JPH04151651A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent harmful coloration from remaining on a photographic sensitive material after processing without lowering sensitivity, degrading a latent image or causing fog by forming a hydrophilic colloidal layer contg. a specified compd. as dispersed solid fine particles. CONSTITUTION:A hydrophilic colloidal layer contg. at least one kind of compd. represented by formula I as dispersed solid fine particles is formed. In the formula I, R1 is 1-8C alkyl, aryl or aralkyl, R2 is alkyl, aryl, aralkyl, substd. amino or alkoxy, each of L1-L5 is methine and each of (m) and (n) is 0 or 1. When the dye-contg. layer is used as an antihalation layer, dyeing can be carried out so that selective absorption in a visible region is ensured, the sensitivity of other layers is not lowered and residual color is remarkably reduced. An absorption spectrum is not changed even by heating in wet conditions and the antihalation ability is maintained.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inactive and easily decolorized during photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted and/or a hydrophilic colloid layer.

(Prior Art) In silver halide photographic materials, photographic emulsion layers and other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, a filter layer may be located between them.

This is because light that is 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 then enters the photographic emulsion layer again. In order to prevent blurring of images, that is, halation, a colored layer called an antihalation layer is provided on the surface opposite to the photographic emulsion layer. When there are multiple photographic emulsion layers, an antihalation layer may be placed between the layers.

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

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

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

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

(3) It should not be bleached during the photographic processing process or be eluted into the processing solution or washing water, leaving no harmful coloring on the photographic material after processing.

(4) Do not diffuse from the dyed layer to other layers.

(5) It has excellent stability over time in solutions or photographic materials and does not change color or fade.

In particular, when the colored layer is a filter layer or an anti-X Rayon layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are It is often necessary to ensure that coloration does not substantially extend to the surface.

This is because, otherwise, not only will it have harmful spectral effects on other layers, but its effectiveness as a filter layer or antihalation layer will be diminished. However, when a dyed layer and another hydrophilic colloid layer come into wet contact, it often occurs that some of the dye diffuses from the former to the latter. Many efforts have been made in the past to prevent such dye diffusion.

For example, U.S. Patent No. 2,548 describes a method in which a dissociated anionic dye and a wood-philic polymer with an opposite charge are made to coexist in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. No. 564, 4,124,3
No. 86, No. 3,625.694, etc.

In addition, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-1200.
No. 30, No. 55-155350, No. 55-15535
No. 1, No. 63-27838, No. 63-197943, No. 52-92716, European Patent No. 15601, No. 2
No. 76566, No. 274723, No. 276566,
This method is disclosed in Japanese Patent No. 299435, World Patent No. 88104794, and the like.

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

However, even with these improved methods, the speed of decolorization during development processing is still slow, and if there are changes in various factors such as speeding up the processing, improving the processing solution composition, or improving the photographic emulsion composition. However, there was a problem in that the decolorizing function could not always be fully demonstrated.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a solid fine particle dispersion designed to dye a specific hydrophilic colloid layer in a photographic light-sensitive material and rapidly decolorize it during development. An object of the present invention is to provide a photographic material containing a dye.

(Means for Solving the Problems) (1) An object of the present invention is to provide a silver halide photographic photosensitive material having a hydrophilic colloid layer containing at least one compound represented by the following general formula (I) as a solid fine particle dispersion. achieved by the material.

General Formula (D) RI R In the formula, R1 each represents an alkyl group (having 1 to 8 carbon atoms), an aryl group, an aralkyl group, an acyl group, a substituted amine group, or an ester group, and in the formula, R2 represents an alkyl group or an aryl group, respectively. group, aralkyl group, acyl group, cyano group, substituted amino group, alkoxy group, ester group, carbamoyl group, and halogen. LL
2, R3, R4, R5 represent methine groups, m and n are 0
or represents l.

(2) A silver halide photograph preferably containing a small amount of each of a solid fine particle dispersion of a dye represented by general formula CI) and a solid fine particle dispersion of a dye represented by general formula [II]. Achieved by photosensitive materials.

