JPS62234153A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material preventing deterioration of photographic characteristics, particularly, generation of fog by forming a photosensitive material comprising a photosensitive silver halide emulsion layer and a hydrolysed product of a quaternary chalcogen azolium salt having a middle chalcogen atom as a ring-constituting atom and a specified quaterizing group. CONSTITUTION:The photographic sensitive material contains a photosensitive silver halide emulsion layer and a hydrolyzed product of a quaternary chalcogen azolium salt having a middle chalcogen atom as a ring-constituting atom and a quaterizing group expressed by the formula. In the formula, L is a divalent joint group; T is -CO-, or -SO2-; V and W are each H atom, or electron attractive group. The hydrolyzed product is pref. added to a photosensitive silver halide emulsion layer, and the amt. to be added is pred. 0.01-10mmol, most pref. 0.015-2mmol per 1mol silver halide. By this constitution, a silver halide photographic sensitive material contg. an antifoggant causing hardly reduction of sensitivity nor softening of gradation due to restraint of development is obtd.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to silver halide photographic materials, particularly! A method that prevents fogging during storage of ε optical material t+

[This is related to J-silver-genide photographic photoluminescent material. [Conventional technology]

Silver halide photographic materials tend to produce fog due to the presence of nuclei that can be developed even without exposure, and the occurrence of fog, especially during storage over time, can cause a decrease in sensitivity or deterioration of gradation. very often leads to Since it is desirable to minimize such undesirable phenomena, it has been known to add antifoggants, stabilizers, etc. to silver halide emulsions. For example, U.S. Patent No. 2.403.927, U.S. Pat.
1 described in No. 4.633, Special Publication No. 39-2825, etc.
-phenyl-5-mercaptotetrazoles, or 4-
Hydroxy-6-methyl-1,3,3a, 7-chitrazaindene and the like have been used as antifoggants. However, these compounds do not necessarily have a sufficient fog-inhibiting effect during storage over time, and have drawbacks such as a decrease in sensitivity and softening of gradations, so that they are not yet satisfactory. In addition, in the case of color photosensitive materials, an antifoggant that not only has good shelf life over time but also does not delay the bleaching time is required. When the conventionally known 1-phenyl-5-mercaptotetrazole is used as an antifoggant in a silver halide emulsion, it deteriorates the desilvering bleaching property (there was a large amount of spraying. Therefore, such a theory i! It is desired to develop a fog suppressing RQ that does not deteriorate the bleaching properties and does not cause the above-mentioned deterioration of photographic performance during storage over time. The first objective was to prevent the deterioration of photographic performance of three-photonic materials during storage over time, and in particular to produce silver halide photographs that suppressed the occurrence of fog. IJ provides photosensitive materials
It's about doing things. A second object of the present invention is to provide a silver halide photoprinter containing a fog suppressant that is less likely to cause a decrease in sensitivity or softening of the periphery due to development inhibition. That's true. A third object of the present invention is to provide a silver halide color photographic light-sensitive material stabilized by a fog suppressant that causes less clustering damage due to SR bleaching in color phenomena. (Structure of the Invention) As a result of extensive research to achieve the above object, we have discovered that the above object can be achieved using a photographic material having the following structure. If you use the photosensitive silver halide emulsion layer and the hammer chalcogen atoms as ring constituent atoms, 1. and a hydrolyzed compound of a primary chalcogen azolium salt having a primary group of the following formula; L: Divalent bonding group T-co- or -5Ot- V, W: Each is a hydrogen atom or an electron-withdrawing group, and at least one of ■ and W is an electron-withdrawing group. Among the above quaternary chalcogen azolium salts, those represented by the following formula are preferred. R1: hydrogen, alkyl group having 1 to 8 carbon atoms, 6 to i carbon atoms
o's -ru group RZ, R3, hydrogen, halogen, aliphatic or aromatic hydrocarbon group bonded to the above ring directly or via -〇- or -S-, -CN, amino group, amide group , sulfonamide group, sulfamoyl group, ureido group, thioureido group, -OH -C0M, -302M (M4 yo -co- or -
