JPH03217838A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To selectively dye a desired layer of a sensitive material, to suppress the lowering of the sensitivity and to accelerate decoloring during development by incorporating dispersed fine particles of a specified compd. into a hydrophilic colloidal layer. CONSTITUTION:This sensitive material contains dispersed solid fine particles of a dye represented by the formula in a hydrophilic colloidal layer, e.g., an antihalation layer. In the formula, R1 is H, alkyl, aralkyl, etc., R2 is alkyl, aryl, cyano, etc., each of R3 and R4 is H, alkyl, aryl, etc., R5 is H, halogen, alkyl, etc., each of L1-L3 is methine and n is 0 or 1. A compd. having -C6H4-CO2 H as R1 in the formula, -NHCOCH3 as R2, -CH3 as each of R3 and R4 and1 as (n) may be used as the dye represented by the formula. When this sensitive material is used, the sharpness of an image is improved and stability is ensured even in the case of storage over a long period of time.

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 the 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, the 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 opalescent layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer, and then enters the photographic emulsion layer again. 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. The photographic emulsion layer is also colored in order to prevent a reduction 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 must satisfy the following conditions. (1) It 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) No harmful coloring should be left on the photographic material after processing due to decolorization during the photographic processing process or elution into the processing solution or washing water. (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 in which a hydrophilic polymer having a charge opposite to that of 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, 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. 55-155351, No. 63-27838
No. 63-197943, No. 52-92716,
European Patent No. 15601, European Patent No. 276566, European Patent No. 2747
No. 23, No. 299435, World Patent 8 B/0 4
7 9 No. 4, 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. Patent No. 2,719,088;
No. 496.841, No. 2,496,843, Japanese Unexamined Patent Publication No. 6
No. 0-45237 and the like.

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 by.

General formula (1) R1 In the formula, R. each represents a hydrogen atom, an alwyl group, an aryl group, or a heterocyclic group, and R is an alwyl group, an aryl group, an aralkyl group, a cyano group, -COOR& , CO
NRJs, COR9, SOJq,
SOR? SONRyRg, OR? ，
NRJs. NR@CONR9NR7CONRJ
g or NRsSOJw (where R6, R, ,
R. represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and R. represents an alkyl group, an aryl group, an aralkyl group, and R, and RIl or R8 and R, are connected to form 5
Alternatively, it may form a 6-membered ring. ), Rs,
Ra represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group, or a sulfonyl group, and R3 and R, or R4 and R, are linked to form a 5-membered or 6-membered ring; Good too. R is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group,
ORv, GOOR, (where R is the same as R defined above). L,,L. , L, each represent a methine group, and n represents 0 or 1.

(2) The object of the present invention is to contain at least one kind of metal compound represented by the general formula (I) as a solid fine particle dispersion, and to contain at least one kind of compound represented by the following general formula (I[) as a solid fine particle dispersion. This was achieved using a photographic material containing silver halide as a body. General formula (I[)? l1 In the formula, R1. is a hydrogen atom, an alkyl group, an aryl group, a cyano group, COOR+x. CORtz, C
ONRI! RI3, 10R1■, -NIICOR
．． 2, and Rl1 represents a hydrogen atom, an alkyl group, or an aryl group.a R+gR+i represents a hydrogen atom, an alkyl group, or an aryl group, respectively. However, the compound represented by general formula (II) has at least one carboxyl group or sulfonamide group in the molecule. L. ,L,,L. ,L. , Ll represents a methine group, m,
Each n represents 0 or 1. Next, the compound represented by general formula (1) will be explained in detail. The aryl group, aralkyl group, or alkyl group represented by R' preferably has at least one carboxylic acid group, alkylsulfonylaminophenyl group, or phenylsulfamoylphenyl group; groups, alkyl groups include substituents other than carboxylic acid groups, alkylsulfonylaminophenyl groups, and phenylsulfamoylphenyl groups {e.g., alkyl groups (e.g., methyl, ethyl), e.g., alkoxy groups (e.g., methoxy, ethoxy), halogen atoms (eg chlorine, bromine, fluorine), amino group (eg dimethylamino, diethylamino), hydroxyl group, cyano group, phenoxy group}. In addition, carboxylic acid groups, alkylsulfamoyl groups, and arylsulfonamide groups not only directly bond to aryl groups, aralkyl groups, and alkyl groups, but also bond to divalent linking groups {for example, -0(CH
z) p1 (CH!). -(R represents an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-hexyl, and p is 1
(representing an integer of ~5)} may be connected via. N
The aryl group represented by R R1 is preferably a carboxyphenyl group, a methanesulfonamidophenyl group, a phenylsulfamoylphenyl group, or the like.

