JP2681525B2 - 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 anti-halation 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) To have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, for example, reduction in sensitivity, regression of image, or fog.

(3) No harmful coloring is left on the processed photographic light-sensitive material by being decolorized during the photographic processing or being eluted in the processing solution or washing water.

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

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

In particular, when the colored layer is a filter layer, or when it is an anti-halation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and other layers are colored. Often need to be substantially below. This is because otherwise, not only does it have a detrimental spectral effect on the other layers, but also its effect as a filter layer or an antihalation layer is diminished. 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 is coexisted in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. , 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
, European Patents 15601, 276566, 274723, 276
No. 566, No. 299435, 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 development processing is still slow, and when various factors such as processing speed, processing solution composition, or photographic emulsion composition are changed, there is a change. Has a problem that the decolorizing function cannot always be sufficiently exhibited.

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

(Means for Solving the Problem) 1) An 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. Will be achieved.

General formula (I) (In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, L ₁ , L ₂ , L ₃ each represents a methine group, and n represents 0 or 1. However, the compound represented by the general formula (I) has at least one carboxyl group, sulfonamide aryl group or phenolic hydroxyl group in the molecule. ) 2) An object of the present invention is to include at least one compound represented by the general formula (I) as solid dispersed fine particles, and at least one compound represented by the following general formula (II) as solid dispersed fine particles. It is achieved by including a silver halide photographic light-sensitive material.

General formula (II) (Wherein, R ₅ is a hydrogen atom, an alkyl group, an aryl group, a cyano group, a hydroxyl _{group, -COOR 7, -CONR 7 R 8} , -OR 7, -NHCOR
₇ , R ₆ , R ₇ , and R ₈ represent an alkyl group and an aryl group, respectively. L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅ each represent a methine group, and p and q each represent 0 or 1. However, general formula (II)
The compound represented by has at least one carboxyl group, sulfonamide aryl group, or phenolic hydroxyl group in the molecule. Next, the compound represented by formula (I) will be described in detail.

The alkyl group represented by R ₁ and R ₂ is an unsubstituted alkyl group (for example, methyl, ethyl, normal propyl, isopropyl, cyclohexyl), or a substituted alkyl group (as a substituent, a phenyl group (for example, benzyl, carboxybenzyl, Hydroxybenzyl), a carboxyl group (for example, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl)}, and R ₁ and R ₂ may be the same or different.

The aryl group represented by R ₁ and R ₂ is an unsubstituted aryl group (for example, phenyl) or a substituted aryl group (a halogen atom (for example, 4-chlorophenyl, 2,5-dichlorophenyl) as a substituent), an alkyl group (for example, 4-methylphenyl), hydroxyl group (eg hydroxyphenyl), carboxyl group (eg carboxyphenyl, 3,5-dicarboxyphenyl), sulfonamide group (eg 4-methanesulfonamidophenyl), alkoxy group (eg 4 −
Methoxyphenyl, 4- (2-hydroxyethoxyphenyl)), amino group (for example, N, N-dimethylaminophenyl, 4- (N-carboxymethyl-N-ethylamino) phenyl), alkoxycarbonyl group (for example, 4-
Ethoxycarbonylphenyl), or sulfonyloxy group (eg 4-methanesulfonyloxyphenyl)}
And R ₁ and R ₂ may be the same or different.

The alkyl group represented by R ₃ and R ₄ is an unsubstituted alkyl group (eg, methyl, ethyl, normal propyl, isopropyl, cyclohexyl), or a substituted alkyl group (as a substituent, a phenyl group (eg, benzyl, carboxybenzyl). , Hydroxybenzyl), a carboxyl group (eg carboxymethyl, 1-carboxyethyl, 2-carboxyethyl), an alkoxycarbonyl group or an acyloxy group (eg ethoxycarbonylmethyl, 2-acetoxyethyl)}.

The alkoxy group represented by R ₃ and R ₄ has an alkyl moiety which is an unsubstituted alkyl group (for example, methyl, ethyl, normal propyl, isopropyl, cyclohexyl) or a substituted alkyl group (as a substituent, a phenyl group ( For example, benzyl, carboxybenzyl, hydroxybenzyl), a carboxyl group (eg carboxymethyl, 1-
It is an alkoxy group having a carboxyethyl group, a 2-carboxyethyl group, an alkoxycarbonyl group or an acyloxy group (eg, ethoxycarbonylmethyl, 2-acetoxyethyl)}.