an atom or group which together with SO,- forms an aldehyde, ketone, acid, ester, thioester, amide or salt), or R2 and R3 may jointly form a ring fused to the above ring. Ω: Quaternized group represented by 2 above X: Middle chalcogen Yl, counter ion: O or 1 The above formula will be explained in detail. As T, a carbonyl group is preferable. It is preferably an alkylene group having 1 to 8 carbon atoms (ie, an alkanediyl group). Especially preferred in the present invention is methylene! (-CH2-) or ethylene &
(-CHzGHz). Examples of the electron-withdrawing groups represented by v and I/J include sulfonyl groups (methanesulfonyl, p-)luenesulfonyl, benzenesulfonyl, trifluoromethanesulfonyl, etc.), sulfamoyl groups (sulfamoyl, N,
N-dimethylaminosulfonyl, N-phenylaminosulfonyl, N-amylaminosulfonyl, etc.), carbonyl groups (acetyl, propionyl, benzoyl, p
- methylbenzoyl, etc.) carbamoyl groups (carbamoyl, N,N-diethylaminocarbonyl, N-methylaminocarbonyl, N-hexylaminocarbonyl, etc.), alkoxysulfonyl groups (methoxysulfonyl, butoxysulfonyl, etc.) (group) Aryloxysulfonyl group (tolyloxysulfonyl, phenyloxysulfonyl, etc.), alkoxycarbonyl group (ethoxycarbonyl, methoxycarbonyl, n-propoxycarbonyl, etc.) aryloxycarbonyl W (p-
) fluoroxycarbonyl, phenoxycarbonyl, etc.) nitro group, cyano group, trifluoromethyl group; As R1, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen and a methyl group are particularly preferable. The middle chalcogen represented by X refers to each atom of sulfur, selenium, or tellurium. pi,! The aliphatic hydrocarbon group represented by 23 (including those bonded directly to the ring and those bonded via -〇-1-8-) is preferably a furkyl group, and the alkyl also includes aralkyl. . The aromatic hydrocarbon group represented by R'' or ';?'' also includes alkaryl. The alkyl group and the alkyl moiety of the aralkyl or alkaryl are preferably those having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl), and particularly those having 1 to 4 carbon atoms. preferable. These alkyls include those having substituents such as halogen, cyano, aryl, carboxy, alkylcarbonyl, arylcarbonyl, and aminocarbonyl. Furthermore, the oraryl group and the oraryl group and the oraryl finger moiety of aralkyl or alkaryl preferably have 6 to 10 carbon atoms (eg, phenyl, naphthyl), and include those having substituents. Examples of the substituent include halogen, cyano, alkyl,
Carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl,
Aminocarbonyl is mentioned. The amine groups represented by R1 and R3 include primary to tertiary amino; the amide groups include acetamide and butyramide; the sulfonamide groups include alkylsulfonamide, aryl, and ruhoni/amide; and the sulfamoyl group includes alkyl Sulfamoyl and arylsulfamoyl are ureido groups such as 1-ureido and 3-phenyl-
1-ureido, 3-methyl-1-ureido, 1-thioureido, 3-phenyl-1-
Examples include thioureido and 3-methyl-1 thioureido. Examples of the ring formed by R2 and R3 together include aromatic hydrocarbon rings such as benzene and naphthazine. These rings may have substituents. Examples include those shown above as examples of RZ and R3 when X is sulfur and selenium, and when X is tellurium, substitution is made directly or via -〇-1-S-. aliphatic or aromatic group, amino group, amido group, sulfonamido group, sulfamoyl group, ureido group, thioureido group, Oll, COM. Examples include SO□M (M is acid, coni; (represents an atom or group necessary to form thyl, thioester, or salt). In particular, as a substituent to the ring formed by R2 and R3 jointly, Preferred are alkyl groups, alniaxy groups, alkylthio groups, and OII, and as the alkyl group and the alkyl moiety of the alkoxy group or alkylthio group, those having 1 to 8 carbon atoms are preferred, and those having 1 to 4 carbon atoms are particularly preferred. is a counter ion for making the quaternary chalcogen azolium salt electrically neutral, and examples thereof include anions such as halide BF, °Cl 01'' or p-toluenesulfonate. When the azolium salt is a betaine type, n is O. The chalcogen azolium salt described above is ring-opened in advance or by hydrolysis in a light-sensitive material to form a compound of the following formula, which produces the effects of the present invention. where R', R'', R3, Q, X and n are shown above. Y: is a counter ion. Y! is a counter ion to make the hydrolyzed compound electrically neutral, Examples include cations such as alkali, alkaline earth, ammonium, and cations generated due to the base used in hydrolysis. When the hydrolyzed compound is betaine type, n is O. Specific examples of the above-mentioned chalcogen azolium salts. ■ R1X(-) l-"'; Synthesis example Exemplary compound (9) 13.0 g (0.1 mol) of ethyl acetoacetate was added to 150 g of ethyl acetoacetate.