R. , R. , R. , R,, R. ，
R,, R. , R, is an unsubstituted alkyl group (for example, methyl, ethyl, normal brobyl, isoprobyl, cyclohexyl) or a substituted alkyl group {a halogen atom as a substituent (for example, 2chloroethyl, 1.l. 2.2-tetrafluoroethyl), phenyl groups (e.g. benzyl, carboxybenzyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxybutylene), alkoxy groups (e.g. 2-methoxyethyl, 2-
(2-hydroxyethoxy)ethyl), carboxy group (
For example, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl), sulfonamide groups (e.g. methanesulfonamidoethyl), amino groups (e.g. 2-(N
, N dimethylaminoethyl), carboxylates (eg ethoxycarbonylmethyl, acetoxyethyl) or sulfonates (eg methoxysulfonylethyl)}. Ri. R3. The aryl group represented by Ra, Rs, R-, R,, R-, R, is an unsubstituted aryl group (for example, phenyl) or a mono-substituted aryl group {a halogen atom as a substituent (for example, 4-chlorophenyl, 2. 5-dichlorophenyl), alkyl groups (e.g. 4-methylphenyl), hydroxyl groups (e.g. hydroxyphenyl), carpoxy groups (e.g. carboxyphenyl, 3,5-dicarboxyphenyl), sulfonamide groups (e.g. 4-methylsulfonylaminophenyl, 4 -sulfamoylmethyl), alkoxy groups (e.g. 4-methoxyphenyl, 4-(2-hydroxyethoxyphenyl) amino groups (e.g. N,N-
dimethylaminophenyl, 4-(N-carpoxymethyl-N-ethylamino)phenyl), carboxylate (
For example, 4-ethoxyluponylphenyl, 4-(2-hydroxyethoxy)phenyl) or sulfonates (eg 4-methoxysulfonylphenyl) are preferred. L. ,L. , L, is preferably an unsubstituted methine group, but may have a substituent (eg, methyl, ethyl, phenyl). Among the compounds represented by the general formula (1), particularly preferred are those that do not have a sulfo group, a sulfo group, or a salt of a carpoxy group as a substituent.

Further, among the compounds represented by the general formula (1), those having at least two groups selected from carboxy groups and sulfonamide groups are preferred. Next, the compound represented by general formula (II) will be explained in detail.

R1. + RII+ RIt+ Alkyl represented by Rl3 is an unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, cyclohexyl) or a substituted alkyl group {a halogen atom as a substituent (e.g., 2-chloroethyl, 1.l) .2.2-tetrafluoroethyl), phenyl groups (e.g. benzyl, carboxyhendyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), alkoxy groups (e.g.
-methoxyethyl, 2-(2-hydroxyethoxy)ethyl), carboxy groups (e.g. carboxymethyl, l-carboxyethyl, 2-carpoxyethyl), sulfonamide groups (e.g. methanesulfonamidoethyl),
Amino group (e.g. 2-(N,N dimethylaminoethyl)
, carboxylates (eg ethoxycarbonylmethyl, acetoxyethyl) or sulfonates (eg methoxysulfonylethyl)} are preferred. R1. R++', R+■. The aryl group represented by R+3 is an unsubstituted aryl group (e.g., phenyl) or a substituted aryl group {as a substituent, a halogen atom (e.g., 4-chlorophenyl, 2,5-dichlorophenyl), an alkyl group (e.g., 4- methylphenyl) hydroxyl group (e.g. hydroxyphenyl), carboxy group (e.g. carboxyphenyl, 3,5-dicarboxyphenyl), sulfonamido group (e.g. 4-methylsulfonylaminophenyl, 4-sulfamoylmethyl), alkoxy group (e.g. 4-methylsulfonylaminophenyl, 4-sulfamoylmethyl), For example, 4-methoxyphenyl, 4-(2-hydroxyethoxyphenyl), amino groups (e.g. N,N-dimethylaminophenyl, 4-(N-carboxymethyl-N-ethylamino)phenyl), carboxylates (e.g. 4- Ethoxycarponylphenyl, 4-(2-hydroxyethoxyphenyl) or sulfonates (e.g. 4-methoxysulfonylphenyl)} are preferred, La,L
The methine group represented by s LhL is preferably an unsubstituted methine group, but may have a substituent (eg, methyl, ethyl, phenyl). Among the compounds represented by the general formula (If), particularly preferred are those which do not have a sulfo group, a sulfo group, or a salt of a carboxy group as a substituent. Furthermore, the general formula (TI
) Preferred compounds have at least two groups selected from carboxy groups and sulfonamide groups. Next, specific examples of the compounds represented by the general formulas (I) and (If) 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. 4868623, and Japanese Patent Publication No. 56-499953.

