JPH03216646A - 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, R1 is H, alkyl, aryl, acyl or a hetero-cyclic group, each of R2 and R3 is H, alkyl, substd. amino, etc., x is 1-5, Y is a single bond or a divalent combining group, each of L1-L3 is methine 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.

It is based on the fact that light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing image blurring, that is, halation, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support, or on the surface of the support opposite to the photographic emulsion layer. When there are multiple photographic emulsion layers, an antihalation layer may be placed between the layers.

Deterioration of image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

These hydrophilic colloid layers to be colored usually contain a dye. This dye needs to satisfy the following conditions.

m. Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, it should not have an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

(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 antihalation layer will 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 in the past to prevent such dye diffusion.

For example, a method is described in US Pat. No. 2,548, in which a hydrophilic polymer having an opposite charge to the dissociated anionic dye is coexisting in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. No. 564, 4,124,3
No. 86, 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. 55-15535, No. 6: l27838
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/O4794, etc.

Further, a method of dyeing a specific layer using metal salt fine particles to which a dye has been adsorbed is disclosed in US Pat. No. 2,719. No. 088, No. 2,496,841, No. 2,496,843,
It is disclosed in Japanese Patent Application Laid-Open No. 60-45237.

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 create 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) (11) 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 (I) as a solid fine particle dispersion. achieved.

General formula (I) R1 In the formula, R1 each represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a heterocyclic group, R2 and R are a hydrogen atom, an alkyl group, -0R4 (R. is a hydrogen atom, represents an alkyl group, aryl group, aralkyl group), or a substituted amino group. X is in the range of 1 to 5, and Y represents a simple bond or a divalent linking group. L. ,L. ,L. each represents a methine group, and n represents 0 or l.

(2) The object of the present invention is to contain at least one compound represented by the general formula (I) as a solid fine particle dispersion, and to contain at least one compound represented by the following general formula (n) as a solid fine particle dispersion. This is achieved by using a silver halide photographic light-sensitive material containing silver halide.

General formula (n) Re Rs
In the formula, R5 is a hydrogen atom, an alkyl group, an aryl group, a cyano group, -COOR, , -COR,, CONR, R. ,
-OR7, -NHCOR, and R6 represents a hydrogen atom, an alkyl group, or an aryl group. R,R. represent a hydrogen atom, an alkyl group, and an aryl group, respectively. However, general formula (n)
The compound represented by has at least one carboxyl group or sulfonamide group in the molecule.

L4, Ls, Ls, Lt, and Ls represent methine groups, and m and n each represent 0 or l.

Next, the compound represented by general formula (I) will be explained in detail.

R. The alkyl group, aryl group, or heterocyclic group represented by is a substituent 1 such as an alkyl group (e.g., methyl, ethyl),
Alkoxy groups (e.g. methoxy, ethoxy), halogen atoms (e.g. chlorine, bromine, fluorine), amino groups (e.g. dimethylamino, diethylamine), hydroxyl groups, cyano groups, phenoxy groups, carboxylic acid groups, alkylsulfamoyl groups (e.g. methyl sulfamoyl group), arylsulfonamide group (e.g. phenylsulfonamide group)
1. Also R. The groups are not only directly bonded but also divalent linking groups {e.g. 0--S--NR
CO-, CONR(CH!), OCO- -NHCO
NHNHOCO (R represents an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-hexyl, and p is 0 to 5
may be connected via 1 (representing an integer of ). The alkyl group represented by R is preferably a methyl group, and the aryl group is preferably phenyl, carboxyphenyl, or the like. X is preferably 1 or 2, and Y is preferably direct or -CH2-.

Among the compounds represented by the general formula (I), particularly preferred are those that do not have a sulfo group, a sulfo group, or a salt of a carboxy group as a substituent.

Further, among the compounds represented by the general formula (I), preferred are those having at least one group selected from a carboxy group and a sulfonamide group.

Next, the compound represented by general formula (II) will be explained in detail.