cc of ethanol, 6.8 g (0.1 mol) of sodium ethoxide was added thereto, and the mixture was stirred at room temperature for 1 hour. To this mixed solution, 17 g of chloroethanesulfonyl chloride dissolved in 50 cc of ethanol was added dropwise at 40°C over 1 hour. After the completion of the dropwise addition, the reaction was continued for another 3 hours at 40°C. After the reaction was completed, the reaction was cooled to 0°C. Filter and wash with 17130 cc of cold water-ethanol. These crystals were recrystallized from water-ethanol 1/1 to give white crystals (
1) Obtained 20g. 13 g of this white crystal and 8 g of 5-chlorobenzthiazole were mixed, heated to 150°C, reacted for 1 hour, and then cooled to room temperature. The obtained solid was dissolved in 200 cc of methanol, 15 g of potassium borofluoride was added, and the mixture was reacted at 50° C. for 1 hour, and then poured into 1 g of acetone for crystallization to obtain 19 g of the desired exemplary compound (9). Synthesis example Exemplified compound (1) Cyanoacetic acid 8.5g (0.1 mol), ethylamine 4
．． 5 g (0.1 mol) and 8 g of silicon tetrachloride were added to a solution of 50 liters of anhydrous pyridine and stirred at room temperature for 10 hours. After the reaction is complete, pour into ice water and extract with ethyl acetate. 10 g of the liquid obtained by concentrating this extract is dissolved in 100 cc of ethanol, 7 g of sodium ethoxide is added thereto, and the mixture is stirred for 1 hour. A solution of 14 g of 2-chloropropionyl chloride dissolved in 20 cc of ethanol was added dropwise to this solution at 40°C over 1 hour, and the reaction was continued for 3 hours after the dropwise addition. After cooling the reaction solution to room temperature, it was poured into water and ethyl acetate was added. Extract with Solid 1 obtained by concentrating this extract
Mix 0g and 5.5g of 4-methylthiazole and heat at 150°C.
After the reaction, the mixture was cooled to room temperature, the resulting solid was dissolved in 100 cc of methanol, 10 g of potassium iodide was added, and the mixture was stirred at 50° C. for 1 hour. After the reaction was completed, it was cooled to room temperature and poured into 600 cc of acetone.
10 g of the desired exemplary compound (1) of the present invention was obtained. The hydrolyzed compound of the present invention is preferably added to a photosensitive silver halide emulsion layer, and the amount added is preferably 0.01 to 10 mmol, particularly 0.015 to 10 mmol, per 11 mol of halide i in the emulsion layer. 2 mmol is preferred. The following margins The silver halide emulsions used in the photographic elements of this invention include 9
, C (cogen 1, silver arsenic, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc.) used in ordinary silver halide emulsions. The silver halide grains used in the silver halide emulsion may be those grown by any of the acid method, neutral method, and ammonia method. The method for producing 0M grains and the method for growing them may be the same or different.The silver halide emulsion may contain halide ions and ion ions at the same time, or may contain either one of them. may be mixed with the other in the solution where the other is present.Also, the pH and pAg in the mixing vessel of the halide/f-on and silver ions may be controlled while taking into account the critical growth rate of silver halide crystals. The silver halide emulsion may also be produced by simultaneously applying the same grain size to the silver halide emulsion.By this method, silver halide crystals having a regular crystal shape and a nearly uniform grain size can be obtained.A silver halide emulsion can be produced by: If necessary, a silver halide emulsion can be used to control the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains. and/or in the growing process, at least one selected from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing). Metal ions can be added to contain these metal elements inside the particles and/or on the surface of the particles, and in a suitable reducing atmosphere (by reducing the metal elements inside the particles and/or on the surface of the particles). Sensitizing nuclei can be added to the halide σ emulsion. Unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained. for,
Research Disclosure
Silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grains, but the inside and surface of the grains may The core/shell grains may have different silver halide compositions depending on the layer.The silver halide grains used in the silver halide emulsion may be grains on which a latent image is mainly formed on the surface. Alternatively, the grains may be formed mainly inside the grains.The silver halide grains used in the silver halide emulsion may have regular crystal shapes such as cubic, octahedral, or dodecahedral. , may have irregular crystal shapes such as spherical or plate-like.In these particles, (100)
Any ratio between the plane and the (111) plane can be used. In addition, grains having a composite form of these crystal forms may also be used (grains of various crystal forms may be mixed. ) is preferably 5 μm or less, particularly preferably 3 μm or less.The silver halide emulsion of the present invention may have any grain size distribution.An emulsion with a wide grain size distribution may be used. Alternatively, emulsions with a narrow grain size distribution may be used alone or in a mixture of several types.The silver halide emulsion may be used by mixing two or more types of silver halide emulsions formed separately.Halogenation The silver emulsion can be chemically sensitized by a conventional method.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.The sensitizing dye may be used alone, but Two or more types may be used in combination.A dye that does not have any spectral sensitizing effect together with the sensitizing dye, or a compound that substantially absorbs visible light and does not have the spectral sensitizing effect of the sensitizing dye. The emulsion may contain a supersensitizer that enhances the sensitization.