Specific example of general formula (II) ■River COOH COOH ■ 2 ■ 3 ■ 4 COOH COO [{ ■dun-6 II-7 COOH ShiIJUM If-8 II-9 ■-1 0 COOH COOH II-11 COOH ■ -1 2 NHSOtCH3 n-13 ? HSO■CHa COOH NHSOtCH3 NHSO2CH. II-14 COOH II-15 ■-1 6 COOH COOH COOH n-17 COO[{ COOH ■-1 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 1 to 1000 μ per rrr of area on the photosensitive material, preferably 1
1 to 800 is used per rd.

When using compounds of general formula (I) or (If) as filter dyes or antihalation dyes, 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 (r) according to the present invention or (I
The solid fine particle dispersion I) 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 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 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 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less. 5 μm
or less, and in some cases 0. More preferably, the particles are fine particles of 1 μm or less.

Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be 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.
ular) 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
micron 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 variation coefficient (projected area In the distribution expressed by the diameter when approximated to a circle, a monodisperse emulsion having a value S/d obtained by dividing the standard deviation S by the diameter a) 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
Photography (Chimie er Physi)
(Photographeque) (Beaulmontel, 1967) G.F. Duffin
F. Duff in) Photographic Emulsion Chemistry
Emulsion Chemistry) (Focal Press, 1966), V. L. Zelikran et al., Making and Coating Photographic Emulsions (Making and Coatin Photographic Emulsions)
g Photographic Emulsion
) (Focal Press, 1964).

In order to control grain growth 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. Patent No. 3, No. 574,628, No. 3,704.130,
4.297439, 4,276,374, etc.), thione compounds (for example, JP-A-51144319, JP-A-53-82408, JP-A-55-77)
7 3 7, etc.), amine compounds (e.g. JP-A No. 5
No. 4-100717, 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, seratin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, 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,
Various synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

In addition to the general-purpose lime-processed gelatin, the ceratin is also available in acid-processed ceratin and the Journal of the Japanese Society of Scientific Photography (Bull.Soc.
Sci. Photo. Japan), Na 1 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-hydroquine-1,3,
5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether or vinylsulfonyl group). Vinyl polymers having side chains, etc.) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) also have a slow curing rate. Faster and 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 melonanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyricine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., Indian Applicable examples include renin nucleus, penzidolenine nucleus, indole nucleus, penzoxazole nucleus, naphthoxazole nucleus, penzothiazole nucleus, naphthothiazole nucleus, penzoselenazole nucleus, penzimidazole nucleus, and quinoline nucleus. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or complex merocyanine dyes have a ketomethylene structure as a virazolin-5 mononucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, and 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. Namely, azoles such as penzothiazolium salts, nitroindazoles, nitropenzimidazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercabutopenzothiazoles, mercabutobenzimidazoles, mercaptothiadiazoles. , aminotriazoles, penzotriazoles,
Nitropenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted
3a. 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 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. An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added 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. Also, any emulsion layer with the same color sensitivity can be considered as two or more emulsion layers with different sensitivities. It is also possible to improve the reach sensitivity by configuring
The graininess may be further improved by using a three-layer structure.

