JPH0458617B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material that has excellent storage stability and a small amount of silver. (Background Art) In recent years, two major trends can be observed in silver halide photosensitive materials, particularly photographic photosensitive materials.
One is higher sensitivity, as exemplified by ASA1600 film, and the other is higher image quality, which corresponds to smaller film sizes. Regarding the former, various methods have been studied, including increasing the size of silver halide grains, increasing coupler activation, and accelerating development. For information on increasing the size of silver halide, see GC Farnell.
As reported in JB Chanter. Furthermore, increasing the size of silver halide grains is accompanied by various side effects such as deterioration of graininess. Many studies have been conducted on increasing the activation of couplers, but they do not contribute enough to sensitivity and have the disadvantage of worsening graininess. To accelerate development, the addition of various development accelerators such as hydrazine compounds to the emulsion layer or developer has been considered, mainly for black-and-white photosensitive materials, but all of these methods are accompanied by increased fog and deterioration of graininess. This is often not practical. Therefore, a coupler that releases a development accelerator and a fogging agent in an image-wise manner was proposed. for example,
U.S. Patent No. 3214377, U.S. Patent No. 3253924, JP-A-51-
No. 17437 discloses thiocyanate ion releasing couplers that promote solution physical development. In addition, JP-A-57-150845 describes the principle of couplers that release fogging agents such as acylhydrazine.
No. 138636 discloses a coupler that releases hydroquinone, aminophenol developer, etc. Furthermore, JP-A-59-50439 and JP-A-58-31611
also discloses a coupler that releases a fogging agent or a silver sulfide nucleus forming agent or its precursor, and describes in detail the sensitization effect, contrast enhancement effect, or development acceleration effect by releasing the fogging agent imagewise. ing. These techniques are certainly effective. However, photosensitive materials are stored for a long period of time after they are manufactured until they are used, and silver halide photosensitive materials containing the above-mentioned compounds suffer from a significant increase in fog and a decrease in sensitivity during storage, which poses some practical problems. . For example, defects become noticeable after 2 to 3 months at a storage temperature of 30°C. (Objective of the Invention) The object of the present invention is to improve the side effects such as increased fog and decreased sensitivity that occur when using a coupler that releases a development accelerator or a fogging agent imagewise, and to improve the side effects such as increased fog and decreased sensitivity during storage. One object of the present invention is to provide a silver halide photographic material with high sensitivity, low silver content, and good storage stability, and to provide a packaging form for the photosensitive material suitable for these purposes. (Structure of the Invention) The object of the present invention is to contain a compound (hereinafter simply referred to as an FR compound) that generates a fogging agent or its precursor in accordance with the amount of developed silver during development, and at a relative humidity of 55% or less. This is achieved by using silver halide photosensitive materials stored in In the present invention, compounds that produce a fogging agent or a development accelerator depending on the amount of developed silver include:
Preferred are those that react with the oxidation products of the developer to release fogging agents or development accelerators. In the present invention, sealed packaging is preferred as a method for preserving the product at a relative humidity of 55% or less. According to the present invention, it can last for 6 months when stored at 25°C, 2 to 3 months when stored at 30°C, and 1 to 5 hours when stored at 60°C, which occurs in a car exposed to direct sunlight in summer. The degree of desensitization and increase in fog is significantly improved. Sealed packaging as used in the present invention refers to moisture-proof packaging that is well known in the field of ordinary packaging. Packaging materials include metals and metal foils such as aluminum plates, tin plates, and aluminum foils, glass, polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide, various polymers, and cellophane. Composite laminated materials (laminated materials in packaging terminology) made of materials such as paper and aluminum foil are used. As a sealing method, an adhesive method using various adhesives, a thermal fusion method such as heat sealing, or another method using a cartridge case, which is common in the photographic industry, can be used. Details of these sealing methods are described in "Food Packaging Technology Handbook" edited by Japan Packaging Technology Association, pages 573 to 609. In the present invention, a cartridge case made of a polymer such as polyethylene or polypropylene is preferable for a roll-type photographic light-sensitive material, and a cartridge case made of a polymer such as polyethylene or the like is preferable for a sheet-type photographic light-sensitive material. These sealed packagings may be done in duplicate. The storage humidity condition of the present invention is more preferably 50%.