The amino group represented by R ₃ and R ₄ may be an unsubstituted amino group, an alkylamino group, or a dialkylamino group, and the alkyl moiety thereof is an unsubstituted alkyl group (for example, methyl, ethyl, normal (Propyl, isopropyl, cyclohexyl), or a substituted alkyl group (as a substituent, a phenyl group (eg, benzyl, carboxybenzyl, hydroxybenzyl), a carboxyl group (eg, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl), an alkoxycarbonyl group Or an acyloxy group (eg, ethoxycarbonylmethyl, 2-
Acetoxyethyl)}.

The substituents represented by R ₃ and R ₄ may be the same or different.

The methine group represented by L ₁ , L ₂ and L ₃ is preferably an unsubstituted methine group, but may have a substituent (for example, methyl, ethyl or phenyl).

 n is 0 or 1.

The compound represented by the general formula (I) is a carboxyl group,
It has at least one group selected from a sulfonamide aryl group or a phenolic hydroxyl group.

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

The alkyl group represented by R ₅ , R ₆ , R ₇ and R ₈ is an unsubstituted alkyl group (for example, methyl, ethyl, normal propyl,
Isopropyl, cyclohexyl), or a substituted alkyl group (a halogen atom as a substituent (eg, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl), a phenyl group (eg, benzyl, carboxybenzyl), a hydroxyl group (eg, 2-hydroxy) Ethyl, 3-hydroxypropyl), alkoxyl groups (eg 2-methoxyethyl, 2
-(2-hydroxyethoxy) ethyl), a carboxyl group (for example, carboxymethyl, 1-carboxyethyl,
2-carboxyethyl), a sulfonamide group (for example, methanesulfonamidoethyl), an amino group (for example, 2-
(N, N dimethylaminoethyl), an alkoxycarbonyl group or an acyloxy group (eg ethoxycarbonylmethyl, acetoxyethyl)}.

The aryl group represented by R ₅ , R ₆ , R ₇ , and R ₈ 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), carboxyl group (eg carboxyphenyl, 3,
5-dicarboxyphenyl), a sulfonamide group or a sulfamoyl group (for example, 4-methanesulfonamidophenyl, 4-sulfamoylphenyl), an alkoxy group (for example, 4-methoxyphenyl, 4- (2-hydroxyethoxy) Phenyl), an amino group (for example, N, N-dimethylaminophenyl, 4- (N-carboxymethyl-N-ethylamino) phenyl), an alkoxycarbonyl group (for example, 4-ethoxycarbonylphenyl, or a sulfonyloxy group ( For example, 4-methanesulfonyloxyphenyl)}.

The methine group represented by L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅ is preferably an unsubstituted methine group, but may have a substituent (for example, methyl, ethyl or phenyl).

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

Further preferred among the compounds represented by the general formula (II) are those having at least one group selected from a carboxyl group, a sulfonamide aryl group and a phenolic hydroxyl group, and more preferably two groups. .

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

The compound represented by the general formula (I) is a heterocyclic com.
pounds, Vol.20; John Wiley & Sons: New York, Londo
n, 1962 and can be synthesized according to the method.

On the other hand, the compound represented by the general formula (II) can be easily synthesized by a condensation reaction between 1,2-di-substituted pyrazolidine-3,5-diones and a corresponding dialdehyde dianyl hydrochloride.
Further, 1,2-di-substituted pyrazolidine-3,5-diones are represented by He
terocyclic Compounds, Vol.20; John Wiley & Sons: N
It can be synthesized according to the method described in ew York, London, 1962.

The compound of the general formula (I) or (II) is used in an amount of 1-1000 mg per area / m ² on the light-sensitive material, preferably 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 compound of formula (I) or (II) according to the present invention can be used in any of the emulsion layer and other hydrophilic colloid layers.

The fine particle dispersion of the compound of the general formula (I) or (II) of the present invention can be prepared by 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 (eg water, alcohol) may coexist) It can be formed by using. 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 microcrystallized by changing the pH. 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 er Physique Photographique 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 (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate) also have high curing rates and are 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, No17123 (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 a color diffusion transfer photographic method, it may be added to any layer in the light-sensitive material, or may be contained as a developer solution component in a processing solution container before use.