R,,R. , Rt, R. The alkyl group represented by is an unsubstituted alkyl group (e.g. methyl, ethyl, normal propyl, isopropyl, cyclohexyl) or a substituted alkyl group {with a halogen atom (e.g. 2-
chloroethyl, l,1,2.2-tetrafluoroethyl), phenyl groups (e.g. benzyl, carboxybenzyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxybutyr), alkoxy groups (e.g. 2-methoxyethyl, 2-(2-hydroxyethoxy)ethyl), carboxy groups (e.g. carboxymethyl, l-carboxyethyl, 2-carboxyethyl), sulfonamide groups (
Preferred are amino groups (eg 2-(N,N dimethylaminoethyl), carpoxylates (eg hydroxycarbonylmethyl, acetoxyethyl), or sulfonates (eg methoxysulfonylethyl)).

R. , R. , Rt, R. The aryl group represented by is an unsubstituted aryl group (e.g., phenyl), or a substituted aryl group.The substituent is a halogen atom (e.g., 4-chlorophenyl, 2,5-dichlorophenyl), or an alkyl group (e.g., 4-methylphenyl). , hydroxyl group (e.g. hydroxyphenyl), carboxy group (e.g. carboxyphenyl, 3,5-dicarpoxyphenyl), sulfonamide group (e.g. 4-methylsulfonylaminophenyl,
4-sulfamoylmethyl), alkoxy groups (e.g. 4-sulfamoylmethyl),
-methoxyphenyl, 4-(2-hydroxyethoxyphenyl), amino groups (e.g. N,N-dimethylaminophenyl, 4-(N-carboxymethyl-N-ethylamino), phenyl), carboxylates (e.g. 4-ethoxy Carbonylphenyl, 4-(2-hydroxyethoxyphenyl), or sulfonates (e.g. 4-methoxysulfonylphenyl)} are preferred. L4, L
5.L. The methine group represented by , L, is preferably an unsubstituted methine group;
phenyl).

Among the compounds represented by the general formula (n), particularly preferred are those that do not have a sulfo group, a sulfo group, or a salt of a carboxy group as a substituent.

Further, among the compounds represented by the general formula (If), those having at least two groups selected from carboxy groups and sulfonamide groups are preferred.

Next, specific examples of the compounds represented by formulas (I) and (U) of the present invention will be shown, but the present invention is not limited thereto.

Next, a method for synthesizing the compound of the present invention will be described.

Generally, the compound of the present invention can be obtained by reacting 1 mol of an aldehyde compound with 1 mol of an acidic core compound such as pyrazolone.

These condensation reactions are described in, for example, JP-A-513623.
Reference may be made to the synthesis methods described in Japanese Patent No. 51-10927, No. 48-68623, and Japanese Patent Publication No. 56-49953.

Specific example of general formula (II) If-1 COOH COOH ■ 2 ■ 3 n-4 COOH COOH 1I-5 ■ 6 COOH ■ 7 COOI{ COOH COOH ■ 8 COOII I1-9 COOH ■ l 0 COOH COOH COOH COOH If- 11 COOH ■ l 2 NHSO. C.I. ■ l 3 NHSO! CH3 COOH NHSO. CH. NHSO! C.I. ■ l 4 COOH ■ l 5 ■ l 6 COOH COOH COO}l ■ l 7 COOH COOH ■ l 8 The compound of general formula (II) is disclosed in JP-A-52-92716,
It can be synthesized according to the methods described in Japanese Patent Publication No. 63-316853, Japanese Patent Publication No. 64-40827, and Japanese Patent Publication No. 58-35544.

The compound of general formula (I) or (II) is used in an amount of i-iooo per 1 d of area on the light-sensitive material, preferably 1 to 800 ml per 1 d.

When using a compound of general formula (I) or (II) as a filter dye or antihalation dye, any effective amount can be used, but so long as the optical density is in the range 0.05 to 3.5. It is preferable to use it.

The addition time may be any step before coating.

Solid fine particle dispersion of general formula (I) or (n
The solid fine particle dispersion () can be used in either the emulsion layer or other hydrophilic colloid layer, and each dispersion may be used in the same layer or in separate layers.

Fine particle dispersions of compounds of general formula (I) or (II) according to the invention can be prepared by methods of precipitating the compounds of the invention in the form of dispersions and/or by known comminution means, e.g. A method of forming by ball milling (ball mill, vibratory ball mill, planetary pole 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 too. Alternatively, the compound of the present invention may be first dissolved by controlling the pH, and then microcrystallized by changing the pH. The microcrystalline particles of the compound of the present invention in the dispersion have an average particle size of 0 μm 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 hydrophilic colloids used for photography can be used.

