JP2604278B2 - Chemical sensitization of silver halide emulsion - Google Patents

Description

The present invention relates to a method for chemically sensitizing a silver halide emulsion.
In particular, the present invention relates to a method for sulfur sensitization of 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, sulfur sensitization, selenium sensitization, noble metal sensitization such as gold, reduction sensitization, and various sensitization methods based on a combination thereof are known, but the most widely used method is universal. The most basic method used in the combination sensitization method is a sulfur sensitization method using an unstable sulfur compound. Specifically, P. Gr
afkides, Chimie et Physique Photographique (Paul
Published by Momtel, 1987, 5th edition), edited by THJames, The
Theory of the Photographic Process (Macmillan, 1977, 4th edition), H. Frieser, Die Grundlagend
er Photographischen Prozess mit Silverhalogeniden
(Akademische Verlagsgeselbshaft, 1968).

By the way, in recent years, silver halide photographic light-sensitive materials have been improved in sensitivity while maintaining excellent graininess and high sharpness, and high-temperature rapid processing for further increasing processing speed, and furthermore, high-temperature development push development (development time has been There has been a strong demand for higher sensitivity and the like in these cases, but these are both liable to enlarge the occurrence of Caribbean and soften the gradation, and the above-mentioned sulfur sensitization method, sulfur-gold sensitization method, There has been a desire for an improved combination sensitization method based on a sulfur sensitization method such as a sulfur-selenium-gold sensitization method.

For example, Japanese Patent Application Laid-Open No. 61-20940 discloses a technique in which a specific sulfur sensitizer is included in cyclodextrin to form a complex, and fog is reduced by chemical sensitization.

(Problems to be Solved by the Invention) However, in this method, cyclodextrin and its derivatives themselves are not completely inactive photographically, have side effects, are expensive, or are actually effective. There were various problems such as a specific sulfur compound.

Therefore, it is low-cost, has no photographic side effects or problems, and is a wide range of sulfur sensitizers, especially when developing at high temperatures or when pressing development (long-term development), There has been a strong demand for a technology that can suppress softening.

(Object of the Invention) It is an object of the present invention to firstly provide a high-sensitivity silver halide emulsion chemical sensitizer with little fog.

A second object of the present invention is to provide a high-sensitivity chemical sensitization method for a silver halide emulsion which is low in cost and has little side effects on photographic performance and little fog.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which is suitable for high-temperature processing and which has less fog and has a gradation with less fog, particularly when development is pressed.

(Means for Solving the Problems) The above objects are characterized in that a sulfur sensitizer excluding a water-soluble sulfide is preliminarily mixed with a gelatin solution, and then added to a silver halide emulsion to chemically sensitize the emulsion. This was achieved by the chemical sensitization of silver halide emulsions.

Conventionally, so-called unstable sulfur sensitizers that can react with silver ions to form silver sulfide include water or a suitable organic solvent miscible with water (for example, alcohols such as methanol, ethanol and propanol, and methyl ether and the like). Ethers,
Glycols such as ethylene glycol, ketones such as acetone, esters such as ethyl acetate, cellosolves such as methoxyethanol, and acides such as dimethylformamide), or as described in patents described in the prior art. The mixture was usually subjected to sulfur sensitization by adding an aqueous solution mixed with cyclodextrin to the silver halide emulsion.

However, the present inventors have prepared a method in which a sulfur sensitizer dissolved in water or an appropriate organic solvent or a solid or oily sulfur sensitizer itself is sufficiently mixed in advance with a gelatin solution, and the gelatin containing the sulfur sensitizer is mixed. When the solution is added to the silver halide emulsion in liquid or solid form (gel form) and subjected to sulfur sensitization, fogging occurs (especially fogging in press development),
Was found to be suppressed. At the same time, in some cases, favorable results such as high contrast and further increase in sensitivity are obtained.

The reasons for these positive results are:
Although it has not been determined, the ion sensitizer molecules are pre-interacted (dispersed or dissolved) with gelatin molecules, which are macromolecules, and then added to the silver halide emulsion to form silver halide microcrystals. It is presumed that the uniformity of the reaction of the sulfur sensitizer is improved.

This is a similar idea to the inclusion complexation with cyclodextrin cited in the prior art, but in contrast, gelatin is
It is inexpensive and commonly used in silver halide emulsions, has no side effects, and has several significant advantages of being effective with a wide range of sulfur sensitizers.

