JPH0437740A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material formed with the dye layer contg. the dyes which have adequate spectral absorption and selectively dye the dye layer without diffusing to other layers by providing hydrophilic colloidal layers contg. a specific compd. as a solid fine particle dispersion. CONSTITUTION:The compd. expressed by general formula (I) is usable in emulsion layers or any other hydrophilic colloidal layers. (In the formula, R<1> denotes respectively a hydrogen atomm, aryl group, cyano group, halogen, -COOR <2> -COR<3> -CONR<3>R<4>, -OR<2>, -NHCOR<3>, -NR<3>R<4>. R<2> denotes an alkyl group, aryl group; R<3>, R<4> respectively denote a hydrogen atom, alkyl group, aryl group. L<1>, L<2>, L<3>, L<4>, L<5> denote a methine group.) This compd. is formed by using a method of setting the compd. in the form of the fine particle dispersion, or known pulverizing means, such as, for example, ball milling, sand milling and colloid milling, in the presence of a dispersant.

Description

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

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

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

This is because light that is scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and then enters the photographic emulsion layer again. A colored layer called an antihalation layer is provided for the purpose of preventing blurring of an image, that is, halation. When there are multiple photographic emulsion layers, an antihalation layer may be placed between the layers.

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

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

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

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

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

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

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

In particular, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. In many cases, it is necessary to ensure that the

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

For example, U.S. Pat. No. 2,548,564 discloses a method in which a hydrophilic polymer having an opposite charge to a dissociated anionic dye is made to coexist in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. 4,124,38
No. 6, No. 3,625.694, etc.

In addition, a method of dyeing a specific layer using metal salt fine particles to which a dye has been adsorbed is disclosed in U.S. Pat.
No. 96,841, No. 2.496843, Japanese Unexamined Patent Publication No. 1983-
No. 45237 and the like.

Furthermore, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in Japanese Patent Application Laid-open Nos. 55-120030 and 56-. 126
No. 39, No. 55-155350, No. 55-15535
No. 1, No. 63-27838, No. 63-197943, No. 52-92716, European Patent No. 15601, No. 2
No. 76566, No. 274723, No. 276566,
This method is disclosed in Japanese Patent No. 299435, World Patent No. 88104794, and the like.

However, even with these improved methods, problems such as dye diffusion in the dye fixed layer and slow decolorization speed during development processing (such as speeding up the processing, improving the processing 'lV1 composition, or photographic When there are changes in various factors such as improvement of the emulsion composition, there is a problem that the decolorizing function cannot always be fully exhibited.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to dye a specific hydrophilic colloid layer in a photographic light-sensitive material, and to prevent the dye from diffusing into other layers during storage, and furthermore, to dye a specific hydrophilic colloid layer in a photographic material. The object of the present invention is to maintain a photographic material containing a dye in solid fine particle dispersion designed to rapidly decolorize.

(Means for Solving the Problems) (1) The object of the present invention is achieved by a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one compound represented by the following general 2 as a solid fine particle dispersion. Ru.

General formula HH In the formula, R1 is a hydrogen atom, an aryl group, a cyano group, a halogen, -COOR"-COR'C0NR3R'
-0R2-NHCOR'-NR''R' represents an alkyl group or an aryl group, and R' and R' each represent a hydrogen atom, an alkyl group, or an aryl group. L', L'',
L' and L'L5 represent methine groups.

The methine groups represented by L', L'', R3, L', and L' are preferably unsubstituted, but may have a substituent such as a methyl group, ethyl group, or phenyl group.

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

The aryl group represented by R1 is a substituent (for example, an alkyl group (for example, methyl, ethyl), an alkoxy group (for example, methoxy, ethoxy), a halogen atom (for example, chlorine, bromine, fluorine), an amino group (for example, dimethylamino, diethylamino), ), cyano group, phenoxy group). In addition, the R1 group is not only directly bonded, but also has a divalent linking group (e.g. -〇--S--NRCO-, -CONR-
(CHt )q OCO, NHCONHNHOCO-, etc. (R represents an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-hexyl, and p represents an integer of O to 5.)
may be connected via. Among the compounds represented by the general formula, particularly preferred are compounds in which the alkyl portion of 1OR'' represented by R1 has an alkoxy group having 1 to 5 carbon atoms.

