filter.

Processing process Processing temperature II Process time ■ Color development 40℃ 20 seconds ■ Bleaching window 11 38℃ 20 seconds ■ Water washing 35℃ 90 seconds Color developer 4-Amino-3-methyl-N-ethyl-N (β-methylsulfone (amidoethyl) aniline sesquisulfate monohydrate 6.1 g Triethanolamine 8.2921-lilotriacetic acid 99 1.59 1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) ' 1.6 g potassium hydroxide
4.2g Tibanol SFP”3
0.89 Potassium carbonate 26.
0g potassium chloride 0.95FN
, N-diethylhydroxylamine 4.0 g Water was added to make 1j, and 111 ml of 10% or 20% potassium hydroxide aqueous solution was added to adjust the pH to 10.10.

*13: Fluorescent brightener (manufactured by Ciba Guyver Actiene Gesellschaft) Bleach-fix solution Ethylenediaminetetraacetate ferric sodium sodium hydrate 48.09 Ethylenediaminetetraacetate disodium trihydrate
24.09 Ammonium thiosulfate (70% aqueous solution) 48 d Sodium hydrogen sulfite (anhydrous) 15.0 SF Water was added to make 1j, and 25% aqueous ammonia or 90% acetic acid was added to adjust the DH to 6.10.

Washing liquid methanol 4.0ml! p-Hydroxybenzoic acid-n-butyl ester 0.01g Thiabendazole 0.10g Ethylene glycol 6. Add Od water to make 1j. DH was 7.45.

The results obtained are shown in Table-5. Note that the sensitivity is at a concentration of 1.5.
It is a value obtained by multiplying the reciprocal of the exposure amount l ooE by 100 to obtain .

Comparative samples 1 and 3 did not provide density changes that would allow a characteristic curve to be drawn in yellow and cyan. Comparing sample 4 of the present invention and comparative sample 2, it can be seen that sample 4 of the present invention is superior in both sensitivity and maximum density.

Table 5 Example 2 Sensitizing dyes as shown in Table 6 were added to emulsions Em-1 to Em-3 of Example 1 per mole of silver, and 4-hydroxy-6-methyl was added as a stabilizer. -1,3,3a,7-chitrazaindene was added at 50 ay per mole of silver halide.

Samples 5 to 8 as shown in Table 8 were prepared by simultaneously coating the first layer (bottom layer) to the seventh layer (top layer) as shown in Table 7 on a polyester film with blank space below the table.

Immediately before coating, 15 μl of 1°2-bis-α-vinylsulfonylacetamido)ethane was added to each layer as a hardening agent per gram of gelatin.

Table 7 below in the margins Exposure, development and measurement were performed in the same manner as in Example 1. The results obtained are shown in Table-9.

Comparative samples 5 and 7 did not provide density changes that would allow a characteristic curve to be drawn for yellow and cyan. Comparing sample 8 of the present invention and comparative sample 6, it can be seen that sample 8 of the present invention is superior in both sensitivity and maximum density.

Table [Effects of the Invention] With the color photosensitive material of the present invention, an image on a CRT expressed in green can be expressed by a difference in hue and a difference in density.

Further, according to the present invention, a color photosensitive material with high sensitivity and high color density can be obtained even with a short development time.

Claims (1)

[Claims] (1) In a silver halide color photosensitive material having at least two or more silver halide emulsion layers containing at least photosensitive silver halide grains and a coupler on a support, the silver halide grains of the silver halide emulsion are It consists of at least 90 mol% or more of silver chloride and has the following general formula (
A silver halide color light-sensitive material which is spectrally sensitized with a sensitizing dye represented by I), and wherein each silver halide emulsion layer contains a coupler that forms a different dye image. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 are alkyl groups with 1 to 6 carbon atoms that may have a sulfo group as a substituent, A is a hydrogen atom, and A is a hydrogen atom, and Alkyl group, aryl group, Y_1 and Y_2 are sulfur atom, oxygen atom, selenium atom, N-R_
3, R_3 represents an alkyl group having 1 to 3 carbon atoms, Z_1 and Z_2 represent a group of nonmetallic atoms necessary to form a benzene nucleus and a naphthalene nucleus, and X represents an anion group. p represents 1 or 2, and when p is 1, an inner salt is formed.