The gelatin used in the present invention is a so-called inert gelatin which is photographically inert, and is a general-purpose lime-processed gelatin,
In addition to acid-treated gelatin, it refers to gelatin derivatives (for example, phthalated gelatin), gelatin that has been treated with an enzyme or hydrolyzed, graft polymers of gelatin with other polymers, and the like. Then, it may be mixed with a sulfur sensitizer.

The amount of gelatin relative to the sulfur sensitizer may be 10 times or more, preferably 30 times or more, more preferably 100 times or more by weight.

The gelatin concentration of the mixture may be any value depending on the sulfur sensitizer used, but is 0.01 wt% or more, preferably 0.05 wt% or more, more preferably 0.1 wt% or more for most of the sulfur sensitizer. Is good.

The sulfur sensitizer used in the present invention is a so-called unstable sulfur compound capable of forming silver sulfide by reacting with silver ions. In addition to the references cited in (Prior Art), US Pat. No. 1,574,944, No. 1,623,449, No. 2,278,947
No. 2,410,689, No. 2,440,206, No. 2,449,15
No. 3, No. 2,728,668, No. 3,189,458, No. 3,501,3
No. 13, No. 3,656,955, No. 4,030,928, No. 4,054,
No. 457, No. 4,067,740, No. 4,266,018, No. 4,81
No. 0,626, German Patent No. 1,422,869, No. 1,572,260,
No. 971,436, No. 228,658, No. 235,929, British Patent No. 1,129,356, No. 99,701, No. 1,403,980,
European Patent Nos. 61,446 and 138,622, Japanese Patent JP 6
3-5355, 63-5336, 58-80634, JP-A-1-
No. 114839, No. 1-227140, No. 58-30570, No. 60
−24457, 62-17216, Research Disclosure 176
Vol. 17643 (December 1978), Vol. 187 No. 18716 (1979
And November) can be used. Specific compounds include: (a) thiosulfate (for example, sodium thiosulfate, P-
(B) thioureas (eg, allyl thiourea, N, N'-
Diphenylthiourea, triethylthiourea, acetylthiourea, N-ethyl-N '-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea, N-allyl-N'-hydroxyethylthiourea, etc.) c) Thioamides (for example, thioacetamide, N-
Phenylthioacetamide, etc.) (d) rhodanines (e.g., rhodanine, N-ethylrhodanine, 5-benzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine, diethyl rhodanine, etc.) (e) Thiohydantoins (e.g., 1,3-diphenyl-2-thiohydantoin, 4-benzylidene-1,3-diphenyl-2-thiohydantoin, etc.) (f) 4-oxo-oxazolidin-2-thiones (for example, 5,5-dimethyl-4) -Oxo-oxazolidine-
2-thione, 3-ethyl-4-oxo-oxazolidine-2-thione, 3-benzyl-4-oxo-oxazolidine-2-thione, etc. (g) Di, polysulfides (for example, dimorpholino disulfide, 1,2 , 3,5,6-pentathiacycloheptane,
(H) thiosulfonic acids (for example, sodium benzenethiosulfonate, sodium P-toluenethiosulfonate, sodium ethylthiosulfonate, sodium n-octylthiosulfonate) (i) ) Mercapto compounds (for example, cysteine) (j) polythionate (k) elemental ion (α-sulfur) and the like.

Of these, particularly preferred are (a), (b),
(C), (d), (f), (g) and (h).

The ion sensitizer of the present invention does not include active gelatin which has been known for a long time. This is often difficult to identify the sensitizer is unknown, and often unstable in performance,
Improper.

The present invention comprises mixing a sulfur compound (sulfur sensitizer) specified on a chemical substance with inert gelatin,
This is completely different from the above-mentioned active gelatin, and the present invention is not suggested by the active gelatin.

In the present invention, the amount of the sulfur sensitizer used varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is generally 10 ^-7 to 10 ^-2 mol, preferably 10 ^-6 to 10 mol per mol of silver halide. About 10 ^-3 mol is used.

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

In the present invention, in addition to sulfur sensitization, noble metal sensitization, selenium sensitization and reduction sensitization can be used alone or in combination.

In precious metal sensitization, a precious metal sensitizer such as gold, platinum, palladium, and iridium can be used in combination. In this case, it is particularly preferable to use a gold sensitizer in combination, and specific examples thereof include chloroauric acid, potassium chloroaurate, potassium authiocyanate, gold sulfide, and gold selenide. , 10 ^-7 to 10 ^-2 mol can be used.