General formula (If) R, R4 R3 represents alkyl, aryl, alkoxycarbonyl, aryloquinecarbonyl, alkoxy, amino, carbamoyl, acylamino, cyano, acyl, phenylsulfonyl, alkylsulfonyl, and R4 represents aralkyl or aryl. L II, Lll, and L II have the same meanings as above, and ml represents 0.1.2. However, the molecule contains at least one group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group.

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

The alkyl group, aryl group, or aralkyl group represented by R1 is a substituent (e.g., alkoxy group (e.g., methoxy,
ethoxy), a halogen atom (for example, chlorine, bromine, fluorine), or an amino group (for example, dimethylamino, diethylamino). Alternatively, an alkyl group (e.g. methyl,
ethyl) may be substituted. Furthermore, the group R is not only directly bonded, but also has a divalent linking group (e.g. -0S--
NRC○-1CONR--(CHri.

0CO--NHCONH--NHOC〇-, etc. (R represents an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-hexyl, and P represents an integer of O to 5). Good too. The alkyl group, aryl group, and aralkyl group represented by R2 are substituents (e.g., alkoxy groups (e.g., methoxy, nidoquin), halogen atoms (e.g., chlorine, bromine, fluorine), amine groups (e.g., dimethylamino,
diethylamino)). Further, the aryl group and the aryl moiety of the aralkyl group may be substituted with an alkyl group (eg, methyl, ethyl). Also R
The substituted amino group represented by 2 is an amino group substituted with one or two C1-05 alkyl groups (eg, methyl group, ethyl group, propyl group). In addition, the group R1 is not only a direct bond, but also a divalent linking group (e.g. -0-
3- -NRCO-1CONR---((J(2).

0CO---NHCONH--NHOCO-, etc. (R represents an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-hexyl, and P represents an integer of 0 to 5). Good too.

Moreover, ~Ls is an unsubstituted methine group, but may be substituted with an alkyl group (eg, methyl group, ethyl group), aryl group (eg, phenyl group), or the like.

Among the compounds represented by general formula (I), preferred are R
' is a methyl group, an ethyl group, R2 is a phenyl group or t-
It is a butyl group, and m and n are both 0.

Next, general formula [II] will be explained in detail.

R3 is preferably 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 (methquin carbonyl, etquin carbonyl, etc.), 7 to 1 carbon atoms
2 aryl carbonyl, e.g. (phenoxycarbonyl, p-methylphenoquine carbonyl, etc.), alkoxy having 1 to 5 carbon atoms, e.g. (methoxy, ethoxy, methoxyethoxy, etc.), cyano, amino, e.g. (dimethylamino, diethylamino, etc.), Carbamoyl having 1 to 6 carbon atoms, for example (carbamoyl, dimethylaminocarbamoyl, etc.), acylamino having 1 to 8 carbon atoms, for example (
acetylamino, methanesulfonylamino, benzoylamino, etc.), acyl having 2 to 8 carbon atoms, e.g. (acyl,
propionyl, benzoyl, etc.), phenylsulfonyl, alkylsulfonyl having 1 to 4 carbon atoms (methanesulfonyl, ethanesulfonyl, etc.), and R4 represents substituted or unsubstituted alkyl having 1 to 5 carbon atoms, such as (methyl,
Substituted or unsubstituted aryl having 6 to 12 carbon atoms (ethyl, hydroxyethyl, cyanethyl, etc.) For example (phenyl, p-carboxyphenyl, chlorophenyl, p-
methylphenyl, p-methoxyphenyl, p-methanesulfonylaminophenyl, 3,5-dicarboxyphenyl). m represents 0, ■ or 2.

However, the molecule contains at least one group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group.

Next, specific examples of general formula CI) used in the present invention will be given. L, , L, , L all represent CH.

