JP2632051B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material. In particular, the present invention relates to a silver halide photographic material using a silver halide emulsion having improved fog and sensitivity.

(Prior Art) A silver halide emulsion used for a silver halide photographic light-sensitive material is usually subjected to chemical sensitization using various chemical substances in order to obtain desired sensitivity, gradation and the like. As typical methods, various methods of sensitization by sulfur sensitization, selenium sensitization, sensitization of noble metals such as gold, reduction sensitization, and a combination thereof are known.

In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, as well as rapid processing in which development progress has been accelerated, and various improvements of the sensitization method have been made. .

Of the above sensitization methods, selenium sensitization method, U.S. Patent Nos. 1574944, 1602592, 1623499, 3297446, 3297447, 3320069, 3320069, 340
No. 8196, No. 3408197, No. 346553, No. 3420670
No. 3591385, French Patent No. 2093038, No. 20
No. 93209, Japanese Patent Publication No. 52-34491, No. 52-34492, No. 53-2
No. 95, No. 57-22090, JP-A-59-180536, No. 59-185
No. 330, No. 59-181337, No. 59-187338, No. 59-19224
No. 1, No. 60-150046, No. 60-151637, No. 61-246738
No., UK Patent Nos. 255846, 861984 and HESpen
cer et al., Jonrnal of Photographic Science, 31
Vol., Pp. 158 to 169 (1983).

(Problems to be Solved by the Invention) However, selenium sensitization generally has a greater sensitizing effect than sulfur sensitization usually performed in the art, but tends to generate large fog and tend to be softened easily. There are many. Although many of the above-mentioned known patents improve on these drawbacks, they have yet to obtain inadequate results, and in particular, there has been a keen need for fundamental improvements in suppressing fogging.

In addition, in addition to sulfur sensitization and selenium sensitization, gold sensitization is used in combination with remarkable increase in sensitivity, but fog also increases at the same time. Compared to gold-sulfur sensitization, gold-selenium sensitization has a particularly large increase in fog, and there has been a strong demand for technology development for suppressing the occurrence of fog.

(Object of the Invention) An object of the present invention is to provide a high-sensitivity silver halide photographic material having an appropriate gradation and a low fog. A second object of the present invention is to provide a silver halide photographic material having high sensitivity suitable for rapid processing.

(Means for Solving the Problems) The above objects have been achieved by the following, and the present invention makes it possible to make full use of the sensitizing effect of selenium sensitization, which has been difficult with conventional techniques. Was. That is, a silver halide emulsion containing at least one compound represented by any of the following general formulas [I], [II] and [III], and sensitized with a sulfur sensitizer and further selenium-sensitized is prepared. This has been attained by a silver halide photographic light-sensitive material characterized by including: Also, a silver halide produced in the presence of at least one compound represented by any of the following formulas [I], [II] or [III], sensitized with a sulfur sensitizer and further selenium sensitized: Achieved by a silver halide photographic material characterized by including an emulsion.

Further, it is characterized by comprising a selenium-sensitized silver halide emulsion produced in the presence of at least one compound represented by any of the following general formulas (I), (II) and (III). Achieved by silver halide photographic materials.

Formula (I) Z-SO ₂ S-M However, Z forms an alkyl group (1 to 18 carbon atoms), an aryl group (6 to 18 carbon atoms), or a heterocyclic group, and Y forms an aryl group (6 to 18 carbon atoms) or a heterocyclic group. M represents a metal cation, an organic cation, or a hydrogen atom, and n represents an integer of 2 to 10.

The compounds represented by the general formulas [I] to [III] of the present invention are known as antifoggants, for example, USP2394198
No. 2,440,206 as antifoggants for use of sulfinic acid compounds, USP (US Pat. No. 3,047,393) as antifoggants for silver iodobromide emulsions, and JP-B-39-25774.
In the issue No. 42-11, an example aimed at stabilizing silver images
No. 305 discloses an example of preventing fogging of a silver iodobromide emulsion by using it in combination with a tetraazaindene compound.
No. 1019 discloses an example of preventing fogging of a silver iodobromide emulsion when an organic thioether compound is used, and JP-A-57-176032 discloses a latent image regression of a silver iodobromide emulsion in combination with a cyanine dye and an antioxidant. Are disclosed. However, no specific example has been reported in which the compounds of the general formulas [I] to [III] are applied to a selenium-sensitized silver halide emulsion. Although it was extremely difficult to predict the antifogging effect and other photographic effects of these compounds, a remarkable effect was obtained when used together with selenium sensitization.

The compound represented by formula (I), (II) or (III) will be described in more detail.

In general formulas [I], [II] and [III], the alkyl group, aryl group, heterocyclic group represented by Z, aryl group represented by Y, and heterocyclic group may be substituted.

Examples of the substituent include a lower aliphatic group such as a methyl group, an ethyl group and a vinyl group, an aryl group such as a phenyl group, an alkoxyl group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, Examples thereof include a carbamoyl group, a sulfamoyl group, a carboxyl group and the like.

