JPS62254145A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain the stable photographic characteristics of a sensitive material even after storage and to prevent fog by developing the sensitive material in the presence of a specified compound after exposure. CONSTITUTION:A silver halide photographic sensitive material having a photosensitive silver halide emulsion layer is exposed and developed in the presence of a compound represented by formula I, wherein R is H, amino, mercapto, carbamoyl, amido, sulfonamide, thioureidoalkyl or thiohydrocarbon group, preferably mercapto or amino, especially preferably mercapto, R1 is H or a substituent such as cyano, n=1-4 and in case of n>=2, the substituents R1 may bond to each other to form a condensed ring.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials.
More specifically, the present invention relates to a processing method that prevents fogging.

[Prior Art] For the purpose of preventing fogging of silver halide photographic materials (hereinafter referred to as "photosensitive materials") over time, stabilizers or fog suppressants, such as 4-hydroxy-6
-Methyl-1,3,3a.

hydroxypolyazaindenes such as 7-titrazaindene, 1-7enyl-5-mercaptotetrazole,
Many mercapto-substituted heterocyclic compounds such as 2-mercaptobenzothiazole and azole derivatives such as benzimidazole, benzotriazole, and indazole are known.

Furthermore, it is widely practiced in the art to use a combination of these conventionally known antifoggants in a certain proportion.

However, in recent years there has been an increasing demand for higher sensitivity of photosensitive materials. In other words, as a photosensitive material for amateurs,
For example, there are color and black-and-white photographic papers that require high-speed shutter speeds to eliminate shutter shake caused by the miniaturization of screen sizes, and quick processing of the visual process. There are photosensitive materials for printing that require high sensitivity due to automation, and there are also medical X-ray photosensitive materials that have high safety requirements and are strongly required to reduce radioactive stones.

Due to the occurrence of fog during storage of photosensitive materials using silver halide emulsions that have been significantly sensitized or sensitized using a technology different from conventional techniques, or due to the recent demand for shortening access times, rapid high-temperature use of 30°C or higher is required. The increase in fog due to the mainstream development has become commonplace, and conventional fog suppressants such as those mentioned above have no effect at all or even promote fog.

Therefore, there is a strong demand for fog suppression technology that suppresses fogging even in high-sensitivity photosensitive materials during storage over time, that sufficiently prevents fogging even during high-temperature rapid processing, and that does not affect photographic properties (gradation, sensitivity, etc.). has been done.

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and its first purpose is to maintain stable photographic characteristics even when a photosensitive material is stored over time and to prevent the occurrence of fog. An object of the present invention is to provide a method for processing photographic materials.

A second object of the present invention is to provide a processing method that is less likely to cause a decrease in sensitivity or softening of gradations due to development inhibition.

A third object is to provide a processing method that significantly reduces the occurrence of fog when developing at a high temperature, particularly at 30° C. or higher.

[Configuration 1 of the Invention The above object of the present invention is achieved by a processing method having the following configuration.

1. A method for processing a silver halide photographic material, which comprises exposing a silver halide photographic material having a light-sensitive silver halide emulsion layer to light and then developing the material in the presence of a compound represented by the following formula.

In the formula, R is hydrogen, an amino group, a mercapto group, a carbamoyl group, an amide group, a sulfonamide group, a thiourido alkyl group, or a hydrocarbon-8- group, R1 is hydrogen or a substituent, and n is 1 to 4. and two or more R1 may be combined to form a condensed ring.

The amino group represented by R includes substituted amino groups (for example, alkylamino such as ethylamino, arylamino such as anilino, etc.), and further includes cyclic amino groups (for example, 1
-piperazinyl, 4-morpholino, 1-pyrrolyl).

The carbamoyl group represented by R includes those substituted with alkyl, aryl, etc.

The amide group and sulfonamide group represented by R include alkyl groups and aryl groups (eg, acetamide, methanesulfonamide, benzamide, benzenesulfonamide, etc.).

The thiourido alkyl represented by R includes, for example, thiouridoethyl.