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, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as chloride or co-1g polymers can also be used. When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably 250 g or more (value measured by baggy method). The photographic emulsion layer and other hydrophilic colloid layers of photographic elements using the silver halide emulsion of the present invention contain one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added 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 H of a photographic element using the silver halide emulsion of the present invention for the purpose of increasing flexibility. In addition to the photographic emulsion layer of the photographic element using the silver halide emulsion of the present invention, other hydrophilic colloid layers include dispersions of water-insoluble or sparingly soluble synthetic polymers (latex) for the purpose of improving dimensional stability R1. ) can be included. The emulsion layer of the photographic element of the present invention undergoes a camping reaction with an oxidized form of an aromatic primary amine developer (e.g., p-phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. A dye-forming coupler is used that acts to form a dye. 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. It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. It may be either 4-equivalent, in which 100 silver ions need to be reduced, or 2-equivalent, in which only 2 molecules of silver ions need to be reduced. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide emulsions, toning agents, hardener capri agents, antifoggants, chemical sensitizers, Compounds that release photographically useful fragments, such as spectral enhancers 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 be used in combination. 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 it may cause color turbidity. If it is not conspicuous, a material that forms a different type of pigment may be used. 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 that do not need to be adsorbed onto the silver halide crystal surface, colored couplers, I) IR couplers, DI
For hydrophobic compounds such as R compounds, image stabilizers, color capri-prevention agents, ultraviolet absorbers, and fluorescent brighteners, various methods are used: solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method. This can be appropriately selected depending on the chemical structure of the hydrophobic 11 compound such as a coupler. Oil-in-ice droplet type pore formation [1 (method) can be applied to the conventionally known method of separating hydrophobic additives such as couplers, and high boiling point organic Low boiling point and/or water as required for the solvent?vIIIl:r″r
I9 is dissolved by using it in conjunction with organic solvent heather, and using a surfactant in a wood-loving powder such as gelatin aqueous solution, IW stamper, homogenizer, etc. Ido Mill, Flowit Mixer9. Ultrasonic device? After emulsifying and dispersing P using a dispersing means, it can be added to the target existing aqueous colloid layer.
Dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, fireflies, which may include a step to remove the low boiling point JA solvent simultaneously with the dispersion or dispersion. When the optical brightener has an acid group such as carboxylic acid or sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. 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 anti-capri agent 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. Hydrophilic colloid layers such as the protective layer and intermediate layer of the photographic element of the great invention absorb ultraviolet rays to prevent fogging due to discharge caused by charging of photosensitive materials due to friction, etc., and to prevent image deterioration due to U light. It may also contain an agent. Formalin scavengers can be used to prevent degradation of magenta dye-forming couplers and the like by formalin during storage of the photographic element. In the photographic element 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 alter developability, such as development accelerators and development retarders, and bleach accelerators may be added to the silver halide emulsion layer and/or other water-developable colloid layers of the photographic elements of this invention. Compounds that can be preferably used as development accelerators are listed in Research Disclosure (Research I).
isclosure) Section XXI B-0 of No. 17463
The development retardant is a compound described in Section XXI of No. 17643, Section E. A black and white developing agent and/or a breaker thereof may be used to accelerate development or for other purposes. The photographic emulsion layer of the photographic element of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines for the purpose of increasing sensitivity, increasing contrast i, or accelerating development.