Next, specific examples of the compound (1) represented by the general formula of the present invention will be shown, but the present invention is not limited thereto.

In the table above, ,L,,L,,L,,Ls are all C
It is H.

The compound of general formula (1) is disclosed in JP-A-52-92716, JP-A No. 63-316853, JP-A No. 64i0827,
It can be synthesized according to the method described in Japanese No. 35544.

The compound of general formula N) may be added in an amount of 1 to 1 per area on the photosensitive material.
1,000 ■ is used, preferably In (1 to 800
■Used.

When using the compound of general formula (1) as a filter dye or antihalation dye, any effective amount can be used, but it should be used so that the optical density is in the range of 0.05 to 3.5. is preferred. The addition time may be any step before coating.

The compound of general formula (1) according to the present invention can be used in both emulsion layers and other hydrophilic colloid layers.

The fine particle dispersion of the compound of general formula (1) 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 by a known pulverization method in the presence of a dispersant, such as ball milling (ball milling). , vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc. [In that case, a solvent (for example, water, alcohol, etc.) may be present]. It can be formed 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 a microcrystalline powder. In that case, a dispersing surfactant 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, particularly preferably 0.5 μm or less, and in some cases 0.5 μm or less. More preferably, the particles are fine particles of 1 μm or less.

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

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

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

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

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

The photographic emulsion used in the present invention is P.
, GIafkides), Shimmy Engineering Physique
Photography ivy (Chimie er Physi)
quePhoLographeque) (Ballmontel, 1967), G.F. Duffin (G.
, F. Duffin), Photographic Ivy Emulsion Chemistry
Emulsion Chemistry) (Zmekal Press, 1966), Bouy El Zelikman (
Making and Coating Photographic Ink Emulsion (hak:ng and Coating Photo) by V, L, Zeme kman) et al.
graphic emulsion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (eg, U.S. Pat. No. 628, No. 3.704.130, No. 4.297439, No. 4.276.374, etc.), thione compounds (e.g., JP-A-53-144319, No. 53-82408, No. 55) -77'737, etc.), amine compounds (for example, JP-A-54-100717), etc. can be used.

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

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

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

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

In the photosensitive material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the hack layer. Specific examples include chromium salts, aldehydes (formaldehye F', glyoxal, gluculaldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), and active halogen compounds (2,4-dichloro-6-hydroxy -13
5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propatol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether or vinylsulfonyl N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio)methanesulfonate) are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. Nato, etc.) and haloamidinium salts (1-(1-chloro-1-pyridinomethylene)pyrrolidinium-2-naphthalenesulfonate, etc.) are also excellent in their fast curing speed.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melonanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxokyl dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these pigments, any of the nuclei commonly used for cyanine pigments can be used as base bioheterocyclic nuclei. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyrinone nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nucleus, benzindolenine nucleus, indole nucleus, henzoxazole nucleus, naphthoxazole nucleus, penzothiazole nucleus, naphthothiazole-7b$3. A benzoselenazole nucleus, a penzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or merocyanine dyes have ketomethylene structures such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-24-dione nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral enhancement effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilhene compounds which are substituted with a nitrogen-containing heterocyclic ring group (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,721
(as described in US Pat. No. 3,143,510), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,143,510), cadmium salts, azaindene compounds, and the like. U.S. Patent Box No. 3615.613, U.S. Patent No. 3.615,
No. 641, No. 3.617, 295, No. 3,635.7
The combinations described in No. 21 are particularly useful.

The silver halide photographic emulsion used in the present invention contains the following ingredients for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or stabilizing photographic performance.
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles. such as hensitriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines;
thioketo compounds such as oxadorinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1°3.3a,
7) Addition of many compounds known as anti-capri agents or stabilizers such as tetraazaindene'R), penquagoindenes, etc.; henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to.

