JPS62250442A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To maintain the stable photographic characteristics of a silver halide photographic sensitive material even after storage and to prevent fogging by exposing the sensitive material and developing it in the presence of an aromatic heterocyclic oxatellurazinium salt. CONSTITUTION:A silver halide photographic sensitive material having a photosensitive silver halide emulsion layer is exposed and developed in the presence of an aromatic heterocyclic oxatellurazinium salt prepd. by condensing an oxatellurazinium ring with an aromatic hetero ring. The compound is incorporated into the sensitive material and/or added to a processing soln. In case of the sensitive material, the compound is incorporated into the photosensitive silver halide emulsion layer or other hydrophilic non-emulsion layer such as the protective layer, intermediate layer or underlayer. In case of a processing soln., the compound is added to a developing soln. and/or a processing soln. used before development and the preferred amount of the compound added is 0.05-0.5mmol per 1l processing soln.

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 1] For the purpose of preventing fogging of silver halide photographic materials (hereinafter referred to as "photosensitive materials") over time, for example, 4-hydroxy-6
-Methyl-1,3,38.

Hydroxyboriazaindenes such as 7-tetrazaindene and 1-phenyl-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 faster shutter speeds to eliminate shutter shake caused by smaller screen sizes and faster development processes. 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 strong demands for reducing radiation exposure.

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 need for fog suppression technology that suppresses fog over time even in high-sensitivity photosensitive materials, sufficiently prevents fog even during high-temperature rapid processing, and does not affect photographic properties (gradation, sensitivity, etc.). It is requested.

[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 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 an aromatic heterocyclic oxatellazinium salt.

The above-mentioned aromatic heterocyclic oxatellazinium salt refers to a compound in which an aromatic heterocycle is fused to an oxatellazinium ring.

A preferred aromatic heterocyclic oxatellazinium salt is represented by the following formula.

In the formula, A represents the atomic group necessary to form an aromatic heterocycle,
R represents hydrogen or a substituent, and X represents halogen or pseudohalogen.

The aromatic heterocycle formed by A includes a furan ring,
Examples include γ-pyran ring, thiophene ring, γ-thiovirane ring, pyridine ring, virol ring, pyrimidine ring, and furthermore, benzifuran ring, benzothiophene ring, quinoline ring,
It may also be a fused polycyclic ring such as an indole ring. In the case of the fused polycyclic ring, the ring directly fused to the oxatellazinium ring may be an aromatic ring.

The aromatic heterocycle formed by A includes a cyano group, a halogen atom (e.g., fluoro, diol, bromo, etc.), an alkyl group (e.g., methyl, trifluoromethyl, etc.), an aryl group (e.g., phenyl group, etc.) , sulfonyl groups (e.g., methanesulfonyl, etc.), acyl groups (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.,
For example, methoxycarbonyl, etc.) may be substituted.

Examples of the substituent represented by R include an amino group (e.g., amino, anilino, etc.), an amide group (e.g., acetamide, etc.), a ureido group (e.g., ureido, phenylureido, etc.), a formamidine disulfide group, a -C-B group. (
B represents an atom or group that forms an acid, ester, thioester, or salt. ), mercapto group, heterocyclic group (
(e.g., pyridyl), hydrocarbon groups bonded to the ring directly or via -〇-1-8- or -co- (e.g.,
Methyl, chloromethyl, trifluoromethyl, hydroxyethylthioethyl, ureidoethyl, ethoxyethyl, methoxy, methylthio, acetyl, p-methylbenzoyl, phenyl, p-chlorphenyl, p-mercaptophenyl, thiouridophenyl, isopropyl, benzylthio, phenoxy, benzoyl, etc.).

Examples of the halogen atom represented by X include O, bromo, and iodo, and examples of pseudohalogen include cyan, thiocyanate, and doxy.

As X, chloro and bromine are preferred.

Next, specific examples of the compounds according to the present invention will be shown.

The aromatic heterocyclic oxatellurium azinium salt compound represented by the above formula can be synthesized by reacting the corresponding compound represented by the following formula at high temperature.

The symbol in the formula represents active hydrogen, and A, R and X have the same meanings as described above.

Next, a synthesis example will be shown.

Synthesis Example (1) Synthesis of Exemplary Compound 6, 500 vJ of formula! The temperature is raised to 120°C while stirring inside.

The reaction was continued for 5 hours while maintaining this temperature, and after the reaction was completed,
Pour the product into ethanol while hot.

The precipitated crystals were recrystallized from ethanol to obtain the target compound. Yield: 20% Synthesis Example (2) Synthesis of Exemplified Compound 9 1 mole is mixed and stirred in 500 J of chloroform.

This mixture was heated to 120°C, and while maintaining that temperature,
Stir more vigorously to melt the solids.