It may also contain thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like. A fluorescent brightener can be used in the photographic element of the present invention for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable. Photographic elements of the present invention can be provided with auxiliary layers such as filter layers, antihalation layers, and/or antiradiation layers. These layers and/or emulsion layers may contain dyes that are washed out or bleached from the light-sensitive material during development. A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the photographic element of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together. A lubricant can be added to reduce the sliding friction of the photosensitive material. Antistatic agents can be added to the photographic elements of this invention for antistatic purposes. The antistatic agent can be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and 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 photographic element of the present invention may include improved coating properties, antistatic properties, improved slipperiness, emulsification dispersion, anti-adhesion, and photographic properties (accelerated development, hardening,
For the purpose of improving (exacerbation, etc.), surfactants of type ν can be used. Supports used in the photographic elements of this invention include fermented cellulose, nitrate cellulose, polystyrene, polyvinyl chloride,
Polyethylene L/Nterefuku L notebook, polycarbonate,
Semi-synthetic materials such as polyamides include films made of synthetic molecules, flexible supports provided with reflective layers on these films 11, glass, metals, ceramics, etc.). A copy of the invention! t, the elements can be applied directly or after subjecting the support surface to corona irradiation, ultraviolet irradiation, flame treatment, etc. as necessary, or to improve the adhesion properties, antistatic properties, and dimensional stability of the support surface 11;
Abrasion resistance 11 Hair resistance, hardness, anti-friction properties, friction customization,
and/or one or more layers of F to improve the properties of the pond.
It is also good to apply it through the 'X I tube. When coating the photographic element of the present invention, a thickener may be used to improve the coating 11. Also, since Reaction-1 is 9, as in the case of a V-film agent, a thickener may be added to the coating solution. ;JOr
For substances that may cause gelation before application,
Preferably, the mixture is mixed using a static mixer prior to placement. In preparing the copy 1 requirements of the present invention, halogen northern limit emulsions and other urine protection materials are disclosed in the Rasevrsh Disclosure.
re) Apply by the method described in A of XV of No. 17463,
It can be dried by the method described in Section B. The photographic elements of this invention can be exposed using electromagnetic radiation in the region of the spectrum to which the emulsion 1 of which it is comprised is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Mercury lamp, xenon flash lamp, carbon arc lamp, xenon lamp →
Light emitted from a phosphor excited by a solar light, a shadow tube flying spot, various types of light, a tip diode light, an electron beam, a chi line, a T line, an alpha gland, etc. Any known light source can be used. The exposure time is not only the 1 millisecond to 1 shot exposure time that is normally used in cameras, but also the 1 microsecond and bi2. Short exposures, such as 100 nanoseconds to 1 microsecond exposure using cathode ray tubes or xenon flash lamps, can be used, or exposures longer than 1 second are possible. The exposure may be performed continuously or intermittently. Any known method can be used for developing the photographic T3 element of the present invention. This development process may be either a process to form an SLI image (black and white development process) or a process to form a color image.If the image is created using the reversal method, first the black and white image is formed. A negative development step is performed, followed by a white exposure or a color development process by treatment with a bath containing a fogging agent. [Also, a dye is contained in the photosensitive material and a black and white development process is performed after exposure! 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. Any method such as a web method or a method of performing a viscous development process may be used. The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Alternatively, the development strip or its precursor may be incorporated into the sensitive material and the development step 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 a liquid treatment process,
A bleach-fixing process can be carried out using a 1-bath bleach-fix solution, or a mono-bath process can be carried out using a 1-bath developing, bleach-fixing solution that allows color development, bleaching and fixing to be carried out in one bath. be able to. In combination with these processing steps, a full 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-drying film process - Neutralizing process - Color development process - Stop-fixing process - Water washing process - Ring bleaching process Constant fixation process - Water 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 - Ring white process Constant blue processing process In addition to these processes, there is a method in which the developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification) described in JP-A-58-154839 are also available. Processing may be performed using a developing method that increases the amount of produced dye, such as processing). [Example] Example-1 4- as a ripening stopper was added to a negative high-strength silver iodobromide emulsion (silver iodide 2.5 mol %) that had been chemically ripened to the highest degree by gold and sulfur sensitization. Hydroxy-6-methyl L3+3
a, 7-chitrazaindene at 1 mole of silver halide
．． 0g was added. A portion of this emulsion was used as a blank (comparison) sample, and the quaternary chalcogen azolium salt and the comparative compound described above were added to the remaining emulsion as shown in Table 1 below to allow sufficient adsorption, and then saponin was added as a coating aid. An appropriate amount of formalin was added as a hardening agent to prepare an emulsion. The obtained emulsion was applied onto a subbed polyester base.