The relative humidity is preferably 45% or less. The relative temperature in the present invention is a value measured at 25°C, and the relative temperature can be measured by a conventional method. For example, heat a part of the heat-sealed package to melt it, immediately insert an electrical resistance hygrometer (temperature and humidity recorder model AR-33YB manufactured by Ace Laboratory Co., Ltd.) into the package, seal it, and keep it at 25℃. It is possible to measure the internal humidity. As a packaging method with a lower relative humidity as in the present invention, the silver halide photographic light-sensitive material may be packaged in a low-humidity chamber, or the material may be dried more than usual when drying. Furthermore, humidity may be reduced by adding a desiccant such as silica gel into the sealed container. When implementing the present invention, static failures often occur due to low humidity. In order to prevent this static failure, it is particularly preferable to add a fluorine-based compound, which is well known as an antistatic agent. As a fluorine-based compound, for example,
Compounds described in JP-A-43130, JP-A-46-7781, JP-A-55-55052, etc. can be used. Further, in order to prevent static failure, it is preferable that the outermost layer contains a matting agent. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matte agent is 0.05μ~
10μ is preferable. The amount to add is 1 to 300
mg/m ² is preferred. Further, it is preferable that a layer outer than the photosensitive silver halide emulsion layer contains an ultraviolet absorber. For example, benzotriazole compounds substituted with aryl groups (such as those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in US Pat. No. 3,314,794,
3352681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805,
3,707,375), butadiene compounds (eg, those described in US Pat. No. 4,045,229), or benzoxide compounds (eg, those described in US Pat. No. 3,700,455). Furthermore, U.S. Patent No. 3499762,
48535, polymerized ultraviolet absorbers disclosed in JP-A-58-111942 and JP-A-58-178331, etc. can be used. In the present invention, the FR compound may be added to any of the photographic layers. FR compounds that can be used in the present invention include the following. () Coupled with the oxidation product of an aromatic primary amine developing agent to form a fogging agent (hereinafter simply referred to as
(referred to as FA) or its precursor. () A coupler that couples with an oxidation product of an aromatic primary amine developing agent to produce a diffusible coupling product, and the coupling product functions as FA or its precursor. () A redox compound that releases FA or its precursor through a redox reaction with an oxidation product of an aromatic primary amine developing agent or a subsequent reaction of the reaction. The above compounds (), () and () are respectively represented by the following general formulas [], [] and []. [] Cp-(TIME) _o -FA [] BALL-Cp(TIME) _o -FA [] RED-(TIME) _o -FA In the above formula, Cp is an oxidized product of an aromatic primary amine developer. BALL represents a diffusion-resistant group that can be separated from Cp by a coupling reaction with an oxidized aromatic primary amine developer, and RED represents a coupler residue capable of coupling reaction with an oxidized aromatic primary amine developer. Represents a compound residue that can undergo a redox reaction with the oxidized form of a drug. TIME represents a timing group that further releases FA after detachment from Cp or RED by a coupling reaction. n represents 0 or 1, and FA is a group that can be separated from Cp or RED by a coupling reaction when n is 0, and a group that can be released from TIME when n is 1 (in the above formula, In the case of the compound represented by [], FA is Cp after the coupling reaction.
or you do not have to leave TIME). Here, FA represents a so-called fogging agent that acts on silver halide grains during development to generate fog nuclei that can initiate development. The FA is a group that acts reductively on silver halide grains during development to produce fog nuclei, or acts on silver halide grains to produce silver sulfide nuclei, which are fog nuclei that can initiate development. can be mentioned. A preferable group as FA is a group containing a group that has adsorption properties to silver halide grains, and can be expressed as follows: AD-(L) _n -X AD is a group that has adsorption properties to silver halide grains; L represents a divalent group, and m represents 0 or 1. X represents a reducing group or a group capable of producing silver sulfide by acting on silver halide. However, if X is the latter, it may also have the function of AD, so in this case it is not necessarily the case.