Examples of the hydrocarbon represented by R in -8- include alkyl and aryl.

Among the above R, preferred are a mercapto group and an amino group, with a mercapto group being particularly preferred.

Examples of the substituent represented by R1 include a cyano group, a halogen atom (e.g., fluoro, chloro, bromine, etc.), an alkyl group (e.g., methyl, trifluoromethyl, etc.), an aryl group (e.g., a phenyl group, etc.), a sulfonyl group (e.g., methanesulfonyl, etc.), acyl group (e.g. acetyl, etc.)
, heterocyclic groups (e.g., chenyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, etc.), alkylthio groups (e.g., methylthio, etc.), hydroxy groups, amino groups (e.g., amino, dimethylamino, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, etc.) ) and the like.

When n is 2 or more, each R1 may be the same or different.

Indicates a compound.

The compound represented by the above formula can be synthesized by reacting the compound represented by the following formula.

R, R+ and n have the same meanings as above, and X represents halogen or pseudohalogen.

Next, a synthesis example will be shown.

Compound Synthesis Example (1) Synthesis of Exemplary Compound 2 14.90% of Compound (I) and 26.9% of Tellurium Tetrachloride
After adding 0 to benzene 801Q and heating to reflux, the external temperature was raised to 120°C and the solvent and HCji! to secretly remove.

Methanol is added to the evaporation residue to disperse it, and approximately 8 g of an aqueous sodium hydroxide solution is added to form a homogeneous solution. Attach a cooling tube and gradually add sodium borohydride under a nitrogen atmosphere until the solution becomes colorless.

Next, cool the container by immersing it in an ice water bath, and then add concentrated hydrochloric acid 501.
g is added to form a strong acid and crystallize. The crude product was repeatedly recrystallized from methanol to obtain 2.6Q of the desired product.

(2) Synthesis of Exemplary Compound 13 28.60% of compound (I) and 26.9% of tellurium tetrachloride
After adding 0 to 80 d of benzene and heating to reflux, the external temperature was raised to 120° C. and the solvent and HCffi were distilled off.

Methanol is added to the evaporation residue to disperse it, and approximately 8 g of an aqueous sodium hydroxide solution is added to form a homogeneous solution. Attach a cooling tube and gradually add sodium borohydride under a nitrogen atmosphere until the solution becomes colorless.

Next, soak the container in an ice water bath and cool it while making salt 1! t
501Q is added to form a strong acid and crystallize. 4. The desired product was obtained by repeatedly recrystallizing the crude product from methanol.
I got 1Q.

The compound according to the present invention represented by the above formula may be added in the photographic material and/or in the processing solution.

In addition to the photosensitive silver halide emulsion layer in photographic light-sensitive materials, it can be added to hydrophilic non-emulsion layers such as protective layers, interlayers, and subbing layers. Among them, the photosensitive silver halide emulsion layer is preferable. . The amount added is preferably 0,005 to 5 mmol per mol of silver halide in the emulsion layer.
Furthermore, 0.01 to 2.0 mmol is preferable.

In the processing solution, it can be added to the developer and/or the processing solution applied before the developer (for example, a pre-hardening solution). The amount added is 0.000% per 12 of the processing solution.
0005 to 0.5 mmol is preferred.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Also, considering the critical growth rate of silver halide crystals, halide ions and silver ions were mixed in IIH in a pot.

It may be produced by controlling and sequentially adding DAO simultaneously. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

When producing a silver halide emulsion, a silver halide solvent can be used as necessary to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are formed by forming cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts including), rhodium salts (complex salts including), and iron salts ( By adding metal ions using at least one selected from complex salts containing complex salts, these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. Reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research [)i
17643.

Silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, but they are core/shell grains in which the silver halide composition is responsible for the interior and surface layers of the grain. Good too.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. The former is preferred.

Silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or irregular crystal shapes such as spherical or plate shapes. It can be something you have. In these particles, (100)
Any ratio between the plane and the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, and particularly preferably 3 μm or less.

