JPH03216645A - 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 or II as dispersed solid fine particles is formed. In the formulae I, II, R<1> is H, alkyl or aryl, each of R<2>-R<5> is H, alkyl, halogen, alkoxy, etc., each of L<1>-L<5> is methine, each of (m) and (n) is 0 or 1, R<6> is H or acyl and each of R<7>-R<11> is H, halogen, alkyl, alkoxy or carboxyl. 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 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, a filter layer may be located between them.

An image based on the fact that light scattered during or after passing through a photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material on the opposite side of the emulsion layer and enters the photographic emulsion layer again. For the purpose of preventing blurring or 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.

il+ 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.

f51 fJ Excellent stability over time in liquid or photographic materials and should not change color or fade. In particular, when the colored layer is a filter layer or is supported by a Halley's siding prevention layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are It is often necessary to avoid substantial staining.

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, there is 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, as described 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. 276566, No. 299435, World Patent No. 88/04794, etc. In addition, a method of dyeing a specific layer using metal salt fine particles to which a dye is adsorbed is disclosed in U.S. Pat. No. 2,719,088;
No. 496.841, No. 2,496,843, Japanese Unexamined Patent Publication No. 6
No. 0-45237, etc. 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 Present Invention] Therefore, the object of the present invention is to provide a solid fine particle dispersion designed to dye a specific hydrophilic colloid layer in a photoluminescent material and to rapidly decolorize it during the development process. An object of the present invention is to provide a photographic light-sensitive material containing a dye of the type.

(Means for Solving the Problems) (1) The object of the present invention is to provide a silver halide layer having a hydrophilic colloid layer containing at least one compound represented by the following general formula (!) or (■) as a solid fine particle dispersion. This is achieved using photographic materials. General formula (N General formula (■)) D4 R1 (In the formula, R1 represents a hydrogen atom, an alkyl group, or an aryl group, and R!, RS, R4, and RS each represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, or an alkoxy represents a carbonyl group, carboxyl group, hydroxyl group, or amino group, L'sL'', L3, and L'L5 each represent a methine group, m and n each represent 0 or l, R6 is a hydrogen atom,
Represents an acyl group, R', R'' R9, RIG, R I
1 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a carboxyl group, respectively. (2) The object of the present invention is to provide a compound represented by the general formula (1) or (■) each having at least one carboxyl group, and a halogen compound having a hydrophilic colloid layer containing this as a solid fine particle dispersion. This can be achieved using silver oxide photographic materials.

(3) The object of the present invention is to contain at least one compound represented by the general formula (1) or (II) as a solid fine particle dispersion, and to contain at least one compound represented by the following general formula (II1) as a solid fine particle dispersion. This is achieved by using a photographic material containing silver halide as a body. General formula (III) R1x R! 1 (R21 in the middle is a hydrogen atom, an alkyl group, an aryl group, a cyano group, -COOR23, COR"CONR"R"
-01? "Go-NHCOR", R22 represents a hydrogen atom, an alkyl group, an aryl group, L11, LL
2, [7'3, L1, LI5 each represent a methine group,
m' and n' each represent O or 1, and R23 and Bza each represent a hydrogen atom, an alkyl group, or an aryl group. However, the compound represented by the general formula (II+) has at least one group selected from a carboxyl group, a hydroxyl group, and a sulfonamide group in the molecule. ) Next, general formulas (1) and (II) will be explained in detail.

The alkyl group represented by R1 is an unsubstituted alkyl group (e.g., methyl, ethyl, isopropyl), or a substituted alkyl group {as a substituent, a halogen atom (e.g., 2-chloroethyl), a phenyl group (e.g., henzyl, carboxyhendyl), or a hydroxyl group. (e.g. 2-hydroxyethyl), alkoxy groups (e.g. 2-methoxyethyl, 2-(2-hydroxyethoxy)ethyl), carboxyl groups (e.g. carboxymethyl, 2-carboxyethyl, l-carboxyethyl), sulfonamide groups (e.g. Methanesulfonamidoethyl), amino groups (e.g. dimethylaminoethyl), and ester groups (e.g. 2-acetoxyethyl, ethoxylponylethyl) are preferred.

The aryl group represented by R1 is an unsubstituted aryl group (e.g. phenyl) or a substituted aryl group {substituents include an alkyl group (e.g. 4-methylphenyl), a hydroxyl group (e.g. hydroxyphenyl), a carboxy group (e.g. carboxyphenyl), 3.5-dicarboxyphenyl), sulfonamido groups (e.g. 4-methylsulfonylaminophenyl, 4-sulfamoylphenyl), alkoxy groups (e.g. 4-methoxyphenyl, 4-(2-hydroxyethoxy)phenyl) , ester groups (eg, ethoxyluponylphenyl, acetoxyphenyl)} are preferred. Particularly preferred Rl is one having a carboxyl group as a substituent.