The alkyl group represented by Z has 1 to 18 carbon atoms, and the aryl group represented by Z and Y has 6 carbon atoms.
~ 18.

Examples of the hetero ring represented by Z and Y include a thiazole, benzthiazole, imidazole, benzimidazole, oxazole ring and the like.

Examples of the metal cation represented by M include an alkali metal cation such as a sodium ion and a potassium ion.
As the organic cation, an ammonium ion, a guanidinium ion and the like are preferable.

 n represents an integer of 2 to 10.

Specific examples of the compound represented by the general formulas [I], [II] or [III] include the following, but are not limited thereto.

5 H ₃ CSO ₂ SN _a 6 C ₂ H ₅ SO ₂ SN _a 7 C ₅ H ₁₁ SO ₂ SN _a 8 C ₈ H ₁₇ SO ₂ SN _a 9 C ₁₂ H ₂₅ SO ₂ SN _a 11 H ₂ NC ₂ H ₄ SO ₂ SK 19 L-cystine-disulfoxide The compound contained in the general formula [I], [II] or [III] can be generally synthesized by a well-known method.

For example, it can be synthesized by reacting the corresponding sulfonyl chloride with sodium sulfide or reacting the corresponding sodium sulfinate with sulfur. On the other hand, these compounds can be easily obtained as commercial products.

General formula [I], [II] or [III] in the present invention
The amount of the compound represented by the formula is per mole of silver halide.
It is 10 ^-2 mol or less, preferably 10 ^{-8 to} 3 × 10 ^-3 , particularly preferably 10 ^-7 to 10 ^-3 mol.

The timing of addition may be any of a particle forming step, a desalting step, a chemical ripening step, or immediately before coating.

As the selenium sensitizer used in the present invention, a selenium compound disclosed in a patent described in (Prior Art) can be used. In particular, an unstable selenium compound capable of forming a silver selenide precipitate by reacting with silver nitrate in an aqueous solution is used. For example, U.S. Patent Nos. 1574944 and 160259
2, selenium compounds described in 1623499 and 3297446 are preferred. More specifically, colloidal metal selenium, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, selenourea; N, N-dimethylselenourea, N, N-diethylselenourea, Selenoureas having an aromatic group such as a phenyl group or a heterocyclic group such as a pyridyl group, etc. selenoketones (eg, selenoacetone, selenoacetophenone, etc.) selenoamides (eg, seleno Acetamide, etc.) selenocarboxylic acids and esters (eg, 2-selenopropionic acid, methyl 3-selenobutyrate, etc.) selenides (eg, dimethyl selenide, diethyl selenide, triphenylphosphine selenide, etc.) Eates (for example, tri-p-tolyl selenophosphate, etc.) The amount of emissions sensitizer, a selenium compound used, the silver halide grains will vary by the chemical ripening condition and the like, generally per mol of silver halide 10 ^-8 to 10 ^-4 mol, preferably
About 10 ^-7 to 10 ^-5 mol is used.

The conditions of the chemical sensitization in the present invention are not particularly limited, but p.Ag is 6 to 11, preferably 7 to 10, more preferably 7 to 9.5, and the temperature is 40 to 95 ° C., preferably Is 50-85 ° C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium in combination. Especially,
It is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^-7 to About 10 ^-2 mol can be used.

In the present invention, a sulfur sensitizer is further used in combination. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea,
Allylthiourea), known labile sulfur compounds such rhodanines can be mentioned, per mol of silver halide 10 ^-7 to
About 10 ^-2 mol can be used.

In the present invention, it is also possible to use a reduction sensitizer in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, etc. No.

In the present invention, selenium sensitization is preferably performed in the presence of a silver halide solvent.

Specifically, thiocyanates (for example, potassium thiocyanate, etc.) and thioether compounds (for example, described in U.S. Pat. Nos. 30221215 and 3271157, JP-B-58-30571, JP-A-60-136736 and the like) Compounds, in particular, 3,6-dithia-1,8-octanediol and the like; tetrasubstituted thiourea compounds (for example, compounds described in JP-B-59-11892, U.S. Pat. No. 4,218,863, especially tetramethylthiourea And the thione compounds described in JP-B-60-11341.
Mercapto compounds described in JP-A-3-29727, JP-A-60-1630
No. 42, a selenoether compound described in U.S. Pat. No. 4782013, a telluro ether compound described in Japanese Patent Application No. 63-173474, a sulfite, and the like. In particular, among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used can be about 10 ^{-5 to} 5 × 10 ^-2 mol per mol of silver halide.

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 consist of 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) May be used. 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 Photographeque by P. Glafkides.
(Paul Montell, 1.967), by GFDuffin, Photographic Emulsion, Chemistry (Photo-graphic Emulsion Chemis)
try) (Focal Press, 1966), V.L.
It can be prepared by a method described in VLZelikman et al., Making and Coating Photographic Emulsion (published by Focal Press, 1964).

