JPH03182742A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material which is photochemically inert and has hydrophilic colloidal layers by incorporating at least one kind of dyes having specific compds. in the state of fine powder dispersions into the material. CONSTITUTION:At least one kind of the dyes of formula I are incorporated in the state of the fine powder dispersions into the material into the silver halide photographic sensitive material. In the formula I, X, Y denote an electron attracting group, i.e. NC-, RCO-, etc.; L1 to L3 denote methyne; Z denotes the nonmetal atom necessary for forming a 5-membered heterocycle; n denotes 0, 1. At least one of the groups selected from a carboxyl group, sulfoneamide group and sulfamoyl group are incorporated into the molecule. R denotes a substd. or unsubstd. alkyl group, substd. or unsubstd. aryl group. The hydrophilic colloidal layers are colored in this way by the dyes which are irreversibly decolored by photographic processing and do not adversely affect the photographic performance of the photographic emulsion.

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. and/or a silver halide photographic light-sensitive material comprising a hydrophilic colloid layer containing a dye to be eluted.

(Prior Art) In silver halide photographic materials, photographic emulsion layers 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 a plurality of 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.

Furthermore, in X-ray photosensitive materials, a colored layer may be provided as a loss-over cut filter to reduce crossover light and to improve sharpness.

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 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. In other words, it should not adversely affect 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) 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.

Much effort has been made by those skilled in the art to find dyes that meet these conditions, and the following dyes are known:9 For example, British Patent No. 506°385;
No. 7.429, No. 1,311,884, No. 1,338
, No. 799, Ibid.

385.371, 1,467.214, 1.4
No. 33.102, No. 1,553,516, Japanese Unexamined Patent Publication No. 1973
-85,130, 49-114゜420, 50
-147,712, 55-161.233, 5
No. 8-143.342, No. 5L-38,742, No. 5
No. 9-111,641, US Pat. No. 59-111.640, US Pat. No. 3,247.127, US Pat. No. 3,469,985, US Pat. oxonol dyes having U.S. Pat. Nos. 2,533,472 and 3,379°533;
Other oxonol dyes described in British Patent No. 1,278,621, British Patent No. 575.691, British Patent No. 6
No. 80,631, No. 599.623, No. 786,90
No. 7, No. 907125, No. 1,045,609, U.S. Patent No. 4.255.326, JP-A-59-211.
Azo dyes described in No. 043, etc., JP-A-1988-100
．． No. 116, No. 5,1118.247, British Patent No. 2
, 014,598 and 750,031, anthraquinone dyes described in U.S. Pat. No. 2,865,752, U.S. Pat. No. 2,538
, No. 009, No. 2゜688.541, No. 2,538,
No. 008, British Patent No. 584.609, British Patent No. 1,210
．． No. 252, JP-A-50-40,625, JP-A No. 51-3
゜623, 51-10,927, 54-118
．． No. 247, Special Publication No. 48-3, 286, No. 59-37
, No. 303, etc., the azomethine dye described in Japanese Patent Publication No. 303, etc.
-3.082, 44-16.594, 51-2
Styryl dyes described in British Patent No. 8,898, etc., British Patent No. 446.583, British Patent No. 1,335,422, JP-A-5
9-228.250 etc., the triarylmethane dye described in British Patent No. 1. O'75,653, same 1゜1
No. 53.341, No. 1,284,730, No. 1.47
5.228, merocyanine dyes described in 1,542.807, etc., U.S. Pat.
Examples include cyanine dyes described in No. 3,294,539 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 photosensitive materials as useful dyes that have little negative effect on photographic emulsions. It's here.

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 been carried out 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, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are Substantially no staining is usually required. This is because, if not, not only the effect as a filter layer or an antihalation layer will be reduced, but also harmful spectral effects will not 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 mordanting methods are used, when the dyed layer and another hydrocolloid layer come into wet contact, it often occurs that some of the dye diffuses from the former to the latter. Such diffusion of the dye naturally depends on the chemical structure of the mordant, but also on the chemical structure of the dye used.