The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

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.
gu lar ) crystal form, or a composite form of these crystal forms. It is also possible to use 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. Also, particles whose latent image is mainly formed on the surface (
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a prefogged direct reversal type emulsion). Preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
A tabular grain emulsion in which grains having a diameter of 0.3 microns or less, preferably 0.6 microns or more, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area; A monodispersed emulsion having a statistical coefficient of variation (value S/d obtained by dividing the standard deviation S by the diameter d in a distribution expressed by a diameter when the projected area is approximated by a circle) of 20% or less is preferable. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is P.
．． Glafkides), Shimmy, Engineering, Physique,
Photography (Chimie er Physi)
(Photographeque) (Beaulmontel, 1967) G.F. Duffin
F. Duffin), Photographic Emulsion Chemistry
Ulsion Chemistry) (7t-Karpeles, 1966), Bui El Zelikman (
V. L. Making and Coating Photographic Emulsions (Zelikman) et al.
It can be prepared using the method described in "Photographic Emulsion" (published by Focal Press, 1964).

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130, No. 4,297,439, No. 4,276,374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 5 3-8 2 4 0 No. 8, No. 5 5-7
7 7 3 7, 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 together.

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 sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylvirazole, etc.. I can do it.

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), Na l 6, 3
Enzyme-treated gelatin such as that described on page 0 (1966) may be used, or a gelatin hydrolyzate may 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 (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) and active vinyl compounds (l,3-bisvinylsulfonyl-2-
Propanol, l,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, vinyl polymers with vinylsulfonyl groups in their side chains, etc.) quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. This is preferable because it gives N-carbamoylpyridinium salts ((1-morpholinocarponyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1-chlorol-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) also have a fast curing speed. Are better.

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 anine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: Nuclei 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 Nucleus, penzidolenine nucleus, indole nucleus, penzoxazole 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 have a ketomethylene structure as a virazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-sion nucleus, a rhodanine nucleus, and a thiobarbituric 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 nitrogen-containing heterocyclic ring groups and are substituted (e.g., U.S. Pat. No. 2,933,390, U.S. Pat.
(as described in US Pat. No. 3,743,510), 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. 3,61
No. 5,641, No. 3,617,295, No. 3,635
, 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.
Various compounds can be included. That is, azoles such as penzothiazolium salts, nitroindazoles, nitropenzimidazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino triazoles, penzotriazoles,
Nitropenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole)
mercaptovirimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3
a, 7) tetraazaindenes), pentaazaindenes, etc.; adding many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. be able to.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The light-sensitive materials made using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as irradiation or antihalation.

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 lidocyanine dyes are also useful. It is. It is also possible to emulsify the oil-soluble dye by a droplet dispersion method in water and add it to the hydrophilic colloid layer.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities 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 that 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.
The layer structure may further improve the graininess.

Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. A reflective layer made of fine grain silver halide or the like may be provided under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve sensitivity.

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 image quality or semiconductor laser exposure.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are 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 polymers. - (for example, polyethylene, polypropylene, ethylene/butene copolymer), etc. coated or laminated paper.

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 support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used. U.S. Patent No. 2,681,294 as appropriate
Multiple layers may be applied simultaneously by coating methods such as those described in US Pat.

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 positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. Research Disclosure, Nal7123 (
(July 1978) or by utilizing a trichromatic coupler mixture as described in U.S. Patent No. 4,126,461.
No. 2 and British Patent No. 2, 102. By using the black coloring coupler described in No. 136 etc.,
The present invention can also be applied to black and white photosensitive materials for X-rays and the like. Plate-making films such as lithography 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 microfilm, 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, 48-33697, JP-A-50-13040 and British Patent No. 1,330,524
Integrated as described in the issue.
It is possible to adopt a structure of a film unit that does not require peeling as described in Japanese Patent Application Laid-Open No. 57-119345.