It was coated uniformly in an amount of 3 g/m'' and dried to obtain a sample according to the present invention.The sample thus prepared was left at room temperature for 3 days as a fresh sample, Humidity 8
A forced deterioration aging sample was prepared by leaving it at 0% temperature for 3 days and leaving it at 55° C. and 7% relative humidity for 3 days. Next, after exposure using a conventional sensitometry wedge, 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 1.5 g Hydroquinone 30 g 5-Nitwindazole 0.25 g Potassium bromide 5.0 g Anhydrous sodium sulfite 55° Potassium hydroxide
30 g
10 g glutaraldehyde (25%)
Add 5g of water to make 11. 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 t2 according to the present invention
9 shows that, despite the harsher storage conditions compared to comparative samples, the sensitivity of fog generation was reduced, the gun density was suppressed, and the stability of the film during storage was improved. I understand.Practice-2 Silver iodobromide emulsion I containing 7 mol% of iodine and having an average diameter of 1.2 μm!: After chemical ripening to maximum sensitivity with gold and sulfur sensitizers, green-sensitive sensitizing dye A green-sensitive silver halide emulsion was prepared and coated by adding an appropriate amount of 5,5'-diphenyl-9-ethyl-3,3'-di-T-sulfopropyloxacarbocyanine sodium salt. per mole, as magenta coupler, 1-(2,4,6-)licrot]phenyl)
3-C3-C2,4 di-t-amylphenoxyacetamide)penzamide]-5-pyrazolone with F+O,,
As a colored magenta coupler, l-(2,4,6-
+-liclophenyl)-4-(1-naphthylazo)-3
-(2-Chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone was weighed with 2.5%, and then 120g of tricresylphosph) and 240ml of ethyl acetate were mixed and added. Dissolve warmly, then add 5 g of sodium tri-isopropylnaphthalene sulfonate and 7.
A coupler solution emulsified and dispersed in 550 n11 of a 5% aqueous gelatin solution 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-
An appropriate amount of sodium hydroxy, 4,6-cyclotriazine was uniformly added to prepare a silver halide emulsion. This emulsion was uniformly dried on a subbed triacetate film for four times to give a sample so that the silver content was 3.0 g/nf. 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 N115).
This is the relative sensitivity when expressed as 100. Also, gamma is expressed by the slope of the straight line. Processing process [Processing temperature 38°C] Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds fixed 6 minutes 30
Washing with water for 3 minutes and 15 seconds Stabilization for 1 minute and 30 seconds Drying The composition of the treatment liquid used in each treatment step is as follows. [Color developer] 4-Amino-3-methyltoethyl-N-(β-hydroxyethyl)-aniline/sulfur Pa salt 4, 75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfur m [2 , Og anhydrous potassium carbonate
37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make 11. [Bleaching; Night] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
10.0mj! Add water to bring the pH to 11, and adjust the pH to 6.0 using aqueous ammonia. [Fixer] Ammonium periosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Water was added to make the solution 11, and the pH was adjusted to 6.0 using acetic acid. [Stabilizing liquid] Formalin (37% aqueous solution) 1.5m
j! Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 1.5 cal
Table 2 @ Comparison (A), (Bl, (C) Compounds identical to those in Example 1) As is clear from Table 2, the samples according to the present invention were stored under harsher storage conditions than the comparative samples. It can be seen that the occurrence of fog, the decrease in sensitivity, and the decrease in gamma are suppressed, and the stability during storage is improved.Example-3 Each layer having the composition shown below is sequentially provided on a cellulose triacetate film support. A multilayer color sensitive round material sample (comparison) was prepared using the following techniques. 1st layer: antihalation layer, black gelatin layer containing colloidal silver, 2nd layer: intermediate layer gelatin, 3rd layer: red-sensitive, low-sensitivity emulsion layer, natural odor. Silver iodide emulsion Silver iodide = 55 mol% Average diameter 0.5 μm -1, 79R/m Sensitizing dye I - - - - 6 x 10 per mole of dye
-'molar sensitizing dye■ -・-・・-3×10− for 1 mole of silver
% mole coupler A---0.06 mole per mole of silverCoupler C---0.003 mole per mole of silverCoupler D---0.06 mole per mole of silver 003 mol tricresyl phosphate coating amount 0.3n+110r 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.7 μm Old silver coating... 1.4 g/resistant Sensitizing dye I---3X10 in 1 mole of silver
-'molar sensitizing dye ■-----1.