Furthermore, 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 time; this is because the binding strength of the mordant to the dye is This is thought to be because the dye or the reversible decolorization product remains in the layer containing the mordant because some binding force still remains, although it becomes considerably weaker in an alkaline liquid such as liquid.

In addition, as another means for fixing the dye in a specific layer in a photographic light-sensitive material,
No. 55-155350, No. 55-155351, No. 51-92716, No. 63-27838, No. 6
No. 3-197943, European Patent 0015601B
No. 1, No. 0276566A1, No. 274,723,
No. 276゜566, No. 299435, World Patent No. 88
It is known to present dyes in dispersed solid form, as disclosed in US Pat. However, according to our experiments, these dyes diffused into other layers, and when rapid processing was performed, dyes remained in the light-sensitive material after photographic processing, making it impossible to obtain the desired effect.

(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 (1) a silver halide photographic light-sensitive material containing at least one dye of general formula [I] in the form of a fine powder dispersion; achieved by

In the formula, X and Y each represent an electron-withdrawing group which may be the same or different, LI, Lx and La represent methine, and Z
represents a nonmetallic atom necessary to form a 5-membered heterocycle. n represents 0 or 1, provided that the molecule contains at least one group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group.

(2) Preferably, in general formula [I], X and Y may be the same or different, and represent NC-1RCO-00 II 11 RS Ot-1ROC-1RNHC-, and R is substituted or unsubstituted. represents an alkyl group, a substituted or unsubstituted aryl group, and has at least one carboxyl group, sulfonamide group, or sulfamoyl group directly bonded to an aromatic ring in the molecule.

LI, t, 2, L3, Z, and n are achieved by a silver halide photographic material characterized by containing at least one dye as in (1) in the form of a fine powder dispersion.

(3) Preferably, it is closely related to a silver halide photographic material characterized by containing at least one compound of general formula (It) in the form of a fine powder dispersion.

t In the formula, X and Y may be the same or different, and NC-
1 CO SO1 1 , ROC- 1 RNHC-, and 1 1 R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

L+, Lx, and Ls represent methine, and Zl represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and the heterocycle may further form a benzo fused metal ring. n represents O or l, provided that the aromatic ring present in the molecule has at least one group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group.

(4) Preferably, the silver halide is characterized by containing at least one of each of a fine powder dispersion of a dye represented by the general formula (II) and a fine powder dispersion of a dye represented by the general formula (III). Photographic materials are used as a warning.

General formula (I[[)% formula% Nyl, arylcarbonyl, alkoxy, hydroxyamino, carbamoyl, acylamino, cyano, acyl,
represents phenylsulfonyl, alkylsulfonyl, R
4 represents aralkyl, aryl, L, l, L
x and Ls have the same meanings as above, and m represents Oll, 2, provided that the molecule contains at least one group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group.

General formula (1) will be explained in more detail.

In the formula, X and Y each represent an electron-withdrawing group which may be the same or different, and are preferably selected from NC-.

R is a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms,
For example (methyl, ethyl, butyl, methoxyethyl, hydroxylethyl, chloroethyl, etc.) 6 to 10 carbon atoms
Substituted or unsubstituted aryl group such as (phenyl,
carboxyphenyl, methoxyphenyl, chlorophenyl, methylphenyl, dicarboxyphenyl, methanesulfonamidophenyl, etc.) L+, Lx, Ls represent methine, n represents 0 or 1, methine is substituted with, for example, a methyl group, etc. Good too.

Z represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and the molecule contains a carboxy group, a sulfonamide group,
It shall have at least one group selected from sulfamoyl groups.

Next, general formula (II) will be explained in detail.

X, Y L+ Lx Lx, n are general formula (1)
eZI represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and the heterocycle may be further benzo-fused. Examples of the heterocycle include pyrrole, indole, and pyrazole. Selected from etc. R,,
R, is a hydrogen atom, substituted or unsubstituted, carbon number 1-10
Alkyl groups such as (methyl, ethyl, butyl, benzyl, methoxyethyl, etc.) Substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, such as (phenyl, naphthyl, p-dimethylaminophenyl, p-carboxyphenyl, ethoxy carbonylphenyl, methylphenyl, methoxyphenyl, methanesulfonylphenyl, etc.).