The use of a polymeric acid layer protected by a neutralizing timing layer in either type of format described above is advantageous in increasing processing temperature latitude. When used in color diffusion transfer photography, it may be added to any layer in the sensitive material, or it may be sealed 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-fired flashbulbs are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or Exposure means combined with 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 light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 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
monoβ-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, 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, penzothiazoles or mercapto compounds. Generally, it contains agents such as agents. Also, if necessary, preservatives such as hydroxylamines, dialkylhydroxylamines, hydrazines, 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 poron hydride, auxiliary developers such as -phenyl-3-virazolidone, viscosity-imparting agents, amino acids. Various chelating agents such as polycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, and antioxidants described in West German patent application (OLS) No. 2,622,950 are used for color development. It may be added to the liquid.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, l-phenyl-
Known black and white developers such as 3-pyrazolidones such as 3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

Not only a color developing solution but also any photographic developing method may be applied to the light-sensitive material of the present invention. The developing agents used in the developer include dihydroxybenzene-based developing agents, l
-Phenyl-3-pyrazolidone type developing agents, p-aminophenol type developing agents, etc., and these can be used singly or in combination (for example, l-phenyl-3-pyrazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzenes). ) can be used. Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone.

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, promohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2.
Examples of 1-phenyl-3-pyrazolidone-based developing agents include 3-dichloronohydroquinone and 2,5-dimethylhydroquinone, and examples of 1-phenyl-3-pyrazolidone-based developing agents include l-phenyl-3-virazolidone, 4,4-dimethyl-l-phenyl-3-virazolidone, and 4-hydroxy. Methyl-4-methyl-1-phenyl-3-virazolidone, 4,4-dihydroxymethyl-1-
p-aminophenol developing agents include p-aminophenol, N
-Methyl-p-aminophenol and the like are used.

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, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer.

As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, diethanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as penzothiazolium salts, nitroindazoles, nitropenzimidazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles. , aminotriazoles, penzotriazoles, nitropenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,
Examples include benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and sodium 2-menolecaptobenzenimidazolate 5-snorephenate.

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 weight of 1,000 to 10,000 is used. It can be contained in a range of 1 to 10 g/l.

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 1-28708, JP-A-6-0-9-3
4 3 Saccharides (e.g. saturose), oximes (e.g. acetoxime), phenols (e.g.
For example, 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,
Examples include thioether compounds, thione compounds, certain mercapto compounds, isoion compounds, and thiocyanates.

This is especially necessary for rapid 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 added to the photosensitive material. can. It can also be added to both the color developing solution 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 therein.

Amine 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 bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (II), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, l,3-diamino-2-propanoltetraacetic acid Aminopolycarboxylic acids such as or 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, ethylenediaminetetraacetic acid iron(III) salt, diethylenetriaminepentaacetic acid iron(III) salt and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. In addition, the ethylenediaminetetraacetate iron (I [ agents can be used.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 513 27 3 6, No. 5357831, No. 3
No. 7418, No. 5 3-6 5 732, No. 5 3-
7 2 6 2 3, 5 3-9 5 630,
No. 53-95631, No. 51104232, No. 53
-124424, 53-141623, 53-
No. 28426, Research Disclosure No. 1
Compounds having a mercapto group or a disulfide group described in No. 7129 (July 1978), etc.;
Thiazolidine derivatives as described in No. 140129: Japanese Patent Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-
Thiourea derivatives described in West German Patent No. 20832, West German Patent No. 53-32735, and US Patent No. 3,706,561; West German Patent No. 966,410, No. 2,
Polyethylene oxides described in No. 748,430;
Polyamine compounds described in Japanese Patent Publication No. 45-88836; other Japanese Patent Publications Nos. 49-42434 and 49-59
No. 644, No. 53-94927, No. 54-35727
No. 55-26506 and No. 58-163940
Compounds described in the No. 1, and iodine and bromide ions can also be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in U.S. Patent No. 3,893.858 and West German Patent No. 1,290,81.
No. 2 and JP-A-5-3-9-56-30 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 bleach-fixing color light-sensitive materials for photography.

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

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment 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 organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing 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. lEng. ), Volume 6, 34
Compounds described on pages 4 to 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 as described in No. 7-8 5 4 3 may also be carried out. In the case of this step, 2 to 9 countercurrent baths are required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. Various buffers (e.g. borate, metaborate, borax,
Representative examples include phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. others,
Chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (penzisothiazolinone, irithiazolone, 4-thiazoline, etc.) as necessary. Various additives such as benzimidazoles, halogenated phenols, sulfanilamides, penzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and two compounds for the same or different purposes may be used. More than one species may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

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 amount of 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 crude drugs.

