JPH01186931A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve presersavable stability without impairing a hard contrast characteristic by incorporating a specific hydrazine deriv. into at least one layer of emulsion layers or other hydrophilic colloid layers and further incorporating hydroxamic acids therein. CONSTITUTION:The hydrazine deriv. expressed by formula I and the hydroxamic acids expressed by formula II are incorporated into at least one layer of the emulsion layers or the other hydrophilic colloid layers. In formula I, R1 denotes an aliphat. group or arom. group. In formula II, R2 denotes a hydrogen atom, alkyl group, aryl group, amino group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, sulfamoyl group, acyl group, carboxy group, etc.; X denotes a hydrogen atom, alkyl group, aryl group, acyl group, sulfonyl group; Y denotes a hydrogen atom or group which can become a hydrogen atom by hydrolysis reaction. The silver halide photographic sensitive material having the high contrast and the excellent preservable stability is thereby obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic material, particularly a light-sensitive material used in the field of photolithography, which can quickly produce ultra-high contrast images using a highly stable processing solution. This invention relates to a silver halide photographic light-sensitive material.

More specifically, the present invention relates to a silver halide photographic material with high contrast and excellent storage stability.

(Prior art) Silver halide photosensitive materials used in the photolithography process in the field of printing reproduction have a structure in which image areas and non-image areas are clearly defined in order to ensure good reproduction of character images, line images, and halftone dot images. Photosensitive materials and image forming systems are required to have photographic characteristics of ultra-high contrast (especially γ of 10 or more) with high image contrast and high blackening density.

For example, a so-called lithium-type silver halide material consisting of a silver chlorobromide emulsion with a silver chloride content of 50 mol% or more is used at a very low effective concentration of sulfite ions (usually 0.1 mol/l). There is a known method for obtaining images with high contrast and high blackening density by processing with a hydroquinone developer (hereinafter referred to as Lith developer).

However, with this method, the developer solution is extremely unstable to air oxidation due to the low sulfite concentration in the developer solution, and various efforts and efforts have been made to keep the developer activity stable. Ta.

Eliminates the instability of image formation in Lith development systems,
U.S. Pat. No. 4,166 discloses a method for obtaining high contrast photographic properties using a processing solution having good storage stability.
．． No. 742, No. 4,168°977, No. 4,221,
No. 857, No. 4,224.401, No. 4,243,7
No. 39, No. 4゜272.606, No. 4,311,78
The method described in No. 1 etc. was proposed and put into practical use. In this method, a silver halide photosensitive material containing a specific hydrazine derivative compound is prepared at a pH level containing a high concentration of sulfite preservative.
It is characterized by processing with a developing solution of 10.5 to 12.3.

With this new image forming system, there is no need to limit the silver chloride content of silver halide emulsions as in Lith development systems, and silver iodobromide emulsions, silver bromide emulsions, silver chlorobromide emulsions, and silver chloride emulsions can be used. Any emulsion can be used.

However, silver halide photographic materials that combine silver chloride emulsions or silver chlorobromide emulsions with hydrazine derivatives have poor stability during storage, and have the disadvantage that fog density increases, especially under low humidity storage conditions. had.

As a method for improving the drawback of increased fog density during storage of silver halide photographic materials, JP-A-52-11
092, No. 59-191031, a method of stabilizing the emulsion by incorporating compounds such as hydroquinone, resorcinol, and dihydroxybenzenes into the emulsion is known.

Furthermore, it is disclosed in US Pat. No. 4,385 that high-contrast silver halide photographic materials containing hydrazine derivatives can contain hydroquinone derivatives, azaindenes, azoles, etc. for various purposes.
No. 108, No. 4,332.878, No. 4.377.6
No. 34, No. 4゜618.574, No. 4,311.78
No. 1, No. 4.272,606, etc.

However, no effective means has yet been found for improving the increase in fog density during storage of silver halide photographic materials containing hydrazine derivatives, especially silver halide photographic materials mainly containing silver chloride emulsions. There wasn't.

(Problems to be Solved by the Present Invention) Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material in which a silver chloride emulsion or a silver chlorobromide emulsion is combined with a hydrazine derivative, without impairing high contrast. An object of the present invention is to provide a silver halide photographic material with improved stability.

(Structure of the Invention) The object of the present invention is to provide a silver chloride emulsion or a silver bromide content of 3.
In a silver halide photographic light-sensitive material having a silver halide emulsion layer consisting of a silver chlorobromide emulsion of 0 mol % or less, at least one layer of the emulsion layer or other hydrophilic colloid layer is represented by the following general formula (I). The inventors have found that this can be achieved by containing a hydrazine derivative such as

General formula (I) %formula% In the formula, R+ represents an aliphatic group or an aromatic group.

General formula (n) R2-C-N-0-Y In general formula (n), R2 is a hydrogen atom, an alkyl group, an aryl group, an amino group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group , represents an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group.

X represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a sulfonyl group. At this time, Rt and X may be connected to form a ring structure.

Y represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

The details of general formula (I) will be explained.

The aliphatic group represented by R in general formula (I) preferably has 1 to 30 carbon atoms, and is particularly preferably a linear branched or cyclic alkyl group having 4 to 20 carbon atoms.