The silver halide emulsion of the present invention may have any grain size distribution. Emulsions with a wide grain size distribution may be used, or emulsions with a narrow grain size distribution may be used alone or in combination.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. Sensitizing dyes may be used alone, but 2
You may use combinations of more than one species. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Silver halide emulsions are added during, at the end of, and/or after chemical ripening for the purpose of preventing fog during storage or during photographic processing, or to maintain stable photographic performance. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, synthetic hydrophilic polymers such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers, etc. Hydrophilic colloids such as molecular substances can also be used.

When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably 250 g or more (value measured by baggy method).

The photographic emulsion layer and other hydrophilic colloid layers of photographic elements using the silver halide emulsion of the present invention contain one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic element using the silver halide emulsion of the present invention contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. can be done.

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing to form a dye. A dye-forming coupler is used.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers can be combined with the oxidized form of a developing agent to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral sensitizers and desensitizers, can be included. Colored couplers that have a color correction effect on these dye-forming couplers, or DI that releases a development inhibitor during development and improves image sharpness and image graininess.
An R coupler may also be used. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

A colorless coupler that undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed onto the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent if necessary, and stir with a surfactant in a hydrophilic binder such as an aqueous gelatin solution.
After emulsifying and dispersing using a dispersion means such as a homogenizer, colloid mill, 70-jit mixer, or ultrasonic device,
It may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they are hydrophilic as an alkaline aqueous solution. It can also be incorporated into sex colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the photographic element of the present invention, causing color turbidity and deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

Image stabilizers can be used in the silver halide photographic elements of this invention to prevent degradation of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to U light. May contain.

A formalin scavenger can be used to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of light-sensitive materials.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material of the present invention. Compounds that can be preferably used as development accelerators are listed in Research Disclosure ty-(Research D
isclosure ) No. 17463 XXI￥A
The compound described in section e-D, and the development retardant is 1764
This is a compound described in Section XXI, Section E of No. 3.

A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of the light-sensitive material of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

In the light-sensitive material of the present invention, a fluorescent whitening agent can be used for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of the photosensitive material.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used in the emulsion layer and/or
It may be used in a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated on the support.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention includes improved coating properties, antistatic properties, improved slipperiness,
Various surfactants can be used for the purpose of emulsification dispersion, prevention of adhesion, and improvement of photographic properties (development acceleration, film hardening, sensitization, etc.).

Supports used in the photographic elements of this invention include cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride,
Films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, polyamide,
These films include flexible supports provided with reflective layers, glass, metal, ceramics, and the like.

The photosensitive material of the present invention can be used directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, or to improve the adhesion, antistatic property, dimensional stability, and abrasion resistance of the support surface. It may be applied through one or more subbing layers to improve hardness, antihalation, frictional properties, and/or other properties.

When coating the photosensitive material of the present invention, a thickener may be used to improve coating properties. Also, for example, as a hardening agent,
For substances that have a fast reactivity and may cause gelation before coating if added to the coating solution in advance, it is preferable to mix them using a static mixer or the like immediately before coating.

In preparing the light-sensitive material of the present invention, the silver halide emulsion and other protective colloid layers were prepared according to Research Disclosure.
It can be applied by the method described in Section A of XV of No. 17463 and dried by the method described in Section B of the same.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region to which the Im-forming emulsion layer is sensitive. Light sources include natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, X-ray, gamma line, α
Any known light source can be used, such as light emitted from a phosphor excited by a beam or the like.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure time shorter than 1 microsecond, for example, the exposure time of 100 nanoseconds to 1 microsecond using a cathode ray tube Yaxenon flash lamp. , exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

Any known method can be used for developing the photosensitive material of the present invention. Depending on the purpose, this development process may be either a process to form a silver image (black and white development process) or a process to form a color image.If the image is created using the reversal method, the black and white negative is first developed. A color development process is carried out, followed by a white exposure or treatment with a bath containing a fogging agent. [Also, silver dye bleaching may be used, in which a dye is contained in the light-sensitive material, a black developer treatment step is performed after exposure to form a silver image, and this is used as a bleaching catalyst to bleach the dye.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods, such as a spray method in which the processing solution is supplied in the form of a spray, or contact with a carrier impregnated with the processing solution, are also used. A web method, a method of viscous development processing, etc. may be used.