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.

Any photographic developing method may be applied to the light-sensitive material of the present invention, not only a color developing solution. 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, oxaacetic acid, diethylenetetraaminepentaacetic acid and the like as a water softening agent to the developer which can be used 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 amino compounds include both inorganic and organic amines, such as, for example, hydroxylamine. The organic amine can be an aliphatic amine, an aromatic amine, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine, primary, secondary and tertiary amines.
Amines and quaternary ammonium compounds are all effective.

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. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing 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. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamine-2-propanoltetrachloride. Aminopolycarboxylic acids such as acetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates; nitrosophenol 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. Specifics of useful bleach accelerators are described in the following specifications: U.S. Patent 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. 5
3-28426, Research Disclosure No. 17129 (July 1978), and other compounds having a mercapto group or a disulfide group; thiazolidine derivatives as described in JP-A-50-140129; JP-B-45 -8506,
JP-A-52-20832, JP-A-53-32735, U.S. Pat.
Thiourea derivatives described in No. 1; West German Patent No. 1,127,715,
Iodide described in JP-A-58-16235; West German Patent No. 966,410
Polyethylene compounds described in JP-B-45-8836; Other JP-A-49-42434, 49-59644, 53-94927,
The compounds described in 54-35727, 55-26506 and 58-163940, iodine, and bromide ions can also be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, US Patent No. 3,893,
Compounds described in 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. In the washing step and the stabilizing step, various known compounds may be added 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 Photographic Science and Engineering by West (LEWest, Pho
t.Sci.Eng.), Vol. 6, pages 344-359 (1965) and the like. 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, aminopolycarbic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners and other various additives may be used. You may use together more than one kind.

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.

When the present invention is a silver halide color light-sensitive material, a color developing agent may be incorporated 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. Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,5
99, Research Disclosure 14850 and 1
Schiff base type compounds described in 5159, aldol compounds described in 13924, metal salt complexes described in U.S. Pat.No. 3,719,492, urethane compounds described in JP-A-53-135628, and JP-A-56-6235. Issue No. 56-16133 Issue No. 56-59
No. 232, No. 56-67842, No. 56-83734, No. 56-83735,
56-83736, 56-89735, 56-81837, 56-544
No. 30, No. 56-106241, No. 56-107236, No. 57-97531, No. 57-83565 and the like can be mentioned 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.

(Examples) Next, the present invention will be described in more detail based on examples.

Example 1 (Preparation of Emulsion A) An aqueous solution of silver nitrate and an aqueous sodium chloride solution containing 0.5 × 10 ⁻⁴ mol of ammonium hexachlororhodium (III) chloride per mol of silver were adjusted to pH in a gelatin solution at 35 ° C. by the double jet method. The monodispersed silver chloride emulsion having an average grain size of 0.07 μm was prepared by mixing while controlling it to 6.5.

After the formation of the particles, the 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 weighed 105g. (Emulsion A) (Preparation of photosensitive material) The following nucleating agent and nucleating 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
A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 3.5 g per unit, and further gelatin (1.3 g / m ² ) was added to the layer above the compound I-7 of the present invention.
(0.12 g / m ² ), as a coating aid, a protective layer containing the following three surfactants, a stabilizer and a matting agent was applied and dried.

Stabilizer Thioctic acid 6.0 Matting agent Polymethylmethacrylate (average particle size 3.5 μm) 50.0 mg / m ² Compound I-7 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-7 in Example 1 (Comparative Sample 1-A). 2) The following dye was used in place of the compound I-7 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-7 of the present invention in Example-1.

Acid-treated gelatin 2.0 g / m ² Stabilizer Thioctic acid 0.006 / m ² Matting agent Polymethylmethacrylate (average particle size 2.5μ) 0.009 / m ² (Performance evaluation) (1) The above four samples were produced by Dainippon Screen Co., Ltd. Mitsumuro Printer P-607 was exposed through an optical wedge, developed with the following developer at 38 ° C. for 20 seconds, fixed by a usual method, washed with water and dried.