The alkyl group represented by RZ, R2, R4, and RS is preferably an alkyl group having 1 to 4 carbon atoms.

Rt, R'', R', R''? ? The halokene atom represented is preferably a chlorine atom, a bromine atom, or a fluorine atom.

The alkoxy group represented by R2, R3, R4 and RS is preferably methoxy, ethoxy, hydroxyethoxy or the like.

The alkoxycarbonyl group represented by R", l'?", l;l', R' is preferably methoxycarbonyl, ethoxycarbonyl, hydroxyethoxycarbonyl, or the like.

R'', R', F?',!?'! 7-
．． /． W is preferably an unsubstituted amino group, dialkylamino group, acetylamino group, or methylsulfonylamino group.

The methine groups represented by L', L'', L', L', and L' are preferably unsubstituted methine groups, but the substituents (
methyl, ethyl, phenyl, etc.).

The acyl group represented by R6 is preferably an acetyl group.

The halogen atom represented by R7, R@, R9, Rl+1, R'' is preferably fluorine or chlorine.

The alkyl group represented by R7, Rl, R9, Rlll, Rl+ is preferably an alkyl group having 1 to 4 carbon atoms. R? , R1, R9, Rl@, Rl' are methoxy, ethoxy, hydroxyeth:
Toshi etc. are preferable.

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

The alkyl group represented by Rit, Rat, R2'', 224 is an unsubstituted alkyl group (e.g., methyl, ethyl, n-propyl, isobrobyl, cyclohexyl) or a substituted alkyl group {a halogen atom (e.g., 2-chloroethyl) as a substituent. , 1, l, 2.2-tetrafluoroethyl), phenyl groups (e.g. henzyl, carboxybenzyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxyl), alkoxy groups (e.g.
-methoxyethyl, 2-(2-hydroxyethoxy)monoethyl), carboxy groups (e.g. carboxymethyl, l
1-carboxyethyl, 2-carboxyethyl), sulfonamide groups (e.g. methanesulfonamidoethyl), amino groups (e.g. 2-(N,N-dimethylaminoethyl)), carboxylates (e.g. ethoxycarbonylmethyl, ace1-xyethyl) or sulfonate (e.g. methoxysulfonylethyl)}. The aryl group represented by Rz+, R1, R!3, R24 is an unsubstituted aryl group (e.g. phenyl) or a substituted aryl group {a halogen atom (e.g. 4- chlorophenyl, 2,5-dichlorophenyl), alkyl groups (e.g. 4-methylphenyl), hydroxyl groups (e.g. hydroxyphenyl), carboxy groups (e.g. carboxyphenyl, 3,5-dicarboxyphenyl), sulfonamide groups (e.g. 4 -methylsulfonylaminophenyl, 4
-sulfamoylmethyl), alkoxy groups (e.g. 4-
methoxyphenyl, 4-(2-hydroxydiethoxy)phenyl), amino groups (e.g. N,N-dimethylaminophenyl, 4-(N-carboxymethyl-N-ethylamino)phenyl), carboxylates (e.g. 4-ethoxy Carbonylphenyl, 4-(2-hydroxyethoxy)phenyl'', or sulfonate (e.g. 4-methoxysulfonylphenyl)} are preferred. L1, L'1,
The methine group represented by 1.13, Ll4, and l-15 is preferably an unsubstituted methine group, but may have a substituent (eg, methyl, ethyl, phenyl). Among the compounds represented by the general formula (III), particularly preferred are those having no sulfo group, sulfo group, or carboxy group salt as a substituent.

Furthermore, among the compounds represented by the general formula (III), those having at least two groups selected from carboxy groups, hydroxyl groups, and sulfonamide groups are preferred. Next, specific examples of the compounds represented by the general formulas (+), (n), and (II1) of the present invention will be shown, but the present invention is not limited thereto. General formula (Specific example of eyes 1-1 I COOH COOI1 ! 2 COOII COOH 1 3 - (Cllx)z (CHz)! COOII COOH ■ 4 C11. COOH COOH CH. COOH COOII ■ 6 Clh COOI+ ■ 7 ■ 8 ClhCHCOOII C112 COOI+ CIIsCtlCOOtl ■ 9 ■ l0 1 - 1 1 ■ 12 ! l3 ■ ■ 4 ■ l5 ■ l6 1 l7 ■ l8 CHgCHxCOOH CIliCHtCOOH l l9 I 20 ■ 2l l 22 ■ 23 ■ 24 Specific example of general formula (n) 1 l ■ 2 CHxCHgCOOIl ■ 3 ■ 4 ■ 5 CIlzCOO!1 ■ 6 II - 7 ■ 8 ■ 9 ■ 10 ■ ■ l ?tlgClltCII■COOI+ CI.CIlCOOIl It-15 ? Cll■CHtCHxCOOII ■ l6 ■ l7 ■ l8 O CIl.COOI1 ■ l9 ■ 20 ■ 22 Specific example of general formula (III) I 1 ■ 2 ■ 3 ■ 4 ■ 5 ■ 6 ■ 7 ■ 8 ■ 9 ■ l0 m l l ■ 12 ■ l3 ■ l4 m 15 ■ l6 ■ l7 ■ l8 The compound represented by the general formula (1) or (II) used in the present invention can be synthesized by the method described in Japanese Patent Publication No. 57-46778, etc. That is, the compound represented by the general formula (IV) and orthoformic acid Esters, N,N-diphenylformamidine, tetramethoxypropane, trimethoxypropene, propenedianyl, pentadienedianyl, etc., in a solvent (e.g. methanol, ethanol, pyridine, acetic acid) with a base (e.g. triethylamine, pyridine) and/or Alternatively, it can be obtained by reaction in the presence of acetic anhydride.

