JPH03216644A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid decoloring during development by forming a hydrophilic colloidal layer contg. at least one kind of specified compd. as dispersed solid fine particles. CONSTITUTION:A hydrophilic colloidal layer contg. at least one kind of compd. represented by formula I as dispersed solid fine particles is formed. In the formula I, each of E<1>-E<4> is an electron attractive group selected among cyano, -COOR<1>, -COR<1>, -CONR<1>R<2> and -SO2R<1>, each of L<1>-L<5> is methine and each of (m) and (n) is 0 or 1. Decoloring can be accelerated at the time of development.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inactive and easily decolorized during photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted and/or a hydrophilic colloid layer. (Prior Art) In silver halide photographic materials, photographic emulsion layers and other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on a photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, a filter layer may be located between them. An image based on the fact that light scattered during or after passing through a photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material on the opposite side of the emulsion layer and enters the photographic emulsion layer again. In order to prevent blurring, or halation, a colored layer called an anti-halation layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer. When there are multiple photographic emulsion layers, an antihalation layer may be placed between the layers. The photographic emulsion layer is also colored to prevent a decrease in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation). These hydrophilic colloid layers to be colored usually contain a dye. This dye needs to satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a decrease in clarity, latent image regression, or capri.

(3) It should not be bleached during the photographic processing process or be eluted into the processing solution or washing water, leaving no harmful coloring on the photographic material after processing.

(4) Do not diffuse from the dyed layer to other layers.

(5) It has excellent stability over time in solutions or photographic materials and does not change color or fade.

In particular, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. In many cases, it is necessary to ensure that the

This is because, otherwise, not only will it have harmful spectral effects on other layers, but its effectiveness as a filter layer or anti-halogen layer will also be diminished. However, when a dyed layer and another hydrophilic colloid layer come into wet contact, it often occurs that some of the dye diffuses from the former to the latter. Many efforts have been made to prevent such dye diffusion. For example, a method in which a hydrophilic polymer with an opposite charge to a dissociated anionic dye is made to coexist in a layer as a mordant and the dye is localized in a specific layer by interaction with dye molecules is disclosed in US Pat. No. 2,548. No. 564, No. 4,124,386, No. 3,625,694, etc. In addition, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-1553.
No. 50, No. 55-155351, No. 63-27838
No. 63-197943, No. 52-92716,
European Patent No. 15601, European Patent No. 276566, European Patent No. 2747
No. 23, No. 276566, No. 299435, World Patent No. 88/04794, etc. In addition, a method of dyeing a specific layer using metal salt fine particles to which a dye has been adsorbed is disclosed in U.S. Pat.
, No. 496.841, No. 2,496,843, and Japanese Unexamined Patent Publication No. 45237/1983. However, even with these improved methods, the speed of decolorization during development processing is still slow, and if there are changes in various factors such as speeding up the processing, improving the processing solution composition, or improving the photographic emulsion composition. However, there was a problem in that the decolorizing function could not always be fully demonstrated. (Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a solid fine particle dispersion designed to dye a specific hydrophilic colloid layer in a photographic light-sensitive material and rapidly decolorize it during development. An object of the present invention is to provide a photographic material containing a dye. (Means for Solving the Problems) (1) The object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one compound represented by the following general formula (1) as a solid fine particle dispersion. Achieved. General formula (!) (In the formula, E', El, E, and E4 each represent an electron-withdrawing group, Ll, Lt, L3, L4, and LS each represent a methine group, and m and n each represent 0 or 1. ) (2) The object of the present invention is to provide a compound represented by the general formula (1) with E+, Eg, Es, Ba, 6 (cyano group, -C
OOR' -CORI -CONRIR''-So,
This is achieved by a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one compound selected from Rl as a solid fine particle dispersion. (R' and Rl each represent a hydrogen atom, an alkyl group, or an aryl group.) (3) The object of the present invention is to contain at least one compound represented by the general formula (1) as a solid fine particle dispersion, and to This is achieved by a silver halide photographic material containing at least one compound represented by formula (II) as a solid fine particle dispersion. General formula (II) R4 R4 aryl group, (wherein R3 is a hydrogen atom, an alkyl group, a cyano group, -COOR'-COR'-CONR'
R"-OR'-NHCORS, R4 represents a hydrogen atom, an alkyl group, an aryl group, m', n
"represents l or 0, respectively, Lll, L1 wealth, L+s
, LI4, l-IS represents a methine group. Rs, Rh
represent a hydrogen atom, an alkyl group, and an aryl group, respectively. However, the compound represented by general formula (II) has at least two carboxyl groups and sulfonamide groups in the molecule. ) Next, general formula (1) will be explained in detail. E in the formula
+, Ez, Es, and Ea each represent an electron-withdrawing group, and preferred electron-withdrawing groups have a Hammett's σρ value of 0.2 or more, particularly preferably a cyano group, -C
OORI -COR'-CONR' R”-S
o. It is Rl. Rl and Rz each represent a hydrogen atom, an alkyl group, and an aryl group.The alkyl group represented by Rl and Rz is an unsubstituted alkyl group (e.g., methyl, ethyl, cyclohexyl) or a substituted alkyl group {substituents include a halogen atom (e.g. 2-chloroethyl, 1.
1.2.2-tetrafluoroethyl), phenyl groups (e.g. benzyl, carboxybenzyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), alkoxy groups (e.g. 2-methoxyethyl, 2-(2-hydroxy) ethoxy) monoethyl), carboxy groups (e.g. carboxymethyl, l-carboxyethyl, 2-carboxyethyl), sulfonamide groups (e.g. methanesulfonamidoethyl), amino groups (e.g. 2(N,N-dimethylaminoethyl), Carboxylates (e.g. ethoxylponylmethyl, acetoxyethyl) or sulfonates (e.g. methoxysulfonylethyl)) are preferred; the aryl group represented by R', R'' is an unsubstituted aryl group (e.g. phenyl, naphthyl) or a substituted aryl group { Substituents include halogen atoms (e.g. 4-chlorophenyl, 25-dichlorophenyl), alkyl groups (e.g. 4-methylphenyl), hydroxyl groups (e.g. hydroxyphenyl), carboxy groups (e.g. carpoxyphenyl, 3.5-dichlorophenyl), carboxyphenyl), sulfonamide groups (e.g. 4methylsulfonylaminophenyl, 4-sulfamoylmethyl), alkoxy groups (e.g. 4-methoxyphenyl, 4-(2-hydroxyethoxy)phenyl), amino groups (e.g. N , N-dimethylaminophenyl, 4-(N-carboxymethylN-ethylamino)phenyl), carpoxylates (e.g. 4-ethoxycarbonylphenyl, 4(2-hydroxyethoxy)phenyl), or sulfonates (e.g. -methoxysulfonylphenyl)} is preferred.Furthermore, Bt, Ez or/and E3, E4 may form a ring.L'
The chin group (represented by SL", L', L', L') is preferably an unsubstituted methine group, but it may have a substituent (for example, methyl, ethyl, phenyl, neobentridene). Particularly preferred among the compounds represented by the general formula (1) are those that do not have a sulfo group or a salt of a sulfo group or a carboxy group as a substituent.Next, regarding the compound represented by the general formula (11) The alkyl group represented by R', R', R', R'' is an unsubstituted alkyl group (for example, methyl, ethyl, n-propyl, isopropyl, cyclohexyl) or a substituted alkyl group {as a substituent. Halogen atoms (e.g. 2-
chloroethyl, 1,1,2.2-tetrafluoroethyl), phenyl groups (e.g. benzyl, carboxybenzyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxybutyvir), alkoxy groups (e.g. 2-methoxyethyl) , 2-(2-hydroxyethoxy)monoethyl) carboxy group (e.g. carboxymethyl, 1-carboxyethyl, 2-carboxyethyl), sulfonamide group (
Preferred are amino groups (eg 2-(N,N-dimethylaminoethyl), carboxylates (eg ethoxycarponylmethyl, acetoxyethyl) or sulfonates (eg methoxysulfonylethyl)).