Developer Basic Formula 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. 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) Tone variability test The above four samples were exposed through a screen screen using the printer described above, and the others were processed in the same manner as in (1) test. 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, the comparative sample 1-A has a significantly reduced tone variability, whereas the sample 1 of the present invention has a high tone variability. this is,
Since the dye used in Comparative Sample 1-A was water-soluble and diffusible, it was 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 irradiation prevention effect. On the other hand, the compound I-7 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 Solution The strips of the sample of the present invention and the sample of Comparative Example obtained by treatment in (2) above were immersed in the following Farmer reducer solution at 20 ° C. for 60 seconds. Washed with water and dried. As a result, in each of the samples, the intensity at the halftone dot area of 50% was reduced to about 33%, but in Comparative Sample 1-C, a strong brown stain was generated over the entire surface. No stain was observed in the samples of the present invention and the comparative samples 1-A and 1-B.

Farmer reducer At the time of use, mix 1st liquid: 2nd liquid: water = 100 parts: 5 parts: 100 parts.

As described above, the sample of the present invention was good in terms 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. Furthermore, disperse in 25 ml of 10% lime-processed gelatin aqueous solution which dissolved 0.5 g of citric acid, remove the sand used with a glass filter, and further remove the dye adhering to the sand on the glass filter to remove 7% gelatin. Solution 100m
I got l. (The average particle size of the fine dye particles was 0.15 μm.) Further, the compounds I-33 1.6 g and II-24 1.6 g of the present invention were similarly prepared.

Paper support A Undercoat layer Gelatin 0.8 g / m ² Paper support B Anti-halation layer Gelatin 0.6 g / m ² Invention compound I-7 25 mg / m ² Invention compound I-31 40 mg / m ² Paper support Body C Anti-halation layer Gelatin 0.6 g / m ² Compound of the present invention I-33 40 mg / m ² Compound of the present invention II-24 40 mg / m ² Paper support Sample A, B and C The following layer constitutions Multilayer color photographic paper samples 2-1 to 2-4 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) 4.4 g and 1.4 g of color image stabilizer (Cpd-7) in ethyl acetate
27.2 cc and 8.2 g of the solvent (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide 0.
2 mol% is localized on the grain surface), and 2.0 × 10 ^-4 mol of the following blue-sensitive sensitizing dye is added per mol of silver to the large-size emulsion, and , 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.

Support Polyethylene laminated paper [Samples A, A, B and C provided with an undercoat layer and an anti-halation layer on the 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 Second 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) Coefficients of variation of grain size distribution are 0.10 and 0.08, 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 (UV absorbing layer) Gelatin 1.58 UV absorber (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 particles having an average particle size of 0.58 μm and 0.45 μm (Ag molar ratio). Variation of particle size distribution. Coefficients are 0.09 and 0.11, and each emulsion is AgBr0.
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 mixture 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 sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3,2)
(00 ° K) to provide a stepwise exposure for sensitometry through the blue, green and red filters. On the other hand, an exposure for measuring the resolution (CTF) was performed, and then the following processing steps were performed. The concentration of the obtained sample was measured and shown in Table-2.
The result shown in was obtained. Step Temperature Time Replenisher ^* Tank capacity Color development 35 ° C. 45 seconds 161 ml 17l blix 30 to 35 ° C. 45 seconds 215 ml 17l Rinse 30 to 35 ° C. 20 seconds - 10l Rinse 30 to 35 ° C. 20 seconds - 10l Rinse 30 to 35 ° C. 20 sec 350 ml 10l drying 70 to 80 ° C. 60 seconds * replenishment rate is composition (3 and a tank countercurrent system. to rinse →) each processing solution per photosensitive material 1 m ² is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water 1000ml pH ( 25 ° C) 6.0 Rinse solution (same for tank solution and replenisher) Deionized water (calcium and magnesium are 3ppm or less each) When the dye according to the present invention is used in the anti-halation layer,
Relatively little decrease in sensitivity, and the amount of residual color is not noticeable,
The resolution can be significantly improved. Further, by using the dyes (I) and (II) of the present invention in combination, the resolution can be remarkably improved in all regions of cyan, magenta and yellow.

Example-3 Preparation of dye fixing layer A transparent PET support having a thickness of 100 μm was used as a 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 undercoat layer made of styrene-butadiene latex was provided and a second undercoat 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, the anti-halation layer was prepared.

