JP2681526B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inert and easily decolorized in the course of photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted.

(Prior Art) In a silver halide photographic material, a photographic emulsion layer and other hydrophilic colloid layers are often colored in order to absorb light in a specific wavelength range.

When it is necessary to control the spectral composition of the light to be 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 a plurality of photographic emulsion layers, the filter layer may be located between them.

An image based on light scattered when passing through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the photosensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing blurring or halation, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an antihalation layer may be provided between the layers.

Coloring of the photographic emulsion layer is also performed to prevent a reduction in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation).

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

(1) It has an appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer is adversely affected in a chemical sense,
For example, do not give a decrease in sensitivity, regression of latent images, or fog.

(3) No decoloration during the photographic processing or elution into the processing solution or washing water, leaving no harmful coloring on the processed photographic light-sensitive material.

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

(5) It is excellent in stability over time in a solution or a photographic material and does not discolor.

In particular, when the coloring layer is a filter layer or an antihalation layer on the same side of the support as the photographic emulsion layer, those layers are selectively colored, and the other layers are colored. Often need to be substantially below. This is because otherwise, not only does it have a detrimental spectral effect on other layers, but it also diminishes its effect as a filter layer or antihalation layer. However, when the layer containing the dye and the other hydrophilic colloid layer come into contact with each other in a wet state, a part of the dye often diffuses from the former to the latter. More efforts have been made in the past to prevent such dye diffusion.

For example, U.S. Pat.No. 2,548,564 discloses a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye coexists in a layer as a mordant, and the dye is localized in a specific layer by interaction with a dye molecule. 4,124,386, 3,625,
No. 694 and the like.

Further, a method of dyeing a specific layer using a water-insoluble dye solid is described in JP-A-56-12639, JP-A-55-155350, and JP-A-55-15.
5351, 63-27838, 63-197943, 52-92716
No., European patents 15601, 276566, 274723, 299
No. 435 and World Patent No. 88/04794.

Further, a method of dyeing a specific layer using metal salt fine particles having a dye adsorbed thereto is disclosed in U.S. Pat.Nos. 2,719,088 and 2,496,841.
No. 2,496,843 and JP-A-60-45237.

However, even if these improved methods are used, the decolorization rate during the development processing is still slow, and there are changes in various factors such as speeding up the processing, improving the processing solution composition, or improving the photographic emulsion composition. Has a problem that the decolorizing function cannot always be sufficiently exhibited.

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

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

General formula (I) In the formula, R ₁ represents a phenyl group having at least one carboxylic acid group, an alkylsulfonamide group or a phenylsulfamoyl group, and R ₂ represents an alkyl group, an aryl group, an aralkyl group, a cyano group, —COOR ₆ , — CONR ₇ R ₈ , -COR ₉ ,-
_{SO 2 R 9, -SOR 9,} -SONR 7 R 8, -OR 7, -NR 7 R 8, -NR 8 COR
₉ , -NR ₆ CONR ₇ R ₈ or -NR ₈ SO ₂ R ₉ (where R ₆ , R ₇ , R ₈
Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₉ represents an alkyl group, an aryl group or an aralkyl group, and R ₇ and R ₈ or R ₈ and R ₉ are linked to each other to form a 5- or 6-membered ring. It may be formed. ), R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group or a sulfonyl group, and R ₃ and R ₅ or R ₄ and
R ₅ may combine to form a 5-membered ring or a 6-membered ring. R ₅ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, -OR _7, -COOR ₇ (wherein R ₇ is the same as R ₇ defined above).

L ₁ , L ₂ and L ₃ each represent a methine group, and n represents 0 or 1.

(2) The object of the present invention is to include at least one compound represented by the general formula (I) as a solid fine particle dispersion, and at least one compound represented by the following general formula (II) as a solid fine particle dispersion. It was also achieved with a silver halide photographic light-sensitive material containing.

General formula (II) In the formula, R ₁₀ is a hydrogen atom, an alkyl group, an aryl group, a cyano group, —COOR ₁₂ , —COR ₁₂ , —CONR ₁₂ R ₁₃ , —OR ₁₂ , or —NH
Represents COR ₁₂ , and R ₁₁ represents a hydrogen atom, an alkyl group, or an aryl group. R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group or an aryl group. However, the compound represented by the general formula (II) has at least one carboxyl group or sulfonamide group in the molecule.

L ₄ , L ₅ , L ₆ , L ₇ , and L ₈ represent methine groups, and m and n each represent 0 or 1.