The aryl group represented by R, R', R', R' is an unsubstituted aryl group (e.g. phenyl) or a substituted aryl group {a halogen atom as a substituent (e.g. 4-chlorophenyl, 2,5-dichloro) phenyl), alkyl groups (e.g. 4-methylphenyl), hydroxyl groups (e.g. hydroxyphenyl), carboxy groups (e.g. carboxyphenyl, 3,5-dicarboxyphenyl), sulfonamide groups (e.g. 4-methylsulfonylaminophenyl) ,
4-sulfamoylmethyl), alkoxy ak (for example 4-methoxyphenyl, 4-(2-hydroxyethoxy)phenyl), amino groups (for example (N,N-dimethylaminophenyl, 4-(N-carboxymethoxy)), (N-ethylamino)phenyl), carboxylates (e.g. 4-
ethoxylponylphenyl, 4-(2-hydroxyethoxy)phenyl), or sulfonates (e.g. 4-
methoxysulfonylphenyl)} is preferred. Ll,
L! , Ll, L4, L% is preferably an unsubstituted methine group, but may have a substituent (eg, methyl, ethyl, phenyl). Among the compounds represented by the general formula (■), particularly preferred are those that do not have a sulfo group or a salt of a sulfo group or a carboxy group as a substituent. Furthermore, preferred among the compounds represented by the general formula (II) are carboxyl groups,
It has at least two groups selected from hydroxyl groups and sulfonamide groups. Next, specific examples of the compounds represented by formulas (1) and (II) of the present invention will be shown, but the present invention is not limited thereto. Specific example of General formula 1 f ■ 2 1-3 0 O 1-4 15 ■-6 ■ 7 1-8 ■ 9 f-10 ■ l l 1-12 1-1 3 ■ l4 0 0 ■ l5 0 ■ 16 0 ■ l7! -1 8 0 0 1-1 9 ■-20 1-2 1 ■ 22 0 0 ■ 23 ■-24 ■ 25 ■-26 0 0 0 ■-27 0 ■ 28 ■-29 1 30 O 0 CHI 0 ■ 31 I-32 Summer-33 1 34 ■ 35 Summer-36 ■ 37 ■ 38 I-39 0 0 Specific example of general formula (n) ■ l 11-2 I1-3 ■ 4 ■ 5 I1-6 υutI COOH ■ 7 ■ 8 COOH ■ 9 coon coon COOH ■-1 0 ■ l 1 COOH COOH ■-1 2 ■-13 ■-1 4 COOH CυOH ■-1 5 ■ 16 UUH COOH ■ l7 ■ l8 General formula used in the present invention Compound (1) is West German patent 8
It can be synthesized according to the method described in No. 33518, US Pat. No. 3,718,472, etc. An example of the synthesis of the compound represented by general formula (1) is shown below. Synthesis of compound 1-1 Ethyl cyanoacetate 18.0 g, ethylamine 8.1
g, propenedianil 8.9 g and ethanol 6 (l
Heat the mixture in step d under reflux for 8 hours. Add 6.0 g of potassium acetate to the reaction solution, dissolve, and then cool. The precipitated crystals were collected by filtration, dissolved in 5 ml of water, and further added with 1 ml of concentrated hydrochloric acid.
Add 5II1. After cooling, the precipitated crystals were collected by filtration and dried to obtain a yellow powder of Compound 1-1. Melting point 15
2-156°C The compound of general formula (If) used in the present invention is
It can be synthesized by the method described in No. 2-92716, No. 64-40827, etc. The compound of general formula (1) or (■) is used in an amount of 1 to too much per ml of area on the photosensitive material, preferably lnl
1~800■ is used per. General formula (1) or (■)
When using the compound as a filter dye or antihalation dye, any effective amount can be used, but it is preferably used so that the optical density is in the range of 0.05 to 3.5. It can be added at any stage before coating. The compound of general formula (1) or (If) according to the present invention can be used in both emulsion layers and other hydrophilic colloid layers. The fine particle dispersion of the compound of general formula (1) or (■) of the present invention can be prepared by a method of precipitating the compound of the present invention in the form of a dispersion, and/or by a known pulverization method in the presence of a dispersant, e.g. A method of forming by ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. [In that case, a solvent (for example, water, alcohol, etc.) may be present.] It can be formed by Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate a microcrystalline powder. In that case, a dispersing surfactant may be used. good. Alternatively, the compound of the present invention may be first melted by controlling the pH, and then microcrystallized by changing the Pti. The microcrystalline particles of the compound of the present invention in the dispersion have an average particle size of 10 tIm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less, and in some cases O. It is more preferable that the particles be fine particles of 1 μm or less.

Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used. The silver halide emulsions used in the present invention include silver bromide, silver iodobromide, silver iodochlorobromide,
Silver chlorobromide and silver chloride are preferred.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use particles consisting of a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms. The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. It may also be a particle in which a latent image is mainly formed on the surface (for example, a negative emulsion),
It may also be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion or a pre-fogged direct inversion type emulsion). Preferably, the particles are such that the latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has a thickness of 0. 5 microns or less, preferably 0
．． A tabular grain emulsion in which grains with a diameter of 3 microns or less, preferably 0.6 microns or more, and an average aspect ratio of 5 or more account for 50% or more of the total projected area, or a statistical coefficient of variation (projected area In the distribution expressed by the diameter when approximated as a circle, the value S/d obtained by dividing the standard deviation S by the diameter d
) is preferably 20% or less. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is B. Grafchides (P
, Glafkides), Shimmy Engineering Physique
Photography (Chimie er Physi)
que Photo-grapheque) (Paul Montel, 1967), G.F. Duffin (
G. F. Duffin), Photographic Emulsion Chemistry
Emulsion Chemjstry) (Focal Press, 1966), Bouy El Zelikman (
V. L. Making and Coating Photographic Emulsions (Zelikman) et al.
Making and Coating Pho
tographic emulsion) (Focal Press, 1964). In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat.
, 271,157, 3,574,628, 3,704,130, 4.297,439, 4,276.374, etc.), thione compounds (for example, JP No. 51-144319, No. 53-82408,
55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.), etc. can be used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