General formula (1v) R4 R (wherein R', R''. R3, R', R' represent the same meanings as above. The compound represented by general formula (rV) is synthesized by Synsetinoku Communications No. x7S, page 803, 1987 ( Synthetic Community
cations, 17, 803, (1987)
), or by the method described in Japanese Patent Publication No. 57-46778.

Synthesis Example 1 Synthesis of Compound 1-2 2.5 g of N-carboxyethylhomophthalimide, I,
3.3-1 Rimethoxy 1-mouth pen 1.4g, triethylamine 3. : A mixture of M and 30 d of ethanol is heated under reflux for 2 hours. After cooling the reaction solution, potassium acetate J. 1.2 g and 10 d of ethanol were added, and the precipitated crystals were collected by filtration. By treating this crystal with dilute hydrochloric acid, compound 1-2 was converted to 0.7
I got g. Melting point 280-285°C. λIIax 6 0
7 nm (DMF) Synthesis Example 2 Synthesis of Compound 1-13 N-(3-carpoxyphenyl) homophthalimide 2.
8g, pentadiene bis(m-chloroanyl) hydrochloride 1
．． 8g, triethylamine 3.8g, acetic anhydride 1.
A mixture of 1 g and 50 d of N,N-dimethylformamide is stirred at room temperature for one day.

Potassium acetate l. Ethanol 1 in which Og was dissolved
50- was added and the precipitated crystals were collected by filtration and treated with dilute hydrochloric acid to obtain 0.6 g of Compound 1-13. λma
x 702 nm (Hz O pH 8).

Synthesis Example 3 Synthesis of Compound U-3 A mixture of 2.3 g of N-carboxyethylhomophthalimide, 1.4 g of penkdiendiyl hydrochloride, 4.2 d of 1.ethylamine, and 50 d of ethanol is stirred at room temperature for 3 hours. Add 5 (ld) of water and 15 mQ of acetic acid to the reaction solution. The precipitate was collected by filtration, washed with acetone, and dried to form compound U-3.
1.4g of was obtained. Melting point: 197-198°C
ax 535 nm (DMF). The compound of general formula (III) used in the present invention is disclosed in JP-A-52-927
16, G4-40827, etc.

The compound of general formula (1), (II) or (III) is used in an amount of 1-1000 mg per 1 rd area on the photosensitive material, preferably 1 to 800 mg per 1 rd area on the photosensitive material. When using the compound of general formula (1), (II) or (III) as a filter dye or antihalation dye, any effective amount can be used, provided that the optical density is 0.
It is preferable to use it in a range of 0.05 to 3.5. The addition time may be any step before coating.

The compound of general formula (!), (n) or (III) according to the present invention can be used in both emulsion layers and other hydrophilic colloid layers.

The fine particle dispersion of the compound of general formula (1), (II) or (I[ pulverization means, such as ball milling (ball mill, vibrating ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. ]. 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 IO μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less, and in some cases 0.5 μm or less. 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 that can be used for photography can be used. The silver halide emulsion used in the present invention includes silver bromide, silver iodobromide,
Silver iodochlorobromide, silver chlorobromide and silver chloride are preferred.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use particles consisting of a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms. The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. It may also be a particle in which a latent image is mainly formed on the surface (for example, a negative emulsion),
It may also be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion or a pre-fogged direct inversion type emulsion). Preferably, the particles are such that the latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has a thickness of 0.5 microns or less, preferably 0.3 microns or less.
Particles with a diameter of 0.6 microns or less, preferably 0.6 microns or more, and an average aspect ratio of 5 or more account for 50% of the total projected area.
% or more, or the statistical coefficient of variation (the value S/d, which is the standard deviation S divided by the diameter d in the distribution expressed by the diameter when the projected area is approximated as a circle) is 20%. The following monodispersed emulsions are preferred. Furthermore, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed. The photographic emulsion used in the present invention is P.
．． Glafkides), Chimie er Phys Photography (Chimie er Phys Photography)
iquePhotographeque) (Ballmontel, 1967), G.F. Duffin (
G.F. Duffin), Photographic Emulsions, Chemistry (Photography
c Emulsion Chemistry) (Published by Focal Press, ■966), Making and Coating Photo Emulsion (Puy El Zeliksan et al.)
It can be prepared using the method described in "GraphicEmulsion" (Focal Press, 1964).

