JPH02191942A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having a dyed hydrophilic colloidal layer which is irreversibly decolored by photographic processing by incorporating a dye represented by a specified formula as fine powder in a dispersed state. CONSTITUTION:This sensitive material contains at least one kind of dye represented by formula I, wherein R1 is alkyl, aryl, cyano, etc., or halogen, each of R2-R4 is H, halogen, alkyl, alkoxy, alkylamino, dialkylamino, arylamino or diarylamino, R5 is H, alkyl or benzyl, each of Za-Zc is -N= or a structure represented by a specified formula, R6 is alkyl or aryl and n is 0 or 1. The dye contains at least one carboxyl, alkylsulfonamido or arylsulfonamido group in the molecule.

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 light-sensitive material comprising a hydrophilic colloid layer containing a dye to be eluted or a hydrophilic colloid layer.

(Prior Art) In silver halide photographic materials, the photographic emulsion layer or other 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 provided on the photographic light-sensitive material 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, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

It is based on the fact that light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion layer again. Between the photographic emulsion layer and the support, for the purpose of preventing image blurring, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of multilayer color photosensitive materials,
An antihalation layer may be placed between each layer.

More X#! In photosensitive materials, a colored layer is sometimes provided as a loss-over cut filter to reduce crossover light and to improve sharpness.

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

These layers to be colored often consist of hydrophilic colloids, and therefore dyes are usually incorporated into the layers for coloring. This dye must satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. Point 9: No adverse effect in a chemical sense on the performance of the silver halide photographic emulsion layer, such as a decrease in sensitivity, latent image regression, or fog.

(3) Although it is decolored during the photographic processing process, it is dissolved and removed and does not leave any harmful coloring on the photographic material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known. For example, British patent no. θ6゜jjj issue, same / , /
77, No. 429, same/13//,! /No.1, same/,
33♂, 2 Tata issue, same/.

3?6.37/issue, same/, 4 to Otsu7. J/4 No., same/
, +133. /θ2 No. 2, same/ , jjj, No. 116,
Tokukai Shoda ♂-♂J, No. 30, rotating tar//4t.

No. 4120, jO-/4t7,772, jj-/
l/, 2jJ No., same j/-/g3, 34tλ No., same j9
-37.7'12, same! War///, 4 da/, same j9-///, 4 da O, U.S. Patent No. 3°, 2 da 7.
7.27, 3.4tg, Wa/j, 4t, 07
7.933, etc., oxonol dyes having a pyrazolone nucleus or a barbylic acid nucleus, US Patent No. J, j
jj, 4?72, same! , 379°! No. 33, British Patent No. 1. Other oxonol dyes described in KO2♂, 6KO/No., etc., British Patent No. 37! , 4ri No. 7, 61θ
, No. 637, from the same? , No. 423, 7r4.907
No. 907゜i, zs, No. 041j, 609, U.S. Patent No. 4t, 2J-j, 326, JP-A-39
-2//, the azo dye described in θ4t No. 3, etc., JP-A-Sho! θ-700,176, j4t-//l, λgua, British Patent No. θ/4t, J-9/7! O1
Azomethine dye described in θ3/etc., U.S. Patent No. 2
, anthraquinone dye described in /47,7// issue,
U.S. Pat. No. λ, 137.009, identical.

611.3<1/No. 2, j3t, No. 00♂, British Patent No.! ♂4t, ≦Ori issue, same/, 2/θ, Kojko issue, Tokukai Sho! σ-ta0.6-! No. J-/-j.

No. 623, same j/-/θ, octopus No. 7, same! Da//? ,
λ4t7, special public Shogu J'-3,276, same! Day 3
Arylidene dyes described in No. 7.303 etc., Tokko Shoko t-3. θ/2, same Geta/6, j941, same!
Tar2/,! Wow! Styryl dyes described in British Patent Nos. A4TT, TTJ, 33J, 22, and JP-A-1999-22? , 2jθ, etc., British Patent No. 1.07! , 633
No., same/.

/33.797, same/, co/g, 230, same/, 4
t7! , λλ♂, same/, f'lλ, merocyanine dyes described in US Patent No. 2゜r4ts,
Examples include cyanine dyes described in No. 4trt, No. 3, 2ri 4t, No. 13, and the like.

Among these, oxonol dyes, which have two pyrazolone nuclei, have the property of being decolorized in developing solutions containing sulfites, and are used as dyes for photographic materials as useful dyes because they have little negative effect on photographic emulsions. has been used.

However, some dyes belonging to this family have little effect on the photographic emulsion itself, but they have a negative effect on the spectrally sensitized emulsion.
It has the disadvantage of causing a decrease in sensitivity, which may be caused by spectral sensitization in unnecessary areas or by desorption of the sensitizing dye.

Furthermore, due to the speeding up of development processing that has become popular in recent years, some residual particles may remain after processing. In order to solve this problem, it has been proposed to use dyes that are highly reactive with sulfite ions, but in this case, the stability in the photographic film is insufficient, and the concentration may decrease over time. It has the disadvantage that the desired photographic effect cannot be obtained.

On the other hand, if the colored layer is a filter layer or an anti-ration 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 usually necessary to prevent coloring from occurring substantially. This is because, otherwise, not only the effect as a filter layer or an antihalation layer will be reduced, but also a harmful spectral effect will be exerted on other layers. There are several methods for selectively coloring a specific hydrophilic colloid layer. The most frequently used method is to localize the dye in a particular layer by interaction with the dye molecules (considered as charge attraction and hydrophobic bonding).

However, when mordant methods are used, wet contact between the dyed layer and another hydrocolloid layer often results in a pore in which a portion of the dye diffuses from the former to the latter. The diffusion of the dye depends not only on the chemical structure of the mordant, but also on the chemical structure of the dye used.

Still, when a polymeric mordant is used, residual coloring on the light-sensitive material is particularly likely to occur after photographic processing, especially after shortened processing times. This is because although the binding force of the mordant to the dye becomes considerably weaker in an alkaline solution such as a developer, some binding force still remains, so the dye or reversible decolorization product remains in the layer containing the mordant. This is thought to be because.

Further, as another means for fixing the dye in a specific layer in a photographic material, JP-A-Shojt-/, No. 2439, Ibid. j-/3j3
jθ number, same j3-/j63! / issue, 32-927/6
No. 43-/9794t3, European Patent Oθ/
! 6θ/B/No., same O core 4j44A/No., world patent z
r/θ4t? It is known to have dyes present in dispersed solid form as disclosed in the Tada issue. However, according to our experiments, these dyes diffuse into other layers. Furthermore, when rapid processing is performed, dyes remain in the photosensitive material after photographic processing, making it impossible to obtain the desired effect. Ta.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to color a hydrophilic colloid layer with a dye that is irreversibly decolored by photographic processing and does not have an adverse effect on the photographic properties of the photographic emulsion. An object of the present invention is to provide a silver halide photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having a hydrophilic colloid layer in which only a desired hydrophilic colloid layer is sufficiently selectively dyed with a dye, and which has excellent decolorization properties through photographic processing. That's true.

A third object of the present invention is to provide a silver halide photograph having a dyed hydrophilic colloid layer which does not adversely affect the photographic properties of the silver halide emulsion layer even with aging. The purpose of the present invention is to provide photosensitive materials.

(Means for Solving the Problems) The above objects are achieved by (1) a silver halide photographic material containing at least one dye represented by the following general formula (1).

1JC=lJ.

In the formula, R1 is an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, amido group, carbamoyl group, alkylcarbamoyl group, dialkylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, sulfamoyl group, alkylsulfamoyl R2, R3 , R4 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group.

R5 represents a hydrogen atom, an alkyl group, or a benzyl group.
0Z a, Z b, Z c bar N=-j fr-
Halo! -('= represents an alkyl group or an aryl group. including.