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, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Various synthetic hydrophilic polymeric substances such as single or copolymers of vinyl alcohol, polyvinyl alcohol partial acetal, polyN-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. It can be used. In addition to general-purpose lime-processed gelatin, gelatin may be used in acid-processed gelatin or in the Journal of the Japanese Society of Scientific Photography (Bull.Soc.
Sci. Photo. Japan), k 1 6, 30
Enzyme-treated gelatin as described in P. (1966) may be used, and gelatin hydrolysates may also be used. In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes M (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxy-1.3
．． 5-triazine and its sodium salt, etc.] and active vinyl compounds (1.3-bisvinylsulfonyl-2-
Propanol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, or vinyl polymers with a vinylsulfonyl group in the side chain) can quickly harden hydrophilic colloids such as gelatin, resulting in stable photographs. This is preferable because it gives characteristics. N-carbamoylpyridinium salt II ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.)
Yaguchi amidinium salts 1 (1-(1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate, etc.) also have a fast curing speed and are excellent. The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. 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. For these pigments, any of the nuclei commonly used for cyanine pigments can be used as basic heterocyclic nuclei. That is, pyrroline 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, that is, indolenine Nuclei, pennzindolenine nucleus, indinoole nucleus, benzoxazole nucleus, naphthoxazole nucleus, penzothiazole nucleus, naphthothiazole nucleus, penzoselenazole nucleus, penzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms. Merocyanine dyes or composite merocyanine dyes include nuclei having a ketomethylene structure such as birazoline-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2.
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus 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. 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, aminostilbene compounds which are substituted nitrogen-containing heterocyclic ring groups (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,72)
1), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3,6
No. 15.641, No. 3.617,295, No. 3.63
The combinations described in No. 5.721 are particularly useful. The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
It can contain various compounds. That is, azoles such as henzothiazolium salts, nitroimidazole, nitropenzimidazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptohenzothiazoles, mercabutobenzimidazoles, mercaptothiadiazoles, amino triazoles, penzotriazoles,
Nitropenzotriazoles, mercaptotetrazoles (particularly l-phenyl 5-mercaptotetrazole), etc.; mercaptopyrimidines frequently; mercaptotriazines; thioketo compounds such as oxadolinthion;
Azaindenes, such as triazaindenes, tetraazaindene II (particularly 4-hydroxy substituted (1.3.3
a. 7) Tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. , the photosensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). May include. The light-sensitive material prepared using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for irradiation or antihalation and other various purposes. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. ．． Oil-soluble dyes can also be emulsified by oil-in-water dispersion and added to the hydrophilic colloid layer. The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral intensities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in this order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure may be used to further improve graininess. Also, 2 with the same color sensitivity
A non-light sensitive layer may be present between the two or more emulsion layers. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. Sensitivity may be improved by providing a reflective layer such as fine-grain silver halide under the high-sensitivity layer, particularly under the high-sensitivity blue-sensitive layer. Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color photography or semiconductor laser exposure. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed on flexible supports such as plastic films, paper, and cloth, or rigid supports such as glass, ceramic, and metal, which are commonly used in photographic light-sensitive materials. It is applied. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polycarbonates. Paper coated with or laminated with polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other hydrophilic colloid layers.
U.S. Patent Nos. 2,681,294 and 276 as necessary.
No. 1791, No. 3526528 and No. 3508
Multiple layers may be applied simultaneously using the coating method described in No. 947 and the like. The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color body film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. Can be done. Research Disclosure, Volume 17123 (1)
(July 978), or by utilizing the black-forming couplers described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136, etc. Therefore, the present invention can also be applied to black-and-white photosensitive materials for X-rays and the like. Films for plate making such as lithium film or scanner film, X-ray film for direct/indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, COM or regular micro film, silver salt diffusion transfer type photosensitive materials, and The present invention can also be applied to print-out type photosensitive materials. When the photographic element of the present invention is applied to color diffusion transfer photography, it may be of the peel-apart (beer-apart) type or
-16356, 4B-33697, JP-A-1983-
13040 and British Patent No. 1,330,524, or a peel-free type film unit as described in JP-A-57-119345. Can be done.
In both types of formats, the use of a polymeric acid layer protected by a neutralizing timing layer is advantageous in increasing the processing temperature tolerance. When used in color diffusion transfer photography, it may be added to any layer in the photosensitive material, or it may be contained in a processing solution container as a developer component. Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flash bulbs are common. Gas, dye solution, or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear arrays are used in microscans using fluorescent surfaces (such as CRTs), liquid crystals (LCDs), and lanthanum-doped lead titanium zirconate (PLZT), which are emitted from phosphors excited by electron beams. Alternatively, an exposure method that combines a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters. The color developing solution used in the development of the photosensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and P-}luenesulfonate. These diamines are generally more stable in their salt form than in their free form, and are therefore preferably used. The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, penzimidazoles, penzothiazole or mercapto compounds. It generally contains agents such as drugs. Also, if necessary, preservatives such as hydroxylamines, dialkylhydroxylamines, hydrazine, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, polyethylene glycol, etc. , quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-vilapridone, viscosity-imparting agents, Various cattle rate agents such as aminobolycarboxylic acid, aminobolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, West German patent M
(OLS) No. 2,622,950 may be added to the color developer. In the development process for reversal color photosensitive materials, black and white development is usually performed, followed by color development. In this black and white developer, known black and white developers such as dihydroxybenzene such as hydroquinone, 3-virazolidone such as l-phenyl-3-pyrazolidone, or aminophenol such as N-methyl-p-aminophenol may be used alone or in combination. It can be used. Not only a color developing solution but also any photographic developing method may be applied to the photosensitive material of the present invention. The developing agents used in the developer include dihydroxybenzene-based developing agents, l
-Phenyl-3-virazolidone type developing agents, p-aminophenol type developing agents, etc., and these can be used alone or in combination (for example, 1-phenyl-3-virazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzene). ) can be used. The light-sensitive material of the present invention may also be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone. In the above, examples of dihydroxybenzene-based developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone,
There are isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc.
As the l-phenyl-3-virazolidone developing agent, l
-Phenyl-3-pyrazolidone, 4,4-dimethyl-l
-Phenyl-3-virazolidone, 4-hydroxymethyl-4-methyl-1 phenyl-3-virazolidone, 4.4
-dihydroxymethyl-1-phenyl-3-virazolidone, etc., and p-aminophenol, N-methyl-P-aminophenol, etc. are used as the P-aminephenol developing agent.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, formaldehyde sodium bisulfite, which gives almost no free sulfite ions in the developer, may be used.The alkaline agents for the developer used in the present invention include potassium hydroxide, sodium hydroxide, potassium carbonate,
Sodium carbonate, sodium acetate, potassium triphosphate, diethanolamine, triethanolamine, etc. are used. The pH of the developer is usually 9 or higher, preferably 9.7.
The settings above are as follows. The developer may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as penzothiazolium salts, nitroindazoles, nitropenzimitazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptopenzimidazoles, Mercaptothiadiazole, aminotriazoles, penzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly l-phenyl-5-mercaptotetrazole), etc.; mercaptovirimidines; mercaptotriazine frequently; such as oxazolinthione Thiogato compounds; azaindenes, such as triazaindenes, tetraazaindene M (especially 4-hydroxy substituted (1,3.
3a, 7) Tetrazaindene W4), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, sodium 2-mercaptobenzimidazole-5-sulfonate, etc. The developer that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide with a molecular size of 1000-10000 is o. l~10g/j! It can be contained within the range of . It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine, xaacetic acid, diethylenetetraaminepentaacetic acid, etc. as a water softener to the developer that can be used in the present invention. The developer used in the present invention includes a compound described in JP-A No. 56-24347 as a silver stain prevention agent, a compound described in JP-A-62-212651 as an agent for preventing uneven development,
As a solubilizing agent, the compounds described in Japanese Patent Application No. 109743/1988 can be used. In the developing solution used in the present invention, a buffering agent is added.
Boric acid described in No. 1-28708, JP-A No. 60-9343
The saccharide (e.g. sucrose), oxime It according to 3.
(eg, acetoxime), phenol If (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), etc. are used. Various compounds may be used as the development accelerator used in the present invention, and these compounds may be added to either the sensitive material or the processing solution. Preferred development accelerators include amine compounds, imidazole compounds, imidazoline compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds, thioether compounds, thione compounds, certain mercapto compounds, mesoionic compounds, and thiocyanic acid. One example is salt. This is especially necessary for quick development processing in a short period of time. It is desirable to add these development accelerators to the color developing solution, but depending on the type of accelerator or the position on the support of the photosensitive layer to be accelerated, it may be necessary to add them to the photosensitive material. You can also. It can also be added to both the color developer and the photosensitive material. Furthermore, depending on the case, a pre-bath for the color developing bath may be provided and the additive may be added thereto. Amino compounds useful as amino compounds include both inorganic amines and organic amines, such as hydroxylamine. Organic amines can be aliphatic amines, aromatic amines, cyclic amines, aliphatic monoaromatic mixed amines or heterocyclic amines; primary, secondary and tertiary amines as well as quaternary ammonium compounds are all useful. be. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Examples of bleaching agents include iron (m), cobalt (■), and chromium (■).
, compounds of polyvalent metals such as copper (II), oxidants, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (DI).
is an organic complex salt of cobalt (III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salts such as primary sulfate; manganate; nitrosophenol, etc. can be used. Among these, ethylenediaminetetraacetic acid iron(II) salt, diethylenetriaminepentaacetic acid iron(II) salt and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complex is particularly useful in both stand-alone bleach and single bath bleach-fix solutions. Bleach accelerators may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Patent No. 1,290,81.
No. 2, No. 2,059,988, JP-A-53-3273
No. 6, No. 5357831, No. 37418, No. 53-
No. 65732, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in Research Disclosure No. 17129 (July 1978), etc.; Thiazolidine derivatives such as those described in No. 140129;
No. 832, No. 53-32735, U.S. Patent No. 3,70
1,000 urea derivatives described in No. 6 561; West German Patent No. 1
, 127,715, and the iodide described in JP-A-58-16235; West German Patent No. 966.410, JP-A No. 2,748
, 430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and other JP-A Nos. 49-42434, 49-59644, 5
No. 3-94927, No. 54-35727, No. 55-2
Compounds described in No. 6506 and No. 58-163940 and iodine and bromine ions can also be used. Among them, compounds having a mercabuto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds having a mercabuto group or a disulfide group are preferred, and in particular, compounds having a mercabuto group or a disulfide group are preferred from the viewpoint of a large promoting effect.
No. 858, West German Patent No. 1,290,812, JP-A-5
The compounds described in No. 3-95630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred.
These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleaching and fixing color photosensitive materials for photography. Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds such as 1,000 ureas, and large amounts of iodides, but thiosulfates are commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After bleach-fixing or fixing, washing and stabilization are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and residual phosphoric acid, and disinfectants and preventive agents that prevent the growth of various bacteria, algae, and molds. A pyrolyte, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants to prevent drying load and unevenness, and various hardening agents can be added as necessary. Or Photographic Science and Engineering magazine by L.E. West.
, Photo. Sci. εng. ), Volume 6, 344~
Compounds described on page 359 (1965) may also be added. The addition of chelating agents and anti-piping agents is particularly effective. In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 may be implemented. In the case of this process, 2 to 9 countercurrent baths are required. In addition to the additives mentioned above, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, the membrane p
Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid) for adjusting H (e.g. pH 3-9) Typical examples include aldehydes such as formalin (used in combination with acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminobolycarboxylic acid,
Spinal phosphoric acid, organic phosphonic acid, aminobolyphosphonic acid,
phosphonocarboxylic acids, etc.), fungicides (penzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenols, sulfanilamide,
penzotriazole, etc.), surfactants, fluorescent brighteners,
Various additives such as hardening agents may be used, and two or more compounds for the same or different purposes may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as membrane pH regulators after treatment. Further, in the case of color photosensitive materials for photography, the normally performed post-fixing (washing and stabilization) process can be replaced with the above-mentioned stabilization process and water washing process (water saving process). At this time, if the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597, Research Disclosure 1485 (1 and US Pat. No. 1515)
9, aldol compounds as described in US Pat. No. 13924, metal salt complexes as described in US Pat. No. 3,719,492, urethane compounds as described in JP-A-53-135628, Showa 56-6235
No. 56-16133, No. 56-59232, No. 56-67842, No. 56-83734, No. 56-
No. 83735, No. 56-83736, No. 56-897
35, No. 56-81837, No. 56-54430, No. 56-10624 1, No. 56-107236, No. 57-97531, No. 57-83565, etc. be able to. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-virazolidones, if necessary, for the purpose of promoting color development. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-1445.
No. 47, No. 57-211147, No. 5B-50532
No. 58-50536, No. 5B-50533, No. 5B-50534, No. 5B-50535 and No. 5
8-115438, etc. The various processing solutions used in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674,499 may be carried out using cobalt intensification or hydrogen oxidation intensification.