Further, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (for example, U.S. Pat. No. 3.2.71,157, U.S. Pat. No. 574,628, No. 3.704,130,
4,297,439, 4,276,374, etc.), thione compounds (for example, JP-A-53-14431)
No. 9, No. 53-82408, No. 55-77737, etc.), amine compounds (e.g., JP-A-54-100717)
etc.) can be used. In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present. As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other woody colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; sugar derivatives such as sodium alginate, starch derivatives, etc. ; Various synthetic highly hydrophilic materials such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylvirazole, etc.; Molecular substances can be used.

In addition to general-purpose lime-processed gelatin, gelatin may be used as acid-processed gelatin or the Japanese Society of Scientific Photography LX: (BullSoc
．． Sci. Photo. Japan). No.
1 6. Enzyme-treated gelatin such as that described on page 30 (1966) may be used, or a gelatin hydrolyzate may be used.

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be set in any of the photosensitive layers or the wood-philic coro-fed layer constituting the photosensitive layer. Specific examples include chromium salts, aldehydes M (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxyl.
3,5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2
-bu[Ipanol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)
Vinyl polymers having ether or vinyl sulfonyl groups in their side chains) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties.

N-carhamoylpyridinium salt M ((1-morpholinocarbonyl-3-viridinio)methanesulfona-1
) and haloamidinium salts (1-(1-k17-l-pyridinomethylene)pyrrolidinium 2-naphthalene sulfonate, etc.) are also excellent in their fast curing speed.

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, holobolar 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, virol 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 nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, henzindolenine nucleus, indole nucleus, penzoxazole nucleus, naphthoxazole nucleus, henzothiazole nucleus, naphthothiazole nucleus, henzoselenazole nucleus, henzimidazole nucleus, quinoline nucleus, etc. can be used. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a nucleus having a ketomethylene structure such as a bilazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thousand oxazolidine-2.
5- to 6-membered heterocyclic nuclei such as a 4-dione nucleus, a thiazolidine-2.4-cyone nucleus, a rhodanine nucleus, and a thioharbituric 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, or a substance that exhibits superchromic sensitization. Substituted aminostilhene compounds that are segmented ring nuclei (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,721)
(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. 3615.613, U.S. Patent No. 3,615
, No. 641, No. 3,617,295, No. 3,635,
The combinations described in No. 721 are particularly useful.

The silver halide photographic emulsion used in this technology has the purpose of preventing capri during the manufacturing process, storage or photographic processing of light-sensitive materials, or stabilizing photographic performance.
Various compounds can be included. That is, azoles such as penzothiazolium salts, nitroimidazoles, nitrohenzimidazoles, chlorohenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptohenzothiazoles, mercaptohenzimidazoles. , mercaptothiadiazoles, aminotriazoles, henzotriadules,
Nitrohenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptote-1-razole)
mercaptopyrimidines; mercaptotriazines frequently; thiogeto compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxydisubstituted (133a,
7) Addition of many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, henzenesulfinic acid, henzenesulfonic acid amide, etc. be able to. The photosensitive material of the present invention is a coating aid, an antistatic agent,
One or more surfactants may be included for various purposes such as improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, promoting development, increasing contrast, and sensitizing).

Photosensitive materials made using the present invention can be used as filter dyes or in hydrophilic colloid layers for irradiation or antihalation and other various purposes. It may also contain a water-soluble dye.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. ．． Oil-soluble dyes can also be emulsified by oil-in-water dispersion and added to the hydrophilic colloid layer. The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral 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 order of listing 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 rectangular color photography 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. It will be done. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefins. Paper coated or laminated with a polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other hydrophilic colloid layers. U.S. Patent No. 268 as appropriate
No. 1294, No. 2761791, No. 352652
Multiple layers may be applied simultaneously using coating methods such as those described in No. 8 and No. 3,508,947.

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color body film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. I can do it. Research Disclosure, Nllll7123
(July 1978), or by utilizing a trichromatic coupler mixture as described in U.S. Pat.
The present invention can also be applied to black-and-white photosensitive materials for X-rays by using the black-coloring couplers described in British Patent No. 1 and British Patent No. 2.102,136. Film for plate making such as lith film or scanner film,
The present invention is also applicable to X-ray film for direct and indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials. can.