Next, general formula (III) will be explained in detail.

R1 is alkyl having 1 to 5 carbon atoms, such as (methyl, ethyl, butyl, etc.) aryl having 6 to 10 carbon atoms, such as (phenyl, p-carboxyphenyl, etc.) alkoxycarbonyl having 2 to 6 carbon atoms, such as (methoxycarbonyl, ethoxy carbonyl, etc.) Aryloxycarbonyl having 7 to 12 carbon atoms; For example, (phenoxycarbonyl, P-methylphenoxycarbonyl, etc.); Alkoxy having 1 to 5 carbon atoms, such as (methoxy, ethoxy, methoxyethoxy, etc.)
Hydroxy, cyano, amino, such as (dimethylamino, diethylamino, etc.) Carbamoyl having 1 to 6 carbon atoms, such as (carbamoyl, dimethylaminocarbamoyl, etc.) Acylamino having 1 to 8 carbon atoms, such as (acetylamino, methanesulfonylamino, benzoylamino, etc.) Acyl having 2 to 8 carbon atoms, such as phenylsulfonyl (acyl, propionyl, benzoyl, etc.), alkylsulfonyl having 1 to 4 carbon atoms (methanesulfonyl, ethanesulfonyl, etc.), and R4 is a substituted or unsubstituted group having 1 to 5 carbon atoms. Alkyl such as (methyl, ethyl, hydroxyethyl, cyanoethyl, etc.) Substituted or unsubstituted C6-12 alkyl such as (phenyl, p-carboxyphenyl, chlorophenyl, p-methylphenyl, p
-methoxyphenyl, p-methanesulfonylaminophenyl, 3,5-dicarboxyphenyl) 0m represents 0, 1 or 2, provided that the molecule contains a group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group. I have at least one.

Next, specific examples of general formulas (1) and (It) used in the present invention will be given. L, , Lt, L+ are all C
Represents H.

General formula (111) Specific example.

During the ceremony, L5, L2, L.

are all CH.

The compounds of general formulas (1) and (II) used in the present invention are synthesized according to the methods disclosed in U.S. Patent No. 2,538,008, U.S. Pat. can do.

Synthesis Example 1 (Compound 1) 5.5 g of 2-acetyl-p-carboxyacetanilide
, 3-hol
In addition to this, a small amount of acetic acid was added, and the mixture was heated under reflux for 4 hours.

Yellow crystals were collected by filtration and washed with ethanol to obtain 2.2 g of Compound 1.

Melting point: 300°C or higher Synthesis Example 2 (Compound 5) 4.7 g of p-methanesulfonamino-W-cyanoacetophenone and 3 g of 3-formulindole were mixed with 6 g of ethanol.
Heat to reflux for 3 hours at 0 d. After cooling, the crystals were collected by filtration to obtain 6.2 g of Compound 5. The compound of general formula [I] used in the present invention has a melting point of 265 to 267°C.
No.-40827, No. 52-92716, Patent Application No. 1-1
It can be synthesized by the method described in No. 42683.

Synthesis Example 7 (Compound ■-3) 1-P-carboxy-3-methyl-5-pyrazolone2.
2g of dimethylformamide and 15+d of dimethylformamide are mixed, and 3.5d of triethylamine is added and dissolved. Add 1.4 g of glutaconaldehyde'diacyl at room temperature and stir for 2 hours. Concentrated hydrochloric acid 2af was added dropwise under cooling, and the precipitated crystals were collected by filtration to obtain 2.2 g of Compound I[1-3.

The dye of general formula [I] having a melting point of 300 DEG C. or more is generally used in an amount of about 1 to 1,000 square meters per area on the light-sensitive material. Preferably, the amount is about 1 to 800 parts per square inch.