Heaters, temperature sensors, liquid level sensors, circulation pumps, filters, floating pigs, squeegees, etc. may be installed in the various processing baths as necessary. In addition, during continuous processing, a constant finish can be obtained by using replenishers for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs. When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed as required, very generally, and even when it is a color photographic material for maximum shadow. (Effects of the Invention) In the silver halide photographic light-sensitive material of the present invention, the dye in the dye layer has appropriate spectral absorption and has an excellent effect of selectively dyeing the dye layer and not diffusing to other layers. ．． The silver halide photographic material containing the compound of the present invention is easily decolorized or eluted by photographic processing, provides a low Dmin, does not reduce sensitivity, and has the effect that sensitivity decreases little due to storage. Furthermore, the silver halide photographic material of the present invention provides images with improved sharpness. Further, photographs obtained from the silver halide photographic material of the present invention do not produce stains, are stable even during long-term storage, and do not deteriorate in photographic performance. (Example) Next, the present invention will be explained in more detail based on an example. Example 1 (Preparation of Emulsion 8) An aqueous solution of silver nitrate and an aqueous sodium chloride solution containing ammonium rhodium (I[l) hexachloride in an amount of 0.5 x 10-' mol per mol of silver were mixed into a gelatin solution at 35°C by the double jet method. The mixture was mixed while controlling the pH to 6.5 in a vacuum chamber to prepare a monodisperse silver chloride emulsion with an average grain size of 0.07 μm.