(2) Achieved by a silver halide photographic material containing a dye of the above general formula (Natsuon) in a microcrystalline dispersed state.

In more detail, the dye represented by general formula (1) will be explained.

In the formula, R1 is a carbon/~g alkyl group (e.g., methyl, ethyl, 2-methoxyethyl, λ-cyanoethyl, λ
-hydroxyethyl, 3-carboxypropyl, benzyl, etc.), aryl groups having 6 to 10 carbon atoms (e.g., phenyl, p-carboxyphenyl, m-hydroxyphenyl, p-)f ruphenyl, p-methanesulfonamidophenyl, etc. alkoxy groups having 7 to y carbon atoms (e.g. methoxy, ethoxy, λ-methoxyethoxy, etc.), aryloxy groups having 6 to 10 carbon atoms (e.g. phenoxy,
p-methylphenoxy, p-carboxyphenoxy, etc.), acyl groups with 2 to θ carbon atoms (e.g. acetyl, benzoyl, etc.), carboxyl groups, alkoxycarbonyl groups with 2 to 2 carbon atoms (e.g. methoxycarbonyl, ethoxycarbonyl groups), l/f = L, λ-methoxyethoxycarbonyl), an aryloxycarbonyl group having 7 to 10 carbon atoms (e.g., phenoxycarbonyl, p-methylphenoxy7carbonyl, etc.), an amide group having a carbon number of /~ (e.g. , acylamino, N-methylacylamino, etc.)
, carbamoyl group, alkylcarbamoyl group having a carbon number of λ to O (for example, methylcarbamoyl, 2-hydroxyethylcarbamoyl, dialkylcarbamoyl group having 3 to 7 carbon atoms (dimethylcarbamoyl, dicohydroxyethyllupamoyl, etc.), carbon number /~B alkylsulfonamide group (e.g. methanesulfonamide, n-
Flobilsulfonamide, N-methylmethanesulfonamide, etc.), arylsulfonamide group having 6 to /θ carbon atoms (e.g. benzenesulfonamide, p-methylbenzenesulfonamide, etc.), sulfamoyl group, carbon number /θ
~B alkylsulfamoyl group (e.g. methylsulfamoyl, ethylsulfamoyl, etc.), carbon number 2~B dialkylsulfamoyl group (e.g. dimethylsulfamoyl, diethylsulfamoyl, etc.), carbon number 6 ~
Arylsulfamoyl group (phenylsulfamoyl, tolylsulfamoyl, etc.) of IO, mono- or dialkylamine group (such as methylamino,
(dimethylamino, etc.), arylamino groups (e.g., phenylamino, p-methoxyphenylamino, etc.), ureido groups (e.g., ureido, methylureido, etc.), alkylsulfonyl groups (e.g., methanesulfonyl, n-propylsulfonyl) with a carbon number of ), 71J-sulfonyl group (e.g., phenylsulfonyl), hydroxy group, cyano group, halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), and R2, R3, R
4 is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group (e.g., methoxy, ethoxy, etc.) with a carbon number/~g, an alkyl group (e.g. methyl, ethyl, etc.) with a carbon number/~g, respectively. ), carbon number/~B alkylamino group (e.g. methylamino, ethylamino, etc.), carbon number/~B dialkylamino group (e.g. dimethylamino, diethylamino, dicarboxymethyl,
N-methyl N-carboxymethyl, dihydroxyethylamino, N-ethyl-N-methanesulfonamidoethyl, etc.), arylamino groups (e.g. N-methyl-N-phenylamino, N-methyl N-p-carboxyphenyl, etc.) , diarylamino group (for example, diphenylamino), etc. Further, R2, R3, and R4 may form a t-membered ring via a nitrogen atom (for example, eurolidine). R5 represents a hydrogen atom, an alkyl group (for example, methyl, ethyl, etc.) having 1 to 3 carbon atoms, or a benzyl group. Za
, ZbXZc represents -N= or -C=, and R6 is an alkyl group having a carbon number of /~/θ (e.g., methyl, ethyl,
Carboxyethyl, etc.) Aryl group with carbon number g~/θ (
Examples: evaphenyl, p-carboxyphenyl fZ). n represents Q or /.

However, the molecule contains at least one carboxyl group, alkylsulfonamide group, or arylsulfonamide group.

Next, specific examples of general formula (1) used in the present invention will be given, but the present invention is not limited thereto.

/.

/3゜ /44 /l /, 2゜ /2 /lr.

/the law of nature −〇.

23° J/.

2 Hiro Koyuko The compounds used in the present invention are compounds represented by -maximum (II) and -maximum (lft) as described in US Patent No. 370! !
It can be obtained by heating and reacting in a polar organic solvent as disclosed in No. 96, No. 37j73θ, No. 3//θ26/, and JP-A-60-213232.

General formula (It) R1 General formula (III) R1, R2, R3, R4, R5, Za, Zb, Zc, n
has the same meaning as above.

Synthesis example/(compound) λ,6-dimethyl-/H-pyrazolo(/ , , 1-b
) (z, koe ” ') ) Riazor jg and da N.

Dissolve N-dicarboxymethylbenzaldehyde/g in ethanol-〇〇ml, add 2ml of acetic acid, and heat to reflux. After cooling, the precipitated crystals were collected and washed with cold ethanol to obtain 4 tg of compound -. Melting point 21θ0
C or more λmBz! / /nm0 Synthesis example (compound /
θ) λ-m-carboxyphenyl-4-methyl-/H-pyrazolo (/, j-b) (/, 2,4t) triazole 3 g
and aN,N dimethylbenzaldehyde/g were dissolved in 100 ml of ethanol, θ, jml of acetic acid was added, and the mixture was heated under reflux for 2 hours. After cooling, the precipitated crystals were collected and washed with cold ethanol to obtain 7 g of the compound /θ. Melting point, 2/θ0C or higher λ:! n1°Hj/! nm0 Generally, the dye of general formula (1) has an area on the photosensitive material/per m2/
~/θθθmg is used. Preferably, it is about rθθmg/7m 2 .

- When using the dye shown in maximum (1) as a filter dye or antihalation dye, any effective amount can be used, but the optical density θ, θ! No,
3. ! It is preferable to use it within the range of . The addition time may be any step before coating.

The dyes according to the invention can be used both in emulsion layers and other hydrophilic colloid layers.

(2) A method for dispersing the dye of the present invention as a microcrystalline dispersion is to dissolve it in a weakly alkaline solution, add it to a hydrophilic colloid layer, and then adjust the pH to make it slightly acidic to produce a microcrystalline dispersion. Alternatively, it can be formed using a known milling method such as ball milling, sand milling, colloid milling, etc. in the presence of a dispersant.

In addition, suitable solvents such as methyl alcohol, ethyl alcohol, flobyl alcohol, methylcellosolve, halogenated alcohols described in JP-A-971J and U.S. Pat. No. 3,736,100, acetone, water, pyridine Alternatively, it can be dissolved in a mixed solvent of these and added to the emulsion in the form of a solution.

The dye particles in the dispersion are less than 70 μm, more preferably 7
It has an average particle size of less than 2 m.

(2) A method in which a solution of a compound dissolved in an oil, that is, a substantially water-insoluble high-boiling solvent having a boiling point of about /lo'c or higher, is added to a hydrophilic colloid solution and dispersed.

As this high boiling point solvent, US Patent No. 2.322゜02
7, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl heptophosphate), citric acid acid esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesate esters (e.g. dibutoxyethyl succinate, diethyl azelate), For example, tridutyl trimesate) can be used. Also, the boiling point is about 3
θ0C or about/! Organic solvents of θ0C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, -butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, and methyl cellosolve acetate, and solvents that are easily soluble in water, such as methanol and Alcohols such as ethanol can also be used.