Compound example of general formula (I) R'R' m nI CH
,-CH,00 2,,101 3// 〃 l 14//
Et-00 5〃 ll 0 1 6 〃 ll 1 17
tt ”prO0 8〃ノ/
0 19 〃 〃
1 110'' ”Bu -00C
H, - tO Pr0- 'BuO ("Pr), N- R φ tO Pr0- "BuO- ("Pr) tN- CH, - t- Pr R" φCH, - 'Pr 'Bu- φ- φCH2 tO- 'PrO 'BuO- R'R' m n8
7 φCH2”BuOl 188
('Pr)zN 0 08
9”!10 1
90 〃 〃 1
The compound of l-Funenin (I) was disclosed in Japanese Patent Application Laid-Open No. 1983-1992.
No. 716, No. 63-316853, No. 64-4082
It can be synthesized according to the method described in No. 7 and Japanese Patent Publication No. 58-35544.

Synthesis Example I-1 (Compound ■-8) 1-Methyl-3-phenyl-2-pyrazolin-5-one 100. og was dissolved in methanol 11 at room temperature. 85.0 g of ethyl orthoformate was added dropwise to this, and the mixture was heated under reflux for 3 hours. The target product began to precipitate about 30 minutes after the start of the reaction.

After the reaction, cool to room temperature, suction filtrate, and dry.78.5
g of Compound I-8 was obtained.

Maximum absorption in methanol is 358 nm ε=1.8
It was 5 x 10'.

General formula [Specific example of ID. In the formula, L,,L,,L.

are all CH.

Synthesis Example 11-1 (Compound ■-3) ■-p~carboxy 3-methyl-5-pyrazoline 2.
2 g of dimethylformamide 15- are mixed, and triethylamine 3.5- is added and dissolved. Add 1.4 g of glutaconaldehydonoanyl at room temperature and stir for 2 hours. Concentrated hydrochloric acid 27I! was added dropwise under cooling, and the precipitated crystals were collected by filtration to obtain 2.2 g of compound llll-3. Melting point 300℃ or higher.

The compound of general formula (I) or (n) is used in an amount of 1 to 1000 μ per 1 area on the photosensitive material, preferably 1 rrl.
1 to 800 ■ are used per day.

When using a compound of general formula (1) or (II) as a filter dye or antihalation dye, any effective amount can be used, but so long as the optical density is in the range of 0.05 to 3.5. It is preferable to use it.

The addition time may be any step before coating.

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

Fine particle dispersions of compounds of general formula (I) or (n) according to the invention can be prepared by methods of precipitating the compounds of the invention in the form of dispersions and/or by known comminution means, e.g. Using a method of forming by ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. (in that case, a solvent (for example, water, alcohol, etc.) may be coexisting). Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate a microcrystalline powder. A surfactant may be used. Alternatively, the compound of the present invention may be first dissolved by pH control and then microcrystalized by changing the pH. Microcrystalline particles of the compound of the present invention in a dispersion. is a fine particle having an average particle size of 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less, and in some cases even more preferably 0.1 μm or less.

Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used.

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

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

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

The silver halide emulsion used in the present invention has a thickness of 0.5
The diameter is preferably 0.3 microns or less, preferably 0.3 microns or less. A tabular grain emulsion in which grains of 6 microns or more and an average aspect ratio of 5 or more account for 50% or more of the total projected area, or a tabular grain emulsion with a statistical coefficient of variation (expressed as the diameter of a circular approximation of the projected area) In terms of distribution, a monodisperse emulsion having a value S/d (standard deviation S divided by diameter d) of 20% or less is preferred. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie er Phys Photographic (Chimie er Phys Photography)
ique Pho-tographeque) (Ballmontel, 1967) G.F. Duffin (
Photographic Emulsion Chemistry (G., F. Duffin)
Emulsion Chemistry) (Focal Press, 1966), V, L, Zelikman et al., Making and Coating Ph Photographic Emulsion (Making and Coating Ph Photographic Emulsion)
otographic emulsion) (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. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