After particle formation, soluble salts are removed by flocculation methods well known in the art, and stabilizers 4-hydroxy-6-methyl-1.3.3a,7-tetraazaindene and l-phenyl- 5-Mercaptotetrazole was added. 1 kg of emulsion contained 55 g of gelatin and 105 g of silver. (Emulsion A) (Preparation of photosensitive material) Add the following nucleating agent and nucleation accelerator to the emulsion A,
Next, polyethyl acrylate latex 7. (3 0
0%/rrf) and further added 2.4 dichloro-6-hydroxy 1,3.51 riazine sodium salt as a hardening agent to make polyethylene terephthalate so that the amount of silver was 3.5 g per rd. Addition amount of lU (■/Po) 1 Jb1 Elbow C10 28. A silver halide emulsion layer was coated on a transparent support, and gelatin (1.3 g/%), compound 1-19 of the present invention (0.1 g/l), and the following coating aids were added to the upper layer. 3
A protective layer containing two surfactants, a stabilizer, and a matting agent was applied and dried. (Sample l) Kai this Meng sex addition it (■/I) CHzCOOCJ+z CIICOOCbtl I 3 37 SO. Na C. F+tsOJcHzcOOK 2. 5 C. Hff Thioctic acid L upper eyebrow polymethyl methacrylate (average particle size 3.5μ) Compound of the present invention ■ A dispersion was prepared and used. (Preparation of dye dispersion) ■Liquid 50. O■/Pol9 was added to the solution (2) at 40°C while stirring the solution (2) according to the following procedure. (Preparation of Comparative Sample) ■ Add the solution little by little l) A sample was prepared by using the following dye in place of Compound 1-19 in Example 1 (Comparative Sample lA) Dye 2) Add the compound ■ in Example I (Next dye B was used instead of comparative sample l l9) 0 0 0. lOg/nf 3) Compound of the present invention of Example-1! Comparative sample 1-C was prepared using the following protective layer instead of the protective layer containing -19. JL-t;”17 2.0
g/rrf苅1υpossible. Og/m CI3 Dye 0. 75g/PoC++HxsCONH(CHz)sN(CHs)x(C
Ilx)asOs0. 53g/poCHtCOOCJ+s CHCOOCJ+s 0. 037 SOJa C. F+tsOJcH*cOOI[ 1 C*N−+ 0. 0025 Thioctic acid 0.006ヱ1 or above Polymethyl methacrylate (average particle size 2.5 μ) 0.009 (performance evaluation) (1) The above four samples were processed at Dainippon Screen Light Manufacturing Department. The film was exposed to light through an optical wedge using a printer P-607, developed with the following developer at 38°C for 20 seconds, fixed in a conventional manner, washed with water, and dried.

11 basic prescription hydroquinone 35. ogN-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Potassium triphosphate
74.0g potassium sulfite
90.0g ethylenediaminetetraacetic acid tetrasodium salt 1.0g potassium bromide 4.0g 5-methylhenzotriazole 0.6g 3-diethylamino1.
2 Add 15.0g of propanediol water
11 (pH=11.5) As a result, Example 1 and Comparative Sample 1-A were completely decolored, but Comparative Samples 1-B and 1-C remained with yellow stains. Comparative samples 1-8 were completely decolored when the development time was increased to 30 seconds. As mentioned above,
The compounds of the present invention are rapidly decolorized. (2) Test of Tone Variability The above four samples were exposed to light through a flat mesh screen using the above printer, and were otherwise developed in the same manner as in the test (1). After determining the exposure time for each sample to return the dot area to l:1,
Exposure was performed for twice and four times as long as that exposure time, and the extent to which the area of the rope point expanded was investigated. The larger the enlargement, the better the tone variability.
The results are shown in Table-1. As can be seen from Table 1, comparative sample 1-A has a markedly reduced tone variability, whereas sample 1 of the present invention has a high tone variability. this is,
Because the dye used in comparative sample 1-A is water-soluble and diffusible, it is uniformly diffused from the added layer to the light-sensitive emulsion layer during storage, so even if the exposure time is increased, the dye This is because the expansion of the halftone dot area was suppressed by the irradiation prevention effect. On the other hand, compound I-19 of the present invention exhibits high tone variability since it is fixed in the added layer.

Comparative samples 1-B and 1-C also showed good tone variability.

Table-1 Tone variability (indicated by increase in halftone dot area) (3)
Evaluation of contamination (stain) due to reducing solution The samples of the present invention and samples of comparative examples obtained by treatment in (2) above were immersed in the following Farmer-X solution for 60 seconds at 20°C and washed with water. , dried. As a result, the dot area of each sample was reduced to about 33% at 50%.
Comparative sample 1-C had an intense brown stain over the entire surface. No stain was observed in the samples of the present invention and comparative samples 1-A and 1-B. When using Farmer's sterilizing liquid, mix 1st liquid: 2nd liquid: water = 100 parts: 5 parts: 100 parts. As described above, the samples of the present invention had good decolorization properties, tone changeability, and force reduction properties.

Example 2 After corona discharge treatment on a paper support laminated on both sides with polyethylene, support samples A, B and C were obtained using a gelatin subbing layer or the following dye dispersion. Dye Dispersion Method The following dye crystals were kneaded and made into fine particles using a sand mill. Additionally, 0.5g of citric acid was dissolved in lO%
Compound 1-1 of the present invention was dispersed in lime-treated gelatin aqueous solution 25+d and the used sand was filtered using a glass filter.
・・・・・・・・・ 1. Og Compound of the invention I-
38 ・・・・・・・・・ 1.6g (surfactant) ? 5i of the solution was removed, and the dye adhering to the sand on the glass filter was removed to obtain 7% gelatin solution 100*. (The average particle size of the dye fine particles was 0.15 μm.) Compound 1-1 of the present invention ・・・・・・・・・・・・ l.
Og Compound of the present invention +1-3 ・・・・・・・・・
- 1.6g was adjusted in the same way.