Here, the usage ratio of dye and high boiling point solvent is 10 to t.
/io (weight ratio) is preferred.

(2) A method of incorporating the dyes and other additives of the present invention into a polymer latex composition filling a photographic emulsion layer or other hydrophilic colloid layer.

Examples of the polymer latex include polyurethane polymers, polymers polymerized from vinyl monomers [suitable vinyl monomers include acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
dodecyl acrylate, glycidyl acrylate, etc.),
α-substituted acrylic ester (methyl methacrylate,
butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butylacrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinegar [vinyl, vinyl butyrate, etc.)], norogenated Hinyl, (vinyl chloride, etc.)
, vinylidene chloride (vinylidene chloride, etc.), vinyl ethers (vinyl methyl ether, vinyl octyl ether, etc.), styrene, x-substituted styrene (α-methylstyrene, etc.), nuclear substituted styrene (hydroxystyrene,
(chlorostyrene, methylstyrene, etc.), ethylene, furopyrene, styrene, phthalene, acrylonitrile, etc. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomers as a minor component. Other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, and the like. ] etc. can be used.

These filled polymer latexes are special! /-39/
No. 33, Tokukai Sho! /-! Tag No. 3, same j3-737/
3/issue, same j goo 32! ! λ No., same j4t-/θ Kuta 4
t1, same jj-/33g 6j, same j6-/ri Qda3
It can be produced according to the method described in No. J6-/904T7, J Otsu-/Kotrio No., and J7-/Dawa θ3♂.

Here, the usage ratio of dye and polymer latex is /
θ to ///θ (weight ratio) is preferable.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may be oligomers or polymers.

For details of this polymer, please refer to
It is stated in No. 2.

(2) A method in which a hydrophilic polymer is used in place of the high-boiling point solvent or in combination with the high-boiling point solvent in (1) above. This method is described, for example, in U.S. Pat. No., West German patent/
,? j7, &, <7.

■ Tokukai Akira? - A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group, etc. in the side chain as described in No. 341341.

In addition, in the hydrophilic colloid dispersion obtained above, for example, Tokkosho! The lipophilic polymer hydrosyl described in No. 3273j may be added.

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 that can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide.

The silver halide grains in the photographic emulsion layer may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape.
It may have a crystalline form (egular) or a composite form of these crystalline forms.

It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

It may also be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion), or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image emulsion, a pre-fogged direct reversal emulsion). It may be.

The silver halide emulsion used in the present invention has a thickness of 0.5 microns or less, preferably 0.3 microns or less, a diameter of preferably o, t microns or more, and grains with an average aspect ratio of 5 or more in the entire projection. of area! It may be a tabular grain that occupies θ or more. For more information on tabular emulsions and how to use them, please see Research Disclosure (RE).
SEARCHDISCLO8URE)Item22! j
41, p, 20~p, j/ (Jan,, /ri/
3), same 1tem22j30, p, ko37~p, 2a
O(May, lq, rj), etc.

Further, the silver halide emulsion used in the present invention may be a monodisperse emulsion in which grains having a grain size within the range θ of the average grain size account for j% or more of the number of grains.

The photographic emulsion used in the present invention is P.
, Glafkidea), Chimie erPhysi Photography (Chimie erPhysi)
que Photographique) (published by Beaumontel, /947), G.F. Duffin (G.
, F. Duffin), Photography)-x.

Martha” 1-Chemistry (Photography
cEmulsion Chemistry (7th Orcal Press, / 6th Year), Bouy El Zelikman (V.

Making and...
Coating Photographic Emulsion (M
making and coating photogr
aphicEmulation) (published by Orcal Press, 1996).

In addition, during the formation of silver halide grains, in order to control grain growth, ammonia, rhodanpotash, rhodanammonium, thioether compounds (for example, U.S. Pat. 3.j74t, No.62♂, No.3, 2θg, No.730, No.2.27゜937, No.4t, λ76.3
7ta, etc.), thione compounds (e.g., JP-A No. 3-/4)
t'13/9, same No. j3-♂, 2da θ1, same No. 31
-77737, etc.), amine compounds (e.g. JP-A No. 77737, etc.), amine compounds (e.g.
4t-/Qθ7/7), 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.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel (H.

Die Grundlagen
er Photography Proze
sse mit Silberhalogeniden)
(7 Kademitssiefuerlagusgeserjacht /9
The method described on pages 62j to 234 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization using noble metal compounds (e.g., total complex salts,
Pt, Ir.

A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, inzimidazoles (particularly nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptothiazoles (especially l-phenyl-j-mercaptotetrazole), mercaptopyrimidines: the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo Compounds such as oxazolinthione; azaindenes such as tetraazoindenes (
In particular, many compounds known as antifoggants or stabilizers can be added, such as hydroxy-substituted (/, 3, 3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; can.

The present invention allows the use of various color couplers, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) It is described in the patent described in Tomb 77 Otsu 413, ■-C to G. As dye-forming couplers, the three subtractive primary colors (i.e. yellow, magenta and cyan)
A coupler that gives color development -tl' is important, and specific examples of diffusion-resistant 4Q-equivalent or λ-equivalent couplers include the couplers described in the patents described in RD/74; In addition, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is a hydrophobic one having a pallast group. - Pyrazolone and pyrazoloazole couplers may be mentioned.

! The -pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. Couplers that can also form cyan dyes that are stable against humidity and temperature are
Typical examples that are preferably used include phenolic cyan couplers having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 3.77J, 002; 2. j-diacyl amino substituted phenolic coupler, having a co-position niphenylureido group and! These include phenolic couplers having an acylamino group at the - position.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Specific examples of magenta couplers are described in US Pat.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat.
/20 etc.

Specific examples of polymerized magenta couplers are described in U.S. Pat.
I, No. 367.272, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD/744tj,
The patent couplers described in paragraphs 1-2 are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. 2. θri 7°/4tO No. 2. /3/
, No. 717.

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

The silver halide photographic emulsion of the present invention may contain known water-soluble dyes other than the dyes disclosed in the present invention (for example, oquinonol dyes, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. It may be used in combination with (dye). Further, as a spectral sensitizer, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

The photosensitive material of the present invention also contains anti-fading agents, hardeners, anti-color capri agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, including the aforementioned RD-7.
It is described in 2tys etc.

The finished emulsion is prepared on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
Applied on other plastic bases or glass plates.

The silver halide photographic material of the present invention includes color positive film, color beno e-, color negative film,
Color reversal (sometimes with couplers, some without), photographic light-sensitive materials for plate making (e.g. lith film, lith dupe film, etc.), light-sensitive materials for cathode ray tube displays (e.g. emulsion X-ray recording light-sensitive materials) materials, materials for direct and indirect photography using screens), silver salt diffusion transfer process (Silver 5alt diffusion transfer process)
transfer process), photosensitive material for color diffusion transfer process, die transfer process (fmbibition transfer)
photosensitive materials for heat development, etc.

Exposure for obtaining a photographic image may be carried out using a conventional method. That is, any of a variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, etc. Exposure times are typically those used in cameras // / 000 seconds to 7 seconds, as well as exposures shorter than 777,000 seconds, such as those using xenon flash lamps or cathode ray tubes //
104~///o A 6 second exposure can be used, or a longer exposure of 7 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, r-rays, α-rays, or the like.

For photographic processing of the light-sensitive material produced using the present invention, any of the known methods and known processing solutions as described in the above-mentioned RD-/7 Book Z3 can be applied.