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,
No. 374) and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, and amine compounds (for example, JP-A-54-100717).

In the course of silver halide grain formation or physical ripening, a cadmium salt, a subsalt, 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 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 and the like, and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) also have a fast curing rate 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,
A tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; , Benzoxadol 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. In addition to 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, aminostilbenzene compounds substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensate (for example, U.S. Pat. No. 3,743,510) ), Cadmium salts,
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 such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, 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; many compounds known as antifoggants or stabilizers such as benzenethiosulfonate, benzenesulfonate, benzenesulfonate and the like Can be added.

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 and 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 formed of a flexible support such as a plastic film, paper, cloth, etc., or a glass, pottery,
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 thereof 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 a dip coating method, a roller coating method, a curtain coating method and an extrusion coating method can be used. U.S. Pat.No. 2,681,294 as required,
Multiple layers may be simultaneously coated by the coating methods 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 paper, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No.17123 (1978
July, 1999) or by using a black color coupler described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136 to obtain a black-and-white image such as for X-rays. The present invention can be applied to a photosensitive material. Plate making film such as lith 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 micro film, silver salt diffusion transfer type photosensitive material The present invention can also 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.
Nos. -16356, 48-33697, JP-A-50-13040 and British Patent 1,330,524, which are incorporated in JP-A-57-119345. Such a film unit that does not need to be peeled can be configured.

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

Various exposure means can be used for the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps, and strobe or metal burning flash bulbs are common. Emit light in the wavelength range from infrared to infrared,
Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources can also be used as recording light sources. Also, a micro-shutter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or lanthanum-doped lead zirconate titanate (PLZT), etc. Exposure means combining a linear or 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 this color developing agent, but p-
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 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.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds or an antifoggant. It generally contains an agent and the like. If necessary, a preservative such as hydroxylamine or sulfite, an organic solvent such as triethanolamine or diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone Viscosifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, antioxidants described in West German Patent Application (OLS) No. 2,622,950, etc. It may be added to a color developing solution.

In the development process of the reversal color photosensitive material, color development is usually performed after black-and-white development is performed. 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.

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

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification. : U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, 2,05
No. 9,988, JP-A-53-32736, JP-A-53-57831, JP-A-37418
No. 53-65732, No. 53-72623, No. 53-95630,
No. 53-95631, No. 53-104232, No. 53-124424, No. 5
Compounds having a mercapto group or a disulfide group described in 3-141623, 53-28426, Research Disclosure No. 17129 (July 1978);
Thiazolidine derivatives as described in JP 140129; JP-B-45-8506; JP-A-52-20832; JP-A-53-32735;
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodides described in JP-A-58-16235; Polyethylene oxides described in West German Patents 966,410 and 2,748,430; Polyamine compounds described in JP-A-83836; and JP-A-49-42434 and JP-A-49-59644.
And the compounds described in JP-A-53-94927, JP-A-54-35727, JP-A-55-26506, and JP-A-58-163940 can also be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,290,812
And the compounds described in JP-A-53-95630 are preferred. 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, and a large amount of iodide, 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 West, Photographic Science and Engineering (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 step as described in -8543 may be performed. 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 buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonium water) for adjusting the membrane pH (for example, pH 3 to 9) ,
Aldehydes such as monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4- Various additives such as thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardeners may be used, and the same or different target compounds may be used. May be used in combination of two or more.

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 the photographic material and the processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Patent No. 3,342,59
No. 7, indoaniline-based compound, No. 3,342,599,
Research Disclosure Nos. 14850 and 15159, Schiff base compounds, the aldol compounds described in 13924, metal salt complexes described in U.S. Pat.No. 3,719,492,
Including the urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133, and JP-A-56-59232.
No. 56-67842, No. 56-83734, No. 56-83735,
56-83736, 56-89735, 56-81837, 56
-54430, 56-106241, 56-107236, 57-9
Examples of the precursors include various salt-type precursors described in Nos. 7531 and 57-83565.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547 and JP-A-57-21114.
No. 7, No. 58-50532, No. 58-50536, No. 58-50533,
Nos. 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 of each processing liquid to prevent fluctuation of 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.

 Hereinafter, specific examples of the present invention will be described.

Example 1 Potassium bromide, thioether (HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (C
H ₂ ) ₂ OH) and gelatin were added and dissolved, and a mixed solution of silver nitrate solution, potassium iodide and potassium bromide was added by stirring to a solution kept at 70 ° C. by a double jet method.

After completion of the addition, the temperature was lowered to 35 ° C., and after removing soluble salts by a conventional flocculation method, the temperature was raised again to 40 ° C., and 60 g of gelatin was added and dissolved to adjust the pH to 6.8. .

The resulting tabular silver halide grains have an average diameter of 1.25μ.
And the average diameter / thickness ratio was 7.4, and silver iodide was 3 mol%. At 40 ° C., the pAg was 8.4.