In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone Selenium compounds such as selenium amides and selenoamides per mole of silver halide
It may be used in an amount of about 10 ^-8 to 10 ^-3 mol.

In the present invention, a reduction sensitizer can be used in combination, and specific examples thereof include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, and polyamine compounds. Can be

The noble metal sensitizer, selenium sensitizer, and the following halogenated solvent used together in the present invention may be dissolved in water or an appropriate organic solvent, or may be prepared in advance similarly to the sulfur sensitizer of the present invention. It may be added in a form mixed with gelatin suspect.

In the present invention, sulfur sensitization can be carried out 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-A-59-11892, U.S. Pat. Urea, etc.) and the thione compounds described in JP-B-60-11341,
Mercapto compounds described in JP-A-3-29727, JP-A-60-1630
No. 42 mesoionic compound, U.S. Pat.
Selenoether compounds described in JP-A-2-132434, telluro ether compounds described in JP-A-2-118566, sulfites and the like. Among them, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used, and thiocyanates are particularly preferable. The amount used can be about 10 ^{-5 to} 5 × 10 ^-2 mol per mol of silver halide. Hereinafter, the silver halide emulsion of the present invention and a light-sensitive material using the same (light-sensitive material of the present invention) will be described in detail.

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, but also 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.

Even when the silver halide grains used in the present invention have different phases between the inside and the surface layer (for example, double or multi-structure silver iodobromide grains having iodine content on the grain surface smaller than inside the grains), the silver halide grains are uniform. May consist of different phases. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) It may be. Preferably, the particles are such that the latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.05
Micron or less, preferably 0.3 micron or less, preferably 0.6 micron or more in diameter, having an average aspect ratio of 3
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 agents and monodispersed emulsions may be mixed.

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

In forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,6
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
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 zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted.

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

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

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. For example, chromium salts, aldehydes (formaldehyde, glyoxal, glitalaldehyde, etc.) and N-methylol compounds (dimethylolurea, etc.) are specific examples. 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 (vinyl Sulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or a vinyl polymer having a vinylsulfonyl group in the side chain, etc.) are preferable because they can quickly cure a hydrophilic colloid such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-morpholinocarbonyl-3-
Pyridinio) methanesulfonate) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene)
Pyrrolidinium 2-naphthalene sulfonate) also has a fast curing rate and is 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, composites, merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine dye. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
Such as a tetrazole nucleus and a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, ie, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus , 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 diazolidine-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, aminostilbene 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 alzaindene compound may be included. U.S. Patent No.
3,615,613, 3,615,641, 3,617,295, 3,63
The combination described in 5,721 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) and the like; mercaptopyrimidines; Thioketo compounds such as thiones; azaindenes such as triazaindenes,
Tetraazaindenes (especially 4-hydroxy-substituted (1,3,
3a.7) Tetraazaindenes, pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonate, benzenesulfonate, and benzenesulfonamide Can be added.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (eg, 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. Further, 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 the graininess may be further improved by a three-layer structure. 2 with the same color sensitivity
A non-light-sensitive layer may be present between one or more emulsion layers. 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
For example, by using a three-color coupler mixture described in US Pat. No. 4,126,461 and British Patent No. 2,102,136. The present invention can also be applied to black-and-white photographic materials. 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.
JP-A-16356, 48-33697, JP-A-50-13040 and British Patent 1,330,524, an integrated type as described in JP-A-57-119345. It is possible to take a configuration of a simple peeling-free film unit.

The use of a polymeric acid layer protected by a neutralization timing layer in any of the above types of formats is useful in increasing the tolerance 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 as a developing solution component by being enclosed in a processing solution container.

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. Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as the recording light source. 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.

Color developing solutions include pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. It is common to include such as. If necessary, 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. This black-and-white developer includes dividroxybenzenes 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. The iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
No. 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 JP-A Nos. 3-141623, 53-28426, and Research Disclosure No. 17129 (July 1978);
Thiazolidine derivatives as described in JP-A No. 45-8506, JP-A Nos. 52-20832 and 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715; Iodides described in JP-A-58-16235;
Polyethylene oxides described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B No. 45-8836; other JP-A Nos. 49-42434 and 49-59644;
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, a compound having a mercapto group or a disulfide group is preferable in terms of a large accelerating effect,
In particular U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95630 are preferred. Furthermore,
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 buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4- 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, the poremarine 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, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent 2,226,770 or US Pat. No. 3,674,499 may be performed.