When most of the chloroform is distilled off, a molten substance remains while generating hydrogen chloride gas. The temperature is further increased to 130°C, and stirring is continued until it becomes a smooth solid. After 2 hours, the reaction is completed and ethanol is added while it is still hot to disperse the reaction product. The desired compound was obtained by recrystallization from ethanol. Yield: 15% The compound according to the present invention represented by the above formula can be added to the photographic material and/or the processing solution.

In addition to the photosensitive silver halide emulsion layer in a photographic light-sensitive material, it can be added to hydrophilic non-emulsion layers such as the RAM1 intermediate layer and the subbing layer, and the photosensitive silver halide emulsion layer is particularly preferred. The amount of addition thereof is preferably o.oos to 5 mmol, more preferably 0.01 to 1.0 mmol, per mole of silver halide in the emulsion layer.

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 addition m is 0.00 m per 11 processing liquids.
05 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 can be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride.

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. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pHlpAg in the mixing pot. With this method,
Silver halide grains with a regular crystal shape and 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 Disclosure) is required.
Closure) It can be carried out based on the method described in No. 17643.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

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 surface and the (iii) surface 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 .mu.I or less, particularly preferably 3 .mu.m 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,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

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 jelly strength l2504) or higher (value measured by the 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 fl-soluble synthetic polymer for the purpose of improving dimensional stability. can be done.

In the emulsion layer of the light-sensitive material of the present invention, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) during color development processing. A dye-forming coupler that forms 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 oxidized forms of developing agents to produce development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, anti-capri agents, 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 D that releases a development inhibitor during development to improve image sharpness and image graininess.
An IR 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 on 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, flow jet 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 'F1 groups such as carboxylic acids and sulfonic acids, alkaline aqueous solutions are used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

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 eye color antifogging agent 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 absorb ultraviolet rays to prevent fogging due to discharge caused by charging of the photosensitive material by rIi rubbing, etc., and to prevent image deterioration due to U light. It may also contain an agent.

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 t-(Research Qi
Section XXI B- of No. 17463
It is a compound described in Section D, and the development retardant is a compound described in Section XXIIjiE of No. 17643.

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 scratching each other.

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 where the emulsion is not vAWi, and may be used as a protective colloid in the emulsion layer and/or the emulsion layer on the side where the emulsion layer is laminated with respect to the support. It may be used in layers.

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 promotion, 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,
A flexible support provided with anti-tJ4m for these films,
Includes glass, metal, ceramics, etc.

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 coated through a subbing layer of 1111 or more to improve hardness, antihalation, friction 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 a spectral region to which the emulsion layer constituting the material is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, xai, gamma rays, alpha rays, etc. Any known light source can be used.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, 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. The photosensitive material is then exposed to white light or processed with a bath containing a fogging agent to perform color development. Silver dye bleaching may be used, in which an image is created and the image 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 sensitive material, and the developing process may be carried out using only an alkaline solution.

A development process using a lithium developer as a developer may be performed.

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 water washing. Instead of the process using a bleach-fix solution, the bleach-fix process can be carried out using a one-bath bleach-fix solution, or one-bath development, bleach-fix, which allows color development, bleaching, and fixing to be performed in one bath. A monobath treatment process using a 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 coloring process - Washing process - Post-hardening process/Color development Development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process / Monopass process / Activator process - Bleach-fixing process / Activator process - Bleach process Constant fixation Processing process In addition to these treatments, there are methods in which the developed silver produced by color development is subjected to halogenation bleaching, a method in which color development is performed again, and various intensification treatments (amplifier processing Fl ), etc., may be used for processing using a developing method that increases the amount of formed dye.

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-tetrazaindene 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. Suitability of formalin as a membrane agent
was added to prepare an emulsion.

The obtained emulsion was uniformly coated on a subbed polyester base so that the silver amount was 3 a/f, 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 hydroquinone 3G (15-nitroindazole 0.25g potassium bromide
5.0g anhydrous sodium sulfite
ssg potassium hydroxide
30Q boric acid 10
g Glutaraldehyde (25%) 5a Add water to bring the volume to 12.

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 fog value + 0.5 position, with the comparison sample set as 100, and gamma is the linear portion on the characteristic curve. It is shown by the slope of .

As is clear from Table 1 above, sample NO.
12 to 9, the occurrence of fog, decrease in sensitivity, and deterioration of gamma were suppressed and the stability under film storage was improved despite the harsh storage conditions compared to the comparative samples. I understand.

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
A suitable 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)penzamide]-5-vilazo O as a colored magenta coupler, 1-(2,4,6-
Triclophenyl)-4-(1-naphthylazo)-3-
Weigh out 2.5 g of (2-chloro0-5-octadecenylsuccinimidoanilino)-5-pyrazolone, then 120 g of tricresyl phosphate and 24 g of ethyl acetate.
01Q was mixed and dissolved by heating, and then a coupler solution obtained by emulsifying and dispersing 5 g of sodium triisopropylnaphthalene sulfonate and a 7.5% gelatin aqueous solution SSO, Q was added to the above emulsion.