AD−(L) _n − is not necessary. When FA is a group represented by AD-(L) _n -X, the bonding position with TIME, Cp or RED is AD
-(L) may be at any position of _n -X. In the general formula [], −(TIME) _o −FA is Cp
The bond is cleaved during the coupling reaction. In the general formula [], BALL is bonded to the coupling position of Cp, and during the coupling reaction,
That bond is cleaved. Also, −(TIME) _o −FA is
Since it binds to the non-coupled position of Cp, the bond is not immediately cleaved by coupling. In the general formula [], -(TIME) _o -FA is,
The RED is bound to a position where it can be released from the RED by a redox reaction with the oxidized aromatic primary amine developer or its subsequent reaction. On the other hand, the group represented by TIME has the general formula []
In some cases, it is a trivalent group. That is, one of the trivalent bonds binds to FA, and one of the remaining two bonds binds to the coupling position of Cp,
The other case is when it binds to the non-coupling position of Cp. A characteristic of compounds with such a structure is that during the coupling reaction with an aromatic primary amine developer, the TIME bonded to the coupling site is
The bond with TIME is broken, but the bond with TIME, which is bonded to the non-coupling position, is not cleaved.
The bond moiety (anion) of TIME can release FA by cleavage of the bond with FA by electron transfer and/or intramolecular nucleophilic substitution reaction within the TIME molecule. Therefore, in the case of such a compound, it is necessary not only to be a trivalent group but also to have a structure capable of releasing FA by intramolecular electron transfer and/or intramolecular nucleophilic substitution reaction. In the present invention, the amount of the FR compound added is 10 ^-9 to 10 -1 mol, preferably 10 ^-3 to 10 ² mol, per 1 mol of silver halide contained in the layer containing the compound or the layer adjacent thereto ^. It is. The general formulas [], [], and [] will be explained in more detail below. In the general formulas [] and [], the coupler residue represented by Cp has a partial structure of the following yellow, magenta, and cyan couplers, as well as a colorless coupler and a black coloring coupler. Here, representative examples of yellow couplers among couplers include US Patent No. 2875057, US Patent No. 2407210,
Same No. 3265506, No. 2298443, No. 3048194, Same No.
It is described in No. 3447928 etc. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred. A typical example of a magenta coupler is the U.S. patent
No. 2600788, No. 2369489, No. 2343703, No.
No. 2311082, No. 3152896, No. 3519429, No. 3519429, No. 3152896, No. 3519429, No.
No. 3062653, No. 2908573, Special Publication No. 1972-27411,
Patent application No. 58-45512, No. 58-23434, No. 58-
It is described in No. 142801, No. 58-151354, No. 59-27745, etc. Among these magenta couplers, pyrazolones or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole,
pyrazolotriazole, pyrazolotetrazole, etc.) are preferred. A typical example of a cyan coupler is a U.S. patent
No. 2772162, No. 2895826, No. 3002836, No.
No. 3034892, No. 2474293, No. 2423730, No. 3034892, No. 2474293, No. 2423730, No.
No. 2367531 and No. 3041236, JP-A-56-
No. 99341, No. 57-155538, No. 57-204545, No. 57-204545, No. 57-155538, No. 57-204545, No.
58-189154 and 59-31953, 58-
No. 118643, No. 58-187928, No. 58-213748, and US Pat. No. 4,333,999. Among these cyan couplers, phenols or naphthols are preferred. Further, Cp may be a so-called colorless coupler. A typical example of a colorless coupler is the U.S. patent
It is described in No. 3912513, No. 4204867, Japanese Patent Application No. 152721/1980, etc. The timing group represented by TIME can be obtained by coupling reaction or redox reaction as described in U.S. Pat.
A device that leaves Cp or RED and then leaves FA by intramolecular substitution reaction, British Patent No. 2072363A,
JP-A No. 57-154234, No. 57-188035, No. 56-
No. 114946, No. 57-56837, No. 58-209736, No.