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

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

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

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

 Hereinafter, the present invention will be described with reference to specific examples.

Example 1 An aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added to a gelatin aqueous solution containing potassium bromide and ammonia kept at 60 ° C. while stirring by a double jet method while keeping the silver potential at +20 mV with respect to a saturated calomel electrode.

After the completion of particle formation, desalting was performed by flocculation, gelatin was added, and the pH and pAg were adjusted to 6.33 and 8.5, respectively.

This silver bromide emulsion has a grain diameter of 0.85 μm (111) face /
It is a monodisperse tetrahedral emulsion having a (100) face ratio of 55/45 and a coefficient of variation in grain diameter of 12%.

After this emulsion was divided into 28 parts, the temperature was raised to 60 ° C., and then sensitizers were added in the forms shown in Table 1 and chemically ripened for 40 minutes.

Thereafter, the following compounds were added, and the resultant was coated on a triacetyl cellulose film support having an undercoat layer together with a protective layer by a simultaneous pressing method.

(1) Emulsion layer Emulsion Emulsion coupler shown in Table 1 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 These samples were exposed to sensitometric exposure (1/100
Sec), and the following color development processing was performed.

The density of the treated sample was measured with a green filter. Table 1 shows the obtained photographic performance results. The relative sensitivity is represented by the reciprocal of the exposure required to obtain an optical density of fog value + 0.2, and the value obtained by developing Sample 1 for 2 minutes and 45 seconds is 100.

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

1. Color development: 2 minutes 45 seconds or 5 minutes 2. Bleaching: 6 minutes 30 seconds 3. Rinse: 3 minutes 15 seconds 4. Fixing: 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 step 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 sulfur salt 2.4 g 4- (N-ethyl-N-βhydroxyethylamino)-
2-Methyl-aniline sulfate 4.5 g Add water 1 l Bleaching solution Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium salt 130 g Glacial acetic acid 14 ml Add water 1 l Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1l Stabilizer Formalin 8.0ml Add water 1l As is evident from Table 1, there is no difference in the development of 2 minutes and 45 seconds with sodium thiosulfate, for which the generation of fog is originally small, but when the development is pressed up to 5 minutes, the mixture is preliminarily mixed with the aqueous gelatin solution before addition. When added in the form of the present invention, the generation of fog was reduced.

In the case of other sulfur sensitizers which have high sensitivity but generate large fog, the fog generation is reduced by the method of the present invention even in development for 2 minutes and 45 seconds, and the compounds which generate more fog are more remarkably fogged. Of course, the difference became larger with 5 minutes development. At the same time, a slight increase in sensitivity was sometimes obtained.

As described above, the method of the present invention which can suppress the occurrence of fog, particularly in the press development by using gelatin which is widely used in silver halide emulsions and has no risk of side effects and which is inexpensive, is very significant in the art. .

Example 2 Method a (Comparative Example) A 3% by weight aqueous solution of gelatin was stirred at 75 ° C. while keeping the pH at 2, and an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added simultaneously over 60 minutes, and the reaction solution was stirred well. While keeping the silver potential constant at -30 mV, the reaction was desalted after completion of the reaction to prepare a photographic emulsion composed of monodispersed octahedral silver bromide grains having an average grain size of 0.25 μm. Separate 100 g of this emulsion, and while stirring at 40 ° C., 10 ml of an aqueous solution of triethylthiourea having various concentrations shown in Table 2 was added instantaneously.
Stir for an additional 15 minutes.

The above emulsion was coated on a cellulose triacetate film base and dried to obtain a film sample. These film samples were tested against a tungsten bulb (color temperature 2854 ゜ K).
After exposure through a wedge for 10 seconds, development was performed at 20 ° C. for 10 minutes using a MAA-1 surface developer, and after fixing, washing and drying, the optical density was measured. The photographic sensitivity was represented by the reciprocal of the exposure required to give an optical density of fog density plus 0.1. The photographic sensitivity values and fog densities obtained are shown in Table 2.

Method b (invention) 100 g of the emulsion prepared by the method a was dispensed at a time, and 10 g of a gel solid of a 10% by weight aqueous gelatin solution in which triethylthiourea of various concentrations shown in Table 2 was dissolved was added. The mixture was dissolved by raising the temperature to 40 ° C and stirred for 15 minutes. Table 2 shows the sensitivity values obtained in the same manner as in method a.