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

R ₁ represents a phenyl group having at least one carboxylic acid group, alkylsulfonamide group or phenylsulfamoyl group. A phenyl group is a carboxylic acid group, an alkylsulfonamide group, a substituent other than a phenylsulfamoyl group (for example, an alkyl group (for example, methyl, ethyl), for example, an alkoxy group (for example, methoxy, ethoxy), a halogen atom (for example, chlorine, bromine, It may have a fluorine), an amino group (for example, dimethylamino, diethylamino), a hydroxyl group, a cyano group, a phenoxy group}. Further, the carboxylic acid group, the alkylsulfonamide group and the phenylsulfamoyl group are not only directly bonded to the phenyl group,
Valent linking group {e.g. _{-O (CH 2) P -,} - NR (CH 2) P - (R is an alkyl group such as methyl, ethyl 1 to 6 carbon atoms, n-
Hexyl, and p represents an integer of 1 to 5)}.

The alkyl group represented by R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is an unsubstituted alkyl group (for example, methyl, ethyl, normal propyl, isopropyl, cyclohexyl) or Substituted alkyl group {halogen atom as a substituent (eg, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl), phenyl group (eg, benzyl, carboxybenzyl), hydroxyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl) ), An alkoxy group (for example, 2-methoxyethyl, 2
-(2-hydroxyethoxy) ethyl), a carboxy group (for example, carboxymethyl, 1-carboxyethyl, 2
-Carboxyethyl), a sulfonamide group (for example, methanesulfonamidoethyl), an amino group (for example, 2-
(N, N dimethylaminoethyl), carboxylate (eg ethoxycarbonylmethyl, acetoxyethyl) or sulfonate (eg methoxysulfonylethyl)} is preferred.

The aryl group represented by R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is an unsubstituted aryl group (eg phenyl) or a substituted aryl group {a halogen atom ( For example, 4-chlorophenyl, 2,5-dichlorophenyl), an alkyl group (for example, 4-methylphenyl), a hydroxyl group (for example, hydroxyphenyl), a carboxy group (for example, carboxyphenyl,
3,5-dicarboxyphenyl), a sulfonamide group (for example, 4-methylsulfonylaminophenyl, 4-
Sulfamoylmethyl), an alkoxy group (eg 4-methoxyphenyl, 4- (2-hydroxyethoxyphenyl)), an amino group (eg N, N-dimethylaminophenyl, 4- (N-carboxymethyl-N-ethylamino) )
Phenyl), carboxylates (eg 4-ethoxycarbonylphenyl, 4- (2-hydroxyethoxy) phenyl) or sulfonates (eg 4-methoxysulfonylphenyl)} are preferred. The methine group represented by L ₁ , L ₂ and L ₃ is preferably an unsubstituted methine group, but may have a substituent (eg methyl, ethyl, phenyl).

Next, the compound represented by formula (II) will be described in detail.

Alkyl represented by R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ is an unsubstituted alkyl group (for example, methyl, ethyl, normal propyl,
Isopropyl, cyclohexyl) or substituted alkyl group (halogen atom as a substituent (eg, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl), phenyl group (eg, benzyl, carboxybenzyl), hydroxyl group (eg, 2-hydroxyethyl) , 3-hydroxypropyl), alkoxy groups (eg 2-methoxyethyl, 2-
(2-hydroxyethoxy) ethyl), carboxy group (for example, carboxymethyl, 1-carboxyethyl, 2
-Carboxyethyl), a sulfonamide group (for example, methanesulfonamidoethyl), an amino group (for example, 2-
(N, N dimethylaminoethyl), carboxylate (eg ethoxycarbonylmethyl, acetoxyethyl) or sulfonate (eg methoxysulfonylethyl)} is preferred.

The aryl group represented by R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ is an unsubstituted aryl group (for example, phenyl) or a substituted aryl group {a halogen atom (for example, 4-chlorophenyl, as a substituent,
2,5-dichlorophenyl), alkyl group (eg 4-methylphenyl), hydroxyl group (eg hydroxyphenyl), carboxy group (eg carboxyphenyl, 3,5
-Dicarboxyphenyl), a sulfonamide group (for example, 4-methylsulfonylaminophenyl, 4-sulfamoylmethyl), an alkoxy group (for example, 4-methoxyphenyl, 4- (2-hydroxyethoxyphenyl)), an amino group (for example, N , N-Dimethylaminophenyl, 4- (N
-Carboxymethyl-N-ethylamino) phenyl),
Carboxylate (for example, 4-ethoxycarbonylphenyl, 4- (2-hydroxyethoxyphenyl) or sulfonate (for example, 4-methoxysulfonylphenyl)) is preferable.Metine group represented by L ₄ , L ₅ , L ₆ and L _7. Is preferably an unsubstituted methine group, but may have a substituent (eg, methyl, ethyl, phenyl).