Gelatin support A Undercoat layer gelatin 0.8g
/rrf Paper support B Antihalation layer gelatin 0.6g
/rrfCompound 1-1 of the present invention...
25mg/rr1 Compound 1-38 of the present invention...
・・・・・・・・・ 40■/Poly paper support C Antihalation layer gelatin ・・・・・・・・・/Q, 5g
/n{Compound 1-1 of the present invention...
40Ilg/rd Compound It-3 of the present invention...
65■/A Multilayer color photographic paper sample 2- with the layer structure shown below on paper support samples A, B, and C.
I got 1 or 2. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1g, color image stabilizer (Cpd-1) 4.4g and color image stabilizer (Cpd-7)
) to 1.4 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was reduced to 1O%
1 containing 8 cc of sodium dodecylhenzenesulfonate
It was emulsified and dispersed in 185 cc of O% gelatin aqueous solution. On the other hand, the coefficient of variation of the grain size distribution of a silver chlorobromide emulsion (cubic, 3:7 mixture (ll molar ratio) of average grain sizes of 0.88 μm and 0.70 μm is 0.08 and 0.1O,
Each breast tissue contains 0.2 mol% silver bromide locally on the grain surface)
The following blue-sensitive sensitizing dyes were added per 1 mol of tIQ at 2.0 x lθ-4 mol each for large emulsions, and 2.5 x each for small emulsions.
A sulfur sensitized product was prepared after adding 10-' mole of the sample. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. l-oxy-3,5-dichloro, s-1-lyazine sodium salt was used as the gelatin hardening agent for each layer. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer SO, θ SOsH-N(CtHs)i (per mol of silver halide, 2.0 x 104 mol each for large size emulsions, and 2.0 x 104 mol each for small size emulsions). 5× l 0 4 mol >> green-sensitive emulsion layer (per 111 mol of halide, 4.OX 10-' mol for large size emulsions, 5.OX 10-' mol for small size emulsions).
6XlO-'mol) and so. e SO3H - N(CtHs)2 (7.OXIO-' mol for large size emulsions and 1.OXIO-' mol for small size emulsions per ill mol of halide) Red-sensitive emulsion layer CtHs Iθ CsH++ (per mole of silver halide, 0.9X1 for large size emulsions)
0-' mole, or 1.0-' mole for small size emulsions. l
For the red-sensitive emulsion layer, the following compound was added at 2.6XlO-' per mole of 1I halide.
Mole added. In addition, 1-(5-methylureidophenyl)-5-mercabutotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a concentration of 8% per mole of silver halide.
．． 5xlO-'mol, 7.7XIO-'mol, 2.5X
10-'mol was added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4hydroxy-6-methyl-1.3.3a
, 7-tetrazaindene were added in amounts of IXIO-' mol and 2XIO-' mol, respectively, per mol of silver halide. One paper support sample A had the following comparative dyes added to its emulsion layer. SO3Na SO. Na 8■/nr and 35wg/po (layer structure) The composition of each layer is shown below. The number is the coating amount (g/rrr
). Silver halide emulsions represent coating amounts in terms of silver. Four kinds of samples A, A, B, and C, in which an undercoat layer and an antihalation layer were provided on the support polyethylene laminated paper [the polyethylene on the first layer side contains a white pigment (Tie.) and a bluish dye (ulmarine)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) 0.19 solvent (Solv-1)
0.35 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin'' 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv
-1) 0.16 solvent (So I v-
4) 0. 08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1=3 mixture of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm (Ag molar ratio). Coefficient of variation of grain size distribution are 0.10 and 0.0
8. Each emulsion contained 8 mol% of AgBrO locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (ExM
) 0.20 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.15 Color image stabilizer (Cpd-4) 0.
02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (
Ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (C
pd-5) 0.05 solvent (So I v-
5) 0. 24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm. Coefficient of variation of grain size distribution are 0.09 and 0.1
1. Each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23 gelatin
1.34 cyan coupler (ExC
) 0.32 color image stabilizer (Cpd-6)
0.17 color image stabilizer (Cpd-7)
o. 40 color image stabilizer (Cpd-8) 0
．． 04 Solvent (Solv-6) 0.15
Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent (C
pd-5) 0.02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
0.17 liquid paraffin
0.03 (Ex Y) Yellow coupler CI l:l mixture (molar ratio) with CtHs (ExM) Magenta coupler CI, C1. (n) and (l of @lB(t): ■Mixture (molar ratio) (ExC) Cyan coupler CI *-cans and C.H9 and 0} (Cpd-1) Color image stabilizer (Cpd-2) Color Image stabilizer (cpa 3) Color image stabilizer (Cpd 4) Color image stabilizer C%H++Ct) C%l+++ (Cノ(cpa 5) Color mixture inhibitor 0 OH (Cpd 6) Color image stabilizer CI-2 : 4 : 4 Mixture (weight ratio) (Cpd 7) Color image stabilizer -fCH.-CH) -- CONHCJ*(t) Average molecular weight 60. 000 (Cpd-8) Color image stabilizer OH OH (cpa 9) Color image stabilizer CH,l CH. (UV 1) Ultraviolet absorber CsH+ + (t) 4:2:4 mixture of CI (weight ratio Te So Iv-1) Solvent (Solv 2) Solvent (Solv-4) Solvent (Solv 5) Solvent COOCsH+t (CHg )s I COOCsH+q (Solv-6) Regarding the solvent-treated samples 2-1 to 2-4, a sensitometer (manufactured by Fuji Photo Film ■, FWH type, color temperature of the light source 3,20
Stepwise exposure for sensitometry was provided through blue, green, and red filters using a high temperature (0°K). On the other hand, the resolution (
CTF) was exposed to light for measurement, and then processed through the following processing steps. The concentration of the obtained sample was measured and Table 2
We obtained the results shown below. LLrJi jlOnce mlL Lt[”kulLl
lColor development 35°C 45 seconds 16lIdl11 Bleach fixing 30-35°C 45 seconds 215d
l7 I! ．． Rinse ■ 30~35°C 2G seconds ■
10N rinse ■ 30-35℃ 20 seconds ■
10ffi rinse■ 30-35℃ 20 seconds 350
d 101 Drying 70 to 80°C for 60 seconds *The replenishment amount is per trrr of photosensitive material (3 tank countercurrent method from rinsing ■ to ■). The composition of each processing solution is as follows. Mutual i 2 ri 1 nail Tsuyoshi L sowing Fukiinu Kyusui
800m 80
0m ethylenediamine-N,N. N,N-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g Potassium carbonate
25g 25gN-ethyl-N-(
β-Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 7.0gN
, N-bis(carboxymethyl)hydrazine 5.5g 7.0g Fluorescent brightener (old TEX 4B, manufactured by Sumitomo Chemical) 1.0g 2.0g
Add water to 1000IiPH (25
°C) 10.05ta constant 11 (tank liquid and replenisher are the same) Ammonium thiosulfate (70%) Sodium sulfite Iron(III) ethylenediaminetetraacetate Ammonium disodium ethylenediaminetetraacetate 1000af 10.45 400m 100m 17g 55g 5g pH (25 °C) 6.0 Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium and magnesium are each 3 ppr)
(1 or less) When the dye according to the present invention is used in an antihalation layer, there is relatively little decrease in sensitivity and no residual color is noticeable. By using this amount, the resolution can be significantly improved. Example 3 Preparation of dye fixed layer Dyes 1-9 and II-3 were each subjected to ball mill treatment by the method described in JP-A-63-197943. 434m of water and TritonX-20OR surfactant (
791ml of a 6.7% aqueous solution of TX-20OR) was placed in a 21 ball mill. 20g of dye was added to this solution. Zirconium oxide (ZrO) beads 400m
(2sm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. When the obtained dye dispersion was observed, the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter. A transparent PET support with a thickness of 100 μm was used as the support. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to a corona discharge treatment, and then a first undercoat layer made of styrene-phytadiene latex was applied. Two undercoat layers were applied. A fine dispersion of the dye was coated on this support as a gelatin dispersion solution in the coating amount shown below. In this way, an antihalation layer was prepared.

