JPS62254146A - 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 each of R<1>-R<3> is H or a substituent, the substituent R<1> is preferably represented by a formula -An-R<4> (where A is S or N-R<5>, R<4> is H or the like, R<5> is H or the like and n=0 or 1), the substituent R<1> is especially preferably mercapto and each of the substituents R<2>, R<3> is preferably methyl, other alkyl or aryl substituted directly or through S.

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.

Hydroxyboriazaindenes such as 7-titrazaindene 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, which require a high level of compliance due to automation, and there are also photosensitive materials for medical use, such as X-ray photosensitive materials, which have high safety requirements and are strongly required to reduce the amount of radiation they are exposed to.

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 during long-term storage 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.

[Objective of the Invention 1 The present invention has been made in view of the above-mentioned circumstances, and its first object is to maintain stable photographic properties even when a photosensitive material is stored over time and to prevent the occurrence of fogging. 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 a compound represented by the following formula.

In the formula, R1, R2 and R3 each represent hydrogen or a substituent.

As the substituent represented by R1, the formula -An-R4 is preferred.

In the formula, A represents a sulfur atom or N-R5, and R4 is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group,
It represents an acyl group, a heterocyclic group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkenyl group, or an alkynyl group, and R5 represents a hydrogen atom, an alkyl group, or an aryl group. n represents an integer of O or 1.

Examples of the alkyl group represented by R4 or R5 include unsubstituted ones such as methyl, ethyl, and isopropyl, as well as those with substituents such as 2-hydroxyethyl, thioethyl, trifluoromethyl, thiouridoethyl, benzyl, and phenethyl. .

Examples of the aryl group represented by R4 or R5 include phenyl, p-tolyl, p-mercaptophenyl, and the like.

Examples of the cycloalkyl group represented by R4 include cyclopentyl and cyclohexyl; examples of the acyl group include acetyl, benzoyl, and p-methylbenzoyl; and examples of the heterocyclic group include pyridyl, pyrrolyl, and morphoryl. , thiazolyl, etc. Alkylsulfonyl groups include, for example, methylsulfonyl, ethylsulfonyl, etc. Arylsulfonyl groups include, for example, p-toluenesulfonyl, m-ethoxycarbonylbenzenesulfonyl, etc. Examples of carbamoyl groups include N-methylcarbamoyl, and examples of sulfamoyl groups include N-ethylsulfamoyl, N. N-dimethylsulfamoyl, N
．． There are various groups such as N-(3-oxapentamethylene)sulfamoyl, alkenyl groups include allyl group, and alkynyl groups include 3-pentynyl,
There are various groups such as 3-butynyl.

Particularly preferred among R1 is a mercapto group.

Preferred substituents for R2 and R3 include alkyl groups and aryl groups substituted directly or via a sulfur atom. Specifically, methyl, ethyl, isopropyl, butyl, t-butyl, phenyl, p
Examples include -tolyl, methylthio, and -tylthio.

R2 and R3 are each a hydrogen atom or a substituent, but preferred among these is the case where at least one of R2 and R3 is an alkyl group or aryl group bonded directly or via a sulfur atom. Next, compound examples are shown.

Synthesis Example (Compound 5) Deruhydride (J, Am, Chem, Soc.

L. Yu, 429 (1949) ") and heat the reaction on a water bath. Unreacted components are removed from the reactant by steam distillation, and the remaining aqueous phase is made alkaline for ether extraction. After washing the ether phase with water, sulfuric anhydride is added. After drying using magnesium, the ether phase was distilled off to obtain a solid.

Re-crystallize from ethanol to obtain colorless prism crystals.

Yield: 0.90 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 addition a is o per 11 of the processing solution.
, ooos 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.

Silver halide emulsions can be prepared by mixing halide ions and silver ions at the same time, or by mixing one of them in a liquid containing the other. It may also be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH in the mixing pot to 1080.By this method, the crystal form is regular and the particle size is uniform Similar silver halide grains are 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.

In the process of forming and/or growing the grains, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts including), Odium salts (complex salts including), and iron salts. By adding metal ions using at least one kind selected from (complex salts containing), 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 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,
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 250 g or more (value measured by baggy method).

The photographic emulsion layer or other hydrophilic colloid layer of a photographic element using the silver halide emulsion of the present invention contains one or two hardeners that crosslink binder (or protective colloid) molecules and increase film toughness. By using the above, hardening can be achieved. A hardening agent can be added to the processing solution to harden the photosensitive material to the extent that it is not necessary to add a hardening agent.
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 poorly 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, a silver genide color photographic material may be produced using a method different from the above combination.