Among the compounds represented by the general formula (II), particularly preferable are those having no sulfo group or carboxy group salt as a substituent.

Further preferred among the compounds represented by the general formula (II) are those having at least two groups selected from a carboxy group and a sulfonamide group.

Next, specific examples of the compounds represented by formulas (I) and (II) of the present invention are shown, but the present invention is not limited thereto.

In the table below The binding position of is ortho to the methine group.

Next, a method for synthesizing the compound of the present invention will be described.

Generally, the compound of the present invention can be obtained by reacting 1 mol of an aldehyde compound with 1 mol of an acidic mother nucleus compound such as pyrazolone.

Regarding these condensation reactions, for example, JP-A-51-3623
No. 51-10927, No. 48-68623, and Japanese Patent Publication No. 56-49953 can be referred to.

Specific examples of general formula (II) The compound of the general formula (II) is disclosed in JP-A Nos. 52-92716 and 63-316.
853, 64-40827, and JP-B-58-35544 can be used for the synthesis.

The compound of the general formula (I) or (II) is used in an amount of 1-1000 mg per 1 m ² area on the light-sensitive material, preferably 1 per 1 m ²
~ 800 mg is used.

When the compound of the general formula (I) or (II) is used as a filter dye or an antihalation dye, any effective amount can be used, but an optical density of 0.05 to
Preferably, it is used so as to be in the range of 3.5. The timing of addition may be any step before coating.

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

The fine particle dispersion of the compound of the general formula (I) or (II) of the present invention is a method of precipitating the compound of the present invention in the form of a dispersion, and / or a known pulverizing means in the presence of a dispersant, for example, Ball milling (ball mill, vibrating ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc., in which case a solvent (for example, water, alcohol, etc. may coexist) is used. Can be formed. 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 microcrystalline powder, in which case a surfactant for dispersion may be used. Good. Alternatively, the compound of the present invention may be first dissolved by controlling the pH, and then the pH may be changed to perform microcrystallization. The microcrystalline particles of the compound of the present invention in the dispersion have an average particle size of 10 μm or less, more preferably 2 μm or less.
μm or less, particularly preferably 0.5 μm or less,
In some cases, fine particles of 0.1 μm or less are more preferable.

As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.

The silver halide emulsion used in the present invention is preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide or silver chloride.

The silver halide grains used in the present invention have a regular crystal form such as cubic or octahedral, or irregular such as spherical or plate-like.
Or a complex form of these crystal forms. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may have a uniform phase. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) It may be. Preferably, the particles are such that the latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
Micron or less, preferably 0.3 micron or less, preferably 0.6 micron or more in diameter, with an average aspect ratio of 5
Either a tabular grain emulsion in which the above grains occupy 50% or more of the total projected area, or a statistical variation coefficient (standard deviation S is divided by diameter in a distribution expressed by diameter when the projected area is approximated by a circle) Monodisperse emulsions having a value S /) of 20% or less are preferred. Further, two or more tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is Chimie Physique Photographeque by P. Glafkides.
(Paul Montell, 1967), GFDuffin, Photographic Emulsion Chemistr
y) (Focal Press, 1966), VLZelikman et al., Making and
Coating Photographic Emulsion (Ma
king and Coating photographic Emulsion) (Focal Press, 1964) and the like.

In forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,6
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
374, etc., and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A No. 54-100717, etc.) and the like can be used.

In the course 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 may be coexisted.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.

As gelatin, besides general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Sci. Pho.
t. Japan), No. 16, page 30 (1966), and an enzyme-treated gelatin may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples thereof include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-
Triazine and its sodium salt, etc. and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or vinylsulfonyl groups as side chains Is preferred since a hydrophilic colloid such as gelatin can be rapidly cured to provide stable photographic characteristics. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3
-Pyridinio) methanesulfonate etc.) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene))
Pyrrolidinium, 2-naphthalene sulfonate, etc.) are also fast and excellent.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. 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 usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
Such as a tetrazole nucleus and a pyridine nucleus; 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, ie, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus , Benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-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 thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510) Described)), cadmium salt,
An azaindene compound may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

The silver halide photographic emulsion used in the present technology should contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the photosensitive material, or stabilizing the photographic performance. Can be. That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; Azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes, pentaazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. Can be.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, acceleration of development, high contrast, sensitization). May be.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or halation or other various purposes. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . The oil-soluble dye may 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 a support. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. Any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or may be composed of three layers to further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity.