Processing temperature starts from normal/♂! o It is chosen between 0C, but
/, the temperature may be lower than 1r0C or higher than 60°C.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known secondary aromatic amine developer, such as phenylenediamines (e.g., daramino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, guamino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-y-amino-N-ethylaniline , guamino-3-methyl-N-ethyl-N-/-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Processing Chemistry" by F. A. Menn, published by Focal Press (/
94. 22t~ko λ page of 2003), U.S. Patent λ, / dej
, 0/j, same λ,! ri2,36g issue, JP-A-4tt-
Those described in gp733 etc. may be used.

The developer may also contain pH buffering agents such as alkali metal sulfites, bisulfites, carbonates, borates, and phosphates;
Development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants may be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers,
Competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifying agents, US Pat. ! 3.7 Jj
The polycarboxylic acid-based quivit agent described in No.
LS), z, 6 ko.

It may contain the antioxidant described in No. 930.

The pH of the developer is preferably 2 or more, and more preferably 9 or more. The concentration of sulfite or bisulfite in the developer is preferably lθ-3 mol/liter or more, more preferably 10-2 mol/liter or more.

Preferably, the fixer or bleach-fixer contains sulfite or bisulfite.

Bleach solutions, bleach-fix solutions, and their prebaths may contain compounds already known as bleach accelerators, such as U.S. Pat.
ty/specification, German Patent No. 1 θ♂/ko specification, same θ! Ta? // No. Specification, JP-A No. 3-32236
No. Publication, same! 3-57t37, 37g/♂, jJ-6j73, 33-72go23, j3-? j Otsu No. 30, same! 3-ta! Otsu No. 3/publication, same j3-/θ4t232 publication, same 73-/2da4
tλy issue, same! 3-Hari No. 623, same j3-.
Compounds having a mercapto group or a disulfide group as described in 2/4t, 2J Publication, and Research Disclosure No. 17/2W, thiazolidine derivatives as described in JP-A No. 2003/1997/4tθ/Co9, Tokuko Akira&j
-JrjO/, Publication No. 12-20!3.2, Publication No. J3-3223J, U.S. Patent No. 3206
The thiourea derivative described in Yo67, German Patent No. 1/27? The iodide described in JP-A-37-/1-236, German Patent No. 76-970, same 7g? 4t? Polyethylene oxides described in the specification of No. θ, Japanese Patent Publication No. 41J-J'! The polyamine compound described in Japanese Patent Publication No. 34, JP-A-Sho Geta-4T2-G34, is published in the same Data! ri 6 guda issue, same! 3-W IIt9
core publication, j4t-36727 publication, jj-2
tJr06 publication, 3F-/63 tag θ publication, etc. can also be used together.

The processing method of the present invention comprises the processing steps such as color development, bleaching and low fixing as described above. After the fixing step or bleach-fixing step, processing steps such as washing with water and stabilization are generally performed; A simple treatment method such as performing only a stabilization treatment step can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a liquid having a buffering capacity of pHj to B, a liquid containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

In addition, the stabilization process may be carried out using two or more tanks if necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for example, 2 to 2 stages), and furthermore, the water washing process can be omitted. can.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericidal or antifungal agents that prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, surfactants that prevent drying load and unevenness, and the like can be used. Or, l,, E, West,
“WaterQuality Cr1teria” 7
Autograph Science and Engineering Link (Photo.

Sci, and Eng,), VOl, ?
Compounds described in A g page J da 4t to 3j (/ri 6ri) etc. can also be used.

Further, the washing step may be carried out using more than one tank if necessary, and the washing water may be saved by carrying out multi-stage countercurrent washing (for example, λ to three stages).

(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 light-sensitive material containing the compound of general formula (1) of the present invention is easily decolorized or eluted by photographic processing, provides low Dmin and does not reduce sensitivity, and has the advantage that there is little decrease in sensitivity due to storage. have.

Further, the silver halide photographic material of the present invention provides images with improved sharpness. In addition, photographs obtained from the silver halide photographic material of the present invention do not cause staining, 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 examples.

Example/ (Preparation of emulsion A) A silver nitrate aqueous solution and a sodium chloride aqueous solution containing ammonium hexachloride rhodium(III) in an amount of θ, jX/θ−4 mol per mol of silver were mixed at 3!0 C by a double jet method. They were mixed in a gelatin solution while controlling the pH to 6.3 to prepare a monodisperse silver chloride emulsion with an average grain size of 0.07 μm.

After particle formation, the soluble salts are removed by flocculation methods well known in the art, and the stabilizers 9-hydroxy-6-methyl-/, 3°3a, 7-tetraazaindene and /-phenyl-yo-mercaptotetrazole was added. How much gelatin is contained in emulsion/kg? ! g1 silver was 707g. (Emulsion A) (Preparation of photosensitive material) Add the following nucleating agent and nucleation accelerator to the emulsion A,
Next, 1 polyethyl acrylate latex (3θQmg
/rn2), and -cJ as a hardening agent.

Terdichlor-6-hydroxy/3. j-) A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support to give a silver content of 3.5 g per 7 m2 by adding riazine sodium salt, and gelatin ( /, jg/m2), the compound of the present invention /θ (0.7g/m2), and the following 3 as coating aids:
A protective layer containing two surfactants, a stabilizer, and a matting agent was applied and dried.

(Sample/) Surfactant Addition amount (mg/mz) Stabilizer thioctic acid 6.0 Matting agent Polymethyl methacrylate (average particle size - 1 j μm ta, θ The compound of the present invention 10Fi) was created and used.

(Preparation of dye dispersion) 1 liquid A liquid CH2Cα)C6H,3 C)fcOOCe H2S 03Na /7g While stirring liquid B at 410°C, liquid 2 was added little by little.

(Preparation of Comparative Sample) /) A sample was prepared using the following dye instead of Compound 10 in Example/ (Comparative Sample/-A) Dye 3) Protection containing Compound 10 of the present invention in Example-/ Comparative sample /-C was prepared using the following protective layer instead of the layer.

Acid-treated gelatin 2.0g/m2
Mordant (0,075 g/m2) c) In Example 1, the following dye was used in place of Compound 10.

(Comparative sample/-B) This dye is exemplified in WOrr104t2 tada.

Dye 0.7jg/m2 CH3 07g/m2 Surfactant Φ C1□H23CONH(CH2)3N(CH3)2 (
CH2) 4803eθ, 63g7m2 Stabilizer thioctic acid o,oot Matting agent polymethyl methacrylate (average particle size 2.!μ) o,oo (performance evaluation) (1) The above three samples were prepared by Dainippon Screen Co., Ltd. It was exposed to light through an optical wedge using a bright room printer P-1.07, developed with the following developer at 31'C for 20 seconds, fixed by a conventional method, washed with water, and dried.

Basic recipe for developer Hydroquinone 10.0g N-methyl-p-aminophenol//cosulfate 0.3g Sodium hydroxide Borate J-sulfosalicylic acid Potassium sulfite Ethylenediaminetetraacetic acid Tetrasodium Potassium chloride bromide! -Methylbenzotriazole λ-mercaptobenzimidazole-osulfonic acid 3-(!-mercaptotetrazole) Sodium benzenesulfonate 6-dimethylamino-l-hexanol Sodium toluenesulfonate/If.

λQ.

30.

l / 0.

0g 0g 0g 0g /, 0g 10, Og O, Hiro g 0.3g 0.2g Hiro・　0g 1z,og Add water /1 Adjust the pH to 7 by adding potassium hydroxide.

As a result, the Example/and Comparative Sample/-A were completely decolorized, but yellow stains remained in Comparative Samples/-B and 1-C. Comparative sample/-33 was completely decolored when the development time was increased to 3Q seconds. As described above, the compounds of the present invention are rapidly processed and decolorized.