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

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

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), N[
116, p. 30 (1966) may be used, or a hydrolyzate of seratin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active compound (2,4-dichloro-6-hydroxy-
1,3゜5-triazine and its sodium salt, etc.) and active vinyl compounds (l,3-bisvinylsulfonyl-2-propatol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether Alternatively, a vinyl polymer having a vinyl sulfonyl group in a side chain) is preferable because it quickly hardens hydrophilic colloids such as gelatin and provides stable photographic properties. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate) yahalamidinium salts (1-(110-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) also have a high curing speed. is faster and better.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melonanine dyes, holobolanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole 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 thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic ring group (e.g., U.S. Pat. Nos. 2,933,390 and 3,635°721)
(described in US Pat. No. 3,743,510), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3.615.613, U.S. Patent No. 3,61
No. 5,641, No. 3,617,295, No. 3,635
, 721 are particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercabutothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino triazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
etc.: Mercaptopyrimidines: Mercaptotriazines; Thioketo compounds such as oxadolinthione; Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3,
3a, 7) Tetraazaindenes), Pentaazaindenes, etc.: Many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

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 made 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, infrared-sensitive layers may be combined to provide pseudocolor homogeneity or semiconductor laser exposure.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

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

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, N (L17123
(July 1978), or by utilizing a trichromatic coupler mixture as described in U.S. Pat.
No. 1 and British Patent No. 2. 102. By using the black color-forming coupler described in No. 136, the present invention can also be applied to black-and-white photosensitive materials for X-rays and the like. Plate-making films such as lithium film or scanner film, X-ray film for direct/indirect medical use or industrial use,
The present invention can also be applied to negative black and white film for photography, black and white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials.

When the photographic element of the present invention is applied to color diffusion transfer photography, it may be of the peel-apart (beer-apart) type or
-16356, 48-33697, JP-A-1973-
13040 and British Patent No. 1,330,524, or a peel-free type film unit as described in JP-A-57-119345. I can do it.

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

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

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear microshutter arrays using fluorescent surfaces (such as CRT), liquid crystals (LCD), and lanthanum-doped lead titanium zirconate (PLZT) emitted from phosphors excited by electron beams, etc. Alternatively, an exposure means combined with a planar light source can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N-diethylaniline, 3-Methyl-4-amino-N-ethyl-N-
β-Hydroquinlethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as In addition, if necessary, preservatives such as hydroxylamines, dialkylhydrokinerulaminos, hydrazines, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, polyethylene Development accelerators such as glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as -phenyl-3-pyrazolidone, viscosity-imparting agents, Various oxidation agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, antioxidants described in West German patent application (OLS) No. 2,622,950, etc. It may be added to a color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as aminophenols such as methyl-p-aminophenol can be used alone or in combination.

Not only a color developing solution but also any photographic developing method may be applied to the light-sensitive material of the present invention. The developing agents used in the developer include dihydroxybenzene-based developing agents, ■
- Phenyl-3-pyrazolidone type developing agents, p-aminophenol type developing agents, etc. These can be used singly or in combination (for example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes, or p-aminophenols and dihydroxybenzenes). ) can be used. Further, the light-sensitive material of the present invention may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone.

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,
Examples include 3-dichlorohydroquinone and 2,5-dimethylhydroquinone, and ■-phenyl-3-pyrazolidone-based developing agents include l-phenyl-3-pyrazolidone,
4.4-dimethyl-1-phenyl-3-pyrazolidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc. p-aminophenol developing agents include p-aminephenol, N-
Methyl-p-aminephenol and the like are used.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer.

As alkaline agents for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, potassium tertiary acid, jetanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines: mercaptotriazines: thioketo compounds, e.g. oxazolinthione; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a.

7) Tetrazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Examples include benzenesulfonic acid amide and sodium 2-mercaptobenzimidazole-5-sulfonate.