Generally, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. For example, a combination of infrared-sensitive layers may be used for pseudo color photographic quality or semiconductor laser exposure.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are plastic films, paper, cloths and other flexible supports or glass, porcelain, etc., which are usually used for photographic light-sensitive materials.
It is applied to a rigid support such as metal. Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
Examples of the film include a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate and polycarbonate, a baryta layer, and paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating and extrusion coating can be used. U.S. Pat.No. 2,681,294 as required,
Multiple layers may be simultaneously coated by the coating method described in JP-A-2761791, JP-A-3526528 and JP-A-3508947.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No.17123 (1978
July, 1999) or by using a black color coupler described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136 to obtain a black-and-white image such as for X-rays. The present invention can be applied to a photosensitive material. Plate making film such as squirrel film or scanner film, direct medical / indirect medical or industrial X-ray film, negative black-and-white film for photography, black-and-white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer photosensitive material and The present invention can be applied to a printout type photosensitive material.

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, a peeling (peel-apart) type or a JP-B-46 can be used.
-16356, 48-33697, JP-A-50-13040 and integrated type as described in British Patent 1,330,524, as described in JP-A-57-119345 A peeling-free type film unit can be adopted.

The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature latitude. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used by being sealed in a processing solution container as a developing solution component.

Various exposure means can be used for the light-sensitive 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 light source or the writing light source. Flashlight sources such as natural light, (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, the fluorescent surface (CRT, etc.) emitted from the fluorescent material excited by the electron beam, liquid crystal (LCD), lanthanum-doped lead titan zirconate (PLZT), etc. An exposure means combining a planar light source can also be used.
If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and as typical examples, 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 sulfates thereof,
Hydrochloride or p-toluenesulfonate may, for example, be mentioned. These diamines are generally more stable in a salt than in a free state, and are preferably used.

Color developing solutions include pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. It is common to include such as. If necessary, preservatives such as hydroxylamines, dialkylhydroxylamines, hydrazines, triethanolamine, triethylenediamine or sulfite, organic solvents such as triethanolamine, diethylene glycol, benzyl alcohol, polyethylene glycol , Quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, Various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, and antioxidants described in West German Patent Application (OLS) No. 2,622,950 are added to a color developer. May be.

In the development process of the reversal color photosensitive material, color development is usually performed after black-and-white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-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 the color developing solution but also any photographic developing method may be applied to the light-sensitive material of the present invention. As a developing agent used in the developer, a dihydroxybenzene-based developing agent,
-Phenyl-3-pyrazolidone type developing agents, p-aminophenol type developing agents, etc., and these are used alone or in combination (for example, 1-phenyl-3-pyrazolidones and dihydroxybenzenes or p-aminophenols and dihydroxybenzenes). Type) can be used. 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, as the dihydroxybenzene-based developing agent, for example, hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Toluhydrohydroquinone, methylhydroquinone, 2,
3-dichlorohydroquinone, 2,5-dimethylhydroquinone and the like, and 1-phenyl-3-pyrazolidone-based developing agents include 1-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 and the like, and p-aminophenol-based developing agents include p-aminophenol and N-methyl-
p-aminophenol or the like is used.

A compound which gives free sulfite ions as a preservative, for example, sodium sulfite, potassium sulfite, potassium metabisulfite, sodium bisulfite and the like are added to the developer. In the case of an infectious developer, sodium formaldehyde sodium bisulfite which hardly gives free sulfite ions in the developer may be used.

As the alkaline agent of the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, potassium tertiary phosphate, diethanolamine, triethanolamine and the like are used. The pH of the developer is usually set to 9 or more, preferably 9.7 or more.

The developer may contain an organic compound known as an antifoggant or a development inhibitor. Examples thereof include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetrazaindenes, pentaazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, sodium 2-mercaptobenzimidazole-5-sulfonate and the like.

The developer usable in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1,000 to 10,000 can be contained in the range of 0.1 to 10 g / l.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetic acid, triethylenetetraamine, xaacetic acid, diethylenetetraaminepentaacetate, or the like as a water softener to the developer usable in the present invention.

In the developer used in the present invention, a compound described in JP-A-56-24347 as a silver stain inhibitor, a compound described in JP-A-62-212651 as a development unevenness inhibitor, and a solubilizer as a special application The compounds described in JP-A-60-109743 can be used.

The developing solution used in the present invention has a buffer
Boric acid described in 61-28708, saccharides described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphate ( For example, sodium salts and potassium salts) are used.