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

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

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalosoanine dyes are also useful. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

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

A 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 each on a support, and the arrangement order of these layers can be arbitrarily selected as necessary. . A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in this order, a blue-colored layer, a green-sensitive layer and a red-colored layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order.

Further, any given emulsion layer having the same sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer composition may be used to further improve graininess.

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

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive 7L layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. You can also do it. For example, it may be used in combination with an infrared window photosensitive layer for pseudo-color photography or semiconductor laser exposure.

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

The support may be colored using dyes or pigments.

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

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. U.S. Pat. No. 2.681,2 as appropriate.
No. 94, No. 2,761.791, No. 3,526,
Multiple layers may be applied simultaneously using coating methods such as those described in US Pat.

The present invention is applicable to a variety of color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. Research Disclosure, No. 17123
(July 1978), or by utilizing a trichromatic coupler mixture as described in U.S. Pat.
No. 1 and British Patent No. 2. 102. By using the black color-forming coupler described in No. 136, the present invention can also be applied to black-and-white photosensitive materials for X-rays and the like. Plate-making films such as lithography film or scanner film, χ-ray film for direct/indirect medical use or industrial use, negative Hakuba film for photography, black and white photographic paper, C0M or regular microfilm, silver salt diffusion transfer type photosensitive materials, and The present invention can also be applied to print-out type photosensitive materials.

When the photographic element of the present invention is applied to color diffusion transfer photography, it may be of the peel-apart (beer-apart) type or
-16356, 48-33697, JP-A-1973-
13040 and British Patent No. 1,330.524;
``It is possible to configure an unnecessary film unit.

In any of the above types of formers 7), it is advantageous to use polymeric acid N protected by a neutralized timing layer in order to widen the processing temperature range. When used in color diffusion transfer photography, it may be added to any layer in the liquid, or it may be sealed in a processing liquid container as a developer component.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the proof or writing light source. Common flash light sources include natural light (sunlight), incandescent lamps, halogen atom-filled lamps, mercury lamps, fluorescent lamps, and slow-burning lamps, metal P, and fired flash bulbs.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or planar arrays can be applied to micrometer arrays using phosphor screens (CRTs, etc.), liquid crystals (LCDs), and lanthanum-doped lead zirconate (PLZT), which are emitted from phosphors excited by electron beams. It is also possible to use an exposure means consisting of seven light sources arranged in a row.

The spectral distribution used for exposure can be adjusted using color filters depending on the type of palm or essential oil.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-NN-diethylaniline, 3-methyl-4- Amino-N-ethyl-Nβ-hydroquinolethylaniline, 3-methyl4-amino-N
-Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, p-h luenesulfonates, etc. can be mentioned. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, hengimidazoles, hendithiazole or mercapto compounds. Generally, it contains agents such as agents. Also, if necessary, preservatives such as hydroxylamine, dialkyl hydroxylamines, hydrazines, triethanolamine, triethylenediamine or gnitrite, triethanolamine, organic solvents such as diethylene glycol, hensyl alcohol, etc. , development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, co-developers such as 1-phenyl-3-virapritone, viscosity. imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylbosphonic acids, and phosphonocarboxylic acids, and antioxidants described in West German Patent Application (OLS) No. 2,622,950. A coloring agent or the like may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black-and-white developer contains dihydroxybenzoic acid such as hydroquinone, 1-phenyl-
3-virapritones such as 3-pyrazolidone or N-
Known color developing straws such as amine phenols such as methyl-p-amine phenol can be used alone or in combination.

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

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,
Examples include 3-dichlorohydroquinone and 25-dimethylhydroquinone, and ■-phenyl-3-pyrazoliton type developing agents include 1-phenyl-3-virapritone,
44-dimethyl-1-phenyl-3-virapritone, 4
-Hydroxymethyl-4-methyl-1-phenyl-3-
Examples include pyrazolidone and 4,4-dihydroxomethyl-1-phenyl-3-virapritone, and p-aminophenol-based developing agents include p-aminephenol and N-methyl-p-aminophenol.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, sodium bisulfite, etc., is added to the developer as a preservative. In the case of a contagious developer, sodium formaldehyde bisulfite may be used, which provides very little free sulfite ion in the developer.