(2)! ! 1] Test of child variability The above-mentioned sample was exposed to light through a plain mesh screen using the above-mentioned printer, and was 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 /:/,
Exposure was carried out for twice as long as that exposure time and x times as long as that, and it was investigated how much the halftone dot area was enlarged. The larger the enlargement, the better the tone variability.

The results are shown in Table-/. As can be seen from the table, Comparative Sample 1/-A has a significantly reduced tone variability, whereas Sample 1 of the present invention has a high tone variability. this is,
Because the dye used in comparative sample t-AIC 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,
This is because the expansion of the halftone dot area was suppressed due to the irradiation prevention effect of the dye. On the other hand, compound 10 of the present invention exhibits high tone variability since it is fixed in the added layer.

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

Table - 1EIi child variability (indicated by increase in halftone dot area) (
3) Evaluation of contamination (stain) by reducing solution The strips of the samples of the present invention and samples of comparative examples obtained by processing in (2) above were added to the following Farmer's reducing solution at λθ0C for 6
It was immersed for 0 seconds, washed with water, and dried. As a result, in all the samples, the force was reduced to about 33t4 at 60% dot area, but in comparison sample i-C, intense brown staining occurred over the entire surface. No stain was observed in the samples of the present invention and comparative samples /-A and /-BK.

farmer reducer liquid When using, 1st liquid: 2nd liquid: water =10θ part:! Part: /θ0 part Mix with

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

Example λ Compound/4t1 and 2 in place of Example/Compound/θ
I used ri.

Similar to Example 1, it had excellent decolorization properties, tone changeability, and force reduction properties.

Example 3 A microcrystalline dispersion prepared in the same manner as described in the previous example was used as a dye layer with the following contents, and an emulsion layer and a surface protective layer with the following contents were applied on a primed 1732 m blue-dyed polyethylene terephthalate film. At the same time, both surfaces were coated to produce photographic materials 3-/-3-6.

(Contents of dye layer - per side) O Gelatin θ, /g/m 20 Dye microcrystalline dispersion Listed in Table 2 (Contents of emulsion layer) Brominating power in 1/2 liters of water! J j g % Potassium iodide 0.01g
.

30 g of gelatin, j% aqueous solution λ of thioether HO(CH2)2S(CH2)2S(CH2)20H.

Add j ee and maintain the temperature at 7j0c, add an aqueous solution of 33 g of silver nitrate and potassium bromide while stirring! .

WA' I g and an aqueous solution containing 0.726 g of potassium iodide were added in Qj seconds by a double jet method. Next, add calico bromide and tg, then add silver nitrate! .

An aqueous solution containing 33 g was added over 7 minutes and 30 seconds so that the flow rate at the end of addition was twice that at the start of addition. Subsequently, an aqueous solution of 3.3 ug of silver nitrate/j and an aqueous solution of potassium bromide were added at a potential of pAg? It was added in 23 minutes by a controlled double jet method while maintaining the temperature at . The flow rate at this time was accelerated so that the flow rate at the end of addition was twice as high as the flow rate at the start of addition.

After the addition is complete, add 2N potassium thiocyanate solution/jcc, and then add Ic/% potassium iodide aqueous solution! Occ to 3θ
Added over seconds. After this, lower the temperature to 3s'C,
After removing soluble salts by the sedimentation method, the temperature was raised to θ0C, and 6 g of gelatin, 2 g of phenol, and 7. jg, and pHt, t! due to sodium chloride and potassium bromide. , PAg♂ was adjusted to 10.

After raising the temperature to 6°C, 7jjmg of a sensitizing dye having the following structure was added. Sodium thiosulfate after 70 minutes
Hydrate j, jmg, potassium thiocyanate/13mg,
3.6 mg of chloroauric acid was added, and 1 minute later, the mixture was rapidly cooled and solidified. The resulting emulsion consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more. /3μm1 Standard deviation //, j%, average thickness is θ.

The aspect ratio is 767μm! ,/l.

The following chemicals were added to this emulsion per mole of silver halide to prepare a coating solution.

e2.6-bis(hydroxyamino)-dardiethylamino/, 3. J-triazine? 4t, j mg・
Sodium polyacrylate (average molecular weight, d/10,000) 2.7 g Ethyl acrylate/acrylic acid/methacrylic acid = 9j/2/3 composition ratio copolymer plasticizer, 2 g, rg Potassium bromide 77 mg emulsion The coating amount of the layer was as follows per one side: - Coated silver amount /, 7 g/m2 - Coated gelatin fk /, 7 g/m2 - Polyacrylamide (average molecular weight, !0,000) 0.4s7g/m2.

(Contents of surface protective layer) The coating amount of the surface protective layer was as follows per one side.

・Gelatin /, 4sg/m2・
Polyacrylamide (average molecular weight, !0,000) 0. ．． 27g7m2・Matting agent (average particle size 3.5μm) 0.03g7m2 Polymethyl methacrylate/Copolymer of methacrylic acid = Ri:/C16H330 (CH2CH20)IOH・C3H1
7So2N(CH2CH20)15H3H7 22-jmg/m2 θmg/m2 tmg/m2 ・(4H17SO2N(CH2CH20)4 (CH2
)4SO3NaC3H7/mg/m2-derhydeaxy-d-methyl-1,3,ja,7-tetrazaindene 2/,7mg/m2 Hardener: l,2-bis(sulfonylacetamido)ethane per side It was applied at a concentration of 57 mg/m2.

(Evaluation of photographic performance) For exposure of photographic materials 3-/~3-g, G-
I used Geclean. Photographic materials 3-/-3-6 were tightly sandwiched between two sheets of G-4 screen and exposed to X-rays through a water fan dome/.theta.cm according to a conventional method.

For processing after exposure, use Fuji Photo Film's RD-
[1] at 3!0C, using Fuji F manufactured by the same company as a fixer, and an automatic processor processing using FPM-<tθθO manufactured by the same company.

The sensitivity was expressed as a relative sensitivity where photographic material 3-/ was set to /θθ.

(Measurement of sharpness (MTF)) The MTF was measured using the combination of the Gt, t screen and automatic processor processing. 30μmXjθθμm a,
Measured with e-chure, the spatial frequency is /.

Optical density is 7.0 using MTF value of θ cycles/mm
It was evaluated in this section.

(Evaluation of residual color) Furthermore, the unexposed film of the photographic material described above was subjected to the above-mentioned treatment, and the level of residual color was sensory evaluated.

A... is a state where you can hardly tell that there is any residual color C...
・Condition E where you notice that there is a residual color, but it is not a big concern in practice: A condition where there is a clear residual color and the residual color becomes a concern in practical use, and B and D are intermediate conditions. And so.

The results of the above evaluation are shown in Table 1 along with the sample contents.

From Table C, it can be seen that the photographic materials J-4t to J-3-B of the present invention are excellent in the balance of relative sensitivity, sharpness (MTF), and residual color.

Comparison Compound/Compound of the Invention 27 Compound of the Invention, 2t/, 0g/g was removed, and the comparison compound λ C,1, Ac1d Violet/? was added to the sand on a glass filter. (C, 1, Q
J, <Jrt) Examples Paper support samples A, B and C were obtained after corona discharge treatment on a paper support laminated on both sides with polyethylene, using a gelatin subbing layer or the following dye dispersions: 〇 Dye dispersion method The following dye crystals were kneaded and made into fine particles using a sand mill. Further, citric acid θ, zg was dissolved in 21 ml of an aqueous lime-treated gelatin solution, and the sand used was filtered using a glass filter. ) Paper support A Undercoat layer gelatin ・・・・・・・・・ 0. ♂g
/m2 Paper support B No-ration fat-retaining layer gelatin ・・・・・・・・・ o, tg
/m2 Compound of the present invention J/ 2
3 mg/m2 Compound of the present invention Koda...
... tlOmg/m2 Paper support C) Sration prevention layer Gelatin ...... σ, tg
/m2 Compound of the present invention Col...... Da θmg/m2 Compound of the present invention, 2 Da...
... 63 mg/m2 On paper support samples A, B and C, multilayer color photographic paper samples Cool/Dark were obtained with the layer configuration shown below.