After dividing the emulsion into 11 parts, the temperature was raised to 62 DEG C. and the sensitizing dye anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt (500 mg / AgX1 mol) and potassium iodide (200 mg / AgX1 mol), the sensitizers shown in Table 1 were added, and chloroauric acid (9 × 10 ⁻⁶ mol / mol AgX) and potassium thiocyanate ( 3.2 × 10 ^-4 mol / mol AgX)
Further, the compounds shown in Table 1 were added, and the mixture was chemically ripened for 30 minutes.

After completion of chemical sensitization, 40 g of each emulsion (including 0.08 mol of Ag)
The solution was dissolved at ℃, and the following was added sequentially with stirring to prepare a solution.

4-hydroxy-6-methylation-1,3,3a, 7- tetrazaindene _{3% 2cc C 17 H 35 -O-} (CH 2 CHO) 25 -H 2% 2.2cc Sodium 2,4-dichloro-6-hydroxy-S-triazine 2% 3 cc A coating solution for the surface protective layer was sequentially added at 40 ° C. with stirring to prepare a solution according to the following.

14% gelatin aqueous solution 56.8 g Polymethyl methacrylate fine particles (average particle size 3.0 μm) 3.9 g H ₂ O 68.8cc The emulsion coating solution and the surface protective layer coating solution obtained as described above were coated on a polyethylene terephthalate film support by a simultaneous extrusion method so that the volume ratio at the time of coating was 103: 45. The applied silver amount is 2.5 g / m ²
It is. These samples were exposed through a yellow filter and an optical wedge using a sensitometer (1/100
After developing with an RD-III developer for an automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) at 35 ° C. for 30 seconds, fixing, washing and drying were performed by a conventional method, and photographic sensitivity was measured. The photographic sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2, and the value of sample 1 is set to 100.

As is clear from Table 1, selenium-gold sensitization and selenium-sulfur-gold sensitization are higher in sensitivity than sulfur-gold sensitization, but generate much fog. However, the combined use of the compound of the present invention significantly suppresses the generation of fog, and the sensitivity is also reduced by sulfur-
Selenium sensitization, which was smaller than expected when used for gold sensitization, resulted in low fog and high sensitivity.

Example 2 (Silver iodobromide tabular grains) Silver iodobromide fine grain emulsion II-A To a 2.6 liter 2.0% by weight gelatin solution containing 0.026 mol of potassium bromide was added, while stirring, 1.2 mol by a double jet method. Silver nitrate solution and 1.11 moles of potassium bromide
An aqueous halide solution containing 0.09 mol of potassium iodide was added to each
1200 ml was added over 15 minutes. During this time the gelatin solution
It was kept at 35 ° C. Thereafter, the emulsion was washed by a conventional flocculation method, and 30 g of gelatin was added and dissolved.
5. Adjusted to pAg8.6. The resulting silver iodobromide fine particles (silver iodide content: 7.5%) had an average particle size of 0.07 μm.

Tabular silver bromide core emulsion II-B A double-jet method is used to prepare 2 l of a 0.8% by weight gelatin solution containing 0.09 mol of potassium bromide while stirring it.
30 cc of a 2.0 molar potassium bromide solution as well as a 0 molar silver nitrate solution are added. During this time, the gelatin solution in the reaction vessel
It was kept at 30 ° C. After addition, raise the temperature to 75 ° C, and add 40 g of gelatin.
Was added. Thereafter, a 1.0 mol silver nitrate solution is added to obtain pBr.
After that, 150 g of silver nitrate was added at an accelerated flow rate (the flow rate at the end was 10 times that at the start) over 60 minutes, and at the same time, a potassium bromide solution was added by the double jet method so that the pBr became 2.55. Was.

Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, added with 60 g of gelatin, dissolved at 40 ° C., and adjusted to pH 6.5 and pAg 8.6. The tabular silver bromide grains were monodisperse tabular grains having an average equivalent circle diameter of 1.4 μm, a grain thickness of 0.2 μm, and a coefficient of variation in equivalent circle diameter of 15%.

Tabular silver iodobromide emulsion II-C Emulsion II-B containing 50 g of silver bromide in silver nitrate was washed with water.
Dissolved in 1.1 and kept the temperature at 75 ° C pBr at 1.5. Next, 1 g of 3,6-dithiaoctane-1,8-diol was added,
Immediately, the fine grain emulsion II-A was added to the reaction vessel at a constant flow rate for 50 minutes so as to be 100 g in terms of silver nitrate. The obtained tabular grains had an average equivalent circle diameter of 2.4 μm and a grain thickness of
It was 0.31 μm.

After that, it is washed with water by the conventional flocculation method to pH 6.
5, adjusted to pAg8.6.