As the alkaline agent for development used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, triethanolamine, etc. are used.Development The pH of i71 is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as antifoggants or development II'll inhibitors. Examples include azoles such as hendthiazolium salts, nitroinodazoles, nitrohenzimidazoles, chlorohenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptothiadiazoles,
Mercaptohenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines, such as oxazolinthione thioketo compounds such as; azaindenes such as triazaindenes, tetrazaindenes (particularly 4-hydroxy substituted (1,
3,3a.

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

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

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

The developer used in the present invention includes a compound described in JP-A No. 56-24347 as a silver stain prevention agent, a compound described in JP-A-62-212651 as an agent for preventing uneven development,
As a solubilizing agent, a compound described in JP-A-61267759 can be used.

In the developing solution used in the present invention, a buffering agent is used.
Boric acid described in No. 2-186259, JP-A-60-93
Saccharides (e.g., sucrose), oximes (e.g., acetoxime), phenol M (e.g., 5-sulfosalicylic acid), tertiary phosphates (e.g., sodium salt, potassium salt), etc., described in No. 433 are used. .

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

Preferred development accelerators include amine compounds, imidacillin compounds, imidacillin compounds, phosphonium compounds, sulfonium compounds, and dorazine compounds.
Examples include thioether compounds, thione compounds, certain mercapto compounds, mesoionic compounds, and thionate salts.

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

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

After color development, the photographic milk 7F11 layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process7 or may be performed separately. In order to further speed up processing,
A method of bleaching and then bleach-fixing may also be used. Examples of bleaching agents include iron (■), cobalt (■), and chromium (
IV), compounds of polyvalent metals such as copper (It), peracids,
Quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferinoanide-deuterromate and iron (Iil).
) or N complex salts of cobalt, such as aminopolycarboxylic acids such as ethylenenoaminetetraacetic acid, noethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-noamino-2-propatoltetraacetic acid, or citric acid, tartaric acid. , complex persulfates of organic acids such as malic acid; manganate; nitrosophenol, etc. can be used.

Among these, ethylenediaminetetraacetic acid (1) salt, diethylenetriaminepentaacetic acid iron(III) salt, and persulfate are preferable from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complexes are particularly useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

A cleanliness accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.858, German Pat.
．． No. 290 812, No. 2.059988, Japanese Unexamined Patent Publication No. 5
No. 3-32736, No. 53-57831, No. 3741
No. 8, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-
Compounds having a mercapto group or disulfide group as described in No. 141623, No. 53-28426, Research Disclosure No. 17129 (July 1978); Thiazolidine derivatives as described in JP-A-50-140129 ; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735,
U.S. Patent No. 3. Thiourea derivatives described in Ma06.561; West German Patent No. 1.127.715, JP-A-58-1
Iodide described in No. 6235; West German Patent No. 966.410
Polyethylene oxide neck described in Japanese Patent Publication No. 2,748.430; Polyamine compounds described in Japanese Patent Publication No. 45-8836; Others Japanese Patent Publication No. 49-42434, Japanese Patent Publication No. 49-5
No. 9644, No. 53-94927, No. 54-3572
No. 7, No. 55-26506 and No. 5B-16394
The compound described in No. 0 and iodine and bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat. No. 3.1393.858 and West German Patent No. 12908.
No. 12 and JP-A-53-95630 are preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thionanates, thioureas of thioether compounds, and a large amount of iodides, but thiosulfates are generally used. As a preservative for the bleach-fix solution and the fixer solution, sulfite, bisulfite, or carbonyl bisulfite (-1 additive) is preferable.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminobocarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, and disinfectants and preventive agents that prevent the growth of various bacteria, algae, and mold. High agent, mug 2
- Metal salts such as soum salt, aluminum salt, and bismuth salt, surfactants to prevent drying load and unevenness, and various hardening agents can be added as necessary. Or Photography Inc. Science and Engineering magazine by West (L, E, We
st, Phot, Sci, Eng,), 6th v:
, pp. 344-359 (1965) may be added. Particularly important is the addition of chelating agents and anti-high agents.
It is effective.