The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Alternatively, a developing agent or its precursor may be incorporated into the sensor and the developing process may be carried out using only an alkaline solution.

A development process using a lithium developer may be performed instead of the developer.

The color development process includes a color development process, a bleaching process, a fixing process, and if necessary, a water washing process, or a stabilization process accompanied by a water washing process. Instead of the processing process using a fixer, a bleach-fixing process can be performed using a one-bath bleach-fix solution, and one-bath development bleaching allows color development, bleaching, and fixing to be performed in one bath. A monobath treatment process using a fixing treatment liquid can also be performed.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step in which a color developing agent or its precursor is contained in the material and development is performed with an activator solution may be performed instead of the color development treatment step, or an activator treatment step may be performed in place of the monobath treatment. The beta treatment, bleaching and fixing treatments may be carried out simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as a final step, for example, either a water washing process or a stabilization process accompanied by a water washing process.) Color development process - Bleaching process Constant fixation process Color development process - Bleach-fixing process/Pre-hardening process - Neutralizing process - Color development process - Stop-fixing process - Washing process - Bleaching process Constant fixing process - Washing process - Post-hardening process Color development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process / Monobath process / Activator process - Bleach-fix process / Activator process culm - Bleaching process Constant fixation treatment process In addition to these treatments, there is a method in which the silver produced by color development is bleached and then color development is performed again, and various intensification methods described in JP-A-58-154839. Processing may be performed using a developing method that increases the amount of produced dye, such as processing (amplification processing).

Example-1 4-Hydroxy-6-methyl 1 was added as a ripening stopper to a negative high-sensitivity silver iodobromide emulsion (silver iodide 2.5 mol%) chemically ripened to maximum sensitivity by gold and sulfur sensitization method. .3.3
a, 7-chitrazaindene per mole of silver halide
1.0g was added.

One part of this emulsion was used as a blank (comparison) sample, and the compounds according to the present invention and comparative compounds as shown in Table 1 below were added to the remaining emulsion and sufficiently adsorbed. An appropriate amount of formalin was added as a film agent to prepare an emulsion.

The obtained emulsion was uniformly coated on a subbed polyester base so that the silver amount was 30/m', and dried to obtain a sample according to the present invention.

The sample prepared in this way was left at room temperature for 3 days as a fresh sample, at a temperature of 50°C and a relative humidity of 80°C.
% for 3 days, temperature 55℃, relative humidity 7
% for 3 days to prepare samples with forced deterioration.

Next, exposure was performed using a conventional sensitometric wedge, and development was performed at 35° C. for 30 seconds using the following developer [A], and after fixing, the film was washed with water and dried, and the sensitivity was measured.

Developer [A] 1-phenyl-3-pyrazolidone 1.5g Hyde O
Quinone 30 (15-nitroindazole 0.25 (] Potassium Bromide
5.0g anhydrous sodium sulfite 55 (potassium monohydroxide
30(]S acid
iog glutaraldehyde (25%)
Add 5° water to make gold stone 1i.

The results obtained are shown in Table 1 below.

However, the fog value is the value obtained by subtracting the base density, the sensitivity value is expressed as a relative sensitivity from the sensitivity at the position of Capri value + 0.5, with the comparative sample being set as 100, and gamma is the linear portion on the characteristic curve. As is clear from Table 1 above, the samples according to the present invention suppressed the occurrence of fogging, decrease in sensitivity, and deterioration of gamma, despite being stored under harsher conditions than the comparative samples. It can be seen that the stability of the film during storage has been improved.