For example, U.S. Pat. No. 3,342. , No. 3,342,599, Research Disclosure No. 14850 and No. 1515.
Including Schiff base type compounds described in No. 9, aldol compounds described in U.S. Pat. No. 13924, metal salt complexes described in U.S. Pat. Showa 5 6-6 2
3 No. 5, No. 56-16133, No. 5 6-5 9
2 3 2, 5 6-6 7 8 4 2, 5 6-8 3 7 3 4, 5 6-8 3 7
3 No. 5, No. 5 6-8 3 7 3 No. 6, No. 5
6-8 9 7 3 5, 56-81837, 5 6-5 4 4 3 0, 56-106241
Examples include various salt-type precursors described in No. 56-107236, No. 57-97531, and No. 57-83565.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A No. 57-14.
No. 4547, No. 57-211147, No. 58-505
No. 32, No. 5 8-5 0 536, No. 5 8-5
0 5 3 No. 3, 5 8-5 0 534, 5
8-5 05 3 5 and 58-11543
It is written in No. 8 etc.

Various processing solutions 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
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674,499 may be performed.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher 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 necessary, very generally, and even when it is a color photographic material for photographing.

Next, the present invention will be specifically explained based on examples.

(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 there is little decrease in sensitivity due to storage.

Further, the silver halide photographic material of the present invention provides images with improved sharpness. Furthermore, photographs obtained from the silver halide photographic material of the present invention do not produce stains, are stable even during long-term storage, and exhibit no deterioration in photographic performance.

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

Example 1 (Preparation of Emulsion A) A silver nitrate aqueous solution and a sodium chloride aqueous solution containing 0.5XlO mol of ammonium hexachloride per mol of silver were adjusted to pH in a gelatin solution at 35°C by a double jet method. A monodisperse silver chloride emulsion with an average grain size of 0.07 μm was prepared by mixing while controlling the grain size to be 6.5 μm.

After particle formation, soluble salts were removed by flocculation methods well known in the art, and stabilizers 4-hydroxy-6-methyl-■,3,3a,7-tetraazaindene and l-phenyl-5 - Added mercabutotetrazole. The amount of gelatin contained in 1 kg of the emulsion was 55 g, and the amount of gelatin contained in 1 kg of the emulsion was 105 g. (Emulsion A) (Preparation of photosensitive material) Add the following nucleating agent and nucleation accelerator to the emulsion A,
Next, polyethyl acrylate latex (300
mg/rr? ), 2,4-dichloro-6-hydroxyl,3.5-1 riazine sodium salt was added as a hardening agent, and the polyethylene terephthalate wound was made to have a silver content of 3.5 g per lrrr.
Addition amount (■/A) Nucleation accelerator 28. A silver halide emulsion layer was coated on a transparent support, and the upper layer was coated with gelatin (1.3 g/rrf), compound I-19 of the present invention (0.1 g/d), and a coating aid. A protective layer containing the following three surfactants, a stabilizer, and a matting agent was applied and dried.

(Sample 1) Amount of addition (■/rd
') CH2COOC. Hl3 1 S OsNa Tomo Koshiro Thioctic Acid Matting Agent Polymethyl Methacrylate (Average Particle Size 3.5 μm) A monodispersion of the compound of the present invention (1) was prepared and used.

(Preparation of dye dispersion) ■Liquid 50.0■/rI? For 19, the following procedure was used: 17 g of liquid (1) While stirring the liquid (2) at 40°C, the liquid (2) was added little by little.

(Preparation of Comparative Sample) l) A sample was prepared using the following dye instead of Compound I-19 in Example 1 (Comparative Sample IA) SO3K SOaK (0.0
75 g/rrr) 2) In Example 1, the following dye was used in place of Compound I-19. (Comparative Sample 1-B) This dye is exemplified in WO88/04794.

3) Comparative sample 1-C was prepared using the following protective layer instead of the protective layer containing the compound I-19 of the present invention in Example-1.

Acid-treated gelatin 2. 0g/nf
Sitting U 0. 75g/n-r SO3K SO. K Kaiou Shield ItemヱC11H2+CONH(CHI)8N(CH3)t(C
HtLSO3e0.53g/rr? CH2COOC6H S 0 3N a Thioctic acid 0.006/anti-matting agent polymethyl methacrylate (average particle size 3.5μ) 0.009/m (performance evaluation) (1) The above four samples were The film was exposed to light through an optical wedge using a P-607 screen printer, developed with the following developer at 38 DEG C. for 20 seconds, fixed in a conventional manner, washed with water, and dried.