As is evident from Table 2, the highest sensitivity was remarkably increased when the composition was added in the form of the present invention which was previously mixed with the aqueous gelatin solution before the addition. Thus, the method of the present invention, which can increase sensitivity by improved chemical sensitization using inexpensive gelatin which is versatile, has no side effects, and is very significant.

Example 3 30 ml of a 25% by weight aqueous ammonia solution was added to a 3.0% by weight gelatin solution 1.21 containing 0.06 mol of potassium bromide while stirring, and 50 cc of a 0.3 mol silver nitrate solution was added to a reaction vessel kept at 75 ° C. 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 over 3 minutes by the double jet method. As a result, nucleation was performed by obtaining silver iodobromide grains having a projected area equivalent circle 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
Over 80 minutes by the double jet method at the same time,
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 wt% gelatin solution were added to a mixer, and a silver bromide shell (second coating layer) was added.
To obtain particles having a first coating layer / second coating layer ratio of 1: 1. The resulting grains were octahedral monodispersed core / shell emulsion grains having a circle equivalent diameter of 1.2 μm.

The resulting emulsion was divided into four portions, heated to 56 ° C., added with a sulfur sensitizer in the form shown in Table 3, and then chloroauric acid (1.2%).
× 10 ⁻⁵ mol / mol Ag) aqueous solution Potassium thiocyanate aqueous solution (4.0 × 10 ⁻⁴ mol / mol Ag) was 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), Add oil-1,2 and an emulsifier containing couplers 1-4 and co-extrusion with protective layer (including gelatin, polymethyl methacrylate particles and H-1, S-1,2),
Coating was performed on a triacetyl cellulose film support having an undercoat layer.

These samples were exposed through a yellow filter (for 1/100 second), and subjected to the same color development processing as in Example 1 (2 minutes 4 minutes).
5 seconds development).

The concentration 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 assuming that sample 39 was 100 for both the foot sensitivity (fog + density of 0.2) and the shoulder sensitivity (fog + density of 1.5).

As is clear from Table 3, the method of the present invention preferably suppresses the occurrence of fogging, and has a slight sensitivity to the shoulder portion with high sharpness, that is, the gradation can be made more tough. Results were also obtained.

Example 4 Potassium bromide, thioether (HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH) and gelatin were added and dissolved, and silver nitrate was stirred in a solution kept at 70 ° C. The solution and a mixed solution of potassium iodide and potassium bromide were added by a double jet method.

After the addition was completed, the temperature was raised to 35 ° C., the soluble salts were removed by a conventional flocculation method, and then 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 the content of silver iodide was 3 mol%. At 40 ° C., the pAg was 8.4.

The emulsion was divided into two parts, and the temperature was raised to 62 DEG C. to raise the sensitizing dye anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium hydroxide. Salt (500 mg / AgX1 mol) and potassium iodide (200 mg / AgX1 mol) were added, and sulfur sensitizer N-ethyl-N '-(4-methyl-2-thiazolyl) -thiourea was added in the form shown in Table 4. (1.2 × 10 ⁻⁵ mol / mol AgX), an aqueous solution of chloroauric acid (9 × 10 ⁻⁶ mol / mol AgX) and an aqueous solution of potassium thiocyanate (3.2 × 10 ⁻⁴ mol / mol AgX) were added. Chemically aged for 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 sequentially added while stirring to prepare a solution.

4-hydroxy-6-methyl-1,3,3a, 7- Tetorazaiden _{3% 2cc C 11 H 35 -O-} (CH 2 CHO) 2 -H 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 56.8g Polymethyl methacrylate fine particles (average particle size
3.0μm) 3.9g Emulsion Gelatin 10% 4.24g 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 using a sensitometer through a yellow filter and an optical wedge (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 was represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value +1.0, and the value of sample 43 was set to 100. The results are shown in Table 4.

As is evident from Table 4, the method of the present invention has obtained favorable results in that fog can be suppressed and the arrival sensitivity can be increased.

(Effect of the Invention) According to the present invention, without any photographic side effects,
In addition, it is possible to suppress the generation of fog due to sulfur sensitization, in particular, that of press development, at a low cost, and to achieve a higher contrast and a high sensitivity equivalent to or higher.

Claims (1)

(57) [Claims] 1. A chemical sensitization of a silver halide emulsion, wherein a sulfur sensitizer excluding a water-soluble sulfide is mixed in advance with a gelatin solution and then added to the silver halide emulsion for chemical sensitization. Law.