Example 2 A silver iodobromide emulsion containing 7 mol % of silver iodide and having an average grain size of 1.2 μm was chemically ripened with gold and sulfur sensitizers to the highest sensitivity, and then used as a green-sensitive sensitizing dye at 5° 5'-diphenyl-9
An appropriate amount of -ethyl-3,3'-di-γ-sulfopropyloxacarbocyanine sodium salt was added to prepare a green-sensitive silver halide emulsion.

Then, per mole of silver halide, 1-(2,4,6-trichlorophenyl)-
80 g of 3-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone and 1-(2,4,6-
Triclophenyl)-4-(1-naphthylazo)-3-
Weigh out 2.5 g of (2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone, then 120 g of tricresyl phosphate and 24 g of ethyl acetate.
0vj2 was mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalene sulfonate and 550 mfi of a 7.5% aqueous gelatin solution was added to the above emulsion.

This emulsion was divided into portions, and the compounds according to the present invention and comparative compounds were added thereto as shown in Table 2 below, and after sufficient adsorption, 2-hydroxy-4,6 was added as a gelatin hardener. An appropriate amount of sodium -cyclotriazine was added to -(1!) to prepare a silver halide emulsion.

This emulsion was coated uniformly on a triacetate film with a silver content of 3.0 (1/n') and dried to prepare a sample.

The obtained film sample was subjected to the same forced deterioration test as in Example 1, then wedge exposed in the usual manner and color developed according to the following color processing steps.

The color sensitometry results obtained from the obtained pieces are shown in Table 2 below.

The fog in the table is the value after subtracting the base concentration, and the sensitivity is based on the blank sample left for 3 days (sample No. 16).
) is expressed as 100. or,
Gamma is expressed by the slope of the straight line.

Processing process [Processing temperature 38°C] Processing time Color development II
Bleach for a minute and 15 seconds
Wash with water for 6 minutes and 30 seconds
Drifting for 3 minutes and 15 seconds
White 6 minutes 30 seconds Wash with water 3 minutes 1
Stabilize for 5 seconds, dry for 1 minute and 30 seconds
The composition of the processing liquid used in each drying process is as follows.

[Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75Q anhydrous sodium sulfite 4.25 (1 hydroxylamine 1/2 sulfur 11M 2. O.

Anhydrous potassium carbonate 37.59 Sodium bromide 1.3 g Nitrilotriacetic acid 8 sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water and make 11
shall be.

[Bleach solution] Iron ethylenediaminetetraacetate Ammonium salt 1oo, o.

Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0! I+glacial acetic acid 10.0ij Add 2 water to make 111, and adjust to pH 6.0 using ammonium water.

[Fixer] Ammonium thiosulfate 175.0Q Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3° Add water to bring the solution to 11, and adjust to pH 6.0 using acetic acid.

[Stabilizing liquid] Formalin (37% aqueous solution) 1.511Q
Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5 d of water to make one volume.

As is clear from Table 2, the samples according to the present invention have improved stability during storage, with less fogging, less pestilence, and less gamma under severe storage conditions than the comparative samples. I understand that.

Example 3 A multilayer color photosensitive material sample (comparison) was prepared by sequentially providing each layer having the composition shown below on a cell 0-striacetate film support.

1st layer: Antihalation layer Black gelatin layer containing colloidal silver 2nd layer: Intermediate gelatin layer 3rd layer: Red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.5 μm Silver coating amount...1.79 (1/i' Sensitizing dye I...6X10-5 per mole of silver
Molar sensitizing dye ■・・・3X10-5 per mole of silver
Molar coupler A: 0.06 T per mole of silver
Nyl coupler C...0.00 per mole of silver
3 mole coupler D...0.0 per mole of silver
03 mol tricresyl phosphate coating amount 0, hJ2/12 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.7 μm Silver coating amount...1.40 /m' Sensitizing dye■...3X10-5 per mole of silver
Molar sensitizing dye ■・・・1.2X 1 per mole of silver
Q-5 mole coupler F...0.0125 per mole of silver
Molar coupler C...0.0016 per mole of silver
Moltricresyl phosphate coating amount 0, 2d/v' 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green sensitive low sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 4 mol% Average grain size 0 .5 μm Silver coating amount...1.00/i' Sensitizing dye ■...3 x 10 per mole of silver
-5 mol sensitizing dye■...1X10-5 per mol of silver
Molar coupler 8: 0.08 mole per mole of silver Coupler M: o, oos per mole of silver
Molar coupler D...0.0015 per mole of silver
Moltricresyl phosphate coating ■ 1, 4v (1/1') 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.75 μm Silver coating amount...1 .60/1" Sensitizing dye■...2゜5xlQ per mole of silver
-5 mol sensitizing dye■...0.8X I per 1 mol of silver
Q-5 mole coupler 8...0.02 moles per mole of silver Coupler M...0,003 moles per mole of silver Tricresyl phosphate Coating amount 0.8 m (2/ m2 8th layer: yellow filter single layer gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.