ΦGelatin 1.8g/nl Dye
1-9, II-3 Quantity listed in Table 3 - Potassium polystyrene sulfonate (average molecular weight 1.6 million) 35 Ilg/I 10
■/Id ●Phenoxyethanol 181g/rrf1.
Preparation of 2-bis(vinylsulfonylacetamido)ethane 100μ/M emulsion coating solution Raw milk #1 shown below is a surface latent image type emulsion, and negative-tone properties can be obtained using a commercially available microfilm general-purpose processing solution. It is something that can be done. Further, by performing reversal processing using a reversal processing solution, positive type characteristics can be obtained. Preparation of raw emulsion #l> Solution 1 75°C solution ■ 35°C solution ■ 35°C solution ■ Solution ■ and solution ■ were added simultaneously over 45 minutes to solution I that was well stirred at room temperature, and then the entire amount was added to solution ■. At the end of the process, a cubic monodisperse emulsion with an average grain size of 0.28 μm was finally obtained. At this time, the addition rate of solution (2) was adjusted so that the PAg value in the mixing container was always 7.50 relative to the addition of solution (2). Note that solution (■) was added over a period of 5 minutes starting 7 minutes after the start of addition of solution (2). After the addition of solution ■ is complete,
After washing with water and desalting by the sedimentation method, inert gelatin 10
It was dispersed in an aqueous solution containing 0 g. For this emulsion! Sodium thiosulfate and chloroauric acid tetrahydrate were added in an amount of 34 μm each per 1 mol, and the p}{,PAg value was 8.9, respectively.
After adjusting the temperature to 7.0 (40°C), chemical sensitization was carried out at 75°C for 60 minutes to obtain a surface latent image type silver halide emulsion. The layer structure and composition of each layer are as follows. Layer structure
Film Thickness (μm) The emulsion layer, surface protection layer, conductive layer, and gel layer other than the antihalation layer were prepared and coated so that each component was coated in the following amounts to obtain a photographic material. <Protective layer><Emulsionlayer> cans photoresist <Back conductive layer> (Ge 11i!> Coating amount ■/m Processing method Reversal development processing Reversal development processing was performed using F-1OR reversal deep tank automatic developing machine manufactured by Allan Products in the United States. Commercially available reversing treatment liquid (FR-5 manufactured by FR Chemicals, USA)
31, 532, 533, 534, 535) under the following conditions.

Negative development processing Negative development processing was carried out under the following conditions using a commercially available general-purpose microfilm processing solution (FR-537 developer made by FR Chemicals, USA) using an F-10 deep tank automatic processor manufactured by Allen Products, USA. I went there.

Evaluation of sharpness Sharpness was evaluated by MTF. The photographic material was exposed to white light for 1/100 seconds using an MTF measurement wedge and processed in an automatic processor as described above.

The MTF was measured with an aperture of 400×2 μM, and the optical density was 1.0 using an MTF value with a spatial frequency of 20 cycles/fflII. Evaluation was made in the 0 part.

The results are shown in Table-3.

Change in residual color After the unexposed film was subjected to the automatic development process described above, it was passed through a Maches Status A filter and the green transmission density and blue transmission density were measured. The results are shown in Table 3. Procedural amendment

Claims (1)

[Scope of Claims] (1) A silver halide photographic light-sensitive material comprising a hydrophilic colloid layer containing at least one compound represented by the following general formula (I) as a solid fine particle dispersion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, E^1, E^2, E^3, E^4 each represent an electron-withdrawing group, L^1, L^2, L^3, L^4, L^
5 each represents a methine group, and m and n each represent 0 or 1. ) (2) General formula (
I) In the compound represented by E^1, E^2, E
^3, E^4 is a cyano group, -COOR^1, -COR^
1, -CONR^1R^2, -SO_2R^1
The silver halide photographic material described in Section 1. (R^1 and R^2 represent a hydrogen atom, an alkyl group, and an aryl group, respectively.) (3) Containing at least one compound represented by the general formula (I) as a solid fine particle dispersion, and containing the following general formula (
A silver halide photographic material comprising at least one of the compounds represented by II) as a solid fine particle dispersion. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 is a hydrogen atom, an alkyl group, an aryl group, a cyano group, -COOR^5, -COR^5, -CONR^
5R^6, -OR^5, -NHCOR^5, R
^4 represents a hydrogen atom, an alkyl group, an aryl group, m
', n' represent 1 or 0, respectively, L^11, L^1
^2, L^1^3, L^1^4, and L^1^5 represent methine groups. R^5 and R^6 each represent a hydrogen atom, an alkyl group, or an aryl group. However, the compound represented by general formula (II) has at least two groups selected from carboxyl groups, hydroxyl groups, and sulfonamide groups in the molecule. )