When using the dye represented by general formula (1) as a filter dye or antihalation dye, any effective amount can be used, but if the optical density is 0.05 or less,
It is preferable to use it in a range of 3.5, and it may be added at any step before coating.

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

■ The dye of the present invention can be dispersed as a fine particle dispersion by dissolving it in a weakly alkaline solution, adding it to a hydrophilic colloid layer, adjusting the pH and making it slightly acidic to form a fine crystalline dispersion; or 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 alcohol, JP-A-48-9
After dissolving in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in No. 715, a poor solvent may be added to precipitate fine particles.

The average particle size of the dye particles in the dispersion is 10 am or less, more preferably 2 μm or less, and particularly preferably 0.5 μm.
It is more preferable that the particle diameter is 0.1 μm or less, and in some cases, 0.1 μm or less.

■ A method in which a compound is dissolved in an oil, that is, a high-boiling solvent that is substantially insoluble in water and has a boiling point of about 160"C or higher, and then added to the hydrophilic colloid solution to disperse it. As this high-boiling solvent, U.S. Pat. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), as described in No. 322027. Citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (for example, tributyl trimesate), etc. can also be used.
°C organic solvents, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethylacetate, methyl cellosolve acetate, and solvents that are easily soluble in water, such as Alcohols such as methanol and ethanol can also be used.

Here, the usage ratio of dye and high boiling point solvent is 10 to 1.
/10 (weight ratio) is preferable.

■ The dye of the present invention and other additives are added to the photographic emulsion layer and other hydrophilic colloid layers filling polymer latex & IL.
How to include it as a prestige item.

Examples of the polymer latex and wax include polyurethane polymers and 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 esters (methyl methacrylate, butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butylacrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl esters ( vinyl acetate,
vinyl acetate, etc.), vinyl halides, (vinyl chloride, etc.)
, vinylidene halides (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, propylene, butylene, butadiene, acrylonitrile and the like. 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,
Examples include sulfoalkyl acrylate, sulfoalkyl acrylate, and styrene sulfonic acid. ] etc. can be used.

These filled polymer latexes are
No. 53, JP-A No. 51-59943, JP-A No. 53-1371
No. 31, No. 54-32552, No. 54-107941
No. 55-133465, No. 56-19043,
No. 56-19047, No. 56-126830, No. 5
It can be produced according to the method described in No. 13-149038.

Here, the usage ratio of dye and polymer latex is 1
0 to 1/10 (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 JP-A-60-15843.
It is stated in No. 7.

(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. Regarding this method, for example, US Pat. No. 3,619,195, West German Pat.
No. 957,467.

(2) Microcapsule method using a polymer having carboxyl group, sulfonic acid group, etc. in the side chain as described in JP-A-59-113434.

Further, in the hydrophilic colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, 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 and light-sensitive material used in the silver halide photographic light-sensitive material of the present invention will be described in detail.

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

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may have a uniform phase. Also, particles whose latent image is mainly formed on the surface (
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a prefogged direct reversal type emulsion). Preferably,
These are particles on which a latent image is formed primarily on the surface.

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

The photographic emulsion used in the present invention is P graphide (P,
Glafkides), Chjmie er Physiq Photography, Inc.
ue Photo.

grapheque) (Published by Paul Montell, 196
7 years), G.F. Duffin
), Photographic Emulsion Case Story (Photo.

graphic EIIpulsion CheI+l
1stry) (published by Focal Press, 1966),
V, L, Zel ik*a
Making and Coating Photographic Ink Emulsion by n) et al.
Coatrng Photographic Emul
sion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130, No. 4.297.439, No. 4.276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 5182408, No. 55-77737, etc.)
, an atonne compound (for example, JP-A-54-100717), etc. can be used.

In the process of silver halide grain formation or physical forces,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, Bo! j-N-vinylpyrrolidone,
Various synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As for gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Phot, Japan), Na l
Enzyme-treated gelatin as described on page 6.30 (1966) may be used, or a hydrolyzate of gelatin may be used.