Hytroquinone 35.0g N-methyl-P-aminophenol l/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-methylbenzotriazole 0.6g 3-diethylamino-1,2 propanediol 15.0g Add water
In (pH=II.5) As a result, Example I and Comparative Sample I-A were completely decolored, while Comparative Samples I-B and IC remained with a yellow stain. Comparative sample 1-B has a development time of 3
When the time was increased to 0 seconds, the color was completely decolored. As described above, the compounds of the present invention are rapidly processed and 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 that can return the halftone area to 1:1 for each sample,
Exposure was carried out for twice and four times the exposure time, and it was examined how much the halftone dot area was expanded. 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 significantly reduced tone variability, whereas sample 1 of the present invention has 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 due to 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.

Comparison sample l showed his sexuality.

B and 1 C also have good adjustment (3) Evaluation of contamination by reducing fluid (stin) Above (2)
The strips of the samples of the present invention and samples of the comparative example obtained by treatment with
It was immersed for 0 seconds, washed with water, and dried. As a result, in all samples, the dot area of 50% was reduced to about 33%, but in Comparative Sample 1-C, severe brown staining occurred over the entire surface. No stain was observed in Sample 1 of the present invention and Comparative Samples I-A and 1-B.

farmer reducer liquid When using: 1st liquid: 2nd liquid: water 100 copies: 5 copies 2 100 copies Mix with

As described above, the samples of the present invention had good decolorization properties, tone changeability, and color reduction properties.

Example 2 Paper support samples A, B and C were obtained using a gelatin subbing layer or the following dye dispersion after corona discharge treatment on a paper support laminated on both sides with polyethylene.

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 I-1 of the present invention was dispersed in 25 yd of lime-treated gelatin aqueous solution and the sand used was filtered through a glass filter.
1. Og Compound 1-38 of the present invention
1. 6g solution (surfactant)
5 and then removed the dye adhering to the sand on the glass filter to obtain a 7% gelatin solution. (The average particle size of the dye fine particles was 0.15 μm.) Compound I-1 of the present invention 1. Og Compound of the present invention I1-3 1. 6g was prepared in the same manner.

Paper support A Undercoat layer gelatin 0. 8g/rrr
Paper support B Antihalation layer gelatin 0. 6 gld Compound I-1 of the present invention 25 g/d Compound I-38 of the present invention 40 gng/rrr Paper support C Antihalation layer Ceratin 0. 6 g/rd Compound I-1 of the present invention 40 ■/M Compound ■-3 of the present invention 65 ■/d Paper support sample A,
On top of B and C were obtained multilayer color photographic paper samples 2-1 to 24 of the layer stiffness shown below.

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
Add and dissolve 8.2 g of lv-1), and add this solution to lO containing 8 cc of 10% sodium dodecylbenzenesulfonate.
% gelatin aqueous solution (185 cc). On the other hand, silver chlorobromide emulsion (cubic, 3=7 mixture of average grain sizes of 0.88 μm and 0.70 μm (silver molar ratio)
The coefficient of variation of particle size distribution is 0.08 and 0.08. 1O, each emulsion contains 0.2 mol% of silver bromide locally on the grain surface) and the following blue-sensitive sensitizing dye was added per mol of silver to 2.0 x 1O- For small size emulsions, sulfur sensitization was carried out after adding 1 mol and 2.5XlO-' mol respectively. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-}ryazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer sose SOsH-N(CtHs)3 (2.OXIO-' mol each for large size emulsions and 2.5XlO-' mol each for small size emulsions per mole of silver halide) ) green-sensitive emulsion layer (per mole of silver halide, 4.OXlO-' moles for large size emulsions and 5.6 moles for small size emulsions)
XlO-'mol) and SOs'':'SOstN(CtHsh (per mole of silver halide, ?.OX10-'mol for large size emulsions, and l for small size emulsions)
．． red-sensitive emulsion layer (0.9XIO-' mole per mole of silver halide for large size emulsions and i
．． For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6XlO-3 mol per mol of silver halide.

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, l-(5-methylureidophenyl)5-mercaptotetrazole was added at 8.0% per mole of silver halide.
5X10-'mol, 7.7xto-'mol, 2.5Xl
O-' moles were added.