The coating solution was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) /g and color image stabilizer (Cpd-/) da, 4tg and (Cpd-7) /,
7 g of ethyl acetate λ7, . 2 cc and solvent (S
olv-j) and (Solv-d) each layer.

7 g was added and dissolved, and this solution was emulsified and dispersed in an aqueous solution of tisgelatin containing θtidedecylbenzenesulfonate sodium ♂CC.

- force field silver bromide emulsion (silver bromide rθ, θmolti, cubic, average grain size o, rjμ, coefficient of variation θ, θt,
Silver bromide to, o morti, cubic, average grain size 0.6
2μ, coefficient of variation Q, θ7 at a ratio of /:3 (Ag
A sulfur-sensitized product was prepared by adding the blue-sensitive sensitizing dye shown below in an amount of t, oxiθ-4 moles per 7 moles of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, /-oxy-3,j-diquaro-8-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

0a- (ft-lyz per mole of silver halide, oxlθ-4 mole) (F per mole of 6111 halide) 4t, OX /
θ-4 mol) and (1 t-ri per mol of silver halide 7.ox 10-
5 mol) To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6x/θ-3 mol per mol of silver halide.

Also, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, /-(r-methylureidophenyl)-! - mercaptotetrazole, respectively, halogen/(tJI1 mole f
ct) 4'-θ×/θ-6 mol, 3°0×/θ-5 mol, /,O 'X/θ-3 mole, co×10-2 2X10-2
Added.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, g-hydroxy-6-methyl-/,! , j&, 7-chitrazaindene per mole of silver halide, respectively.
2 moles, 1. /×/θ−2 mol was added.

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

represents.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye (ulmarine blue)] Samples A, A, B with a K undercoat layer and an antihalation layer,
species of C and 7.7 mg/m2 The above-mentioned silver chlorobromide emulsion (AgBr: Gelatin yellow coupler (ExY) Color image stabilizer (Cpd-/) (Cpd-7) Solvent (Solv-3) '(Solv- 6) 20 mol%) 0.26/1. ♂ 3 0, t3 Q, / 9 θ, Ot θ, / ♂ θ, //..., 2/mg/m2 (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion has a coating amount in terms of silver. Gelatin color mixing inhibitor (Cpd-6 Solvent (SOIV-/) (Solv-da) ) Silver chlorobromide emulsions (AgBr9θ morti, cubic, average grain size θ, guaμ, coefficient of variation θ, /λ and AgB
rqO molten, cubic, average particle size 0.36 μ, coefficient of variation 0.09 /2/ ratio (Ag molar ratio)
θ, /6 Gelatin 7.79 Magenta coupler (Ex M) 0.3.2 Color image stabilizer (Cpd-j) 0.20 (Cpd-j)
0.0J (Cpd-da) 0.0/ (Cpd-9) θ, θda solvent (SOIV-, 2), 0.6j gelatin /, jl ultraviolet absorber (UV-/) o, 4 layers 2 color mixture Inhibitor (Cpd-j) θ, Oj Solvent (Sol
v-j) 0.2tl silver chlorobromide (Ag
Br70 molti, cube, average particle size θ, 4t9μ
, coefficient of variation θ, θ♂ and Ag B r 70 molti, cubic, average particle size 0.34tμ, coefficient of variation θ,
10 and mixed at a ratio of /:2 (Ag molar ratio)) 0
．． 23 Gelatin / 3 Guccian coupler (ExC) 0.30 Color image stabilizer (
Cpd-6) θ, /7(Cpd-7)
θ, G0 Solvent (Solv-4) 0. , Z0 Gelatin Ultraviolet absorber (UV-/) Color mixing inhibitor (Cpd-, t) Solvent (Solv-j) 0, jj θ, / 6 0, θkoO, θ♂ Gelatin 7.33 Acrylic modification of polyvinyl alcohol Copolymer (degree of modification/7chi)
0. /7 Liquid paraffin 0.03 (Cpd-/) Color image stabilizer (Cpd-j) Color mixing inhibitor (Cpd-, <) Color image stabilizer (Cpd-j) Color image stabilizer (Cpd-g) Color image Stabilizer (JM Co:G:4 mixture (weight ratio) (Cpd-7) Color image stabilizer average molecular weight tθ O0 (Cpd-♂) Color image stabilizer 4t::G mixture (weight ratio) (3o1v -/) Solvent (cpa-2) Color image stabilizer (Solv-2) Solvent (UV-/) Ultraviolet absorber λ: /Mixture (volume ratio) (Solv-j) Solvent (ExY) Yellow coupler (Solv- g) Solvent (Solv-j) Solvent (Ex M) Magenta coupler Cα) C6H17 (CH2)a Cα) CgH17 (Solv-6) Solvent (ExC) Cyan coupler (manufactured by Fuji Photo Film ■, FWH type, color of light source temperature 3,
Stepwise exposure for sensitometry was provided through blue, green, and red filters using 2θθ'K). On the other hand, exposure was performed to measure resolution (CTF), and then the following development treatment was performed.

The concentration of the obtained sample was measured and the results shown in Table D were obtained.

When the dye according to the invention is used in the anti-nolation layer,
There is relatively little decrease in sensitivity and there is no noticeable residual color. By using such an amount, the resolution can be significantly improved.

(Processing process) Color development 37°0 3 minutes 30 seconds Bleach-fixing at 33°C 7 minutes 30 seconds Water Washing 2g~3a0c 3 revolutions Drying 20~rθ'C/min (processing solution) Color developer water ♂θO
ml diethylenetriaminepentaacetic acid/, θg nitrilotriacetic acid λ, θg/-hydroxyethylidene/.

/-diphosphonic acid (6θ solution) /, 0ml benzyl alcohol 11ml diethylene glycol 10ml sodium sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-guaminoaniline sulfate hydroxylamine Sulfate optical brightener (WHITEX 4t.

(manufactured by Sumitomo Chemical) Add water to pH (, lt'C) Bleach-fix solution water Ammonium thiosulfate <70%) Sodium sulfite Iron ethylenediaminetetraacetate (ammonium ethylenediaminetetraacetic acid disodium λ , 0g / , 0g 30g da , jg 3.0g / , 0g 7000ml 10.26 ooml /!Oml 72g jg Add water to pH (ko, t'c) Washing water Tap water is deionized using an ion exchange resin to reduce calcium and magnesium to 3ppm each. The pH of this water was A, and the pH of this water was A.

Rapidly developable color photographic paper (EP No. 273') prepared using support samples B and C and having a high silver chloride emulsion layer thereon
A29, No. 2734AJO, and patent application No. 1973-717
Similar results are obtained for the multi-layer structure described in , No. 7).

Example 1: On a cellulose triacetate film support with a primer coating,
Sample 10/, which is a multilayer photosensitive material having each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rn2 of silver for silver halide and colloidal silver, and the amount expressed in g/m2 for couplers, additives and gelatin.
The sensitizing dyes are expressed in moles per mole of silver halide in the same layer.

Note that the symbols indicating additives have the meanings shown below.

However, if a substance has multiple effects, one of them is listed as a representative.