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the bank layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active halogen compound (2,4-dichloro-6-hydroxy-1,3
5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, 1,2-bis(vinylsulfonylacedoamido)ethane, bis(vinylsulfonylmethyl)ether or vinyl Vinyl polymers having sulfonyl groups in their side chains) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.) and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium 2-naphthalenesulfonate, etc.) also have a slow curing rate. Faster and better.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. 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.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, henzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthothiazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiasilysia 2,4-dione nucleus, a rhodanine nucleus, a thiobarbicuric acid nucleus, etc. can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613,
No. 615,641, No. 3,617,295, No. 3,6
The combinations described in No. 35,721 are particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzigoazoles, promohenzigoazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl 5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthion;
Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy I'm(13,3a
, 7) tetraazaindenes), pentaazaindenes, etc.; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. I can do it.

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

The photographic material prepared using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as anti-irradiation or anti-halation.

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. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity.
The layer structure may further improve the graininess.

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

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color 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. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

The surface of these supports, which may be black for the purpose of blocking light, is generally subjected to a subbing treatment to improve adhesion with photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

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

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. Research Disclosure, 17123 (1)
or by utilizing the black-forming couplers described in U.S. Patent No. 4,126.461 and British Patent No. 2,102,136, etc. Therefore, the present invention can also be applied to black-and-white photosensitive materials for X-rays and the like. Films for plate making such as lithography film or scanner film, X-ray film for direct placement, indirect medical use or industrial use, negative black and white film for photography, black and white photographic paper, COM or regular micro film, and printout type photosensitive materials. The present invention can be applied.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or Exposure means combined with a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary alkyl color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and P-1 luenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or fogging agents such as bromides, iodides, hendigodazoles, hendithiazoles or mercapto compounds. It generally contains an inhibitor. Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, agonists, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary development such as 1-phenyl-3-pyrazolidone. medicine, viscosity-imparting agent, aminopolycarboxylic acid,
Addition of various chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, and the antioxidant described in West German Patent Application (○LS) No. 2,622.950 to the color developing solution. You may.

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (II), 3I4 acids,
Quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (I[t
) or its salts of cobalt(III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Complex salts of aminopolycarboxylic acids such as nitrilotriacetic acid and 1,3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, labialic acid, and malic acid; persulfates;
Manganate; nitrosophenol, etc. can be used. Of these, iron ethylenediaminetetraacetate (In
) salt, diethylenetriaminepentaacetic acid iron(I[I) salt, and persulfate salt are preferred from the viewpoint of rapid processing and environmental pollution.

Additionally, the ethylenediaminetetraacetic acid iron (II [Hf salt) is particularly useful in both stand-alone bleach solutions and -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. 3,893,858, German Pat.
．． No. 290,812, No. 2,059988, JP-A-5
No. 3-32736, No. 53-57831, No. 3741
No. 8, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-
Compounds having a mercapto group or disulfide group as described in No. 141623, No. 53-28426, Research Disclosure No. 17129 (July 1978); Thiazolidine derivatives as described in JP-A-50-140129; Thiourea derivatives described in Japanese Patent Publication Nos. 45-8506, 52-20832, 53-32735, and U.S. Patent No. 3.706.561;
West German Patent No. 1,127,715, JP-A-58-162
Iodide described in No. 35: West German Patent No. 966.410,
Polyethylene oxide compounds described in JP-A No. 2,748,430; polyamine compounds described in JP-A-45-8836; and other JP-A-49-42434, JP-A-4!1596
Compounds described in No. 44, No. 53-94927, No. 54-35727, No. 55-26506 and No. 58-163940, as well as iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat. No. 3,893.858 and West German Patent No. 1.290.812.
The compounds described in 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. When bleaching and fixing color photosensitive materials for photography,
These bleach accelerators are particularly effective.