This emulsion was divided into 15 parts, the compounds according to the present invention and the comparative compounds were added thereto as shown in Table 2 below, and after sufficient adsorption, 2 parts were added as a gelatin hardener.
A suitable amount of sodium -hydroxy-4,6-dichlorotriazine was uniformly added to form a silver halide emulsion.

This emulsion is mixed with 3. A sample was prepared by uniformly coating and drying it on a triacetate film that had been subbed so as to have an OIJ /f.

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 and processing temperature: 38℃] Processing time: Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds, float for 3 minutes and 15 seconds.
white 6 minutes 30
Wash with water for 3 seconds
Stabilization for 1 minute and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.7541 Anhydrous sodium sulfite 4.25 (1 hydroxylamine 1/2 sulfate 2. 0g Anhydrous potassium carbonate 37.59 Sodium bromide
1.3g Nitrilotriacetic acid 8sodium salt (monohydrate) 2.5Q potassium hydroxide 1. Add OQ water 1
Totosu.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100. O(]Ethylenediaminetetraacetic acid iron ammonium salt 10. OQ ammonium bromide 150. OIJ glacial acetic acid
10. (h12 Water is added to make the solution 12, and the pH is adjusted to 6.0 using ammonium water.

[Fixer] Ammonium thiosulfate 175.0Q Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.39 Add water to bring the solution to 11, and adjust to pH 6.0 using acetic acid.

[Stabilizing liquid] Formalin (37% aqueous solution) 1.5ij2
Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.51J2
Add water to make 111.

”””ij.

As is clear from Table 2, the samples according to the present invention suppress the occurrence of capri, decrease in sensitivity, and decrease in gamma under harsh storage conditions, and have improved stability during storage, compared to the comparative samples. I understand that.

Example 3 A multilayer color photosensitive forest material sample n (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support.

1st WJ: Antihalation layer Black gelatin layer containing colloidal silver 2nd layer: Intermediate gelatin layer 3rd N! : Red-sensitive, low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size: 0.5 μm Silver coating: 1.79 Q/f Sensitizing dye processing: 1 mol of silver against 6X10-5
Molar sensitizing dye■・・・・・・For 1 mole of silver □3X1
0-5 mol Coupler A...0.06 mol per 1 mol of silver Coupler C...0.003 mol per 1 mol of silver Coupler D... 0.06 mol per 1 mol of silver Te 0.003
Moltricresyl phosphate coating amount 0.3 mN/f 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 4 mol% Average grain size 0.7 μl Silver coater...1.40/ f Sensitizing dye processing: 3 x 10' mol per 1 mol of silver Sensitizing dye: 1.2 x 1 per mol of silver
0-5 mole coupler F...0.0125 per mole of silver
Molar coupler C...0.0016 per mole of silver
Coating amount of mol tricresyl phosphate 0.2 iN/f 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. 5μ ugly silver coating n...1. Og /f Sensitizing dye■...3X10-5 per mole of silver
Molar sensitizing dye ■・・・1X10-5 per mole of silver
Molar coupler B: 0.08 mol per mol of silver Coupler M: 0,008 mol per mol of silver Coupler D: 0.08 mol per mol of silver 0015
Moltricresyl phosphate coating group 1.4t12/l' Part 8: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.75 μm Silver coating amount...1.6 (]/1' Sensitizing dye■...2.5X per mole of silver 1
0-5 mole sensitizing dye IV...0.8X per mole of silver
10-5 mole coupler B...0.02 mole per mole of silver Coupler M...0,003 mole per mole of silver Tricresyl phosphate coating amount 0.8 mN/f 8FI: Yellow filter single layer gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.

No. 911: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol % Average grain size 0.70 μI Silver coating amount... 0.5 g/f Coupler Y... 1 mol of silver 0.125 mol tricresyl phosphate coating amount: 0.3 μm/f 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 6 mol% Average grain size: 0.8 μm Silver coating amount: -o, eo /f Coupler Y... 0.04 mol tricresyl phosphate coating per 1 mol of silver m 0, 11 g/1 11th layer: Protective layer polymethyl methacrylate particles (diameter 1 Apply a gelatin layer containing .5μI).

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 human oxide pyridium salt sensitizing dye ■: Anhydro-9-ethyl-3°3'-di(
γ-sulfopropyl)-4,5,4'.