Uv: ultraviolet absorber, 501v: high boiling point organic solvent, Ex
F: dye, ExS: sensitizing dye, ExC nitrogen coupler, ExM: magenta coupler ExY: yellow cazolar, cpct; additive black colloidal silver gelatin UV-/UV-CoUV-3 Solv-λ ExF-/ExF- λ 0 , / j θ , θ 3 θ , 06 θ , 07 θ , Q♂ O, θ / θ , θ / Silver iodobromide emulsion (Ag I 4t morch, homogeneous AgI type,
Equivalent sphere diameter 0.4tμm1 Coefficient of variation of equivalent sphere diameter 37chi,
Plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0. <1 Gelatin 00tExS
-/ 2. ,? X/θ-4ExS-j ExS-7 ExC-/ExC-j 7.4t×/θ-4 2,3X10-4 r, O×10-6 0, / 7 0, 03 0, / 3 Silver iodobromide emulsion (Ag I 6 molti, core shell ratio 2:
/'s internal height AgI type, equivalent sphere diameter θ, core! μm1 Coefficient of variation of equivalent sphere diameter 2j%, plate-shaped particles, diameter/thickness ratio 2.0)
Coated silver amount θ, silver iodobromide emulsion (Ag I 4t morch, uniform AgI type, equivalent sphere diameter 0.yμm1, coefficient of variation of equivalent sphere diameter 32%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount θ, / Gelatin / QExS-
/2×1O-4ExS-2/
,,2X10-4 ExS-t ko×1O-4ExS
−72×io 6 ExC-/ExC-2 ExC-j 0 , 37 θ , θ / θ , θ 6 Silver iodobromide emulsion (Ag I & Morch, core-shell ratio 2:
/ internal high AgI type, equivalent sphere diameter 0.7 μm1, coefficient of variation of equivalent sphere diameter, 2t%, plate-shaped particles, diameter/thickness ratio
Coated silver amount θ, Wagelatin
θ, tExS-/ /, , gX/
Q-4ExS-J/, tXlo-4E
xS-j /, tXlo-4ExS-7
ax/θ-4 ExC-10,07 ExC-da 0.0jSolv
−/θ, θ7Solv−λ
θ, θCpd-74t, bu×1
O-4 UV-4t
o, o3UV-j
o, oriCpd-/
0.7 polyethyl acrylate latex
Q, θ1Solv-/ θ, O
j Silver iodobromide emulsion (AgI4t morch, uniform AgI type, equivalent sphere diameter 0.<1 μm1, coefficient of variation of equivalent sphere diameter 37 inches, plate-like grains, diameter/thickness ratio, θ) Coated silver amount 0. /r Gelatin O,g ExS
-72×/θ-4 ExS-4t 7X/θ-4Ex
S-j /x10-4ExM-
, t θ, //ExM-7
0,0j ExY-10,θ/5olv-/θ,θri5o
lv-G θ, 0/gelatin 0, 6 Silver iodobromide emulsion (Ag I 4t mol%, core shell ratio/
:/ surface height AgI type, equivalent sphere diameter θ,! μm1 Coefficient of variation of equivalent sphere diameter - 〇chi, plate-like particle, diameter/thickness ratio g, 0)
Coated silver amount 0.27 gelatin
θ, 6ExS−j ko×
/θ-4ExS-4t 7X/θ-
4EXS-1/x70-4 Ex M -to, /2
ExM-70, QguEXY-J'0. θko5olv-/0. /41So
lv-da θ, θ cogelatin ExS-gE x S -j Ext-/ Ex M -J ExY-t ExY-, r ExC-/ ExC-g5olv-/ 5olv-co5olv-g Cpd-7 θ, /! ,,2 × 10-4 7×/ θ-4 0,3X/ θ-4 0, I O, θ3 0 , θ2 θ , θko θ , θ / θ ,, 2 I O, Oro 0 , O/ /×70-4 Silver iodobromide emulsion (AgI/, 7 molti, S amount ratio 3:da:2
Multi-layer structure particle, AgI content is 5 tit mole, 0 mole, 3 mole, equivalent sphere diameter 0.7 μm1, coefficient of variation of equivalent sphere diameter 2 -, plate-like particle, diameter/thickness ratio 7.6) Coated silver Amount 0.7 Gelatin Cpd-, t Polyethyl acrylate latex 5olv ~ / θ, 6 0.0 < 10, / Co θ, O Co silver iodobromide emulsion (AgI, core-shell ratio, internal height of AgI) Mold, equivalent sphere diameter 0.7μm1 Coefficient of variation of equivalent sphere diameter 2!chi, plate-like particle, diameter/thickness ratio 2.0
) Coated silver amount θ, 6/Silver iodobromide emulsion (AgI4t morch, uniform AgI type, equivalent sphere diameter 0.4t μm1, coefficient of variation of equivalent sphere diameter 37'lb% plate-like grains, diameter/thickness ratio 3.
0) Coated silver amount θ, / Tagelatin /, 0ExS-
j 4X/θ-4ExM-/θ
θ, /wa5olv-/
θ, θ Yellow colloidal silver gelatin Cpd-2 Solv-/ Cp d-/ Cpd-t H-/ 1st co-layer (low-sensitivity blue-sensitive emulsion layer) θ, θ iO, ♂ θ + / 3 θ, / 3 Q, θ 2 θ, θθkoO, / 3 Silver iodobromide emulsion (AgI da, ! Morch, uniform AgI type, equivalent sphere diameter 0.7 μm 1 Coefficient of variation of equivalent sphere diameter / 6%, tabular grains, Diameter/thickness ratio 7.O) Coated silver amount 0. J Silver iodobromide emulsion (AgIJ morch, uniform AgI type, equivalent sphere diameter 0.3 μm, reciprocal of fluctuation of 1 sphere equivalent diameter 3o'%, plate-like grains, diameter/thickness ratio 2.θ) Coated silver amount θ, /j Gelatin Ha♂ExS-t
tXlo-4ExC-10,06 ExC-da θ, θ3ExY-wa θ, /gExY-//
θ,! Wa5olv-10. Gucogelatin ExY-/J Solv-/ 1st G layer (high sensitivity blue-sensitive emulsion layer) 0.7 0.20 θ, 34t Silver iodobromide emulsion (AgI/θ morch, internal high AgI type, equivalent sphere diameter 1. 0 μm1 Coefficient of variation of equivalent sphere diameter 2!, multiple twinned plate-like particles, diameter/thickness ratio, θ)
Coated silver amount o, t gelatin
θ・! ExS-t /x10
-4ExY-90, θ/ ExY-// θ, 2θEx
C-/θ, Qko5olv
-/θ, /θ Fine-grain silver iodobromide emulsion (AgI2 molten, uniform AgI type, equivalent sphere diameter 080
7 μm) Coated silver amount θ, /2 Gelatin θ・Re UV-da
θ, //UV-, r
θ, /6Solv-30. θλ H-/ θ, /3Cpd-
j O,/θ polyethyl acrylate latex 0.0? Fine grain silver iodobromide emulsion (Ag
I2 morch, uniform AgI type, equivalent sphere diameter 0.07 μm) Coated silver amount 0. j & gelatin 0. j2 polymethyl methacrylate particles (diameter/, jμm) θ, coH-/
θ, /7 In addition to the above components, one emulsion of stabilizer Cpd-J (θ, 07g
/m2), surfactant Cp d -1 (0.03g/m
2) was added as a coating aid.

UV-/ UV-2 Solv-/ tricresyl phosphate o1v-2 dibutyl phthalate 5olv-da UV-3 Solv-j trihexyl phosphate ExF-/ x near = 70:jQ (wt%) UV-t ExF-2 Ext-/ ExS-ko E x S -6 ExS-7 ExS-r ExS　　　j ExS-G 'ExS-s ExC-/ ExC-2 H3 ExC-j ExM-j ExM-6 mul, wt, about ao, oo.