The developer that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide with a molecular weight of 1,000 to 10,000 is 0.1 to Log/j! It can be contained within the range of.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine, hexaacetic acid, diethylenetetraamine pentaacetic acid, etc. as a water softener to the developer that can be used in the present invention.

The developer used in the present invention includes a compound described in JP-A No. 56-24347 as a silver stain prevention agent, a compound described in JP-A-62-212651 as an agent for preventing uneven development,
As a solubilizing agent, the compounds described in Japanese Patent Application No. 109743/1988 can be used.

In the developing solution used in the present invention, a buffering agent is added.
Boric acid described in No. 1-28708, JP-A No. 60-9343
The saccharides (e.g. sucrose), oximes (
For example, acetoxime), phenols (for example, 5
-sulfosalicylic acid), tertiary phosphates (eg, sodium salts, potassium salts), and the like.

Various compounds may be used as the development accelerator used in the present invention, and these compounds may be added to either the sensitive material or the processing solution.

Preferred development accelerators include amine compounds, imidazole compounds, imidacillin compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds,
Examples include thioether compounds, thione compounds, certain mercapto compounds, isoion compounds, and thiocyanates.

This is especially necessary for rapid development processing in a short period of time. It is desirable to add these development accelerators to the color developing solution, but depending on the type of accelerator or the position on the support of the photosensitive layer to be accelerated, it may be added to the photosensitive material. can. It can also be added to both the color developing solution and the photosensitive material. Furthermore, depending on the case, a pre-bath for the color developing bath may be provided and the additive may be added therein.

Amino compounds useful as amino compounds include both inorganic amines and organic amines, such as hydroxylamine. Organic amines can be aliphatic amines, aromatic amines, cyclic amines, mixed aliphatic-aromatic amines or heterocyclic amines; primary, secondary and tertiary amines as well as quaternary ammonium compounds are all useful. be.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (n), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide-dichromate: organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, ■,3-diamino-2-propatoltetraacetic acid Aminopolycarboxylic acids such as acetic acid or complex salts of organic acids such as citric acid, tartaric acid, and malic acid, such as persulfates; manganates; and nitrosophenols, can be used.

Among these, ethylenediaminetetraacetate iron (m> salt, diethylenetriaminepentaacetate iron (III) salt, and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, ethylenediaminetetraacetate iron (III) complex salt is used in a separate bleaching solution. are also particularly useful in -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. 2,059°988, JP-A No. 53-32736, No. 53-57831, No. 374
No. 18, No. 53-65732, No. 53-72623, No. 53-95630, No. 53-95631, No. 5
No. 3-104232, No. 53-124424, No. 53
-141623, 53-28426, Research 6
Disclosure No. NrL17129 (July 1978
Compounds having a mercapto group or disulfide group such as those described in Japanese Patent Publication No. 1987-140129; Thiazolidine derivatives such as those described in Japanese Patent Publication No. 140129/1983;
Thiourea derivatives described in JP-A-52-20832, JP-A-53-32735, and U.S. Pat. No. 3.706.561;
Iodide described in No. 16235; West German Patent No. 966.41
0, polyethylene oxides described in JP-A No. 2,748,430; polyamine compounds described in JP-A No. 45-8836; others JP-A-49-42434, JP-A-49-
No. 59644, No. 53-94927, No. 54-357
No. 27, No. 55-26506 and No. 58-1639
Compounds described in No. 40 and iodine and bromide ions can also be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent No. 1.290,81.
No. 2, JP-A No. 53-95630 is preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred.

These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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

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

In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 may be implemented. In the case of this step, 2 to 9 countercurrent columns 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, the membrane p
Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid) for adjusting H (e.g. pH 3-9) Typical examples include aldehydes such as formalin (using a combination of acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid,
Organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid,
phosphonocarboxylic acids, etc.), fungicides (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenol, sulfanilamide,
benzotriazole, etc.), surfactants, fluorescent brighteners,
Various additives such as hardening agents may be used, and two or more compounds for the same or different purposes 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 periosulfate.