The resulting emulsion is divided into 6 parts, and the mixture is heated to 56 DEG C. and the sensitizing dye anhydro-5-chloro-5'-phenyl-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydrochloride is obtained. After adding the oxide sodium salt, the compounds shown in Table 2 and a sensitizer were added, and then chloroauric acid (1 × 10 ⁻⁵ mol / mol AgX) and potassium thiocyanate (6 × 10 ⁻⁴ mol / mol). AgX) was added, and the mixture was optimally chemically aged. Thereafter, the following compounds were added, and the resultant was coated on a triacetylcellulose film support having an undercoat layer together with a protective layer by a simultaneous extrusion method.

(1) Emulsion layer o Emulsion ... Emulsion shown in Table 2 o Coupler ○ Tricresyl phosphate ○ Stabilizer 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene ○ Coating aid sodium dodecylbenzenesulfonate (2) Protective layer ○ Polymethyl methacrylate fine particles ○ 2,4-Dichloro-6-hydroxy-s-triazine sodium salt ○ Gelatin Exposure to these samples for sensitometry (1/100 second)
And the following color development processing was performed.

The density of the treated sample was measured with a green filter. Table 2 shows the obtained photographic performance results. Relative sensitivity is sample
12 was set to 100.

 The development treatment used here was performed at 38 ° C. under the following conditions.

1. Color development ... 2 minutes 45 seconds 2. Bleaching ... 6 minutes 30 seconds 3. Rinse ... 3 minutes 15 seconds 4. Settle down ... 6 minutes 30 seconds 5. Rinse ... 3 minutes 15 seconds 6. Stable: 3 minutes 15 seconds The composition of the processing solution used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline Sulfate 4.5g Add water 1 Bleach solution Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraacetate sodium salt 130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 As is clear from Table 2, selenium sensitization has high sensitivity, but fog is particularly remarkable in color development. However, the combination of the compound of the present invention provided an unexpected effect that fog was remarkably suppressed and higher sensitivity was obtained.

Example 3 To 1.2 l of a 3.0% by weight gelatin solution containing 0.06 mol of potassium bromide was added, while stirring, 30 ml of a 25% by weight aqueous ammonia solution, and a 0.3 mol silver nitrate solution was added to a reaction vessel kept at 75 ° C. 50cc and 0.063 mol of potassium iodide and 0.1
50 cc of a halogen salt aqueous solution containing 9 mol of potassium bromide was added by a double jet method over 3 minutes. Thus, nucleation was carried out by obtaining silver iodobromide grains having a projected area circle equivalent diameter of 0.2 μm and a silver iodide content of 25 mol%. Subsequently, at 75 ° C., the aqueous ammonia solution is
Add 800 ml of 1.5 mol silver nitrate, 800 ml of halogen salt solution containing 0.375 mol potassium iodide and 1.13 mol potassium bromide
Are added simultaneously by the double jet method over 80 minutes,
A first coating layer was formed. The resulting emulsion grains were octahedral silver iodobromide emulsions having an average projected area circle equivalent diameter of 0.95 μm. (Iodide content: 25 mol%).

Subsequently, acetic acid was added for neutralization, and then a 1.5 mol silver nitrate solution, a 1.5 mol potassium bromide solution and a 2% by weight gelatin solution were added to a mixer, and a silver bromide shell (second coating layer) was added.
By forming the particles, particles having a first coating layer / second coating layer ratio of 1: 1 were obtained. The resulting grains were octahedral monodispersed core / shell emulsion grains having an equivalent circle diameter of 1.2 μm.

The resulting emulsion was divided into 5 parts, heated to 56 ° C., added with the compounds shown in Table 3 and a sensitizer, and then chloroauric acid (1.2 × 10 ^−5).
Mol / mol Ag) and potassium thiocyanate (4.0 × 10 ⁻⁴ mol / mol Ag) were added, and the mixture was optimally aged. Next, the following sensitizing dyes I to III were added, and further, a coating aid (sodium dodecylbenzenesulfonate), a stabilizer (4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene), Oil−
Emulsifiers containing 1,2 and couplers 1-4 are added, and the protective layer (gelatin, polymethylmethacrylate particles, H-1, S-1,2
) On a triacetylcellulose film support having an undercoat layer.

Oil-1 Tricresyl phosphate Oil-2 Bis (2-ethylhexyl) phthalate These samples were exposed through a yellow filter (1/100 second) and subjected to the same color development processing as in Example 2.

The density of the treated sample was measured with a red filter, and the results shown in Table 3 were obtained.

 The relative sensitivity was determined by setting Sample 18 to 100.

As is evident from Table 3, the use of the compound of the present invention significantly suppressed fog generation and maintained high sensitivity in gold selenium sensitization in which fog generation was remarkable.

In addition, even in the case of selenium sensitization alone without using chloroauric acid, fog could be remarkably suppressed by the combined use of the compound of the present invention without substantially lowering the sensitivity.