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. It can be either 2nd grade or 1st grade. 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 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 acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic 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 an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV 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 visibility, 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 Di
Section XXI B- of No. 17463
It is a compound described in Section D, and the development retardant is a compound described in Section XXllrjE 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 plague, 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 may be used for the purpose of increasing 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 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,
A flexible support provided with one layer on 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 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 are prepared according to Research Disclosure.
It can be applied by the method described in No. 17463, Section XV-8, 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 scale laser beams, light emitting diode light, electron beams, X-rays, 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. 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 silver image is formed by performing a black development process after exposure, 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 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.

As a color development process, 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 are performed. Instead of a processing step using a 1-bath bleach-fix solution, a bleach-fix processing step can be performed using a 1-bath bleach-fix solution, or a 1-bath development process that allows color development, bleaching, and fixing to be performed in one bath. A monobath processing step using a bleach-fix processing solution can also be carried out.

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 processing may be carried out simultaneously with bleaching and fixing processing. 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 - Bleach 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 - Bleach process Fixed fixation treatment process In addition to these treatments, there is a method in which the developed silver produced by color development is subjected to herogenation bleaching and then color development is performed again, and various intensification treatments ( It may be processed using a developing method that increases the amount of dye produced, such as amplifier 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 emulsion was prepared by adding saponin as a coating aid and formalin as a hardening agent.

The resulting emulsion was coated with silver 1 on a subbed polyester base.
It was applied uniformly so that the ratio was 30/v' 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, with a thirst mark of 50°C and a relative humidity of 80°C.
% for 3 days, temperature 55℃, relative humidity 7
% for 3 days to prepare forced deterioration samples.

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 [A1 1-phenyl-3-pyrazolidone 1.5g Hydroquinone 30115-nitroindazole 0.250 Potassium bromide
5.0g anhydrous sodium sulfite
550 potassium hydroxide
30 (1 boric acid i
o.

Glutaraldehyde (25%) 5 (+ add water to make total volume 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, the sample according to the present invention has
It can be seen that the occurrence of fog, decrease in sensitivity, and deterioration of gamma were suppressed, and the stability of the film during storage was improved, despite the harsh storage conditions compared to the comparative sample.

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)penzamide]-5-pyrazolone and 1-(2,4,6-
Triclophenyl)-4-(1-naphthylazo)-3-
Weighed 2.5 g of (2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone, and then added tricresyl phosphate 120 (1, ethyl acetate 2
401 g were mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalene sulfonate and 7.5% gelatin aqueous solution 550112 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. - cyclotriazine sodium 3
A silver halide emulsion was prepared by uniformly adding am.

This emulsion was coated uniformly on a subbed triacetate film at a silver content of 3.0 (1/m2) 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 natural release @ 3 days (test FIN 0.1).
6) is expressed as 100. Also, gamma is expressed by the slope of the straight line.

Processing process [Processing temperature 38℃] Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Bleach for 3 minutes and 15 seconds. Wash with water for 6 minutes and 30 seconds.
Stabilized for 3 minutes 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 developing solution] 4-amino-3-medyl-N-ethyl-N-(β-hydroxyethyl)-aniline/sulfuric acid [4,75 (1) Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate
37.59 Sodium Bromide
1.3g Nitrilotriacetic acid 8sodium salt (monohydrate) 2.5 (potassium monohydroxide 1.011 Add water to make 1y.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0 (ammonium monobromide 150.OQ glacial acetic acid
10. 11 by adding Od water
and adjust the pH to 6.0 using ammonium water.

[Fixer] Ammonium thiosulfate 175.0 (1 anhydrous sodium sulfite 8.6Q sodium metasulfite 2.39 Add water to make 1f, adjust to pl-16.0 using acetic acid.

[Stabilizing liquid] Formalin (37% aqueous solution) 1.5iN Konidax (Konishi Roku Photo Industry Co., Ltd.) 7.5d 2nd
As is clear from the table, the samples according to the present invention suppress the occurrence of fogging, decrease in sensitivity, and decrease in gamma under severe storage conditions, and have improved stability during storage, compared to the comparative samples. Recognize.

Example 3 A multilayer color photosensitive material sample (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate 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 processing: 6X10-5 per mole of silver
Molar sensitizing dye ■・・・3X10-5 per mole of silver
Molar coupler A: 0.06 mol per mol of silver. Coupler C: 0.003 mol per mol of silver. Coupler D: 0.06 mol per mol of silver. 003
Moltricresyl phosphate coating amount 0, 3i (2/v' 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 .4 (1/i' Sensitizing dyestuff...3X10-5 per mole of silver
Molar sensitizing dye ■・・・1゜2XIQ per mole of silver
-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 0-2mj2/12 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. 5μm Trowel application a...1.00/m2 Sensitizing dye ■...3X10-5 per mole of silver
Molar sensitizing dye ■...'lX10- for 1 mole of silver
5 mole coupler B: 0.08 mole per mole of silver Coupler M: o, ooa per mole of silver Mole coupler: 0:0 per mole of silver .0015
Moltricresyl phosphate coating amount 1.41Q/f 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/ i' Sensitizing dye■...2.5X 1 per mole of silver
Q-5 mole sensitizing dye■...0.8X 1 per mole of silver
0-5 mole coupler B...0.02 mole per mole of silver Coupler M...0,003 mole tricresyl phosphate coating amount per mole of silver 0.8ij2/1' 8th layer: yellow filter single layer gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.