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, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 15159
Including Schiff base type compounds described in No. 13924, aldol compounds described in U.S. Pat. No. 13924, metal salt complexes described in U.S. Pat. Showa 56-6235
No. 56-16133, No. 56-59232, No. 56-67842, No. 56-83734, No. 56-
No. 83735, No. 56-83736, No. 56-897
No. 35, No. 56-81837, No. 56-54430, No. 56-106241, No. 56-107236,
Examples include various salt-type precursors described in Japanese Patent No. 57-97531 and Japanese Patent No. 57-83565.

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

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate the processing and shorten the processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. Furthermore, in order to save silver on photosensitive materials, West German Patent No. 2.226.770 or U.S. Patent No. 3.
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

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

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

When the light-sensitive material of the present invention is a color paper, standard fixing processing can be carried out very generally, and also when it is a color photographic material for photographing, as required.

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

(Effects of the Invention) In the silver halide photographic light-sensitive material of the present invention, the dye in the dye layer has appropriate spectral absorption and has an excellent effect of selectively dyeing the dye layer and not diffusing to other layers. .

The silver halide photographic material containing the compound of the present invention is easily decolorized or eluted by photographic processing, provides a low Dmin, does not reduce sensitivity, and has the effect that there is little decrease in sensitivity due to storage.

Further, the silver halide photographic material of the present invention provides images with improved sharpness. 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 specifically explained based on examples.

Example-1 Support> A biaxially stretched 100 μm polyethylene terephthalate film was subjected to corona discharge treatment, and coated with a wire bar coater to the following coating amount.
It was dried at 70°C for 1 minute.

(First undercoat layer) 0 Butadiene-styrene typical combined latex (butanene/styrene weight ratio = 31/69) 0. 16 g/i02.
4-dichloro-6-hydroxy-5-triazidin sodium salt 4.2 g/distance (second undercoat layer) A second undercoat layer was applied on the first undercoat layer to have the following coating amount: 175 g It was prepared by drying at ℃ for 1 minute.

0 gelatin 0.08g/rrroc
+tH2so(CHtCHzO)1oH7,5mg/r
Preparation of rr Emulsion (1) Solution I 75°C Solution ■ 35°C Solution ■ 35°C Solution ■ Solution ■ and Solution ■ were added to room temperature solution I for 5 minutes to form a solution with an average particle size of 0.10 μm. When octahedral particles were formed, the addition of liquids ① and ② was temporarily stopped, and the
11 each of sodium thiosulfate and chloroauric acid tetrahydrate
5 microns were added at a time, followed by chemical sensitization treatment at 75°C for 60 minutes. Simultaneous addition of solution (■) and solution (2) to the chemically sensitized core particles thus obtained was continued again, and 5 minutes after the addition of solution (■) was resumed, solution (2) was added over a period of 5 minutes to increase the pAg of the mixed solution.
The entire amount of Solution (2) was added over 40 minutes at 75° C. while adjusting the addition rate of Solution (2) so that the value was 7.50. In this way, a cubic core/shell emulsion with an average grain size of 0.28 μm was finally obtained. After washing with water and desalting by the sedimentation method, the mixture was dispersed in an aqueous solution containing 90 g of inert gelatin. 1 silver in this emulsion
Sodium thiosulfate and chloroauric acid tetrahydrate were added at 34 μm each per mole, and the pH and pAg values were adjusted to 8.
9 and 7.0 (40°C), then 60°C at 75°C.
Chemical sensitization treatment was performed for 1 minute.

<Preparation of antihalation CAH layer) 1-Q> 0 gelatin 1.7 g/dO compound
167. 8wrg/rrrCH.