In the washing process, two or more paddles of layers are generally washed with 1 lfl water. Furthermore, a multi-stage countercurrent stabilization treatment process as described in JP-A-57-8543 may be performed immediately after the water washing process. In the case of this step, 2 to 9 countercurrent columns are required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images.

For example, various buffers (e.g., In borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sulfur hydroxide) for adjusting membrane pH (e.g., pH 3-9).
) Rum, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. are used in combination, and aldehydes such as formalin are representative examples. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, amoborisulfonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (hendiisothiazolinone, irithiaduron, 4 - Various additives such as thiazolines (henzimidazole, halogenated phenols, sulfanilamide, henctriazole, etc.), surfactants, optical brighteners, hardeners, etc. may be used, and compounds for the same or different purposes may be used. More than one species may be used in combination.

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

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.

For example, indoaniline compounds described in US Pat. No. 3,342,597, Research Disclosure No. 14850 and US Pat. No. 15159.
In addition to Schiff base type compounds described in JP-A No. 13924, aldol compounds described in US Pat. No. 13924, metal salt complexes described in US Pat. No. 56-6235, No. 56-16133, No. 56-59232, No. 5
No. 6-67842, No. 56-83734, No. 56-8
No. 3735, No. 56-83736, No. 56-8973
No. 5, No. 56-81837, No. 56-54430,
Examples include various salt-type precursors described in No. 56-106241, No. 56-107236, No. 57-97531, and No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547, JP-A-57-211147, JP-A-58-50532, JP-A-5B-50536, JP-A-58-50533, JP-A-58.
-50534, 58-50535 and 58-
115438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. Also, photosensitive materials!
For ff silver, treatment with cobalt or hydrogen peroxide intensification as described in German Patent No. 2.226.770 or US Pat. No. 3,674.499 may be carried out.

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

In addition, during continuous processing, a constant finish can be obtained by using replenishers for each processing solution to prevent compositional fluctuations over a period of 7 days. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

When the light-sensitive material of the present invention is a color paper, it can be subjected to bleach-fixing treatment as required, most preferably in the case of a color photograph for photographing (even if it is rough).

(Effect of the invention) In the silver halide photographic light-sensitive material book 4 of the present invention, dyeing 1'
The four layers of dye have appropriate spectral absorption, and have the excellent effect of selectively dyeing the four dye layers without spreading to other layers.

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

Furthermore, the silver halide photographic window optical material of the present invention provides images with improved sharpness. Furthermore, photographs obtained from the silver halide photographic material of the present invention do not produce staining, are stable even during long-term storage, and do not deteriorate in photographic performance.

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

Example 1 Preparation of Dye Fixed Layer The dyes shown in Table 1 were each subjected to a ball mill treatment according to the method described in JP-A-63-197943.

434 d of water and 791 ml of a 7% aqueous solution of Triton (2m+n diameter) was added and the contents were ground for 4 days.After this, 160g 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 pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter.

A transparent PET support with a thickness of 100 μm was used as the support. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butashun latex was applied, and a second undercoat layer of gelatin 0°08g/nf was applied on top of this. Layers were provided.

A fine dispersion of the dye was coated on this support as a gelatin dispersion solution in the coating amount shown below. In this way, an antihalation layer was prepared.

・Gelatin 1.8g/bo ・Dye 1
-5 Quantity listed in Table-3 - Potassium polystyrene sulfonate (average molecular weight 600,000) 35mg/r+(1
0■/Pophenoxyethanol 18■/n?・1.
2-Bis(vinylsulfonylacetamido)ethane 100 μm / Preparation of Emulsion Coating Solution The raw milk #1 shown below is a surface latent image type emulsion, and it has a lance-shaped characteristic with a commercially available microfilm general-purpose processing liquid. That's what you get. Further, by performing a reversal process (rehearsal process) using a reversal processing liquid, positive type characteristics can be obtained.