No. 58-209737, No. 58-209738, No. 58-209740
No. 58-98728, which leaves FA by electron transfer through a conjugated system, JP-A-57-
Examples include coupling components such as No. 111536 that can release FA through a coupling reaction with an oxidized product of an aromatic primary amine developer. These reactions may occur in one step or in multiple steps. Also preferred, as previously mentioned, is a trivalent TIME that binds to the coupling and non-coupling moieties and FA (an example of its incorporation into a yellow coupler is described in JP-A-58-209740). When FA is a group containing AD-(L) _n -X, AD may be directly bonded to the carbon atom at the coupling position, or if L or X can be separated by a coupling reaction. These may be bonded to the coupling carbon. Furthermore, what is known as a so-called 2-equivalent leaving group may be present between the coupling carbon and AD. These groups include alkoxy groups (e.g. methoxy groups),
Aryloxy group (e.g. phenoxy group), alkylthio group (e.g. ethylthio group), arylthio group (e.g. phenylthio group), heterocyclic oxy group (e.g. tetrazolyloxy), heterocyclic thio group (e.g. pyridylthio), heterocyclic group ( Examples include hydantoinyl group, pyrazolyl group, triazolyl group, benzotriazolyl group, etc.). In addition, those described in British Patent Publication No. 2011391 can be used as FA. Groups adsorbable to silver halide represented by AD include nitrogen heterocycles with dissociable hydrogen atoms (pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, uracil, tetra azaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), heterocycles with at least one nitrogen atom and another heteroatom (oxygen atom, sulfur atom, selenium atom, etc.) in the ring (oxazole, thiazole, Thiazoline, thiazolidine, thiadiazole, benzothiazole, benzoxazole,
benzselenazole, etc.), heterocycles with mercapto groups (2-mercaptobenzthiazole, 2-
mercaptopyrimidine, 2-mercaptobenzoxazole, 1-phenyl-5-mercaptotetrazole, etc.), quaternary salts (tertiary amine, pyridine,
(Quaternary salts of quinoline, benzthiazole, benzimidazole, benzoxazole, etc.), thiophenols, alkylthiols (cysteine, etc.)

Examples include compounds having a partial structure of the formula (for example, thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbituric acid, etc.). The divalent linking group represented by L in FA includes alkylene, alkenylene, phenylene, naphthylene, -O-, -S-, -SO-, -SO ₂ -, -N=N
-, carbonyl, amide, thioamide, sulfonamide, ureido, thioureido, heterocycle, etc. If a group that can be cleaved by the action of components in the developer (e.g., hydroxide ion, hydroxylamine, sulfite ion, etc.) is appropriately selected as one of the divalent linking groups constituting L, the fogging effect can be adjusted. It is also possible to deactivate it. When represented by X, the group is a reducing compound (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol,
quaternary salts such as p-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamines, aldehydes, polyamines, acetylene, aminoborane, tetrazolium salts, ethylene bispyridinium salts (carbazic acid, etc.) or compounds that can form silver sulfide during development. (e.g. thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidinethione)

Compounds having a partial structure of [Formula], etc.) can be mentioned. Among the groups represented by X, some of the groups capable of forming silver sulfide during development have adsorption properties to silver halide grains, and can also serve as adsorption groups AD. Particularly preferable FAs are represented by the following general formulas [] and []. General formula [] General formula [] In the formula, R ₁ represents an acyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, or sulfamoyl group, and R ₂ represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. R ₃ represents a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a carbonamide group or a sulfonamide group. m represents an integer of 0 to 4, and when m is 2 or more, R ₃ may be the same or different, or two or more may form a fused ring at the bond. L has the same meaning as before, ie represents two linking groups, and n represents 0 or 1. Z ₁ represents a monocyclic or fused heterocycle, and Z ₂ represents

Represents a monocyclic or condensed heterocyclic ring formed with [Formula]. Examples of substituents are described in more detail below. R ₁
As, acyl group (formyl group, acetyl group,
propionyl group, trifluoroacetyl group, pyruvoyl group, etc.), carbamoyl group (dimethylcarbamoyl group, etc.), alkylsulfonyl group (methanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.) , an aryloxycarbonyl group (such as a phenoxycarbonyl group) or a sulfamoyl group (such as a methylsulfamoyl group),
R ₂ is a hydrogen atom, an acyl group (such as a trifluoroacetyl group), an alkoxycarbonyl group (such as a methoxycarbonyl group), or an aryloxycarbonyl group (such as a phenoxycarbonyl group),
_R3 is a halogen atom (fluorine atom, chlorine atom, etc.), an alkoxy group (methoxy group, methoxyethoxy group, etc.), an alkyl group (methyl group, hydroxymethyl group, etc.), an alkenyl group (allyl group, etc.), an aryl group. (phenyl group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (methylthio group, etc.), arylthio group (phenylthio group, etc.), carbonamide group (acetamide group, etc.) or sulfonamide group (methanesulfonamide group, etc.) can be mentioned.