0 dye■ 0 dye 0 SO, K SO, 68°5■/d 0 dye 0 C)1. CI(!5O3K C)12CH,
SO, 68.5 mg/ni'<Creation of antihalation layer (AH layer) ■-■> 0 Seratin 1.7 g/I0 dye (I-
8) 90.6■/dO dye (n-3)
95.1■/, (01,3-bis(vinylsulfonyl)-2-proparamyl) 59.5■/Po dyeing (I-8 and ■-3) Preparation of liquid Hiromoto (434d) and Trito
nX-200■ Surfactant (TX-200■) (
53g') (sold by Rohm & Hass)
A 6.7% solution of 1.5% was placed in a 1.51 screw cap bottle. To this, 20 g of dye and zirconium oxide (ZrO) beads (800 J) (2 town diameter) were added, the lid of the hin was tightly closed and placed in the mill, and the contents were ground for 4 days.

The contents were added to a 12.5% Seratin aqueous solution (160 g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove Zr○ beads.

After this, particles larger than 1 μm were substantially removed.

<Creation of antihalation layer (AH layer) 1-■> 0 Seratin 1. 7g/rr? 0 dye (I-7) 74.6■/bo 0 dye (II
-3) 149mg/rrfo1,3-
Bis(vinylsulfonyl)-2-proparamyl 59.5/- The dye used was dispersed in the same manner as the dye in antihalation layer 1--.

<Creation of antihalation layer (AH layer) ■-■> 0 gelatin 1.7 g/I0 dye (I-
31) 147■/I0 dye (II-3)
109 mg/mof, 3-bis(vinylsulfonyl)-2-proparamyl 59.5/d dye (I-31
) and (II-3) were dispersed in solid form in the same manner as the dye in antihalation layer 1-2.

<Creation of antihalation layer (AH layer) 1-■> 0 gelatin 1.7 g/r&0 comparative dye O 0OH 144 ■/Iof, 3-bis(vinylsulfonyl)-2-proparamyl 59° 5■/I dye is A dye dispersed in the same manner as the dye in antihalation layer 1-(Ei) was used.

<Antihalation layer CAH layer) 1-Creation of ID> 0
Ceratin 1.7g/0 ratio tie dye CA) 48. 5mg/mO dye (n-
3) 95. 1mg/rn'O1,3-
The bis(vinylsulfonyl)-2-proparamyl 59.5/ITI' dye was dispersed in the same manner as the dye in the antihalation layer 1-2.

The average absorbance of antihalation layer 1-■, ■, ■, ■, ■, ■ in the visible range of 400 to 800 nm was 0.7.

<Antihalation layer CAH layer) 1-(Creation of iD>
0 Gelatin 1.7g/I01.3
-Bis(vinylsulfonyl)-2-proparamyl 59.5 ■/I <Emulsion layer> Wetting agent (compound 0) Sensitizing dye (compound ■) 2HB (CH2)3SO18 2H5 Nucleating agent (compound ■) CH, C4 :CH Wetting agent (compound O) CH <Protective layer> Lysine potassium salt 5° Antihalation layer (AH layer) emulsion layer and protective layer were coated on the support in this order and dried, as shown in Table 1. Photographic material 1-A-1-G was obtained.

Table 1 Evaluation of photographic performance Imagewise exposure was carried out from the emulsion coated surface under a safety light for 10-8 seconds through a continuous density wedge using a MARK xenon flanille sensitometer manufactured by E, G, &G, USA. Ta.

General-purpose processing liquid for microfilm (USA, FRChe+n
Using an automatic developing solution (FR-537 developer manufactured by Cals Inc.), processing was carried out using an automatic developing machine under the following conditions.

Evaluation of sharpness Sharpness was evaluated by MTF. The photographic material was exposed to white light for 1/100 seconds using an MTF measuring wedge and subjected to the automatic development process described above.

The MTF was measured using an aperture of 400×2 μM, and the MTF value at a spatial frequency of 20 cycles/mm was used to evaluate the area where the optical density was 1.0.

Evaluation of residual color Photographic materials 1-A to 1-G were subjected to the same treatment as in the evaluation of photographic performance described above without being exposed to light.

The residual color after treatment was sensory evaluated and the results are summarized in Table 3.