Example 4 Silver iodobromide seeds A and B having a silver iodide content of 6 mol% and having a uniform halogen distribution structure were prepared. A is sphere equivalent diameter 0.50
Coefficient of variation showing a size distribution of octahedral regular grains of μm is about 14%, while B is a parallel double twin tabular grain having a sphere equivalent diameter of 0.53 μm, a variation coefficient of 23% and an average of all grains. The aspect ratio was 11.5.

1.15 g of silver iodobromide having a silver iodide content of 30 mol% using seed crystal A
After growing to μm, the equivalent sphere diameter of silver bromide is 1.
Emulsion I was further grown to 4 μm.

Using seed crystal B, 1.15 with silver iodobromide having a silver iodide content of 30 mol%
After growing to μm, emulsion II was prepared by growing to 1.4 μm with silver bromide. The coefficient of variation of the size distribution was 18%, and the average aspect ratio of all particles was 7.0.

In the course of growing the grains into Emulsions I and II using the seed crystal A or B, the compound 6 of the present invention was added to 6.
0 × 10 ^-5 mol was added. All of these emulsions were redispersed at 40 ° C. under the conditions of pAg 8.9 and pH 6.3 through a usual desalting and washing step. Here, the emulsion was divided into two, and one of the emulsions was optimally chemically sensitized using 6 × 10 ^-6 mol of sodium thiosulfate and 2 × 10 ^-6 mol of chloroauric acid per mol of silver halide. . The other emulsion was composed of 4 × 10 ^-6 mole of sodium thiosulfate, 1 × 10 ^-6 mole of dimethyl selenium urea and 2 × 10 ^-6 mole
Optimal chemical sensitization with molar chloroauric acid.

The emulsion and the protective layer were coated at the coating amounts shown in Table 4 on a triacetyl cellulose film support provided with an undercoat layer.

Table 4 (1) Emulsion layer Emulsion Emulsion shown in Table 4 (silver 1.7 × 10 ^-2 mol / m ² ) Coupler (1.5 × 10 ^-3 mol / m ² ) ・ Tricresyl phosphate (1.10 g / m ² ) ・ gelatin (2.30 g / m ² ) (2) protective layer ・ 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium salt (0.08 g / m 2) ² ) Gelatin (1.80 g / m ² ) These samples were exposed to sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a green filter. Table 4 shows the obtained photographic performance results.

 The development treatment used here was performed at 38 ° C. under the following conditions.

1. Color development ... 2 minutes 45 seconds 2. Bleaching ... 6 minutes 30 seconds 3. Rinse ... 3 minutes 15 seconds 4. Settle down ... 6 minutes 30 seconds 5. Rinse ... 3 minutes 15 seconds 6. Stable: 3 minutes 15 seconds The treatment composition used for each process is as follows.

Color developer Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methyl- Aniline sulfate 4.5 g Add water 1 Bleach Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetate ammonium salt 100 g Ethylenediamine-tetraacetate sodium salt 10 g Glacial acetic acid 14 ml Add water 1 Fixing solution Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1 Stabilizer Formalin 8.0 ml Add water 1 Exposure is 1 second and 1/100 A normal wedge exposure was performed in seconds.

A light source adjusted to a color temperature of 4800 ° K using a filter was used, and a blue filter (BPN42, manufactured by Fuji Photo Film Co., Ltd.) or a yellow filter was used. The sensitivity was compared at a point of 0.2 in optical density from fog.

Gamma is the slope of the characteristic curve, and the larger the value, the higher the contrast. The blue sensitivities of Sample 1 of octahedral grains and Sample 5 of tabular grains are each set to 100 as a standard for the sensitivity of each of Emulsions I and II.

As shown in the examples, it was found that an extremely favorable effect was obtained when selenium-sensitized an emulsion in which thiosulfonic acid was present during the preparation of the emulsion.

Example 5 The following dyes were added to the emulsions used in Sample Nos. 5, 6, 7, and 8 prepared in Example 4 to prepare red-, green-, and blue-sensitive emulsions. did.

Dye group (red dye) Dye group 2 (green dye) Dye Group 3 (Blue Dye) Sensitizing Dye VIII 2.2 × 10 ^-5 mol / mol Ag On each cellulose triacetate film support subbed with these emulsions, each layer having the following composition is overlaid. By coating, a multilayer color light-sensitive material was prepared.