When the photographic element of the present invention is used in color diffusion transfer photography, it may be used in color diffusion transfer photography.
No. 16356, No. 1B-33697, Japanese Unexamined Patent Publication No. 1973-
13040 and British Patent No. 1,330,524, or a peel-free type film unit as described in JP-A-57-119345. be able to.
In either type of format described above, the use of a polymeric acid layer protected by a neutralized timing layer is advantageous in increasing the processing temperature tolerance. When used in color diffusion transfer photography, it may be added to any layer in the 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-burning flashlights are common.

Gas, dye solution, or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or An exposure method that combines a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters. The color developing solution used in the development of the 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 used as color developing agents, but p-
Preferably, phenylenediamine compounds are used, typical examples of which are 3-methyl-4-amino-NN-diethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-
Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like.

These diamines are generally more stable in their salt form than in their IS state, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-capri agents such as bromides, iodides, penzimidazoles, henzothiazoles or mercapto compounds. Generally, it includes such things as Also, if necessary, preservatives such as hydroxylamines, di-root-hydroxylamines, hydrazines, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, and henzyl alcohol. , development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as i-phenyl-3-virazolidone, viscosity. Various chelating agents, such as aminobolycarboxylic acids, aminobolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Antioxidants described in OLS No. 2,622,950 and 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, l-phenyl-
Known black and white developers such as 3-virazolidones such as 3-virazolidone 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 used for the light-sensitive material of the present invention. The developing agents used in the developer include dihydroxybenzene-based developing agents, l
-Phenyl-3-virazolidone type developing agents, p-aminophenol type developing agents, etc., and these can be used singly or in combination (for example, l-phenyl-3-virazolidones and dihydroxyhensens, or p-aminophenols and dihydroxy benzenes) can be used. The light-sensitive material of the present invention may also be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone. In the above, examples of dihydroxybenzene-based developing chemicals include hydroquinone, chlorohydroquinone, promohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc.
-As a phenyl-3-pyrazolidone-based developer, l-
Phenyl-3-virazolidone, 4,4-dimethyl-1-
Phenyl-3-virazolidone, 4-hydroxymethyl-
4-Methyl-1 phenyl-3-virazolidone, 4.4-
Examples include dihydroxymethyl-1-phenyl-3-virazolidone, and p-aminophenol, N-methyl-p-aminophenol, and the like are used as p-aminephenol developing agents. A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, formaldehyde sodium bisulfite, which gives almost no free sulfite ions in the developer, may be used.The alkaline agents for the developer used in the present invention include potassium hydroxide, sodium hydroxide, potassium carbonate,
Sodium carbonate, sodium acetate, potassium triphosphate, diethanolamine, triethanolamine, etc. are used. The pH of the developer is usually 9 or higher, preferably 9.7.
The settings above are as follows. The developer may also contain organic compounds known as anti-capri agents or development inhibitors. Examples include azoles such as penzothiazolium salts, nitroindazoles, nitropenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptopenzimidazoles, mercaptothiadiazoles. such as aminotriazoles, henzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; , such as triazaindenes, tetrazaindenes (particularly 4-hydroxy substituted (1,3,
3a, 7) tetrazaindenes), pentaazaindenes, etc.: such as henzenethiosulfonic acid, henzenesulfinic acid, henzenesulfonic acid amide, sodium 2mercaptohenzimidadur-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 having a molecular weight of 11,000 to 100,000 can be contained in a range of 0.1 to 10 g/A.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetein acid, triethylenetetraamine, xaacetinocando, 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. 60109743 can be used. In the developing solution used in the present invention, a buffering agent is added.
Boric acid described in No. 1-28708, JP-A No. 60-9343
3. Saccharides (e.g., sucrose), oximes (e.g., acetoxime), phenols (e.g., 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 impression solution 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, mesoion 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.