[Formula] and

An example of [Formula] is shown in the AD example given below. An example of the FR compound used in the present invention is
No. 57-150845, No. 59-50439, patent application No. 58-31610
No. 58-31611, No. 58-146097, No. 58-
It is described in No. 214805, No. 58-237101, etc. In the present invention, a known method such as the method described in US Pat. No. 2,322,027 can be used to introduce the compound of the present application and a coupler that can be used in combination into the silver halide emulsion layer. Also, Special Publication No. 51-39853,
The dispersion method using a polymer described in JP-A-51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Binders or protective colloids that can be used in the intermediate layer of the emulsion layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, gelatin may be either lime-treated gelatin or acid-treated gelatin. For more information on how to make gelatin, see The Macromolecular Chemistry by Arthur Vuis.
Of Gelatin, (Academic Press, 1964
Published in 2013). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. Particle size can be narrow, wide, or staggered. The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube, an octahedron, or a tetradecahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape. Alternatively, it may be a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), by GF Duffin
Photographic Emulsion Chemistry (The
Focal Press, 1966), VLZelikman et al.
AuthorMaking and Coating Photographic
It can be adjusted using the method described in Emulsion (The Focal Press, 1964).
That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed using any of the one-sided mixing method, simultaneous mixing method, and a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Prozesse
mit Silber−halogeniden”
(Akademischeverlagsgesellschaft, 1968) 675
The method described on pages 734 to 734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. In the photographic light-sensitive material used in the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a dispersion of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. As the color developing agent, a known primary aromatic amine developer can be used. OthersPhoto-graphic by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromines, iodides, and organic antifoggants. It can also contain agents such as After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the same or other photographic emulsion layers or non-light-sensitive layers of the photographic light-sensitive materials made using the present invention, in addition to the aforementioned compounds of the present application, other dye-forming couplers,
That is, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) may be used in the color development process. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
Pyrazoloimidazole couplers, pyrazolo pyrazole couplers, pyrazolotriazole couplers,
There are pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides),
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ion. In addition, colored couplers have the effect of color correction,
Alternatively, it may be a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.
In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
dioxane-derived couples (such as 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (such as 2 , 4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Example 1 Sample 101 was prepared by coating a triacetylcellulose film provided with an undercoat layer on a support with an emulsion layer as shown below. The amount of each substance applied was expressed numerically in the box as g/m ² or mol/m ² . (Sample 101) (1) Emulsion layer negative silver iodobromide emulsion (grain size 1.8μ)
(Silver 1.6×10 ^-2 mol/m ² ) Magenta coupler C-1
(1.33×10 ^-3 mol/m ² ) Gelatin (2.50 g/m ² ) (2) Protective layer gelatin (1.30 g/m ² ) 2,4-dichloro-6-hydroxy-S-triazine sodium salt (50 mg/m 2 ) m ² ) (Samples 102 to 104) The FR compound of the present invention (I-
6) at 4×10 ^-6 mol/m ² , (I-7) at 1.33×
10 ^-5 mol/m ² and (I-13) 1.33×
Samples 102 and 10 ^-5 mol/m ² were added, respectively.