Various compounds may be used as the development accelerator used in the present invention, and these compounds may be added to the light-sensitive material.
It may be added to any of the treatment liquids. Preferred development accelerators include amine compounds, imidazole compounds, imidazoline compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds, thioether compounds, thione compounds, certain mercapto compounds, isoionic compounds, and thiocyanic acid. Salts.

In particular, it is necessary to carry out rapid development processing in a short time.
These development accelerators are desirably added to the color developing solution, but may be added to the photosensitive material depending on the type of the accelerator or depending on the position of the photosensitive layer to be developed on the support. it can. Further, it can be added to both the color developing solution and the photosensitive material. In some cases, a pre-bath may be provided before the color developing bath, and may be added therein.

Amino compounds useful as development accelerators include both inorganic and organic amines such as hydroxylamine. The organic amine can be an aliphatic amine, an aromatic amine, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine, with primary, secondary and tertiary amines and quaternary ammonium compounds all being effective. is there.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. In order to further speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. Examples of the bleaching agent include iron (III), cobalt (III), chromium (I
Compounds of polyvalent metals such as V) and copper (II), peracids, quinones, nitrones and the like are used. Ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid as representative bleaching agents Such as aminopolycarboxylic acids or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates; nitrosophenols and the like can be used. Of these, iron (III) ethylenediaminetetraacetate, iron (III) diethylenetriaminepentaacetate and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Further, the iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
988, JP-A-53-32736, 53-57831, 37418,
53-65732, 53-72623, 53-95630, 53-956
No. 31, No. 53-104232, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. 1
Compounds having a mercapto group or a disulfide group described in JP-A-7129 (July 1978); thiazolidine derivatives as described in JP-A-50-140129; JP-B-45-850
6, JP-A-52-20832, JP-A-53-32735, U.S. Pat.
Thiourea derivatives described in 06,561; West German Patent 1,127,71
5, iodide described in JP-A-58-16235; West German Patent No. 96
Polyethylene oxides described in 6,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434, 49-59644, 53-94927,
The compounds described in JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940, and iodine and bromide ions can also be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
The compounds described in 3,858, West German Patent 1,290,812, and JP-A-53-95630 are preferable. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

Examples of the fixing agent include thiosulfate, thiocyanate, thioether-based compound thioureas, a large amount of iodide, and the like, and thiosulfate is generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. Various known compounds may be added to the washing step and the stabilizing step for the purpose of preventing precipitation and saving water. For example, to prevent precipitation,
Hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid; fungicides and antibacterial agents for preventing the occurrence of various bacteria, algae and mold; magnesium salts and aluminum salts bismuth salts Metal salts represented by the formula (1), a surfactant for preventing drying load and unevenness, various hardeners, and the like can be added as necessary. Or West Photographic Science and Engineering magazine (LEWest, Phot
o.Sci.Eng.), Volume 6, pp. 344-359 (1965), etc. may be added. In particular, the addition of a chelating agent or an anti-binder is effective.

In the water washing step, two or more tanks are generally countercurrently washed to save water. Furthermore, instead of the washing step, Japanese Patent Laid-Open No.
A multi-stage countercurrent stabilization treatment step as described in No. 8543 may be carried out. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners and the like. More than one species may be used in combination.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

In the color light-sensitive material for photographing, the step (washing-stabilization) usually performed after fixing can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). On this occasion,
When the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilizing treatment time of the present invention varies depending on the type of photosensitive 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 the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Patent No. 3,342,59
No. 7, indoaniline-based compound, No. 3,342,599,
Schiff base type compounds described in Research Disclosure Nos. 14850 and 15159, aldol compounds described in No. 13924, metal salt complexes described in U.S. Patent No. 3,719,492,
Starting with the urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133, and JP-A-56-59232
No. 56, No. 56-67842, No. 56-83734, No. 56-83735, No. 56
-83736, 56-89735, 56-81837, 56-54430
No. 56-106241, No. 56-107236, No. 57-97531 and No. 57-83565, and various salt-type precursors.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are JP-A Nos. 56-64339, 57-144547, and 57-211147.
No. 58, No. 58-50532, No. 58-50536, No. 58-50533, No. 58
-50534, 58-50535 and 58-115438.

The various processing solutions 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 accelerate processing and reduce processing time, and conversely, lower temperatures can improve image quality and improve processing solution stability. it can. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

A heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating pig, a squeegee, and the like may be provided in the various treatment baths as needed.

In the case of continuous processing, a certain finish can be obtained by using a replenisher for each processing liquid to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like.

When the light-sensitive material of the present invention is a color paper, it can be subjected to a bleach-fixing process, if necessary, even if it is a color photographic material for photography.