2
Mol coupler c --------・0.00 per mole of grudge
16 mol tricresyl phosphate coating amount 0.2 mt! /m 5th N: Same as the second intermediate layer 6th M: Green-sensitive, low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.5 μm Root material - 1.0 g/m m Sensitizing dye 1Ii-----3X10-' moles per mole of silver Sensitizing dye ■-----lXl0-' moles per mole of silver Coupler B----- Coupler M: 0.08 mole per mole of silver 0.00 mole per mole of silver
8 mole coupler D -------・0.0015 mole per mole of silver tricresyl phosphate coating lid 1.4 IIJ/nf 7th layer: Green sensitive low sensitivity emulsion layer Silver iodobromide emulsion Silver iodide : 5 mol% Average particle size 0.75 μm S coating h1 ・−・ 1.6 g/+n sensitizing dye ■・−
・------・2.5 Xl0-' per mole of silver
Molar sensitizing dye ■---0.8 Xl0 per mole of silver
-”Mole coupler B-----0.0 per mole of silver
2 mole coupler M - - - = - - 0 for 1 mole of silver
．． 003 Moltricresyl phosphate coating 0.8 mA/No. 81; Yellow filter single layer gelatin water soluble: Gelatin layer containing yellow colloid layer during the night. 9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Iodide & 1:6 mol% Average grain size 0.70 μm Silver coating amount - 0.5 g/rd Coupler Y - - per 1 mol of side 0.12525 mol tricresyl phosphate coating amount 3n+A/rm 1st ON: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol% Average grain size 0.8 μm Silver coating amount - 0.6 g/nf Coupler Y...--0.04 per mole of 8ml
Moltricresyl phosphate coating amount: 0.1 ml/go 11th layer: Protective layer A gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) was coated. For each jΔ coupler, add the coupler to a solution of tricresyl phosphate and ethyl acetate, add sodium p-dodecylbenzenesulfonate as an emulsifier, dissolve by heating, mix with heated 10% gelatin solution, and emulsify with a colloid mill. I used the one I made. 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 I: Anhydro 5,5'-dichloro-3,3
'-di(γ, sulphur-propyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitizing dye ■: anhydro-9-ethyl-3,3'-di(
γ-sulfopropyl)-4,5,4',5'-dibenzothialylpocyanine hydroxide triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5,5'-dichloro-3,3'-di(γ -Sulfopropyl)oxacarbocyanine hydroxide sodium salt sensitizing dye■:
Anhydro5.6.5',6'-tetrachloro1.1'-diethyl-3,3'-di(β-[β-(r
-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler A QH(t)CsIi+ + coupler B coupler C () 8'7 coupler F H coupler M The four red-sensitive layers and the sixth and seventh green-sensitive layers are each coated with 4-hydroxy-6 as a known stabilizer after adding a sensitizing dye.
- 3 g of methyl-1,3,3a,7-titrazaindene per mole of silver halide and 110 g of 1-phenyl-5-mercaptotetrazole per mole of silver halide.
It was stabilized by adding 11I. The ninth and tenth layers of the next blue-sensitive emulsion layer contain coupler Y.