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

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides and anti-piping agents that prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardening agents can be added as necessary. Or Photographic Science and Engineering magazine by West (L, E, West
, Phot, Sci, Eng,), Volume 6, 344~
Compounds described on page 359 (1965) may also be added. The addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 may be implemented. In the case of this step, 2 to 9 countercurrent baths are required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example 1I
various buffering agents (e.g. borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, mono- Typical examples include (using a combination of carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (true phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (benzisothiazolinone, isothiazolone, - Various additives such as thiazolines (benzimidazole, halogenated phenols, sulfanilamide, henctriazole, 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 in combination.

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

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). 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, Research Disclosure No. 14850 and US Pat. No. 15159.
The ship base type compound described in No. 13924, the metal salt complex described in U.S. Patent No. 13924, the metal salt complex described in U.S. Pat. No. 56-6235, No. 56-16133, No. 56-59232, No. 5
No. 6-67842, No. 56-83734, No. 56-8
No. 3735, No. 56-83736, No. 56-8973
No. 5, No. 56-81837, No. 56-54430,
Examples include various salt-type precursors described in Japanese Patent Nos. 56-106241, 56-107236, 57-97531, and 5'l-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Compounds of this type are JP-A-56-64339, JP-A-57-144547, JP-A-57-211147, JP-A-58-50532, JP-A-58-50536, JP-A-58-50533, JP-A-55-
No. 50534, No. 58-50535 and No. 58-1
It is described in No. 15438, etc.

The various processing solutions used in the present invention are used at temperatures between 10"C and 50°C. The standard temperature is between 33°C and 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature.Also, for the department of photosensitive materials, it is described in West German Special Kitsuki No. 2゜226.770 or United States Special Kitsuki No. 3,674゜499. Treatment using cobalt intensification or hydrogen peroxide intensification may be performed.

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

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

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

EXAMPLES Example 1 Paper support samples A, B and C were obtained using a gelatin subbing layer or the following dye dispersion after corona discharge treatment on a paper support laminated on both sides with polyethylene.

Dye Dispersion Method The following dye crystals were kneaded and made into fine particles using a sand mill. Furthermore, 10% by dissolving 0.5g of citric acid.
The sand was dispersed in a lime-treated gelatin aqueous solution (25 mL), the used sand was removed using a glass filter, the dye adhering to the sand on the glass filter was removed, and 100 d of a 7% gelatin solution was added. (The average particle size of dye particles is 0.1
It was 5 μm. ) Compound 6 of the present invention 1.
OgCompound 26 of the present invention...
1.6g Compound 6 of the present invention
・1. Og Compound of the present invention 111-3 ・
...... 1.6g was adjusted in the same manner.

Paper support A Undercoat layer gelatin 0.8g
/r/Paper support B Antihalation layer gelatin 0.6g
1rd Compound 6 of the present invention...
25■/n (Compound 26 of the present invention...
・・40■/d Paper support C antihalation layer gelatin ・・・・・・・・・ 0.6
glrdCompound 6 of the present invention...
40■/n (Compound DI-3 of the present invention...
... 65 ■/d Multilayer color photographic paper samples 1-1 to 1 having the layer structure shown below on paper support samples A, B, and C.
I got -4.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 1.4 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) Add 8.2g of dissolved MfL and dilute this solution to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution. On the other hand, the coefficient of variation of the grain size distribution of a silver chlorobromide emulsion (cubic, 3=7 mixture (silver molar ratio) of average grain sizes of 0.88 μm and 0.70 μm is 0.08 and 0.10, respectively. Both emulsions contained 0.2 mol % of silver bromide locally on the grain surface. For large-sized emulsions, 2.0 x 10-' mol of each blue-sensitive sensitizing dye shown below was added per 1 mol of TFF. For small size emulsions, 2.5×10
-' mol was added and then sulfur sensitized.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