The following level classification was applied as evaluation criteria.

◎...No residual color bothers me at all.

○: There is a slight residual color, but there is no practical problem.

×...I'm concerned about residual color. There are practical problems.

Thermostability of dyes The reflection spectra of photographic materials 1-A to 1-G in the visible range of 400 to 7 nm were measured under an infrared lamp without exposure to light. Next, put photographic materials 1-A to 1-G in a dark box at 50℃80%R.
After being left under H conditions for 3 days, the reflection spectrum in the visible range was measured.

Ratio of absorbance at wavelengths of 450 nm, 550 nm, and 650 nm; (Absorbance after thermostat)/(Absorbance before thermostat)X
100 (%) was calculated.

Results in Table 3 In sample 1-G, the reflection spectra before and after the thermostat did not change. However, since l-G does not contain dye, it is shown in parentheses in Table 3.

The sensitivity of photographic material 1-A-1-F was the same, and there was no problem in practical use.

As is clear from Table 3, when the dye combination of the present invention is used, the dye is rapidly decolored and there is no residual color. It is also found that a photographic material having a layer that absorbs light in the visible region can be obtained, which has an excellent antihalation effect and whose effect remains unchanged even when heated.

In particular, compared to Photographic Material 1-F, which is considered to be the best among the current technologies, the photographic material of the present invention is not inferior in performance, and a photographic material with even better thermostability has been invented. This is noteworthy.

Example-2 Water (434d) and TritonX-200 surfactant (TX-200) (53g) (Rohm &
A 6.7% solution (sold by Hass) was placed in a 1.51 screw cap bottle. To this, 20 g of dye and zirconium oxide (ZrO) beads (8001d) (2 mm diameter) were added, and the bottle was tightly capped and placed in a mill to grind the contents for 4 days. Add to 12° 5% aqueous gelatin solution (160g) and place on a roll mill for 10 minutes.
Mix for a minute to reduce foam. The resulting mixture was filtered to remove ZrO beads.

This seratin dispersion was mixed with the desired coating aids and applied to a film support at a rate of 2 g of seratin per square meter.

The thus obtained dye dispersion sample was immersed in a buffer solution with pH = 5.7 for 5 minutes, and after drying, the rate of change in the measured absorption spectrum area was determined as the fixed rate, and 10 g of sodium sulfite was added to buffer solution 11 with pH = 10. Table 4 shows the spectral change after immersing the sample in the dissolved solution for 45 seconds as the residual color rate.

Table 4 Compounds Fixed rate (%) Remaining color rate (%) pH = 5
pH=7 I-8100920 I-49100900 Comparative Compound 95 15 4 Comparative Compound H (Effects of the Invention) When a layer containing the dye combination of the present invention is used as an antihalation layer, absorption in the visible region can be sufficiently selectively achieved. It can be dyed to last longer, without reducing the sensitivity of other layers, and there is significantly less residual color. Furthermore, even when heat was applied under humid conditions, the absorption spectrum did not change and the antihalation ability remained unchanged, demonstrating a remarkable effect.

Claims (2)

[Claims] (1) A silver halide photographic material comprising a hydrophilic colloid layer containing at least one compound represented by the following general formula (I) as a solid fine particle dispersion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an alkyl group (1 to 8 carbon atoms), an aryl group, or an aralkyl group, and R^2 in the formula represents an alkyl group or an aryl group, respectively. , represents an aralkyl group, a substituted amino group, or an alkoxy group. L_1, L_2, L_3, L_4, L_
5 represents a methine group, m and n represent 0 or 1. (2) A silver halide photographic material containing at least one solid fine particle dispersion of a dye represented by the general formula [I] and at least one solid fine particle dispersion of a dye represented by the general formula [II]. . General formula (II) ▲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_1, L_1_2, and L_1_3 have the same meanings as above, and m_1 represents 0, 1, and 2. However, it has at least one group selected from carboxyl group, sulfonamide group, and sulfamoyl group in the molecule.