Furthermore, 4hydroxy-6-methyl-1.3.3a. 7-tetrazaindene was added in IXIO-'' moles and 2XIO-' moles, respectively, per mole of silver halide.

One paper support sample A had the following comparative dyes added to its emulsion layer.

S.O. Na SO+Na 8■/M and H (Layer structure) The composition of each layer is shown below.

The number is the coating amount (g/ d) represents.

For silver halide emulsions, calculate the coating amount in terms of silver. represent.

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 (T+Ot) and a bluish dye (ulmarine blue)] Single layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd-1)
0.19 solvent (Solv-1)
o. 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. 1 6 solvent (Solv-4
) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ)
l=3 mixture of 0.39μm and 0.39μm (A
g molar ratio). The coefficient of variation of particle size distribution is 0. lO and 0
．． 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.2 0 Color image stabilizer (C
pd-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 absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (Cpd
-5) 0.05 solvent (Solv-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. Grain size distribution The coefficient of variation is 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 (E
xC) 0.32 color image stabilizer (Cpd-6)
0.1 7-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 inhibitor/(Cp
d-5) 0.02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 (ExY) 1:1 mixture with yellow coupler (molar ratio ) (ExM) l:l mixture (molar ratio) of macenta coupler (ExC) Cyan coupler R = C2Hs and C.I. H. and 0H CI! 2:4 by weight of each mixture (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer cooctus (Cpd 3) Color image stabilizer (Cpd 4) Color image stabilizer (Cpd 5) Color mixture Inhibitor song (Cpd-6) Color image stabilizer song C4Hs(t) 0H C<Hs(t) 0H c. lt) 2:4:4 mixture (weight ratio) of (Cpd-7) color image stabilizer+CH2CH-)-, CONHC. Hs(t) Average molecular weight 60,000 (Cpd 8) Color image stabilizer 0■ 0■ (Cpd 9) Color image stabilizer CH. CH. (UV l) Ultraviolet absorber 0 ■ CiH++ (t) C<He (t) Song CaHs (t) 4:2:4 mixture (weight ratio) (Solv-1) Solvent (Solv~2) Solvent 2: ■Mixture (volume ratio) (Solv-4) Solvent (So?v-5) Solvent COOC. H,, (CHt)* COOC. H, ■ (Solv-6) Regarding samples 2-1 to 2-4 obtained with solvent, a sensitometer (manufactured by Fuji Photo Film ■, FWH type, color temperature of light source 3,゛2
Stepwise exposure for sensitometry was provided through blue, green, and red filters using 00°K). On the other hand, exposure was performed to measure resolution (CTF), and then the following processing steps were performed. Measure the concentration of the obtained sample and record it in the table.
The results shown in 2 were obtained.

Tokosarakooka ■Ryu ■Mitsuka゜F Hajime 1 color development
35℃ 45 seconds 161yd 111 bleach fixing 30-35℃ 45 seconds 215d l71 rinse ■
30-35℃ 20 seconds - 101 Rinse ■ 30-35℃ 20 seconds - lOR rinse ■ 30-35℃ 20 seconds 350ml 101
Drying: 70 to 80°C for 60 seconds *The amount of replenishment is per photosensitive material In {3-tank countercurrent system from rinsing ■→■.} The composition of each processing solution is as follows.

22 ri on the left, Eishika
800+It800+l1/
Ethylenediamine - N, N, N, N-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g Triethanolamine 8.0g 12.0g Sodium chloride
1.4g Potassium carbonate 25g 25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate N,N-bis(carpoxymethyl)hydrazine optical brightener (Wl{lTEX4B, 5.0g 5.5g 7.0g 7.0g Add water 1000d 100(7
! pH (25°C) 10.05
10.45 star page Huangfenglu (tank fluid and refill fluid are the same) water
400m! Ammonium thiosulfate (70%) load Sodium sulfite 17g Ammonium ethylenediaminetetraacetate iron (III) 55g Dipotassium ethylenediaminetetraacetate 5g Add water l000ipH (25
℃) 6.0 Yue Tamashika (tank fluid and refill fluid are the same) Ion exchange water (calcium and magnesium are each 3pp
m or less) When the dye according to the present invention is used in an antihalation layer, the decrease in sensitivity is relatively small (and there is no noticeable residual color). By using such an amount, the resolution can be significantly improved.