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

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer 0se SOsH-N(CJs)i (CHJa (CHx)a SO18 SOsNH(CgHs)s (per 11 mole of halide, 2.0X10-' mole each for large size emulsion, also for small size emulsion green-sensitive emulsion layer (per mole of silver halide, 4.0X10'' moles for large emulsions and 5.6 moles for small emulsions)
X10-'mol> Oje SO3M-N(CgHs)s (per mole of silver halide, for large size emulsions 0x10-' mol, and for small size emulsions 1
red-sensitive emulsion layer CzHs I eCsH++ (per mole of silver halide, 0.9X10-' mole for large size emulsions and 1 for small size emulsions)
．． For the red-sensitive emulsion layer, the following compounds were added to the halogenated i
2.6 x 10-' moles were added per 11 moles.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was added to each mole of halogenated 5fi, 8.5XIO-'mol, 7°7X 10-'mol,
2.5 x 10-' moles were added.

Further, 1X10-' mol and 2X10-' mol of 4hydroxy-6-methyl-1,3,3a7-titrazaindene were added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively, per mol of silver halide.

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

7゜5■/bo and)10H (Layer structure) The composition of each layer is shown below, and the numbers represent the coating amount (g/n()).The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (T iOz ) and a bluish dye (ulmarine blue)]
Samples A, A, with an undercoat layer and an antihalation layer provided on the
First layer of four types B and C (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 I, lo-coupler (ExY) 0.82 Color image stabilizer (Cpd
-1>0.197 volume (Solv-1)
0. 35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Sol
v-1) 0.16 solvent (Solv-
4>0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55 μm
A l:3 mixture of 0.39 μm and 0.39 μm (Ag
molar ratio). The coefficient of variation of particle size distribution is 0.10 and 0.10.
08, each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin E, 24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cp
d-2) 0.03 color image stabilizer (Cpd-
3) 0.15 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-9)
0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (
Cpd-5) 0.05 Solvent (Solv-
5> 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.58 μm
A l:4 mixture of 0.45 μm and 0.45 μm (Ag
molar ratio). The coefficient of variation of particle size distribution is 0.09 and 0.09.
11. Each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cp
d-6) 0.17 color image stabilizer (Cpd-
7) 0.40 color image stabilizer (Cpd-8)
0.04 liter capacity (Solv-6)
0. 15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (LJV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv
-5) 0.08 Seventh layer (protection N) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.17 liquid paraffin
0.03 (ExY) Yellow coupler Js (ExM) Magenta coupler CHl, u, 5 (n) 1:1 mixture (molar ratio) (ExC) Cyan coupler L R=C, H5, CaHq and H 1 A mixture of 2:4:4 (Cpd 1) Color image stabilizer (Cpd 2) Color image stabilizer (Cpd 3) Color image stabilizer (Cpd-5) Color mixing inhibitor 0 (Cpd) 6) 2:4:4 mixture of color image stabilizer (weight ratio> (Cpd 7) Color image stabilizer → CH!-CH)-,1 CON[(CJw(t) Average molecular weight 60,000 (Cpd-8 ) Color image stabilizer H Suh (Cpd-9) Color image stabilizer ([JV-1) Ultraviolet absorber (3o1v 1) Solvent (3o1v 2) Solvent (Solv 4) Solvent (3o1v 5) Solvent C00CsH+t (CHiL C00CsH+t (3o1v 6) Regarding samples 1-1 to 1-4 obtained with solvent, a photosensitive needle (manufactured by Fuji Photo Film ■, FWH type, color temperature of light source 3,20
Stepwise exposure for sensitometry was provided through blue, green and red filters using a resolution of 0”K).
Exposure for CTF) measurement was performed, and then the following development treatment was performed. The concentration of the obtained sample was measured and the results shown in Table 1 were obtained.

When the dye according to the present invention is used in an antihalation layer, the decrease in sensitivity is relatively small and residual color is not noticeable. By using such an amount, the resolution can be significantly improved.

Further, by using the general formula (n) and the general formula (I[[]), the residual color becomes even less noticeable.