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

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 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.
X
The present invention can also be applied to black-and-white photosensitive materials such as those for lines. 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 Laid-Open No. 57-1193-4.5.

In either type of format described above, the use of a polymeric acid layer protected by a neutralizing timing layer is advantageous in providing a wider range of processing temperatures. 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.

Gases, dye solutions, semiconductor lasers, light emitting diodes, and plasma light sources that emit light in a wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, micro-shutters using fluorescent surfaces (such as CRT), liquid crystals (LCD), and lanthanum-doped lead titanium zirconate (PLZT) emitted from phosphors excited by electron beams, etc. Exposure means in which an array is combined with a linear or 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. As this color developing agent, aminophenol compounds are also useful, but p-phenyl diamine compounds are preferably used, and representative examples thereof 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
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-4 luenesulfonate. 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, henzimidazoles, penzothiazoles or mercapto compounds. Generally, it contains agents such as agents. Also, if necessary, preservatives such as hydroxylamines, sialkylhydroxylamines, hydrazines, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, etc. , polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hytride, auxiliary developers such as 1-phenyl-3-pyrazolidone, Viscosifiers, various lactic agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, oxidation as described in West German Patent Application (OLS) No. 2,622,950 An inhibitor or the like 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. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-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, ■
-Phenyl-3-virazolidone type developing agents, p-aminophenol type developing agents, etc., and these can be used singly or in combination (for example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzene). ) 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 include 3-dichlorohydroquinone and 2,5-dimethylhydroquinone, and examples of 1-phenyl-3-virazolidone developing agents include 1-phenyl-3-virazolidone,
4.4-dimethyl-1-phenyl-3-virazolidone,
4-hydroxymethyl-4-methyl-1 phenyl-3-
Examples of 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 , such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,
3. (3a, 7) tetrazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, sodium 2mercaptobenzimidazole-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 weight of 1000-0000. It can be contained in a range of 1 to 10 g/f.

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, 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 thionate salts.

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 for accelerating development, they may also be added to the photosensitive material. I'll come. 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.

Amino compounds useful as amino compounds include both inorganic and organic amines, such as hydroquinylamine. 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 very suitable. It is valid.

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 (I[I) or cobalt (III), such as ethylenedianetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2- Aminopolycarboxylic acids such as propanoltetraacetic acid or complex persulfates of organic acids such as citric acid, tartaric acid, and malic acid; manganates, nitrosophenols, etc. can be used. Among these, ethylenediaminetetraacetic acid iron(II) salt, diethylenetriaminepentaacetic acid iron(III) salt, and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Additionally, the ethylenediaminetetraacetic acid iron(III) complex is particularly useful in both stand-alone bleach solutions and single-bath bleach-fix solutions. can be used.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858;
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 5357831, No. 3741
No. 8, No. 51-6 5 732, No. 5 3-7 2
6 2 3, 51-9 5 630, 53-9
No. 5631, No. 5:3-104232, No. 53-12
No. 4424, No. 53-l4l623, No. 5 3-2
8 4 2 No. 6, Research Disclosure Nα
Compounds having a mercapto group or a disulfite group described in No. 17129 (July 1978) etc.; JP-A-5C
Thiazolisine derivatives as described in No. I-140129: Japanese Patent Publication No. 45-8506, Japanese Unexamined Patent Publication No. 1973
Thiourea derivatives described in No. 2-20 832, No. 53-32735, and U.S. Patent No. 3,706,561 West German Patent No. 1.127,715, JP-A-58-1623
Iodides described in No. 5: polyethylene oxides described in West German Patent No. 966,410 and West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-88836; others No. 49-42434, 49
-5 9 6 4 No. 4, No. 53-94927, No. 5
Compounds and iodine described in Nos. 4-3 5 7 2 7, 55-26506 and 58-163940,
Bromine 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 US Pat.
The compounds described in No. 5630 are preferred. Furthermore,
Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of 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. We
st, Photo. Sci. Eng. ), Volume 6, pages 344-359 (1965), etc. may 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 macenta 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, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 15159
In addition to the ship base type compounds described in US Pat. No. 13924, the metal salt complexes described in US Pat. No. 56-6235, No. 56-16133, No. 56-5 9 2 3
No. 2, No. 5 6-6 7 8 4 No. 2, No. 5 6-8
3 7 3 4, 5 6-8 3 7 3 5, 5 6-8 3 7 3 6, 56-8973
No. 5, No. 56-81837, No. 5 6-5 4 4
30, No. 56-106241, No. 56-1072
No. 36, No. 57-97531 and No. 57-8356
Various salt-type precursors described in No. 5 and the like can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A No. 56-64339, JP-A No. 57-144547, JP-A No. 5L-211147, JP-A No. 5 B-5 0 5 3
No. 2, No. 5 8-5 0 536, No. 5 8-5
0 5 3 3, 5115 0 534, 5
8-5 05 3 5 and 58-115438
It is written in the number etc.