103 and 104. These samples were placed in aluminum cans under A condition (50℃, 40%), B condition (50℃, 50%), C condition (50℃, 60%) and D condition (5℃, 40%) for 3 days in the dark. After sealing, imagewise exposure for sensitometry was applied, followed by color development. Color development process Time Temperature 1 Color development 3′15″ 38℃ 2 Bleaching 6′30″ 〃 3 Water washing 2′ 〃 4 Fixing 4′ 〃 5 Water washing 4′ 〃 6 Stability 1′ 〃 Here The composition of each processing solution in the color development process is as follows. Color developer water 800ml 4-(N-ethyl-N-hydroxyethyl)amino-2-methianiline, sulfuric acid position 5g Sodium sulfite 5g Hydroxyalumine sulfate 2g Potassium carbonate 30g Potassium bicarbonate 1.2g Potassium bromide 1.2g Sodium chloride 0.2 g Trisodium nitrilotriacetate 1.2g Add water 1 (PH10.1) Bleach solution Water 800ml Ferric ammonium salt of ethylenediaminetetraacetic acid 100g Disodium ethylenediaminetetraacetic acid 10g Potassium bromide 150g Acetic acid 10g Add water 1 (PH6 .0) Fixing solution Water 800ml Ammonium thiosulfate 150g Sodium sulfite 10g Sodium hydrogen sulfite 2.5g Add water 1 (PH6.0) Stabilizer Water 800ml Formalin (37%) 5ml Dry well 3ml Add water and photo obtained in 1 Table 1 shows the gender.

[Table] Samples containing the FA compound of the present invention from Table 1
It can be seen that Samples Nos. 102 to 104 exhibit little desensitization and high sensitivity when stored in a sealed container under low-humidity conditions, but the sensitivity decreases significantly under high-humidity conditions. The magenta coupler C-1 used here is as follows. Example 2 In order to evaluate the effectiveness of the compound of the present invention, a multilayer color photosensitive material sample consisting of each layer having the composition shown below on a cellulose triacetate support was prepared.
Created 201. The amount of emulsion coated was expressed as the amount of silver coated. (Sample 201) 1st layer: Antihalation layer Gelatin layer containing black colloidal silver 0.189g/m ² Ultraviolet absorber U-1 0.12g/m ² Ultraviolet absorber U-2 0.17g/m ² 2nd layer: Intermediate layer 2 ,5-di-t-pentadecylhydroquinone
0.18g/m ² Coupler Cp-7 0.11g/m ² Silver iodobromide emulsion 0.15g/m ² (Silver iodide average grain size 1 mol% 0.07μ) Third layer: First red-sensitive emulsion Layer Silver iodobromide emulsion 0.72g/ ^m2 Silver iodide Average grain size 6mol% 0.6μ) Sensitizing dye...7.0×10 ^-5 mol per 1 mol of silver Sensitizing dye...2.0 per mol of silver ×10 ^-5 mol Sensitizing dye...2.8 x 10 ^-4 mol per mol of silver Sensitizing dye...2.0 x 10 ^-5 mol per mol of silver Coupler Cp-1 0.020g/m ² Coupler Cp-2 Gelatin layer containing 0.093 g/m ² coupler Cp-3 0.31 g/m ² coupler Cp-4 0.010 g/m ² 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion 1.6 g/m ² (iodide Silver Average particle size 8 mol% 1.5μ) Sensitizing dye...5.2 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...1.5 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...For 1 mol of silver Sensitizing dye: 1.5 x ^{10 -5} mol per mole of silver Coupler Cp-1 0.051g/m ² Coupler Cp-2 0.10g/m ² Coupler Cp-3 0.061g/m ² Coupler Cp-4 0.005 g/m ² Coupler Cp-5 0.0469 g/m ² Gelatin layer 5th layer: Third red-sensitive emulsion layer (Silver iodobromide