ExM-7 ExM-10 ExY-r ExY-9 Cpd-/ Cpd-, 2 Cpd-i H3 6H13 Eagle ExY-// Ex Y-/CoCpd-j Cpd-j cpct-gH-/ Furthermore, 1st For the Cpd-2 layer, Cpd-/ and 5olv-/ were dissolved together in ethyl acetate by heating at OoC, and then emulsified and dispersed in an aqueous gelatin solution containing sodium dodecylbenzenesulfonate using a household mixer. Mixed with silver halide emulsion.

(Preparation of sample jO-) Sample! In place of Cp d-J in the O/first/layer, the compound of the present invention -/ was substituted in an equimolar amount with Cpd-J. The method for dispersing the compound of the present invention is shown below.

Note that Cp d-J was removed (Cpd-/ and 5olv-/ dispersions were obtained in the same manner as in preparing sample 10/.Other than that, they were prepared in the same manner as sample jθ/.

Method for dispersing the compound of the present invention: Methyl ethyl ketone and sodium dodecylbenzenesulfonate were removed using an ultrafiltration membrane.

(Preparation of Sample! θ3) It was prepared in the same manner as sample jO2 except that the compound-3 of the present invention was used instead of the compound-3 of the present invention in the first layer of sample j02.

Samples of color photographic materials as above! 07~! After exposure to light of θ3, processing was performed according to the method described in Table-j.

Table-! Processing method A fine dispersion of the exemplified compound -/ was obtained by putting the first liquid into the barrel of a syringe and squirting it into the second liquid from a nozzle with a diameter of 0.2 mm. Next, the composition of the treatment liquid from this dispersion will be described.

Color developer (Unit: g) diethylenetriaminepentaacetic acid /-Hydroxyethylidene-/.

/-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate Gu [N-ethyl-N-(β- hydroxyethyl)amino] 1,2-methylaniline sulfate add water H bleaching solution /, θ ! ,0 Gu, Q jO,0 ／　＋　da /, jmg 2.4t the law of nature ,! 80L / θ, θJ (Unit: g) Ferric ethylenediaminetetraacetate ammonium dihydrate salt / 2θ, θ Ethylenediaminetetraacetic acid disodium lium salt ammonium bromide ammonium nitrate bleach accelerator Ammonia water (27ch) add water H bleach-fix solution Ferric ethylenediaminetetraacetate ammonium dihydrate salt Ethylenediaminetetraacetic acid disodium lium salt sodium sulfite Ammonium thiosulfate aqueous solution (70To> / θ + 0 100.0 / θ, θ 0.003 mole /j, Oml /、OL 6, 3 (Unit: g) 60° ! , θ /2, θ , 24t O.

θml Ammonia water (27ml) 6. θm/Add water /, 0L pH 7, λ Washing liquid Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-/CoOB manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR). -110θ) to reduce the concentration of calcium and magnesium ions to below j mg/L,
Subsequently, dibasic lithium salt solution was added to adjust the pH of the sample.The results shown in Figure 2 were obtained.

θ, θ! 80L ! , θ−! , θ tree and table- Table one second The pH of the liquid is 4. It is in the range of j-7,7.

Stabilizing liquid formalin [7%] Pholyoxyethylene-p-monononylphenyl ether (average degree of polymerization lθ) Ethylenediaminetetraacetic acid dinato (unit: g) 0 ml 0.3 Treatment residual color*: [In the treatment of this example Obtained Dmin (minimum concentration)] -
[Dmin obtained by further processing with a solution of KSSjθg/l for 70 minutes] By using the dye of the present invention in the yellow filter layer, it is possible to obtain a color photographic material with little loss of sensitivity and little residual color after processing.

Example 6 The blue-sensitive emulsion used in Example 6 was transformed into a silver chlorobromide emulsion (cubic, average grain size o, rμ) with a silver bromide content of 0.6 mol.
The coefficient of variation o, or) is the silver bromide content of the green-sensitive emulsion/,
λ Morch silver chlorobromide emulsion (cubic, average grain size Q,
≠ 2 μ coefficient of variation 007), and the red-sensitive emulsion layer was changed to a silver chlorobromide emulsion (cubic, average grain size o, tts μ coefficient of variation o, o7) with silver bromide content /, j morti. Samples 4-/6-Hiro corresponding to samples 4-/6-Hiro were prepared from sample 4-/6-Hiro in the same manner as sample 6-Hiro.

Each of the blue, green, and red emulsions contains the following spectral sensitizing dye and Cpd-10, and silver bromide exists in a part of the grains forming a localized phase.

Blue-sensitive emulsion layer (l per mole of silver halide)2, jx to
mole) and (#) co, j x 10 mole per mole of silver halide)
Green-sensitive emulsion layer (# per mole of silver halide, 0x10-' mole)
and (7, O x 0 mol per mol of silver halide) red-sensitive emulsion layer (O 0 x 10 mol per mol of silver halide) (Cpd-/<7) (respectively for each emulsion)・Silver rhodanide per mole
Using the obtained sensitive material (with 0-'mol added), the same tests as in Example ≠ were conducted using the following processing solution and processing steps, and the results shown in Table 7 were obtained.

Processing process Temperature Time Color development
Jj'C da! Bleach fixing Stable for 30-36°Cqj seconds ■ Stable for 20 seconds at 30-37°C ■ Stable for 30-37°C λO seconds ■ Stable for 2g seconds at 3Q-37°C ■ 3Q-37° (dry for 30 seconds)
70 to tz0c to seconds (Hirotank countercurrent flow from stable ■ to ■ was used.) The composition of each treatment liquid was as follows.

Color developer water 1r
00td Ethylenediaminetetraacetic acid 2.0g
Triethanolamine r, og Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-≠-aminoaniline sulfate N,N-diethylhydroxylamine j, A-dihydroxybenze/- 7 , 2, μ-trisulfonic acid optical brightener (4c, μ′-diaminostilbene water added to H) Bleach-fix solution water Ammonium thiosulfate (70%) Sodium sulfite l, Reference g 2j, Og 5.0 g 11, jg 0.3g ko, Qg iooo*t 10 .10 hirooctal oozl tg ethylenediamine/iron(II) tetraacetate Ammonium ethylenediaminetetraacetic acid disodium glacial acetic acid 11g 3g 3g Add water and add H 1000gj,j Stabilizing liquid formalin ( 37%) Formalin-sulfite adduct!-chloroλ-methyl-Hiro-inthiazolin-3-one 0.02g co-methyl-Hiro-isothiazolin-3-one o, otg sulfuric acid steel
Add 0.00gg water
1000ttttpH4'・O o,t g 0.7g Table 7 As shown in Table 7, sample bu-J%4-<< is sample 6
-2 had higher sensitivity in both the red and green sensitive layers. In addition, I) min of both samples J-j and 4-Hiro was as low as that of sample 6-2, and the resolution was higher than that of the other samples.

Claims (2)

[Claims] (1) A silver halide photographic material containing at least one dye represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 is an alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, amide group , carbamoyl group, alkylcarbamoyl group, dialkylcarbamoyl group, alkylsulfonamide group,
Arylsulfonamide group, sulfamoyl group, alkylsulfamoyl group, dialkylsulfamoyl group, arylsulfamoyl group, mono- or dialkylamino group, arylamino group, ureido group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, They represent a cyano group and a halogen atom, and R_2, R_3, and R_4 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group. R_5 represents a hydrogen atom, an alkyl group, or a benzyl group. Za, Zb, and Zc represent -N= or ▲There are numerical formulas, chemical formulas, tables, etc.▼, and R_6 represents an alkyl group or an aryl group. n represents 0 or 1. However, the molecule contains at least one carboxyl group, alkylsulfonamide group, or arylsulfonamide group. (2) The silver halide photographic material according to claim (1), characterized in that the dye is contained dispersed in microcrystals.