Various treatment liquids 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, for saving silver in 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 peroxide intensification.

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 do not suffer from 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 0.5XIO mol of ammonium hexachloride per mol of silver were adjusted to pH in a ceratin solution at 35°C by a double jet method. A monodisperse silver chloride emulsion having an average grain size of 0.07 μm was prepared by mixing the mixture while controlling the grain size to be 6.5 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 (300
mg/mr), further adding 2,4-dichloro-6-hydroxyl,3,5-triazine sodium salt as a hardening agent to obtain lrr? Polyethylene terephthalate production so that the amount of silver is 3.5g per
Addition amount (■/m') Nucleation accelerator 28. A silver halide emulsion layer was coated on a transparent support, and gelatin (1.3 g/m) and compound I-1 of the present invention (0.1 g/m) were further coated on the upper layer. A protective layer containing the following three surfactants, a stabilizer, and a matting agent as auxiliary agents was applied and dried.

(Sample 1) Surfactant addition amount (mg/po)C
H. COOC6H. ．． CHCOOC6H 37 SO, N a Genko ethioctic acid matting agent polymethyl methacrylate (average particle size 3.5 μm) Compound I of the present invention A dispersion was prepared and used.

(Preparation of Dye Dispersion) Solution (1) 50.0 mg/rn' 19 was prepared in the following manner: (17 g) Solution (2) was stirred at 40°C, and then Solution (2) was added little by little.

(Preparation of Comparative Sample) 1) A sample was prepared using the following dye instead of compound ■-19 in Example 1 (Comparative Sample IA) CH3-C-C= CH-C--C-CH
3II I II ilSO
3K SO3K (0.0 7
5 g/rn') 2) In Example 1, the following dye was used in place of Compound A19. (Comparative Sample 1-B) This dye is exemplified in WO8/04794.

3) Example Compound 1 of the present invention in 1 ■ Contains 9 Comparative samples were prepared using the following protective layer instead of the protective layer shown in Created C.

Acid treated Seratin 2, 0 g/rr? COOCH2CH,NH(C2Hs),-Cpe dye O. 75g/m SO3K SO3K Surfactant C. ．． H. 3CONH(CH2). N(CH3)2(C
H2). 50. e0. 53g/m CH2COOC. H CHCOOC, H 0. 037/IS OWN a C. H, Supporting agent thioctic acid 0.006/m 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 printer P-607, developed with the following developer at 38° C. for 20 seconds, fixed in a conventional manner, washed with water, and dried.

Hydroquinone 35 0c! 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 l. 0. Potassium bromide 4.0g 5-methylbenzotriazole 0.6g 3-diethylamino 1,
2 - Add 15.0 g of propanediol water (pH = 11.5) As a result, Example 1 and Comparative Sample 1-A were completely decolorized, but Comparative Samples I-B and I-10 were A yellow stain remained. Comparative sample 1-B was completely decolored when the development time was increased to 30 seconds. As mentioned above,
The compounds of this 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 that can return the halftone dot area to l = 1 for each sample,
Exposure was carried out for twice and four times as long as that exposure time, and it was determined 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, the tone variability of comparative sample 1-A is significantly reduced, whereas the 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 stains due to reducing fluid (2) above
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 1-A and 1-H.