emulsion Silver iodide 1.6 g/m ² 12 mol% ) Average particle size 2.2μ Sensitizing dye...5.5 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...1.6 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...2.2 x per 1 mol of silver 10 ^-5 mol Sensitizing dye...1.6 x 10 ^-5 mol per mol of silver Coupler Cp-3 0.05g/m ² Gelatin layer containing coupler Cp-5 0.45g/ ^m 6th layer: Intermediate layer Gelatin layer 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion 0.55 g/m ² (Silver iodide 5 mol%, average grain size 0.5 μ) Sensitizing dye...3.8 x 10 ^-4 mol increase per 1 mol of silver Sensitizing dye...3.0 x 10 ^-5 mol per mol of silver Sensitizing dye... 1.2 x 10 ^-4 mol per mol of silver Coupler Cp-6 0.29g/m ² coupler Cp-7 0.040g/m ² coupler Cp-8 0.055g/m ² Coupler Cp-9 0.058g/m ² 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion 1.5g/m ² (Silver iodide 6 mol% Average grain size 1.5μ) Sensitizing dye...2.7 x 10 ^-4 mol per mol of silver Sensitizing dye...2.1 x 10 ^-5 mol per mol of silver Sensitizing dye...8.5 x 10 ^-5 mol per mol of silver Coupler Cp -6 0.25 g/m ² coupler Cp-7 0.013 g/m ² coupler Cp-8 0.009/m ² coupler Cp-9 9th layer of gelatin layer containing 0.011 g/m ² : Third green-sensitive emulsion layer Iodobromide Silver emulsion 1.5g/m ² (silver iodide 12 mol% average grain size 2.2μ) Sensitizing dye...3.0 x 10 ^-4 mol per 1 mol of silver Sensitizing dye...2.4 x 10 ^- per 1 mol of silver ⁵ mol Sensitizing dye...9.5 x 10 ^-5 mol per mol of silver Coupler Cp-10 0.070g/m ² Coupler Cp-7 0.013g/m ² Gelatin layer containing tricresyl phosphate 0.40g/m ² 10th layer: Yellow filter layer Yellow colloidal silver 0.04g/m ² 2,5-di-t-pentadecylhydroquinone
Gelatin layer 11th layer containing 0.031g/ ^m2 : First blue-sensitive emulsion layer Silver iodobromide emulsion 0.32g/ ^m2 (silver iodide 6 mol% average grain size 0.4μ) Coupler Cp-11 0.77g/m ² Gelatin layer containing coupler Cp-12 0.030 g/m ² Tricresyl phosphate 0.52 g/m ² 12th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion 0.40 g/m ² (Silver iodide average grain Size 10 mol% 1.0 μ) Coupler Cp-11 0.25 g/m ² Tricresyl phosphate 0.17 g/m ² Sensitizing dye... 13th layer of gelatin layer containing 2.2 x 10 ^-4 mol per mol of silver: Fine grain emulsion layer: Gelatin layer containing silver iodobromide emulsion 0.25 g/m ² (silver iodide 2 mol%, average grain size 0.15 μ) 14th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion 1.00 g/m ² (Silver iodide average grain size 10 mol% 2.3 μ) Coupler Cp-11 0.22 g/m ² FA compound of the present invention (-9) 0.5 mg/m ² Tricresyl phosphate 0.14 g/m ² Sensitizing dye... 2.3×10 ^-4 mol per mole of silver 15th layer: 1st protective layer Gelatin layer containing UV absorber U-1 0.14 g/m ² Ultraviolet absorber U-2 0.22 g/m ² 16th layer: Second protective layer Polymethyl methacrylate particles (diameter 1.5 μ) 0.05 g/m ² Fluorine compound F-1 0.004 g/m ² Silver iodobromide emulsion 0.30 g/m ² (Silver iodide 2 mol% Average grain size In addition to the above composition, each layer contains a gelatin hardening agent H-
1 and a surfactant were applied. After coating and drying this sample, it was cut into pieces 3.5 cm wide and 124 cm long, the perforation was opened, and the film was packed into a 24-shot cartridge. These samples were heated to 20°C.