・ Gelatin 1.8g / m ²・ Dye Dye and amount shown in Table-3 ・ Potassium polystyrene sulfonate (average molecular weight 600,000) 35mg / m ² ・ Phenoxyethanol 18mg / m ²・ 1,2-bis (sulfonylacetamide) ethane 100mg / m
² Preparation of Emulsion Coating Solution Raw milk # 1 shown below is a surface latent image type emulsion, and a negative type property can be obtained by a commercially available microfilm general purpose processing solution. Further, by performing reversal processing (reversal processing) using a reversal processing liquid, positive type characteristics can be obtained.

<Preparation of original emulsion # 1> Solution II and solution III are simultaneously added to well-stirred solution I for 45 minutes.
Then, the solution II and the total amount of the solution II were added, and finally a cubic monodisperse emulsion having an average grain size of 0.28 μm was 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 addition of the solution II. After completion of addition of solution II,
After washing and desalting by sedimentation method, inert gelatin 100g
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.

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

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 processing Negative development processing was performed under the following conditions using a general-purpose processing solution for microfilm (FR-537 developing solution manufactured by FR Chemicals, USA) commercially available on the F-10 deep tank automatic processor manufactured by Allen Products, USA. I 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 treatment was performed.

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 with a spatial frequency of 20 cycles / mm.

 The results are shown in Table-3.

(2) 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.

As is clear from Table 3, the present invention can provide a light-sensitive material excellent in sharpness and decolorization.

Example-4 The same solution used to prepare Raw Emulsion # 1 in Example-3 was used. However, the following points are different.

Solution II and Solution III were simultaneously added to Solution I for 5 minutes, and when octahedral particles having an average particle size of 0.10 μm were formed, the addition of Solution II and Solution III was suspended, and 1 mole of silver was added. Sodium thiosulfate and chloroauric acid tetrahydrate
115 mg each was added, followed by a chemical sensitization treatment at 75 ° C. for 60 minutes. The solution was added to the chemically sensitized core particles thus obtained again.
Simultaneous addition of II and solution III was continued, and solution IV was added over 5 minutes 5 minutes after resuming addition of solution II, and the pAg value of the mixture was reduced.
Adjust the addition rate of Solution III to 7.50,
Solution II was added at 40 ° C. over 40 minutes. Thus, finally, a cubic core / jeel emulsion having an average grain size of 0.28 μm was obtained.
Operations after washing and desalting are exactly the same as those of the raw milk # 1. Thus, the inner latent image type cube core whose surface is chemically sensitized /
A shell emulsion was obtained. (Raw milk # 2) The raw emulsion of # 2 is a so-called core / shell type internal latent image type emulsion, and when used in combination with a nucleating agent, a positive image can be directly obtained by one-time development using a general-purpose processing solution for microfilm. It is what is done.

In the preparation of the emulsion layer in Example 3, the following nucleating agent (compound) was added so that the coating amount was 394 mg / m ^2, and a photographic material was obtained in the same manner as in Example 3.

The sharpness was evaluated in the same manner as in Example-3.

For the evaluation of residual color, an exposed film was used instead of the unexposed film used in Example 3 so that Dmin was obtained.
Other than that, it performed like Example-3.

The development processing was performed in the same manner as the negative development processing of Example-3.

As is clear from Table 4, the present invention can provide a light-sensitive material excellent in sharpness and decolorization.

Claims (2)

(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 and R ₂ each represent an alkyl group or an aryl group, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, and L ₁ and L ₂ , L ₃ each represent a methine group, and n represents 0 or 1. However, the compound represented by the general formula (I) has at least one carboxyl group, sulfonamide aryl group, or phenolic hydroxyl group in the molecule. .) 2. A solid dispersion fine particle containing at least one compound represented by the general formula (I) and at least one compound represented by the following general formula (II) as a solid dispersion fine particle. And a silver halide photographic light-sensitive material. General formula (II) (Wherein, R ₅ is a hydrogen atom, an alkyl group, an aryl group, a cyano group, a hydroxyl _{group, -COOR 7, -CONR 7 R 8} , -OR 7, -NHCOR 7
And R ₆ , R ₇ , and R ₈ represent an alkyl group and an aryl group, respectively. L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅ each represent a methine group, and p and q each represent 0 or 1. However, general formula (II)
The compound represented by has at least one carboxyl group, sulfonamide aryl group, or phenolic hydroxyl group in the molecule. )