farmer reducer liquid When using: 1st liquid: 2nd liquid: water 100 copies = 5 copies = 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%
The compound of the present invention 1-5 was dispersed in an aqueous solution of lime-treated gelatin 25 and the sand used was filtered through a glass filter.
・・・・・・・・・ 1. Og Compound of the invention I
-40・・・・・・・・・ 1.68 and then remove the dye attached to the sand on the glass filter.
% gelatin solution 100* was obtained. (The average particle size of the dye fine particles was 0.15 μm.) Compound of the present invention 1-5 ...... 1
．． Og Compound of the present invention ■-3 ・・・・・・・・・
1.6g was prepared in the same manner.

Paper support A Undercoat layer gelatin 0.8g
/rrf Paper support B Antihalation layer gelatin 0.6g
/trr Compound of the present invention 1-5...
・25g/of compound of the present invention I-40...
・・・・・・ 40g/n {Paper support C Halleyshiron prevention layer gelatin ・・・・・・・・・ 0.6g
/d Compound of the present invention 1-5 ......
40■/bo Compound of the present invention II-3...
...65/A Multilayer color photographic paper samples 2-1 to 24 having the layer structure shown below were obtained on paper support samples A, B and C.

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 solution (So
lv-1) 8.2g was added and dissolved, and this solution was diluted to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution. On the other hand, silver chloroiodobromide emulsion (cubic, average grain size 0.88 μm)
The coefficient of variation of the particle size distribution of a 3:7 mixture (silver molar ratio) of 0.70 and cam is 0.08 and 0.1.
0.0, each emulsion contains 0.2 mol % of silver bromide locally on the grain surface) and the following blue-sensitive sensitizing dyes were added per mol of silver to 2.0 x 10 - Add 4 moles and for small size emulsions, add 2.5X1 each.
A sample was prepared in which sulfur sensitization was applied after adding 0-'mol. 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. 1-oxy-35-dichloroS-triazine sodium salt was used as the gelatin hardening material for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer 50, Lj SO3HN(CJS)2 (2.OXIO-' moles each for large size emulsions and 2.5X10-' moles each for small size emulsions per mole of silver halide) ) green-sensitive emulsion layer (per 11 moles of halide, 4.OXIO-' mol, 5.6×10-' mol) and for large size emulsions vs. for small size emulsions (1 mol of silver halide) per 7.OX10-' mol for large emulsions and 1 mol for small emulsions.
．． O
10-' moles, or 1.0-' mole for small size emulsions. IXI
For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-' mol per mol of silver halide. In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)=5-mercabutotetrazole was added at 8.5X10-' mole and 7.7XIO per ill mole of halogenation, respectively. -'Mole, 2.5
X10-' moles were added. Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1.3,
3a,7-tetrazaindene each with 1 silver halide
Per mole, IXIO-' moles and 2X10-' moles were added. One paper support sample A had the following comparative dyes added to its emulsion layer. 8■/A and 35■/Bo (layer structure) The composition of each layer is shown below. The number is the coating amount (g/rrr)
represents. Silver halide emulsions represent coating amounts in terms of silver. Four types 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 (TiOx) and a bluish dye (ulmarine blue)] Single layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Iniro Cobra (ExY) 0.82 Color image stabilizer (C
pd-1) 0. 1 9 solvent (SOIV-1) 0.
3 Five-color image stabilizer (Cpd-7)
0. 0 6 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. 0 8 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture (Ag molar ratio) of average particle size of 0.55 μm and 0.39 μm. Particle size distribution The coefficient of variation is 0.10 and 0.0
8. Each milkweed has AgBr 0. (8 mol% was locally contained on the particle surface)
0.12 gelatin 1.24
Magenta coupler (EXM) 0.20
Color image stabilizer (Cpd-2) 0.
0 3-color image stabilizer (Cpd-3)
0. 1 5-color image stabilizer (Cpd-4)
0. 0 Two-color image stabilizer (Cpd-9)
0. 02 solvent (Solv-2)
0. 4 0 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0. 4 7 Color mixture prevention agent (Cpd-5) 0. 0
5 solvent (SOIV-5) 0
．． 2 4 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.58,
1=4 mixture of um and 0.45 μm (