Relative humidity 40% (a), 45% (b), 50% (c) and 55% (d)
After leaving it overnight in a cool room, it was placed in a polypropylene cartridge case and sealed. Samples from some of the cartridges were taken out, and the relative humidity inside the cartridge case was measured at 25°C using an ACE recording hygrometer, and found to be 41%, 46%, 52%, and 57%, respectively. These samples were kept in the cartridge case at 50°C and 60°C for 3 days. Thereafter, these samples and sample 201 were subjected to the same color development process as in Example 1, in which a control sample was left overnight at 40° C. and 65% relative humidity and subjected to sensitometry-like exposure. The photographic properties obtained are shown in Table 2.

[Table] Table 2 shows that the fog of the blue-sensitive emulsion layer containing the FR compound of the present invention has a significantly greater humidity dependence than that of the green-sensitive emulsion layer and the red-sensitive emulsion layer to which no FR compound is added. It is clear that only under the low humidity conditions of the embodiments of the invention there is less fog increase during storage. Example 3 Polydisperse emulsion A and monodisperse emulsion B as follows:
adjusted. Preparation method for emulsion A: 80 g of an aqueous solution of 200 g of inert gelatin, 950 g of potassium bromide, and 97.5 g of potassium iodide.
The mixture was stirred at
A 10 mol % silver iodobromide emulsion was obtained. Dehydrochloric acid in the usual way, sodium thiosulfate 20mg, chloroauric acid 10mg
was added and aged at 57°C for 75 minutes for chemical sensitization. This emulsion had an average grain size (number average) of 1.5 μm, a grain size variation coefficient of 0.43, and a wide grain size distribution. Preparation of Emulsion B An octahedral monodispersed silver iodobromide emulsion (core emulsion) having an Agl content of 20 mol % and an average grain size of 1.6 μm was prepared by a controlled double jet method in the presence of ammonia. After washing the core emulsion with water, shelling was performed with pure silver bromide so that the amount of silver in the core part and the shell part were equal. After desalting in a conventional manner, 35 mg of sodium thiosulfate and 15 mg of chloroauric acid were added, and the mixture was aged at 55° C. for 60 minutes for chemical sensitization. The average grain size (number average) of this emulsion was 2.1 μm, the coefficient of variation was 0.13, and the grain size distribution was narrow. To measure the grain size of these emulsions, the area-equivalent diameter (ri) of the projected area of each emulsion grain was photographed using an electron microscope.
The Photographic Process” 3rd edition 2nd edition
Measurements were made based on the method described in Chapter 1, published by Macmillan (1966). Also, the coefficient of variation is S/
r, and S (standard deviation) and (average particle size) were determined using the following formula. S=√Σ(ri−r) ²・ni ² /Σni, = Σni・ri/Σni (Samples 301, 302) Silver iodobromide containing emulsions A and B in the 14th layer of sample 201 Samples 301 and 302 were prepared in the same manner as sample 201 except that . (Samples 303, 304) Contained in the 14th layer of samples 301 and 302
Samples 303 and 304 were prepared in the same manner except that the FR compound (-9) was removed. After sealing these samples under conditions A, C, and D of Example 1, imagewise exposure for sensitometry was performed, and the same color development process as in Example 1 was performed.
The concentration was measured using a blue filter. The photographic properties obtained are shown in Table 3.

[Table] Reciprocal of exposure amount.
From Table 3, embodiments of the present invention (Samples 301, 302
It can be seen that conditions A and D) have lower fog and higher sensitivity than conditions C, which are outside the scope of the present invention. It can also be seen that sample 302 using a monodisperse emulsion has lower fog and higher sensitivity than sample 301 using a polydisperse emulsion.

Claims (1)

[Claims] 1. A silver halide photographic material containing a compound that produces a fogging agent or its precursor in proportion to the amount of developed silver during development, and which is stored at a relative humidity of 55% or less.