Amino compounds useful as amine compounds include both inorganic amines and organic amines, such as hydroxylamine. Organic amines can be aliphatic amines, aromatic amines, cyclic amines, mixed aliphatic monoaromatic amines or diheterocyclic 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 carried out simultaneously with the fixing process, or may be carried out separately. Furthermore, in order to speed up the processing,
A method of bleaching and then bleach-fixing may also be used. Examples of bleaching agents include iron (■), cobalt (■), and chromium (
(2), compounds of polyvalent metals such as copper, peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron ([[) or cobalt (In), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid] Aminobolycarboxylic acids such as citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates; nitrosophenols, etc. can be used. Among these, ethylenediaminetetraacetic acid iron (■) salt, diethylenetriaminepentaacetic acid iron ([[l) salt] and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complex salt is particularly useful in both stand-alone bleach and single bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,1158, German Pat. No. 53-32736, No. 5357831, No. 374
No. 18, No. 53-65732, No. 53-72623, No. 53-95630, No. 53-95631, No. 5
No. 3-104232, No. 53-124424, No. 53
-141623, 53-2842.6, Research Disclosure No. Compounds having a mercapto group or disulfide group as described in Japanese Patent Publication No. 17129 (July 1978); Thiazolidine derivatives as described in JP-A-50-140129; Japanese Patent Publication No. 45-850
No. 6, JP-A-52-20832, JP-A No. 53-32735
Thiourea derivatives described in No. 1, U.S. Pat. No. 3,706,561;
-1 Iodide described in 6235; West German Patent No. 966,
Polyethylene oxides described in Japanese Patent Publication No. 410 and No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42434 and No. 4
No.9-59644, No.53-949271, No.54-
No. 35727, No. 55-26506 and No. 5B-1
The compounds described in No. 63940 and iodine and bromide ions can also be used. Among them, compounds having a mercabuto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, US Pat. No. 3,893,858 and West German Patent No. 1.2 are preferred.
Compounds described in No. 90,812 and JP-A-53-95630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds thioureas, and large amounts of iodides, but thiosulfates are commonly used. Preservatives for bleach-fix solutions and fix solutions are preferably sulfites, bisulfites, or carbonyl bisulfite adducts. After bleach-fixing or fixing, washing and stabilization are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent sedimentation, use water softeners such as inorganic phosphoric acid, aminobolycarboxylic acid, organic aminobolyphosphonic acid, and organic phosphoric acid, and disinfectants and anti-piping agents that prevent the growth of various bacteria, algae, and molds. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants to prevent drying load and unevenness, and various hardening agents can be added as necessary. Or Photography Science and Engineering Magazine by L.E. Wes
t, Photo. Sci. Eng. ) + Volume 6, 3
Compounds described on pages 44 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.-8543 may also be carried out. In the case of this process, 2 to 9 countercurrent baths are required. In addition to the additives mentioned above, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, the membrane p
Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid) for adjusting H (e.g. pH 3-9) Typical examples include aldehydes such as formalin (used in combination with acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminobolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, amoboriphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (penzisothiazolinone, irithiazolone, - Various additives such as thiazolines (henzimidazole, halogenated phenols, sulfanilamide, penzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and compounds for the same or different purposes may be used. Two or more types may be used together. 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. For this purpose, it is preferable to use various precursors of color developing agents.

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
The Schiff base type compound described in JP-A No. 13924, the metal salt complex described in U.S. Pat. No. 56-6235, No. 56 16133, No. 56-59232, No. 56-67842, No. 56-83734, No. 56-
No. 83735, No. 56-83736, No. 56-897
No. 35, No. 56-81837, No. 56-54430, No. 56-106241, No. 56-107236,
Examples include various salt-type precursors described in Japanese Patent No. 57-97531 and Japanese Patent No. 57-83565. The silver halide color brightening material of the present invention may contain various 1-phenyl-3-virazolidones, if necessary, for the purpose of promoting color development. Typical compounds are JP-A-56-64339 and JP-A-57-14454.
No. 7, No. 57-211147, No. 5B-50532, No. 5B-50536, No. 58-50533, No. 5
No. 8-50534, No. 58-50535 and No. 58
-115438 etc.

Various processing solutions in the present invention are used at IO'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. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2226.770 or US Pat. No. 3,674,499 may be carried out.

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.

In addition, during continuous processing, a constant finish can be obtained by using replenishers for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can also be lowered to half or half the standard replenishment amount for cost reduction.

When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed if necessary, very generally, and even when it is a color photographic material for photographing.

(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. Further, photographs obtained from the silver halide photographic material of the present invention do not produce stains, are stable even during long-term storage, and do not deteriorate in photographic performance. (Example) Next, the present invention will be explained in more detail based on an example. Example 1 (Preparation of Emulsion A) A silver nitrate aqueous solution and a sodium chloride aqueous solution containing 0.5XlO mol of ammonium hexachloride rhodium(m) per 1 mol were brought to pH 6.0 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 so that the grain size was 0.07 μm.

After particle formation, soluble salts were removed by flocculation methods well known in the art, and stabilizers 4-hydroxy-6-methyl-1,3,38,7-tetraazaindene and l-phenyl-5 were added. -Mercaptotetrazole was added. 1 kg of emulsion contained 55 g of gelatin and 105 g of silver. (Emulsion A) (Preparation of irradiation material) Adding the following nucleating agent and nucleation accelerator to the emulsion A,
Next, polyethyl acrylate latinx (300Il
g/po), and 2,4-dichloro-6- as a hardening agent.
Hydroxy 1,3.5-1-riazine sodium salt was added to give a silver content of 3.5 g per lnf.■ Addition of polyethylene terephthalate! (■/Po) C1θ 28. A silver halide emulsion layer was coated on a transparent support, and the upper layer was coated with gelatin (1.3 g/rrf),
A protective layer containing the compound II-4 of the present invention (0.1 g/bo) and the following three surfactants, a stabilizer, and a matting agent as coating aids was coated and dried.