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

The silver halide photographic light-sensitive material containing the compound of the present invention is easily decolorized or eluted by photographic processing, gives a low Dmin, and does not lower the sensitivity at the same time, and has the effect that the decrease in sensitivity upon storage is small.

Further, the silver halide photographic light-sensitive material of the present invention gives an image with improved sharpness. Further, the photograph obtained from the silver halide photographic light-sensitive material of the present invention does not generate stains, is stable even for long-term storage, and does not deteriorate in photographic performance.

(Examples) Next, the present invention will be described in more detail based on Examples. Example 1 (Preparation of Emulsion A) Aqueous silver nitrate solution and 0.5 × 10 ^-4 mol of ammonium hexachlororhodium (III) chloride per mol of silver. Was mixed with a double jet method in a gelatin solution at 35 ° C. while controlling the pH to 6.5 to prepare a monodisperse silver chloride emulsion having an average grain size of 0.07 μm.

After particle formation, soluble salts are removed by a flocculation method well known in the art, and 4-
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 1-phenyl-5-mercaptotetrazole were added. 55 g of gelatin and 1 g of silver contained in 1 kg of emulsion
It was 105 g. (Emulsion A) (Preparation of Photosensitive Material) The following nucleating agent and nucleation accelerator were added to the emulsion A, and then polyethyl acrylate latex (300 mg /
m ² ), and further adding 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt as a hardening agent to give 1 m ²
Polyethylene terephthalate so that the amount of silver is 3.5 g per A silver halide emulsion layer is coated on a transparent support, and gelatin (1.3 g / m ² ) is further formed on the silver halide emulsion layer.
-19 (0.1 g / m ² ), as a coating aid, a protective layer containing the following three surfactants, stabilizers and matting agents is applied,
Dried.

(Sample 1) Stabilizer: thioctic acid 6.0 matting agent: polymethylmethacrylate (average particle size: 3.5 μ) 50.0 mg / m ² Compound I-19 of the present invention was used by preparing a dispersion according to the following procedure.

(Preparation of dye dispersion) Solution I was added little by little while stirring Solution II at 40 ° C.

(Preparation of Comparative Sample) 1) A sample was prepared by using the following dye instead of the compound I-19 in Example 1 (Comparative Sample 1-A). 2) The following dye was used in place of compound I-19 in Example 1. (Comparative Sample 1-B) This dye is exemplified in WO 88/04794.

3) Comparative Sample 1-C was prepared by using the following protective layer instead of the protective layer containing the compound I-19 of the present invention in Example-1. Acid-treated gelatin 2.0g / m ² Stabilizer thioctic acid 0.006 / m ² Matting agent Polymethylmethacrylate (average particle size 3.5μ) 0.009 / m ² (Performance evaluation) (1) The above four samples were taken from Dainippon Screen Co., Ltd. Mitsumuro Printer P At -607, it was exposed through an optical wedge, developed with the following developer for 20 seconds at 38 ° C, fixed in the usual way, washed with water and dried.

Basic formulation of developer Hydroquinone 35.0g N-methyl-P-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Potassium triphosphate 74.0g Potassium sulfite 90.0g Ethylenediaminetetraacetic acid tetrasodium salt 1.0g Potassium bromide 4.0 g 5-Methylbenzotriazole 0.6 g 3-diethylamino-1,2-propanediol 15.0 g Water was added 1 (pH = 11.5) As a result, Example 1 and Comparative Sample 1-A were completely decolorized, Comparative samples 1-B and 1-C had yellow stains remaining. Comparative Sample 1-B completely decolorized when the development time was increased to 30 seconds. As mentioned above,
The compounds of the invention are rapidly decolorized upon treatment.

(2) Test for Tone Variability The above four samples were exposed through a flat screen using the above-mentioned printer, and the other samples were developed in the same manner as in the test of (1). After determining the exposure time that can return the halftone dot area to 1: 1 for each sample, perform the exposure twice or four times the exposure time, and enlarge the halftone dot area. I checked what to do. It shows that the greater the magnification, the better the tone variability. The results are shown in Table 1. As can be seen from Table 1, Comparative Sample 1-A has significantly reduced tone variability, whereas Sample 1 of the present invention has high tone variability. this is,
Since the dye used in Comparative Sample 1-A is water-soluble and diffusible, the dye is uniformly diffused from the layer added during storage to the photosensitive emulsion layer. This is because the expansion of the halftone dot area was suppressed by the effect of preventing irradiation. On the other hand, the compound I-19 of the present invention is fixed in the layer to which it is added, and thus exhibits high tone variability.