9th II: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide = 6 mol % Average grain size 0.70 μm Trowel application 1...0.5 Q/m'' Coupler Y... 1 mol of silver 0.125 mol tricresyl phosphate coating amount 0.311 (2/1) 10th layer: blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion 26 mol% silver iodide Average grain size 0.8 μm Silver coating D...0.6 g/m' Coupler Y...0.04 mole tricresyl phosphate coating amount per 1 mole of silver 0-1 mj2/1' 11th layer: Preservation III layer polymethyl meth Apply a gelatin layer containing acrylate particles (1.5 μm in diameter).

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 dye ■: Anhydro-5,5'-dichloro-3,3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide 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-3,31-di(γ-sulfopropyl)oxacarbocyanine hydroxide/sodium salt sensitization Dye ■: anhydro-5,6,5',6'-tetrachloroO-1,1'-diethyl-3,3'-di(β-[
β-(γ-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt Coupler A Coupler C Coupler D Coupler F Coupler M 4-human nx-6- known as a ripening stopper
1 g of methyl-1,3,3a and fuchtrazaindene were 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, 1 to licresyl phosphate, etc. were added as described above, and then a hardening agent was added. An appropriate amount of sodium 2-human[1x-4,6-cyclotriazine was added to prepare the sample, 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.

In addition, the fog in the table shows the value after subtracting the base concentration, and the sensitivity is the sensitivity of the blue-sensitive layer of the sample containing neither the compound of the present invention nor the comparative compound left for 3 days.
It is the relative sensitivity when expressed as 0.

'J8 1987-254146 (15) 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% silver chloride (silver conversion 0.28
(J, containing 1.2 g of gelatin) was sulfur-sensitized, and then a blue sensitizing dye (BSD-1) was added at 5.5 x 10-' mole/mole of silver halide to form a blue-sensitive halide. A silver emulsion was prepared.

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 112 Yellow coupler (Y-1) 0.75g2.
5-di-t-octylhydroquinone 0.015<1 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 retention Mother gelatin per IFJ/1i'
1.4g hardener (bisvinylsulfonyl methyl ether) 0.10 (BSD
-1) CH*CHtSOsH (yellow coupler Y-1) j2 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 colored according to the following color processing steps. Developed.

The color hingemetry 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) Coloring image 33℃ 3 minutes 30 seconds (2) Bleaching window @ 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 12112 benzyl alcohol 121g anhydrous potassium carbonate
301J anhydrous potassium sulfite
2g N-ethyl-N-(β-methanesulfonamido)ethyl-3-methyl-4-aminoanoline sulfate 4.5g sodium chloride 1.0g Add water to make 11.

l1l-1=1 with 10% potassium hydroxide or 20% sulfuric acid
Adjust to 0.2.

(Bleach-fix solution) Pure water 7501R Iron(III) ethylenediaminetetraacetate Sodium 50 (1 Ammonium thiosulfate 85Q Sodium bisulfite 10 (1 Sodium metabisulfite)
2g Disodium ethylenediaminetetraacetic acid 0g Sodium bromide 3.0 (1 Add pure water to make 1y, and adjust to pH = 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 a developer solution [A] used in Example 1 to which a compound according to the present invention and a 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.

From the results shown in Table 5, it can be seen that the compounds according to the present invention, even when added to the developer, prevent the occurrence of fog in high-temperature rapid processing, and do not lower the sensitivity like the comparative compounds.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Procedure r13 j-, [HOE' (Method) % Formula % 2, Name of Invention Processing Method of Silver Halide Photographic IrI 3, Person Making Amendment, Case Relationship Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishi Rokueta Shin Kogyo Co., Ltd.
Stamp Production 4, Agent 102 Address Kudan-Rosaka Pill, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 (Shipping date) June 24, 1986 6, Subject to amendment

Claims (1)

[Scope of Claims] Processing of a silver halide photographic material comprising exposing a silver halide photographic material having a light-sensitive silver halide emulsion layer and then developing it in the presence of a compound represented by the following formula: Method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1, R^2 and R^3 each represent hydrogen or a substituent.