(Sample 1) Five plated stand M Addition l (■/%) CHC
OOCJ+s 37 So, Na? aFl? SOzNCII■coox C3H, 2. 5 Thioctic acid with 49% polymethyl methacrylate (average particle size 3.5μ) 50. 6. A dispersion of the compound of the present invention was prepared and used.

(Preparation of dye dispersion) Solution (4) was prepared using the following procedure: Separate 17 g of solution (2) While stirring solution (2) at 40°C, solution (2) was added little by little. (Preparation of Comparative Sample) l) A sample was prepared using the following dye instead of Compound 11-4 in Example 1 (Comparative Sample 1-A). 2) In Example 1, the following dye was used in place of compound 1-4. (Comparative sample l-B) This dye is exemplified in W08B/04794.

0.1 g/+d 3) Comparative sample 1-C was prepared by using the following protective layer in place of the protective layer containing compound 1-4 of the present invention in Example 11.

M Choki (Puten 7 2.0g/Bo soot dye 4 elbow?OOCII■CHJII (Calls) z・C1
Shoichi 41 0. 75g/rrl? IhCII■SO3K CI? 1■3CONll(CIl■)J(Clh)t(CH
z) ssO+0. 53g/po? ll■COOC&ll13 CHCOOC6111 3 SO3Na 0. 037/po? IIF+tSO■NCIItCOOK''lllt 0.0025/if Desired 1L thioctic acid 0.006/+rrel■ Polymethyl methacrylate (average particle size 3.5μ) 0.009/I (performance evaluation) (1) Above The four samples were exposed to light through an optical wedge using Dainippon Screen Co., Ltd.'s Meisho Printer P-607, developed with the following developer at 38° C. for 20 seconds, fixed in a conventional manner, washed with water, and dried.

Moezooka Basic Recipe Hydroquinone 35.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Potassium triphosphate 74.0g Potassium sulfite
90.0g Ethylenediaminetetraacetic acid tetrasodium salt 1. Og Potassium Bromide 4.0g5-Methylhenzotriazur 0.6g3-Diethylamine-1
．． 2 Add 15.0 g of propanediol water iz (pH = 11.5) As a result, Example 1 and Comparative Sample 1-A were completely decolorized, but Comparative Samples 1-B and 1C had a yellow stain. remained. 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 for each sample to return the halftone area to 1:1,
Exposure was carried out for twice and four times as long as the exposure time, and it was examined how much the area of the rope point 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 lower 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 emulsion layer during storage, so even if the exposure time is increased, This is because the expansion of the halftone dot area was suppressed by the irradiation prevention effect of the dye. On the other hand, compound Rho 4 of the present invention exhibits high tone variability since it is fixed in the added layer.

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

Table 1 Tone variability (indicated by increase in halftone dot area) (3)
Evaluation of contamination (stain) by reducing solution The strisops of the samples of the present invention and samples of comparative examples obtained by the treatment in (2) above were added to the following Farmer's reducing solution at 20°C for 6 hours.
Dipped for 0 seconds, washed with water, and dried. As a result, the dot area of each sample was reduced to about 33% at 50%, but in comparison sample 1-C, severe brown staining occurred over the entire surface. No stain was observed in the samples of the present invention and comparative samples 1-A and 1-B. When using Farmer's reducing solution, mix 1st solution: 2nd solution: 100 parts of water: 5 parts: XOO parts. As described above, the samples of the present invention had good decolorization properties, tone changeability, and color reduction properties.

Example 2 Preparation of dye fixed layer Dyes 1-2 and I11-3 were each subjected to ball mill treatment by the method described in JP-A-63-197943.

6.7% aqueous solution of water 434d and Triton X-20OR surfactant (TX-20OR) 7 9 1
ttrl was placed in a 21 ball mill. 20g of dye was added to this solution. 400 m (2 am diameter) of zirconium oxide (ZrO) beads were added and the contents were ground 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 latenox was applied, and the upper layer was coated with 0.08 g of gelatin / IIf. Two undercoat layers were applied. A fine dispersion of the dye was coated on this support as a gelatin dispersion solution in the coating amount shown below. In this way, an antihalation layer was prepared.

●Gelatin 1.8g/Po ●Dye! −
2 Quantity listed in Table-2 Potassium polystyrene sulfonate (average molecular weight 600,000) 35g/po10/r+
? ●Phenoxyethanol 18g/nl●1,2
- Bis(vinylsulfonylacetamido)ethane 100 μ/Preparation of emulsion coating solution The 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 something. Further, by performing reversal processing using a reversal processing solution, positive type characteristics can be obtained. <Preparation of raw emulsion #l> Solution 1 75°C Melt 1i ■ 35°C solution ■ 35°C solution ■ Well-stirred solution at room temperature! Solution (2) and solution (M) were added simultaneously over a period of 45 minutes, and when the entire amount of solution (2) had been 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 (■) 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 3 each of sodium lithiosulfate and chloroauric acid tetrahydrate per mole of silver.
After adjusting the pH and PAg values to 8.9 and 7.0 (40°C), respectively, chemical sensitization was carried out at 75°C for 60 minutes to produce surface latent image halogenation. A silver emulsion was obtained.