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

(3) Evaluation of Contamination (Stain) by Reducer Liquid The strips of the sample of the present invention and the sample of the comparative example obtained by treatment in the above (2) were immersed in the following Farmer reducer liquid at 20 ° C. for 60 seconds. Washed with water and dried. As a result, in all of the samples, the area of 50% halftone dot area was reduced to 33%, but in Comparative Sample 1-C, violent brown stencil was generated over the entire surface. No stain was observed in Sample 1 of the present invention and Comparative Samples 1-A and 1-B.

Farmer reducer When used, mix 1st liquid: 2nd liquid: water = 100 parts: 5 parts: 100 parts.

As described above, the sample of the present invention was good in all of decoloring property, tone variability, and reducing property.

Example 2 Paper support samples A, B and C were obtained after corona discharge treatment on a paper support laminated on both sides with polyethylene and using a gelatin subbing layer or the following dye dispersion.

Dye dispersion method The following dye crystals are kneaded and sand-milled.
Finely divided. Further, 0.5 g of citric acid was dissolved in 25 ml of a 10% lime-processed gelatin aqueous solution, and the sand was used with a glass filter. Compound of the present invention I-5 ... 1.0 g Compound of the present invention I-40 ... 1.6g Then, the dye adhering to the sand on the glass filter was removed to obtain 100 ml of a 7% gelatin solution. (The average particle size of the dye fine particles was 0.15 μm.) Compound I-5 of the present invention: 1.0 g Compound II-3 of the present invention: 1.6 g was similarly prepared.

Paper support A Subbing layer Gelatin ... 0.8 g / m ² Paper support B Antihalation layer Gelatin 0.6 g / m ² Compound of the present invention I-5 25 g / m ² Compound of the present invention I-40 ...... 40 g / m ² paper support C antihalation layer gelatin …… 0.6 g / m ² compound of the present invention I-5 …… 40 mg / m ² compound of the present invention II-3 …… 65 mg / m ² paper support On the samples A, B and C, multilayer color photographic paper samples 2-1 to 2-4 having the following layer constitution were obtained.

 The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) Ethyl acetate 2 in 4.4 g and 1.4 g of color image stabilizer (Cpd-7)
7.2 cc and 8.2 g of the solution (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chloroiodobromide emulsion (cubic, 3: 7 mixture of average grain size 0.88 μm and 0.70 μm (silver mole ratio). Coefficient of variation of grain size distribution is 0.08 and 0.10, each emulsion is brominated. Silver
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were 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 were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

To one of the paper support samples A, the following comparative dye was added to the emulsion layer.

and (Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Supports Polyethylene laminated paper [Samples A, A, B, and C in which an undercoat layer and an antihalation layer are provided on a first layer side polyethylene containing a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)] First layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 2nd layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, average) 1: 3 mixture of 0.55 μm grain size and 0.39 μm grain size (Ag molar ratio) Coefficient of variation of grain size distribution is 0.10 and 0.08, and each emulsion has AgBr0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-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 absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Variation in grain size distribution The coefficients are 0.09 and 0.11, AgBr0 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.17 Liquid paraffin 0.03 Regarding the obtained samples 2-1 to 2-4, a photometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3,2)
A stepwise exposure for sensitometry was given through blue, green and red filters using 00 ° K. On the other hand, resolution (CT
F) Exposure for measurement was performed, and then the following processing steps were performed. The concentration of the obtained sample was measured and the results shown in Table 2 were obtained. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17l Bleach fixing 30-35 ℃ 45 seconds 215ml 17l Rinse 30-35 ℃ 20 seconds -10l Rinse 30-35 ℃ 20 seconds -10l Rinse 30- 35 ℃ 20 seconds 350ml 10l Dry 70〜80 ℃ 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse-to-tank counterflow method) The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm or less for calcium and magnesium, respectively) When the dye according to the present invention is used in the antihalation layer,
Relatively little decrease in sensitivity and little residual color. By using such an amount, the resolving power can be remarkably improved.

Example-3 Preparation of dye fixing layer Dyes I-13 and II-5 were ball-milled by the method described in JP-A-63-19743.

Water 434 ml and Triton X-200R surfactant (TX-200
R) and 791 ml of 6.7% aqueous solution were placed in a 2 l ball mill.
20 g of dye were added to this solution. Zirconium oxide (Zr
400 ml (2 mm diameter) beads of O) were added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. When the obtained dye dispersion was observed, the particle size of the crushed dye had a wide distribution in the diameter range of 0.05 to 1.15 μm.