5'-dibenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5゜5'-dichloro-3,3'-di(T-sulfopropyl)oxacarbocyanine hydroxide/sodium salt increase Sensitive dye ■: anhydride 0-5.6.5', 6'-tetrachloro-1,1'-diethyl-3,3'-di(β-[
β-(γ-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler A coupler C coupler D coupler F to l coupler Y The emulsion layers of the above samples were all added with the above sensitizing dye. 4-Hydroxy-6- which is known as a ripening stopper
1 g of methyl-1,3,38,7-ti-razaindene was added per 111 moles of halogenide.

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-cyclotriazine was added and adjusted, and the samples were 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.

Note that Capri in the table indicates the value obtained by 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.
It is the relative sensitivity when expressed as .

Table 3 above shows that in the case of multilayer color photosensitive materials, Sample R1 according to the present invention has excellent storage stability over time.

In addition, regarding the desilvering bleaching performance when the bleaching interval is shortened, the samples of the present invention show less deterioration in A than the comparative samples.
won.

Example 4 A silver halide color photographic light-sensitive material of the present invention was prepared by coating the following layers on a paper support coated with polyethylene 41iffi on both sides.

ml: Blue-sensitive emulsion layer silver chlorobromide emulsion containing 20 mol% silver chloride (silver exchange nO, 28
G, containing 1.2 g of gelatin) was sulfur-sensitized, and then a blue sensitizing dye ([380-1) was added at 5.5 x 10-+ mol/
Added per mole of silver halide to form an Ff-sensitive silver halide emulsion 'J! 4! IJ Shita.

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 / Amount per 1f Yellow coupler (Y-1) 0.75a2.
5-di-t-octylhydroquinone 0.0159 dioctyl phthalate 0.4 g Next, the following layer 2 was coated as a protective layer on this emulsion layer to prepare a sample according to the present invention.

Layer 2 Gelatin protection FJ/a gelatin per 1f
1.4g hardener (bisvinylsulfonyl methyl ether) 0.1"t-'
? ! - (BSD-1) CHICH, 5Osll (Yellow coupler Y-1) The obtained color photosensitive material was subjected to a forced deterioration test in the same manner as in Example-1, and then subjected to wedge exposure in the usual manner, and subjected to the following color processing steps. Color development was performed according to the following. 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 natural number of m3 days of the comparison sample (blank) of each layer is expressed as 100.

Processing process Temperature Time (1) Color development 33°C 3 minutes 30 seconds (2) Bleach fixing 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 8001β ethylene glycol 121g Benzyl alcohol 121g Anhydrous potassium carbonate
30 (1 anhydrous M1 potassium acid
29N-I del-N-(β-methanesulfonamide)conibule-3-mepur-4aminoanoline v1m salt 4.5g Thorium chloride
Add 1.0% water (to 1.0%).

pf-I=10 with 10% potassium hydroxide or 20% sulfuric acid
．． Adjust to 2.

(Bleach-fix solution) Pure water 7501Q Ethylenediaminetetraacetate iron (I
', 7A 10 (1 metabisulfite) Lium 2 lyethylenediaminetetravinegar R
Add 3.0 g of 2-ptrium 20-thorium tribromide to make 11, and adjust the pH to -7.0 with 20% aqueous ammonia or 20% sulfuric acid. ：、：、' Therefore, from the results in Table 4, it is clear that the compound according to the present invention does not cause deterioration of photographic properties even in color light-sensitive materials, and provides a low level of desensitization. I understand that. .

Example 4j The blank (comparative) sample used in Example 1 was exposed using a conventional sensitometry river wedge, and then exposed to light using a conventional sensitometry river wedge.
The compound J according to the present invention and the comparative compound were added to the developer [A] used in 1 and subjected to high-temperature rapid processing at 35° C. for 60 seconds. The photographic properties obtained are shown in Table 5.

However, the fog value indicates the value after subtracting the base density, and the sensitivity aI is the relative sensitivity r when expressed as 100 when developed with the developer [A] to which neither the compound according to the present invention nor the comparative compound is added. The expression, ga]/ma, is indicated by the slope of the straight line part of the characteristic curve.

From the results shown in Table 5, the compound according to the present invention prevents fogging during high-temperature rapid processing even when added to the developer, and compared It can be seen that this compound does not reduce the sensitivity like the compound.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedural Amendment Date (formerly July 19, 1985 1 Patent Application No. 93920 of 1988 2. Title of Invention Method for Processing Silver Halide Photographic Light-sensitive Materials 3. Amendments to be made Relationship with the case Patent applicant address Nishi-Shinjuku 1-26%, Shinjuku-ku, Tokyo: 114 Name (127) Konishiroku Photo Industry Co., Ltd. Representative Director 1 Keio 4, Agent 102 Address 4 Kudankita, Chiyoda-ku, Tokyo Chome 1-1 Kudan - Rosaka Pill Telephone 263-9524 (Shipping date) June 24, 1985 6, Subject to amendment

Claims (1)

[Claims] 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 an aromatic heterocyclic oxateluazinium salt.