8g molar ratio). The coefficient of variation of the grain size distribution is 0.09 and 0.11, and each emulsion has AgBr 0 . (6 mol% was locally contained on a part of the particle surface)
0.23 gelatin
1.34 cyan coupler (ExC)
0. 3 Two-color image stabilizer (Cpd-6)
0. 1 7-color image stabilizer (Cpd-7)
0. 40 color image stabilizer (Cpd
-8) 0. 04 solvent (So
lv-6) 0. 1 5 Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing prevention agent (Cpd-5) Solvent (Solv-5) Seventh layer (protective layer) Gelatin polyvinyl alcohol scum (denaturation degree 17%) ) Liquid paraffin 1. 33 Lyr modified copolymer 0.17 0.03 (ExY) Yellow coupler Ctlls (ExM) l:1 mixture (molar ratio) of magenta coupler (BxC) Cyan coupler - α R c! Mixture of Hs, CaHq and 0■ 2 = 4:4 by weight of each country (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture prevention +111 0H (Cpd-6) 2:4:4 mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer = {C H x - C H h-CONHCaHt(t) Average molecular weight 60.000 (Cpd-8) Color image stabilizer 0H 0H (Cpd-9) Color image stabilizer (IJV-1) Ultraviolet absorber (Solv-1) Solvent (Solν-2 ) Solvent (Solv-4) Solvent (Solv-5) Solvent COOCsH+t (CL)s 1 COOCJ+v (Solv-6) Solvent? For samples 2-1 to 2-4, a light-sensitive needle (manufactured by Fuji Photo Film ■, FWH type, color temperature of light source 3,20
Stepwise exposure for sensitometry was given through blue, green, and red filters using 0@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.
We obtained the results shown in 2. Processing ■ 1-Ichiki Hogata Mikaku 0 kiln next day 1 color development 3
5℃ 45 seconds 161d l? ffi bleach fixing 30-35°C 45 seconds 215d l7 f
Rinse ■ 30~35°C 20 seconds ■ 10 f
fi rinse ■ 30~35℃ 20 seconds ■ 10 f
fi rinse■ 30-35℃ 20 seconds 350+d
10 f drying 70-80°C 60 seconds *The amount of replenishment was for one photosensitive material (the tank countercurrent method was used from rinsing ■ to ■). The composition of each processing solution was as follows. Left Puni Return Hair Box U Phlegm Fukisha Kisui
800 d 800 a
f 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
25 g 25 gN=ethyl N
-(β-methanesulfonamidoethyl)-3-methyl-4-monoaminoaniline sulfate 5.0 g 7.0 g
N,N-bis(carboxymethyl)hydrazine 5.5 g 7.0 g
Fluorescent brightener (i1 old↑EX 4B. Manufactured by Sumitomo Chemical) Add 1.0g2.0g water 1000jd 1000dp
H (25℃) 10.05
10.451 Hakusei 1 Hill (tank fluid and refill fluid are the same) water
400
dAmmonium 1,000 sulfate (70%) too
d Sodium sulfite 17 g Ethylenediaminetetraacetate iron (I[I) Ammonium 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Add water
1000 mpH (25°C)6. Onλ wave (tank fluid and replenisher fluid are the same) Ion exchange water (calcium and magnesium are each 3 1
) $111 or less) When the dye according to the present invention is used in the anti-halation layer, the decrease in sensitivity is relatively small and no residual color is noticeable. By using this amount, the resolution can be significantly improved. Example 3 Preparation of dye fixed layer Dyes ■-13 and II-5 were each treated with a pole mill according to the method described in JP-A-63-19743. Water 43Ld and Triton X-20OR surfactant (TX-
20 O R) 6.7% aqueous solution 791jd and 22
I put it in a ball mill. 20g of dye was added to this solution. Zirconium oxide (ZrO) beads 400d (2
m diameter) was added and the contents were crushed for 4 days. After this, 12
．． 160 g of 5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. When observing the obtained dye dispersion, it was found that the particle size of the pulverized dye was 0.0 in diameter.
It had a wide distribution ranging from 5 to 1.15 μm. A transparent PET support with a thickness of 100 pm was used as the support. In order to improve the adhesion with the water-visible 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/rrl of gelatin was applied on top of the first undercoat layer. I set up a layer. A fine dispersion of the above dye was coated as a gelatin dispersion solution on this support in the coating amount shown below. In this way, an antihalation layer was prepared. ●Gelatin 1.8g/Bo ●Dye I
-13 Quantity listed in Table 3●Potassium polystyrene sulfonate (average molecular weight 600,000) 35■/10■/Po●Phenoxyethanol 18g/nf●1,
Preparation of 2-bis(vinylsulfonylacetamido)ethane 100/I 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. Furthermore, positive type characteristics can be obtained by performing reversal processing using a reversal processing liquid.