Example 3 Preparation of dye fixed layer Dyes 1-5 and II-5 were each subjected to ball mill treatment by the method described in JP-A-63-197943.

Water 4341d and Triton X-200
6.7% of R surfactant (TX-200R)
Aqueous solution 791 and 791 were placed in a 2 liter ball mill. dye 2
0 g was added to this solution. Zirconium oxide (ZrO
) beads (400+J (2 m diameter)) were 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 corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was applied, and a second undercoat layer of 0.08 g/rd of gelatin was applied on top of the first undercoat layer. Layers were set up.

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.

・Gelatin・Dye I-5 ・Polystyrene sulfonic acid strength (average molecular weight 600,000) 1.8 g/n {Amount listed in Table 3 35 ■/d ・Phenoxyethanol・l, 2-bis(vinylsulfonylacetamide) ethane emulsion Preparation of Coating Solution 1O■/Resistance 18■/d 100■/d Raw milk #1 shown below is a surface latent image type emulsion, and negative-tone characteristics can be obtained using a commercially available microfilm general-purpose processing solution. It is. Furthermore, by performing reversal processing using a reversal processing liquid, positive type characteristics can be obtained.

<Preparation of raw emulsion #l> Solution I 75°C Solution ■ 35°C Solution ■ 35°C Add distilled water and make solution ■ Room temperature 1000d Add solution ■ and solution ■ to well-stirred solution ■ at the same time for 45 minutes. When the entire amount of solution (1) was added, 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 (2) was added over a period of 5 minutes starting 7 minutes after the start of addition of solution (2). After addition of solution ■,
After washing with water and desalting by the sedimentation method, inert gelatin 10
It was dispersed in an aqueous solution containing 0 g. To this emulsion were added sodium thiosulfate and chlorauric acid tetrahydrate at 3 3 3 each per mole of silver.
4 ■ each to adjust the pH and pAg values to 8.9 and 7, respectively.
．． After adjusting the temperature to 0 (40°C), chemical sensitization was performed at 75°C for 60 minutes to obtain a surface latent image type silver halide emulsion.

It is like that.

The layer structure and the composition of each layer are as follows.Excluding the antihalation layer, the emulsion layer, the surface protection layer, the conductive layer, and the Get layer were prepared and coated so that each component was coated in the following coating amount to obtain a photographic material.

<Protective layer><Emulsionlayer> Sara Tokyu left (compound ■) czua (CH!)ssOse CtHs <Back conductive layer><Ge 1 layer> Coating amount ■/d Processing method Reverse development process Reverse development process is performed by Alien Products in the United States A commercially available processing solution for reversal (FR-5 manufactured by FR Chemicals, USA) is
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) in 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 using a 400×2μ aperture, and the optical density was 1.0 using the MTF value at a spatial frequency of 20 cycles/M. Evaluation was made in the 0 part.

The results are shown in Table-3.

Evaluation of residual color After the unexposed film was subjected to the automatic development process described above, it was passed through a Macbeth Status A filter and the green transmission density and blue transmission density were measured.

The results are shown in Table-3.

Procedural amendment

Claims (2)

[Claims] (1) A silver halide photographic 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, R_1 is a hydrogen atom, an alkyl group, an aryl group,
Represents an acyl group or a heterocyclic group, R_2 and R_3 are hydrogen atoms, alkyl groups, -OR_4 (R_4 is hydrogen atoms,
Represents an alkyl group, an aryl group, or an aralkyl group. ), or a substituted amino group. x is in the range of 1 to 5, and Y represents a simple bond or a divalent linking group. L_1, L_
2 and L_3 each represent a methine group, and n represents 0 or 1. (2) Contains at least one compound represented by the general formula (I) as a solid fine particle dispersion, and contains the following general formula (I)
A silver halide photographic material comprising at least one of the compounds represented by I) as a solid fine particle dispersion. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_5 is a hydrogen atom, an alkyl group, an aryl group, a cyano group, -COOR_7, -COR_7, -CONR_7
R_8, -OR_7, -NHCOR_7, R_6
represents a hydrogen atom, an alkyl group, or an aryl group. R_7R
_8 each represents a hydrogen atom, an alkyl group, or an aryl group. However, the compound represented by general formula (II) has at least one carboxyl group or sulfonamide group in the molecule. L_4, L_5, L_6, L_7, and L_8 represent methine groups, and m and n each represent 0 or 1.