9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 6 mol% Average grain size 0.70 μm Silver coated pigeon...0.5Q/1' Coupler Y...1 mole of silver 0.125 mol 1 to licresyl phosphate coating amount 0, hR/m' 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide 20 mol% Average grain size 0.8 μm Coating amount of silver: 0.611/m' Coupler Y: O:04 for 1 mole of silver Coating amount of tricresyl bosphate: 0, 1n (2/12 11th layer: Protective layer A gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) is applied.

The couplers in each layer are prepared by adding the couplers to a solution of tricresyl phosphate and ethyl acetate, adding sodium p-dodecylbenzenesulfonate as an emulsifier and dissolving them by heating.
The mixture was mixed with a heated 10% gelatin solution and emulsified using a colloid mill.

In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer.

Compound used to make the sample.

Sensitizing dyestuff: anhydro-5,5'-dichloro-3,3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxydium salt sensitizing dye ■: Anhydro-9-ethyl-3.

3'-di(γ-sulfopropyl)-4.5.4'.

5'-Dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye ■: Anhydro O-9-ethyl-5.

5'-dichloro-3.3'-di(γ-sulfopropyl)oxacarbocyanine hydroxide sodium salt sensitizing dye ■: anhydro-5.6.5', 6'-tetrachloro-1.1'- Diethyl-3,3'-di(β-[
β-(γ-Sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide coupler 8 Kabutsu C Kabutsu D Coupler F Coupler M Shil The emulsion layers of the above samples were all ripened after adding the sensitizing dye. 4-hydroxy-6- known as a terminator
1 g of methyl-1,3,3a,7-chitrazaindene was added per mole of silver halide.

Next, the compounds of the present invention and comparative compounds were added as shown in Table 3, and after they were sufficiently adsorbed, couplers, tricresyl phosphate, etc. were added as described above, and then 2- An appropriate amount of sodium hydroxy-4,6-dichlorotriazine was added and adjusted, and the sample was coated in multiple layers.

The obtained multilayer color light-sensitive material was subjected to the same processing as in Example 1 for the storage test, followed by ordinary wedge exposure, and then subjected to the same color processing as in Example 2.

The obtained color sensitometric results are shown in Table 3 below.

The fog in the table indicates the value after subtracting the base concentration, and the sensitivity is the sensitivity of the blue-sensitive layer after 3 days of natural storage of a sample containing neither the compound of the present invention nor the comparative compound.
Relative sensitivity when expressed as Table 3 above shows that the samples according to the present invention have excellent storage stability over time even in the case of multilayer color photosensitive materials.

Furthermore, the desilvering bleaching properties of the samples of the present invention showed less deterioration than the comparative samples when the bleaching time was shortened.

Example 4 A silver halide color photographic material of the present invention was prepared by coating the following layers on a paper support coated on both sides with polyethylene resin.

Layer 1: Blue-sensitive emulsion layer Silver chlorobromide emulsion containing 20 mol% of silver chloride (calculated as silver: 0.28
(1, containing 1.2 g of gelatin) was sulfur-sensitized, and then blue sensitizing dye (BSD-1) was added at 5.5 x 10-gin moles/
It was added per mole of silver halide to prepare a blue-sensitive silver halide emulsion.