Before adding the compound, the comparative compound and the compound of the present invention were added as shown in Table 3 below, and the mixture was prepared and multilayered. The obtained multilayer color light-sensitive material was subjected to high temperature and high humidity processing for the storage test in the same manner as in Example 1, and then subjected to ordinary wedge exposure and then subjected to the same color processing as in Example 2. The sensimetry results are shown in Table 3. Table 3 above shows that the samples according to the present invention have excellent storage stability even in the case of multilayer color photosensitive materials. Furthermore, the desilvering bleaching properties of the samples of the present invention showed less deterioration than the comparative samples when the bleaching time was shortened. Example 4 A silver halide color photographic material of the present invention was prepared by coating the following layers on a paper support coated on both sides with polyethylene resin. Layer 1: Blue-sensitive emulsion layer Silver chlorobromide emulsion containing 20 mol% of silver chloride (0.28
g, containing 1.2 g of gelatin) was sulfur sensitized and then a blue sensitizing dye (BSD-1) was added to 5.5×10 −′ mol/
It was added per mole of silver halide to prepare a blue-sensitive silver halide emulsion. This emulsion was divided into 16 equal parts, and a comparative compound and a compound 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 / 1 resistance Atari Nobo Yellow Coupler (Y-1) 0.75 g 2.5-di-t-octylhydroquinone 0.015 g Dioctyl phthalate 0.4 g Next, N2 below was coated on this emulsion layer as a protective layer. This was a sample according to the invention. Layer 2: Gelatin fill ji Amount per 1 rri Gelatin 1.4 g N1117
flll (bisvinylsulfonyl methyl ether)
0.1g (BS Low 1) CzHs thsO3tI to C11z
(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 wedge exposed in the usual manner, and color developed according to the following color processing steps. The color sensimetry results obtained from the obtained samples are shown in Table 4 below. The sensitivities in the table are relative sensitivities when the comparison sample (blank) of each layer left for 3 days is set as 100. Processing process Temperature Time (1) Color development 33°C 3 minutes 30 seconds (2) Bleach fixing
33℃ 1 minute 30 seconds (3) Water? fc30~
34℃ 3 minutes (4) Drying 60~9
The composition of the treatment liquid used in each step at 0°C is as follows. (Color developer) Pure water Boom e ethylene fuglycol 12mj! Benzyl alcohol 12m j! Anhydrous potassium carbonate
30g anhydrous potassium sulfite
2g N-ethyl-N-(β-methanesulfonamido)ethyl-3-methyl-4 aminoaniline sulfate,! ,
5゜Sodium chloride Add 1.13g water to make 1z. pl+-10 with 10% potassium hydroxide or 20% sulfuric acid,
Adjust to 2. (Liquid) Pure r'g 750ml Iron ethylenediaminetetraacetate (III> Sodium 0g Ammonium thiosulfate 85g Sodium bisulfite 10g Sodium metabisulfite 2g Disodium ethylenediaminetetraacetate 20g Sodium bromide
Add 3.0 g of pure water to make IIl, and adjust the pH to -7.0 with 20% aqueous ammonia or 20% sulfuric acid. Below are the margins: Table 4 * Comparative Compounds The results in Table 4 show that the compound of the present invention suppresses fog with no deterioration of photographic properties even in color light-sensitive materials, and with little desensitization. It turns out that it is effective. Patent applicant Konishi Roku Photo Industry Co., Ltd. Agent Patent attorney Hirate Takatsuki (Method) % formula % 1, Indication of case 1986 Patent application No. 77882 2, Name of invention Photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 5, Date of amendment order Spontaneous 6, Subject of amendment Specification procedure Principal Ho (spontaneous) January 20, 1988 Commissioner of the Patent Office Kuro 1) Akira Mr. Yu 1, Indication of the case 1986 Patent application No. 077882 2, Name of foaming Photographic light-sensitive material 3, Relationship with the amended person case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Contents of the amendment As shown in the attached sheet: ＼ (1) Page 58 of the engraving specification attached to the written amendment submitted on June 19, 1985 'Yellow coupler Y-
1" is corrected as follows. (2) Add the following statement after "I understand." on page 62, line 4 of the same book. "[Effects of the Invention] According to the present invention, it is possible to obtain a photographic material in which a decrease in sensitivity is prevented, and the occurrence of fog and softening of gradations are suppressed."

Claims (1)

[Scope of Claims] A photosensitive silver halide emulsion layer and a hydrolyzed compound of a quaternary chalcogen azolium salt containing a middle chalcogen atom as a ring-constituting atom and having a quaternizing group of the following formula. photographic material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ L: Divalent bonding group T: -CO- or -SO_2- V, W: Each is a hydrogen atom or an electron-withdrawing group, and at least one of V and W is an electron-withdrawing group It is a sexual group.