Processed grain: Inspection, Toyokuni color development, 35°C, 45 seconds bleach fixing 3
0~36℃ Stable for 45 seconds ■ 30~37℃
Stable for 20 seconds ■ Stable at 30-37℃ for 20 seconds ■ Stable at 30-37℃ for 20 seconds ■ Stable at 30-37℃ for 30 seconds (Four tank countercurrent method from stable ■ to ■.) The composition of each treatment solution is as follows. That's right.

Standing i2 development blood water 80
〇-Ethylenediaminetetraacetic acid H2.0g Triethanolaone Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonadoethyl)-3-methyl-4-agonoaniline sulfate N,N-diethylhydroxyl 8 , 0g 1,4g 25.0g On 5.6-hydroxybenzene 1.2.4-trisulfonic acid optical brightener (add 4,4'-diamino water) Ammonium sulfate (70%) Sodium sulfite ethylene thiamine iron tetraacetate (Iff) 1000d 10°40 〇- 00- 8g Ammonium 55g Disodium ethylenediaminetetraacetate 3g Glacial acetic acid
Add 8g water
100 (ldpH5.5 Formalin (37%>0.1g formalin-sulfite adduct 0.7g5-chloro-
2-Methyl-4-isothiazolin-3-one 0.02g2-Methyl-4-isothiazolin-3-one 0.01gCopper sulfate
Add 0.005g water
10QOdpH4,0 Example 2 A dispersion of the dye of the present invention was prepared in the same manner as in Example 1. 2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt was used as a hardening agent. A sample was prepared in which the compound of the present invention was coated on a polyethylene terephthalate transparent support at a concentration of 0.1 g/rd.

The sample was immersed in water at pH 7 for 5 minutes, and the change in concentration was measured. The sample was immersed in water with a pH of 10 for 30 seconds, and the change in concentration was measured.

The results are shown in Table-2.

Table 2 0 From these results, it can be seen that the compound of the present invention hardly flows out even when immersed in water, indicating that it has resistance to flowing out to other layers in a multilayer photograph. It is also clear that the color is easily decolored in alkaline aqueous solutions used in photographic processing, and that staining, which is harmful to photographs, is low.

(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. 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.

Claims (4)

[Claims] (1) A silver halide photographic material containing at least one dye of the general formula [I] in the form of a fine powder dispersion. [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X and Y each represent an electron-withdrawing group which may be the same or different. L_1, L_2, L_3 represent methine, Z represents a nonmetallic atom necessary to form a 5-membered heterocycle, and n represents 0 or 1. However, the molecule contains at least one group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group. (2) In the general formula [I], X and Y may be the same or different, and include NC-, RCO-, RSO_2-▲ Numerical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas, tables, etc. represents ▼, and R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. The silver halide photographic material according to claim 1, further comprising at least one carboxyl group, sulfonamide group, or sulfamoyl group directly bonded to an aromatic ring in the molecule. (3) The silver halide photographic material according to claim 1, which contains at least one compound of general formula [II] in the form of a fine powder dispersion. [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X and Y may be the same or different, and NC-
, RCO-, RSO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R, R_1, and R_2 are hydrogen atoms, substituted or unsubstituted carbon atoms of 1 to 5 represents an alkyl group or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. L_1, L_2, L_
3 represents methine, Z_1 represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and the heterocycle may further form a benzo-fused ring. n represents 0 or 1. However, the aromatic ring present in the molecule shall have at least one group selected from carboxyl group, sulfonamide group, and sulfamoyl group. (4) A silver halide photographic light-sensitive material containing at least one of each of a fine powder dispersion of a dye represented by the general formula [II] and a fine powder dispersion of a dye represented by the general formula [III]. . General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_3 is alkyl, aryl, alkoxycarbonyl,
Represents arylcarbonyl, alkoxy, hydroxy, cyano, amino, carbamoyl, acylamino, acyl, phenylsulfonyl, alkylsulfonyl, R_4
represents aralkyl or aryl. L_1, L_2, and L_3 have the same meanings as above, and m represents 0, 1, and 2. However, carboxyl groups in the molecule,
It has at least one group selected from a sulfonamide group and a sulfamoyl group.