After this emulsion was separated, comparative compounds and compounds according to the present invention were added as shown in Table 4 below.

After sufficient adsorption, the following was added as a coupler solution.

Coupler solution /11? Amount per yellow coupler (Y-1>0.75g2.
5-di-t-octylhydroquinone 0.015 (1 dioctyl phthalate 0.40) Next, the following layer 2 was coated on this emulsion layer as a Ml retainer to prepare a sample according to the present invention.

Layer 2 Gelatin retention 1 gelatin per m'lA/im' 1.4 g Hardener (bisvinylsulfonyl methyl ether) 0.1° (BSD
-1) (Yellow coupler Y-1) Cj! The obtained color photosensitive material was subjected to a forced deterioration test in the same manner as in Example 1, and then wedge exposed in the usual manner, and color developed according to the following color processing steps.

The color sensimetry results obtained from the obtained samples are shown in Table 4 below.

The sensitivities in the table are relative sensitivities when the comparison sample (blank) of each layer left for 3 days is set as 100.

Processing process Temperature Time (1) Color development 33℃ 3 minutes 30 seconds (2) Bleaching room @ 3
3℃ 1 minute 30 seconds (3) Washing with water 30-34℃
3 minutes (4) Drying 60-90℃
- The composition of the treatment liquid used in each step is as follows.

(Color developer) Pure water 8001Q ethylene glycol 121g benzyl alcohol 12d anhydrous potassium carbonate
30 (J anhydrous potassium sulfite
2ON=1 Chill N-(β-Methanesul Small Synamide Komi 1-Rue 3-Medyl-1 Amitunol Norin Combic acid 1.,i 4.!+(1 Notorium petrified 1.0!Add 1 water and 1'C
11! , 1 J in 1° with 10% potassium hydroxide or 20% sulfuric acid.
Adjust to 2.

(Bleach-fix solution) Pure water 750d Iron diaminetetraacetate (1) Sodium 50g Ammonium thiosulfate 85gm Sodium sulfite 10 (1 Sodium metabisulfite)
2g Ethylenediaminetetraacetic acid disodium I.Lium bromide 3.0g Add pure water, 1Q, adjust to I) l-1 = 7.0 with 20% aqueous ammonia or 20% sulfuric acid.

The results in Table 4 also show that the compounds according to the present invention do not cause deterioration of photographic properties even in color light-sensitive materials and can provide a fog suppressing effect with little desensitization.

Example 5 After exposing the blank (comparative) sample used in Example 1 using a conventional sensitometry wedge, Example-
High-temperature rapid development was carried out at 35° C. for 60 seconds using the developer [A] used in 1, to which the compound according to the present invention and the comparative compound were added. The photographic properties obtained are shown in Table 5. However, the fog value indicates the value after subtracting the base density, and the sensitivity value is expressed as the relative sensitivity when the value developed with the developer [A] to which neither the compound according to the present invention nor the comparative compound is added is expressed as 100. , gamma is indicated by the slope of the straight part of the characteristic curve.

Table 5 From the results in Table 5, it can be seen that even when the compound according to the present invention is added to the developer, it prevents the occurrence of fog in rapid flood processing and does not cause a decrease in sensitivity like the comparative compounds. I understand.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedural Amendment Form) % Formula % 2. Name of the invention Processing method for silver halide photographic light-sensitive materials 3. Relationship with the person making the amendment Patent Applicant Address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Ide 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 (Shipping date) June 24, 1988 6, Subject to amendment

Claims (1)

[Scope of Claims] Processing of a silver halide photographic material, which is characterized in that, after exposing a silver halide photographic material having a light-sensitive silver halide emulsion layer, the material is developed in the presence of a compound represented by the following formula: Method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R is hydrogen, an amino group, a mercapto group, a carbamoyl group, an amide group, a sulfonamide group, a thioureido alkyl group, or a hydrocarbon-S- group, and R_1 is hydrogen or In the substituent, n represents 1 to 4, and two or more R_1 may be bonded to form a condensed ring.