A 100 μm thick transparent PET support was used as the support.
In order to improve the adhesion of the support to the hydrophilic colloid layer, the surface was previously treated by corona discharge and then a first subbing layer consisting of styrene-butadiene latex was provided and a second subbing of gelatin 0.08 g / m ² was provided on top of it. Layers were provided.

The fine dispersion of the dye was coated as a gelatin dispersion solution on the support so as to have the following coating amount. Thus, an antihalation layer was prepared.

・ Gelatin 1.8 g / m ²・ Dye I-13 Amount shown in Table 3 ・ Potassium polystyrene sulfonate (average molecular weight 60
10,000) 35 mg / m ² ・ Phenoxyethanol 18mg / m ²・ 1,2-bis (vinylsulfonylacetamide) ethane 1
Preparation of 00 mg / m ² Emulsion Coating Solution Raw milk # 1 shown below is a surface latent image type emulsion, and negative type characteristics can be obtained by a commercially available microfilm general purpose processing solution. Further, by performing a reversal process (reversal process) using a reversal processing solution, a positive type characteristic can be obtained.

<Preparation of Raw Emulsion # 1> Solution II and solution III are simultaneously added to well-stirred solution I for 45 minutes.
After the addition of the solution II and the whole amount, a cubic monodispersed emulsion having an average particle size of 0.28 μm was finally obtained.

At this time, the addition rate of the solution III was adjusted with respect to the addition of the solution II while adjusting the pAg value in the mixing vessel to always be 7.50. The solution IV was added over 5 minutes from 7 minutes after the start of the addition of the solution II. After completion of addition of solution II,
After washing with water and desalting by the precipitation method, 100 g of inert gelatin
Was dispersed in an aqueous solution containing. To this emulsion, 34 mg each of sodium thiosulfate and tetrachloroaurate were added per mol of silver, and the pH and pAg values were adjusted to 8.9 and 7.0 (40 ° C), respectively, and then chemistries were performed at 75 ° C for 60 minutes. Sensitization treatment was carried out to obtain a surface latent image type silver halide emulsion.

 The layer constitution and the composition of each layer are as follows.

The emulsion layers other than the antihalation layer, the surface protective layer, the conductive layer, and the Ge1 layer were prepared and coated so that the respective components had the following coating amounts, to obtain a photographic material.

<Emulsion layer> Processing method Reversal development processing Reversal development processing is the F-10R reverse deep tank automatic developing machine manufactured by Allen Products, USA
FR-531,532,533,534,535 manufactured by emicals) was used under the following conditions.

Negative development treatment Negative development treatment was carried out under the following conditions using a general-purpose processing solution for microfilm (US, FR Chemicals FR-537 developing solution) commercially available with an F-10R deep tank automatic developing machine manufactured by Allen Products of the United States. went.

Evaluation of Sharpness Sharpness was evaluated by MTF. The photographic material was exposed to white light for 1/100 second using an MTF measuring wedge, and the above-mentioned automatic processor processing was performed.

The MTF was measured with an aperture of 400 × 2 μm ² , and evaluated at a portion where the optical density was 1.0 using an MTF value having a spatial frequency of 20 cycles / mm.

 The results are shown in Table-3.

Evaluation of residual color After the unexposed film was subjected to the above-mentioned automatic development processing, the green transmission density and the blue transmission density were measured through a Macbeth Status A filter.

 The results are shown in Table-3.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having 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) In the formula, R ₁ represents a phenyl group having at least one carboxylic acid group, an alkylsulfonamide group or a phenylsulfamoyl group, and R ₂ represents an alkyl group, an aryl group, an aralkyl group, a cyano group, —COOR ₆ , — CONR ₇ R ₈ , -COR ₉ , -SO
₂ R ₉ , -SOR ₉ , -SONR ₇ R ₈ , -OR ₇ , -NR ₇ R ₈ , -NR ₈ CO
R ₉ , -NR ₆ CONR ₇ R ₈ or -NR ₈ SO ₂ R ₉ (where R ₆ , R ₇ , R ₈
Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, R ₉ represents an alkyl group, an aryl group or an aralkyl group, and R ₇ and R ₈ or R ₈ and R ₉ are linked to form a 5- or 6-membered ring. You may form. ), R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group or a sulfonyl group, and R ₃ and R ₅ or R ₄ and R ₅ are linked to each other to form a 5-membered group. It may form a ring or a 6-membered ring.
R ₅ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, -OR _7, -COOR ₇ (wherein R ₇ is the same as R ₇ defined above). L ₁ , L ₂ and L ₃ each represent a methine group, and n represents 0 or 1.