<Preparation of raw emulsion #1> Solution 1 75”C solution ■ 35°C solution ■ 35°C melt ■ Add solution ■ and solution ■ simultaneously over 45 minutes to solution ■ stirred well at room temperature, and then add solution ■ and the entire amount. At the end of the process, a cubic monodisperse emulsion with an average particle size of 0.28 μm was finally obtained. At this time, the addition rate of solution (2) was determined so that the p and Ag values in the mixing container increased relative to the addition of solution (2). The solution was added while adjusting the concentration to 7.50 at all times.The solution (■) was added for 5 minutes starting 7 minutes after the start of the addition of the solution (■).After the addition of the solution (■) was completed, the solution was washed with water and desalted by the sedimentation method. , inert gelatin 1
It was dispersed in an aqueous solution containing 00 g. To this emulsion, 34 μl each of sodium thiosulfate and gold chloride #4 hydrate were added per mole of silver, and the PH and PAg values were adjusted to 8.9 and 7.0 (at 40°C), respectively. Chemical sensitization was carried out at °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><Protectivelayer> 11 Negative millet (compound ■) CJs Back conductive layer><Ge!Layer> Coating amount ■/A Processing method Reversal development processing Reversal development processing was performed using a commercially available reversal processing solution (FR-5 manufactured by FR Chemicals, USA) using an F10R automatic reversal deep tank automatic developing machine manufactured by ^11en Products, 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 manufactured by FR Chemicals, USA) using an F10 deep tank automatic processor manufactured by Alien Products, USA. went.

Evaluation of sharpness Sharpness was evaluated using 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 x 2 am" and evaluated at the part where the optical density was 1.0 using the spatial frequency of 20 cycles/lll OMTF value. The results are shown in Table 3.
It was shown to. Evaluation of residual color After the unexposed film was subjected to the automatic development process described above, the green transmission density and blue transmission density were measured through a Macbeth Status A filter. The results are shown in Table 3. 4. “Detailed description of the invention” of the specification subject to amendment 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 numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and R_2 represents an alkyl group,
Aryl group, aralkyl group, cyano group, -COOR_6
, -CONR_7R_9, -COR_9, -SO_2R
_9, -SOR_9, -SONR_7R_6, -OR_
7, -NR_7R_8, -NR_8CONR_9, -N
R_7CONR_7R_8 or NR_8SO_2R_
9 (here, R_6, R_7, R_8 represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, R_9 represents an alkyl group, an aryl group, an aralkyl group, and R_7 and R_8 or R_8 and R_9 are connected to form 5 or may form a 6-membered ring), R_3 and R_4 represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group, or a sulfonyl group, and R_3
and R_5 or R_4 and R_5 may be connected to form a 5-membered ring or a 6-membered ring. R_5 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, -OR_7, -COOR_7 (here, R_7 is the same as R_7 defined above). L_1, L_2, L_3 each represent a methine group, and n is 0
Or represents 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_1_0 is a hydrogen atom, an alkyl group, an aryl group,
Cyano group, -COOR_1_2, -COR_1_2, -
CONR_1_2R_3, -OR_1_2, -NHCO
R_1_2 represents a hydrogen atom, an alkyl group, or an aryl group. R_1_2R_1_3 each represent a hydrogen atom, an alkyl group, or an aryl group. However, the general formula (
The compound represented by 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.