(Composition of photosensitive layer) The coating amount is g / g for silver halide and colloidal silver.
The amount of silver expressed in m ² units, the amount expressed in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes Indicated by

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.04 Cpd-2 0.02 Solv-1 0.30 Solv-2 0.01 Second layer: Intermediate layer Fine particle iodobromination Silver (AgI 1.0 mol%, equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.0 ExC-4 0.03 Cpd-3 0.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface height AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, spherical) 0.4 μm equivalent diameter, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.40 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExC-1 0.50 ExC-2 0.11 ExC-3 0.009 ExC-4 0.023 Solv-1 0.24 Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, Ball equivalent diameter 1.0μ 25% coefficient of variation of the sphere-equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) silver coverage 0.85 Gelatin 0.7 ExS-1 3 × 10 ^-4 mol ExS-2 1 × 10 ^-4 mol ExS-3 0.3 × 10 ^-4 mol ExC-1 0.10 ExC-2 0.05 ExC-4 0.025 Solv-1 0.10 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount 1.50 Gelatin 0.6 ExC-2 0.08 ExC-4 0.01 ExC -5 0.06 Solv-1 0.12 Solv-2 0.12 6th layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Solv-1 0.1 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface height) AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, spherical) 0.4 μm equivalent diameter, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.16 Gelatin 1.2 ExS-5 5 × 10 ^-4 mol ExS-6 2 × 10 ^-4 mol ExS-7 1 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM 5 0.03 Solv-1 0.2 Solv-4 0.03 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high iodine type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%) , Plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 mol ExS-6 1.4 × 10 ^-4 mol ExS-7 0.7 × 10 ^-4 mol ExM-1 0.12 ExM- 2 0.01 ExM-3 0.03 Solv-1 0.15 Solv-4 0.03 Ninth layer: Intermediate layer Gelatin 0.5 Solv-1 0.02 10th layer: Third green sensitive emulsion layer Silver iodobromide emulsion II Silver coating amount 1.3 Gelatin 0.8 ExM- 4 0.04 ExC-4 0.005 ExM-6 0.01 Cpd-5 0.01 Solv-1 0.2 Layer 11: Yellow filter layer Cpd-6 0.05 Gelatin 0.5 Solv-1 0.1 Layer 12: Intermediate layer Gelatin 0.5 Cpd-3 0.1 Layer 13 : First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform iodine type, equivalent sphere diameter 0.55 μm, variation coefficient of equivalent sphere diameter 25%, tabular grains, diameter / thickness ratio 7.0) Silver coating Amount 0.2 Gelatin 1.0 ExS-8 3 × 10 ^-4 mol ExY-1 0.6 ExY-2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type) Sphere equivalent diameter 1.0 μm, sphere equivalent diameter variation coefficient 16%, octahedral particles) Silver coating 0.19 gelatin 0.3 ExS-8 2 × 10 ^-4 mol ExY-1 0.22 Solv-1 0.07 15th layer: middle layer Fine grain silver iodobromide (AgI 2 mol%, uniform iodine type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.2 gelatin 0.36 16th layer: third layer blue-sensitive emulsion layer Silver iodobromide emulsion III Silver coating amount 1.55 gelatin 0.5 ExY-1 0.2 Solv-1 0.07 17th layer: 1st protective layer Gelatin 1.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protective layer Fine grain silver chloride (sphere equivalent diameter 0.07 μm) silver coating amount 0.36 gelatin 0.7 polymethyl methacrylate particles (diameter 1.5 μm) 0.2 W-1 0.02 H-1 0.4 Cpd-7 1.0 In addition to the above, B-1 (total 0.2) 0g / m ^2), 1,2-
Benzisothiazolin-3-one (about 200 ppm based on gelatin), n-butyl, p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm) were added.

Fifth, tenth and sixteenth layers of silver iodobromide emulsions I and II and
III, multilayer color light-sensitive materials 501 and 505 were prepared by incorporating emulsions 5, 6, 7, and 8 prepared in Example 4 to which spectral sensitizing dyes having respective sensitivities were added.

These samples were subjected to sensitometric exposure and subjected to the following color development processing.

Filter the processed sample with a red filter, green filter,
The density was measured with a blue filter.

Processing Method Color development was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stable 1 minute 05 seconds The composition of the processing solution used in each process is as follows. Was.

Color developing solution Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mL Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Add water 1.0 l pH 10.0 Bleaching solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Sodium ethylenediaminetetraacetate 10.0 g Bromide Ammonium 150.0g Ammonium nitrate 10.0g Add water 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid sodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0l pH 6.6 Stabilizer Formalin (40%) 2.0ml Polyoxyethylene-p-monononylphenylate Ter (Average degree of polymerization 10) 0.3 g Add water 1.0 l Water-sensitive material 504 (Emulsion 8) is remarkably higher than Photo-sensitive materials 501-503 (Emulsions 5-7) as well as the photographic characteristics of a single layer coated sample. The characteristic of low sensitivity, low fog and high contrast is also shown in the multilayer color photosensitive material.

Example 6 Samples 501 to 504 of the present invention and comparative examples were exposed in the same manner as in Example 5, and then processed using an automatic developing machine by the method described below.

Processing method Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching and fixing 3 minutes 15 seconds 38 ° C Rinse with water (1) 40 seconds 35 ° C Rinse with water (2) 1 minute 00 seconds 35 ° C Stable 40 Second 38 ° C Drying 1 minute 15 seconds 55 ° C Next, the composition of the processing solution is described.

(Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching solution) (unit g) Ferric ethylenediaminetetraacetate Ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid Disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0ml Add water 1.0l pH 6.3 (Bleaching / fixing solution) (unit g) Ferric ethylenediaminetetraacetate ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 aqueous solution of ammonium thiosulfate (70%) 240.0ml Ammonia water (27%) 6.0ml Add water 1.0l pH 7.2 (Washing solution) Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) Water is passed through a mixed-bed column packed with an OH-type anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / l sodium diisocyanurate sodium And 1.5 g / l of sodium sulfate. The pH of this solution is in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit g) Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Sodium ethylenediaminetetraacetate disodium salt 0.05 Add water 1.0l pH 5.0 ~ 8.0 Sample 504 of the present invention also showed good results by this treatment as in Example 5.

Example 7 Samples 501 to 504 of the present invention and comparative examples were exposed in the same manner as in Example 5, and then processed by an automatic developing machine in the following manner.

Processing method Process Processing time Processing temperature Color development 2 minutes 30 seconds 40 ° C Bleaching and fixing 3 minutes 00 seconds 40 ° C Rinse with water (1) 20 seconds 35 ° C Rinse with water (2) 20 seconds 35 ° C Stable 20 seconds 35 ° C Drying 50 seconds 65 ° C Next The composition of the processing solution is described below.

(Color developing solution) (unit: g) diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water 1.0l pH 10.05 (Bleaching / fixing solution) (g) Ferric ethylenediaminetetraacetate ammonium salt 50.0 Ethylenediaminetetraacetic acid Sodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator 0.01 mol Add water and add 1.0 l pH 6.0 (wash water) Tap water is converted to H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium isocyanurate dichloride and 0.15 g / l of sodium sulfate were added.

 The pH of this solution ranges from 6.5 to 7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Sodium ethylenediaminetetraacetate disodium salt 0.05 Add water 1.0l pH 5.0 ~ 8.0 Sample 504 of the present invention also showed good results by this treatment as in Example 5.

Example 8 Emulsions 5, 6, 7, and 8 used in Sample Nos. 5, 6, 7, and 8 prepared in Example 4 were added with 4- (2- [2
-Methyl (3- [4-sulfonatobutyl] benzothiazoline-2-ylidene) -1-propenyl] -3-benzothiazolio) butanesulfonate = pyridinium was added in an amount of 0.36 mmol per mole of silver halide and tetral as a stabilizer. Azaindene was added, and a coating aid, dodecylbenzenesulfonate, and a thickener, polybotashium-p-
Vinyl benzene sulfonate was added to obtain a coating solution. These coating solutions were coated on a triacetylcellulose support at the same time as the surface protective layer to prepare photosensitive materials 801 to 804.

The surface protective layer contained, in addition to gelatin, a thickener sodium polystyrene sulfonate, a matting agent, and a hardener N, N'-ethylenebis (vinylsulfonylamide coating aid, sodium t-octylphenoxyethoxyethoxyethoxyethanesulfonate). A 10 wt% gelatin aqueous solution was used, and the coated silver amount of the photosensitive silver halide emulsion layer was 3.5 g / m ² ,
The gelatin coating amount of the surface protective layer is 1.3 g / m ² and the thickness is 1.0 μm
Met.

Each sample was exposed to tungsten light of 400 lux for 1/10 second through an optical wedge, and then developed with the following developer at 20 ° C for 7 minutes and 12 minutes, respectively. The photographic sensitivity at a constant density (optical density of 0.1) higher than the fog density was measured for each of the fixed, washed and dried samples.

Developer Fixer The light-sensitive material 804 (emulsion 8) is a light-sensitive material 801 to 803 (emulsion 5).
In contrast to (7), the characteristics of extremely high sensitivity and low fog and the characteristics of high gradation and high contrast were also confirmed in black-and-white development.

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula [I], [II] or [III]
A silver halide photographic material comprising at least one compound represented by any one of the above, and a silver halide emulsion sensitized by a sulfur sensitizer and further sensitized by selenium. Formula (I) Z-SO ₂ S-M However, Z forms an alkyl group (1 to 18 carbon atoms), an aryl group (6 to 18 carbon atoms), or a heterocyclic group, and Y forms an aryl group (6 to 18 carbon atoms) or a heterocyclic group. M represents a metal cation, an organic cation,
Or a hydrogen atom, and n represents an integer of 2 to 10. 2. A compound represented by the following general formula [I], [II] or [III]
And a selenium-sensitized silver halide emulsion sensitized with a sulfur sensitizer and produced in the presence of at least one compound represented by any one of the above. Formula (I) Z-SO ₂ S-M However, Z forms an alkyl group (1 to 18 carbon atoms), an aryl group (6 to 18 carbon atoms), or a heterocyclic group, and Y forms an aryl group (6 to 18 carbon atoms) or a heterocyclic group. M represents a metal cation, an organic cation,
Or a hydrogen atom, and n represents an integer of 2 to 10.