<Preparation of raw emulsion #1> Solution T 75°C Inert gelatin 24g Distilled water
900mlKBr
4g 10% phosphoric acid water soluble!
Water resistant 2me Sodium benzenesulfinate 5 X 10-'mol 1.2-bis(2-hydroxyethylthio)ethane 2.5X10-3g7 volume liquid I
At 35 °C, add 4 volumes of solution ■ and 7 volumes of solution ■ to 18 volumes of well-stirred solution I at room temperature.
The solution was added for 5 minutes, and when the entire amount of solution (1) was added, a cubic monodisperse emulsion with an average grain size of 0.28 μm was finally obtained.

At this time, the addition rate of solution (2) was adjusted so that the PAg value in the mixing container was always 7.50 relative to the addition of solution (2). Incidentally, *' was added to the solution for 5 minutes starting 7 minutes after the start of addition of the solution (2). ? After the addition of gan was completed, the mixture was washed with water and desalted by a sedimentation method, and then dispersed in an aqueous solution containing 100 g of inert gelatin. To this emulsion, 34 μ each of sodium thiosulfate and chloroauric acid tetrahydrate were added per mole of silver, and the T'H and pAg values were adjusted to 8°9 and 7.0 (40'C), respectively. From, 75
A chemical sensitization treatment was performed at °C for 60 minutes to obtain a surface latent image type silver halide emulsion. The layer structure and the composition of each layer are as follows.

Layer configuration Film thickness (μm) <Emulsion layer> H Emulsion layers other than the antihalation layer, surface protection layer, conductive layer, and Ge1 layer were prepared and coated so that each component was coated in the following coating amount to obtain a photographic material. Ta.

<Protective layer> Sodium bis(vinyl sulfonate) Sodium styrene sulfonate (compound ■) C21 (5 (T"/an+°"' Bar fluorophtance coating amount ■/bo <Bank conductive layer><Ge1layer> Dihequinol-alpha-sulfosuccinate sodium 34 Sodium polystyrene sulfonate 4 Proxel 5 Processing method Reverse development process Reverse development process is from FlJ Alien Product
A commercially available reversal processing solution for the F10R reversal deep tank automatic processor manufactured by S Company (FR Chemicals, USA)
-5 3 1, 532.533.534.535) under the following conditions.

Negative development processing Negative development processing is performed by A11en Products in the United States.
The test was carried out using a commercially available general-purpose processing solution for microfilms (FR-537 developer, manufactured by FR Chemicals, Inc., USA) using an F10 deep tank automatic developing machine manufactured by Co., Ltd. under the following conditions.

Evaluation of sharpness Sharpness was evaluated by MTF. The photographic material was exposed to white light for 1/100 seconds using an MTF measurement wedge and processed in an automatic processor as described above.

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

The results are shown in Table-1.

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

The results are shown in Table-1.

Procedural amendment 4. Subject of amendment: Specification column "Detailed description of the invention" Display of incidents 1990 patent application No. 1 43861, name of invention silver germide photographic material person who makes corrections Relationship with the incident

Claims (1)

[Claims] (1) 2-pyrazoline represented by the following general formula (I)
1. A silver halide photographic material comprising a hydrophilic colloid layer containing at least one 5-one oxonol dye as a solid fine particle dispersion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 is a hydrogen atom, aryl group, cyano group, halogen, -COOR^2, -COR^3, -CONR^, respectively.
3R^4, -OR^2, -NHCOR^3, -NR^3
Represents R^4. R^2 represents an alkyl group or an aryl group, and R^3 and R^4 represent a hydrogen atom, an alkyl group, or an aryl group, respectively. L^1, L^2, L^3, L^4, L^5
represents a methine group.