The layer structure and composition of each layer are as follows. layer
Structure Thickness (μm) The emulsion layers other than the antihalation layer, the surface protection layer, the conductive layer, and the EEL layer were prepared and coated so that each component was coated in the following amounts to obtain a photographic material.

〈Protective layer〉 〈Emulsion layer〉 Addition of 100 plans (compound ■) C! IIS? CI+■)38030 C! HS <Back conductive layer><Gellayer> Coating lmg/nf Processing method Reverse development process Reverse development process is F manufactured by AllH products in the United States
-1 OR A commercially available reversal processing solution for a deep tank automatic processor (FR Chemicals, USA)
-531.532, 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 11en Products Co., 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 measuring wedge and subjected to the automatic processor processing described above. MTF is 400X2p
It was measured with an aperture of m", and the MTF value with a spatial frequency of 20 cycles/■ was used to evaluate the area where the optical density was 1.0. The results are shown in Table 2. Evaluation of residual color Unexposed film After carrying out 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 2.Example 3 The raw emulsion #l in Example 2 The same solution used for the preparation was used, with the following differences:

For solution 1, solution ■? 8 and Liquid (2) were simultaneously added for 5 minutes, and when octahedral particles with an average particle size of 0.10 lIm were formed, the addition of Liquid (2) and (2) was temporarily stopped, and sodium 100 sulfate and chloride were added per mole of III. 1 15 Ilg of gold acid tetrahydrate were added to each sample, followed by chemical sensitization treatment at 75°C for 60 minutes. The chemically sensitized core particles obtained in this way are again subjected to the simultaneous addition of solutions ■ and solutions ■.
5 minutes after restarting the addition of the solution, add the solution (■) over a period of 5 minutes, and while adjusting the addition rate of the II solution so that the PAg value of the mixed solution becomes 7.50, add the solution (■) over a period of 40 minutes at 75°C. The entire amount was added. In this way, the final average particle size is 0. 28μ
A cubic core/shell emulsion of m was obtained. The operations after water washing and desalting are exactly the same as for raw milk #1. In this way, an internal latent image type cubic core/shell emulsion whose surface was chemically amplified was obtained. (Raw milk #2) Raw emulsion #2 is a so-called core/shell type internal latent image emulsion, and when used in combination with a nucleating agent, a positive image can be obtained directly in one development using a general-purpose microfilm processing solution. It is something that can be done.

A photographic material was obtained in the same manner as in Example 2, except that in the preparation of the emulsion layer in Example 2, the following nucleating agent (compound 2) was added so that the coating amount was 394 .mu./M.

Zoshin Prisoner 1 (Compound ■) S0 1I;1 Cll ZC3 Cll Evaluation of sharpness was performed in the same manner as in Example-2.

For the 8.r value of the residual color, a film exposed to obtain Dmin was used instead of the unexposed film used in Example-2. The rest was carried out in the same manner as in Example-2.

The development process was performed in the same manner as the negative development process of Example-2.

Claims (3)

[Claims] (1) A silver halide photographic material comprising a hydrophilic colloid layer containing at least one compound represented by the following general formula (I) or (II) as a solid fine particle dispersion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydrogen atom, an alkyl group, an aryl group, and R^ 2, R^3, R^4, R^5 each represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, an amino group, and L^1, L^2, L ^3, L^4, L^5 each represent a methine group, m and n each represent 0 or 1,
R^6 represents a hydrogen atom or an acyl group, R^7, R^8
, R^9, R^1^0, and R^1^1 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a carboxyl group. ) (2) The silver halide photographic material according to claim 1, wherein each of the compounds represented by formula (I) or (II) has at least one carboxyl group. (3) At least one compound represented by general formula (I) or (II) is contained as a solid fine particle dispersion, and at least one compound represented by the following general formula (III) is contained as a solid fine particle dispersion. A silver halide photographic material according to claim 1, which is characterized by: General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2^1 is a hydrogen atom, an alkyl group, an aryl group, a cyano group, -COOR^2^3, COR^2^3, -
CONR^2^3R^2^4, -OR^2^3, -NH
Represents COR^2^3, R^2^2 represents a hydrogen atom, an alkyl group, or an aryl group, and L^1^1, L^1^2
, L^1^3, L^1^4, and L^1^5 each represent a methine group, m' and n' each represent 0 or 1, and R^2
^3 and R^2^4 each represent a hydrogen atom, an alkyl group, or an aryl group. However, the compound represented by the general formula (III) has at least one group selected from a carboxyl group, a hydroxyl group, and a sulfonamide group in the molecule. )