The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

The aromatic group represented by R1 in the general formula ([) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with a monocyclic or bicyclic ring group to form a heteroaryl group. For example, a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, Examples include a pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms);
Aralkyl group (preferably the alkyl moiety has 1 to 1 carbon atoms)
3 monocyclic or bicyclic), alkoxy groups (preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms),
Examples include an acylamino group (preferably one having 2 to 30 carbon atoms) and a ureido group (preferably one having 1 to 30 carbon atoms).

The hydrazine derivative of general formula (I) used in the present invention has a pH of 10.5 to 12.3, contains a sulfite preservative of 0.15 mol/1 or more, and has good storage stability when processed with a developer. , is added for the purpose of obtaining ultra-high contrast photographic characteristics.

The amount of hydrazine derivative added is halogenated! Preferably it contains from 1 x 10-h mol to 5 x 10-'' mol per 11 mol, especially from 1 x 10''5 to 2 x 1 mol.
The preferred addition amount is in the 0-'' mole range.

Next, details of general formula (It) will be explained.

In general formula (n), R2 hydrogen development, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted amino group, substituted or unsubstituted heterocyclic group, if-substituted or unsubstituted It represents an alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. Substituents include halogen atoms, aryl groups, alkyl groups, alkoxy groups, aryloxy groups, hydroxy groups, sulfonyl groups, sulfonamide groups, sulfamoyl groups, sulfo groups, amide groups, ureido groups, cyano groups, carboxy groups, and nitro groups. , amine group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic group, and the like. Preferably R7 is a substituted or unsubstituted aryl group.

In general formula (II), X represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group, or a sulfonyl group.

At this time, R2 and X may be connected to form a ring structure,
The substituents are the same as those listed for R2. Preferably X is a hydrogen atom.

In general formula (II), Y represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

Specific examples when Y represents a group that can be converted into a hydrogen atom by hydrolysis include (method of protection with an I1-ester bond or urethane bond, (2) protection with an imidomethyl capping group described in JP-A-57-158638; There are various methods, etc. Preferably, X is a hydrogen atom.

The compound represented by compound (I) can be synthesized by the known method shown below.

Organic Functional Group
Preparations mP406-432 (Acades+ic Press) Synthetic Organic Chemi
stryP, 419,565,569,576.577
(John Wiley & 5ona, Inc.)
The amount of the compound of general formula (If) used in the present invention is 1X10-' to 5X10'' per 111 moles of halogenide.
A particularly preferable addition amount is in the range of 1.times.10@-" moles to 3.times.10@-" moles.

Specific examples of the compounds represented by the general formula (■) and the general formula (■) are shown below, but the present invention is not limited to the following compounds.

C Tomi Hs ■-10 C Tomi H5 ■-12 ■-13 ■-15 ■-16 ■-19 ■-22 ■-23 ■-24 ■-25 ■-28 ■-29 ■-30 t-1 C) 13-C-NH-OH ncz H? -CNHOH I-3 HO! CCHx CHx -CNHOHCjICHt
CHz-C-NHOH ■-8 n-t.

■-11 ■-12 ■-13 II-16 ■-17 ■-18 II-19
n-20f-21 CHx ■-22 ■-23 The silver halide in the silver halide photographic light-sensitive material used in the present invention is mainly silver chloride, and the silver halide emulsion or silver bromide content is is a silver chlorobromide emulsion in which the amount of silver is 30 mol % or less. Particularly preferred are silver chlorobromide emulsions having a silver bromide content of 10 mol % or less, or pure silver chloride emulsions.

The average grain size of the silver halide used in the present invention is 0
．． It is preferably 5 μm or less, particularly preferably 0
．． It is in the range of 0.05 μm to 0.4 μm. Average grain size is a commonly used and easily understood term in the field of silver halide photographic science. For more information on how to determine average grain size (Mies, James, The Theory of the Photographic Process C, E
, 5ees and 'l', )1. Written by James;
The theory of the Photography
phic ProcessJ)s 3rd edition~36~4
3 pages (I966, Macmillan Rancmillan J
Please refer to the company publication).

There are no particular restrictions on the shape of the silver halide grains, and they may be regular such as cubes or octahedrons, or mixed crystal shapes, but they must be monodisperse emulsions with a relatively narrow grain size distribution. The monodisperse emulsion referred to herein refers to an emulsion in which 90%, more preferably 95% of the total number of grains fall within a grain size range of ±40% of the average grain size.

The silver halide having the above average grain size and grain size distribution used in the present invention can be obtained by any known method, for example, U.S. Pat.
No. 7, No. 3. 317. No. 322, same No. 2.222
, No. 264, No. 3,320.069, No. 3.20
6,313, each specification is ``Journal of Photographic Science (J, Phot, S
ci, ) J Volume 12, No. 5 (September, October issue), 196
4, pp. 242-251. It is also possible to use a mixture of silver halides prepared by methods different from these methods.

In order to prepare the silver halide emulsion in the present invention, a method for reacting a soluble root salt with a soluble halide salt may be any one of the following methods, including one-sided mixing method, simultaneous mixing method, and back-mixing method in which silver ions are formed under excess silver ions. However, for the purpose of the present invention, a simultaneous mixing method in which a soluble silver salt and a soluble halogen salt are simultaneously added to form particles in an acidic solution is particularly preferred. For more information, please refer to Re5earch Discl.
osure 176 @Item 17643, Section 1, Section 2 (I978, 12).

The silver halide emulsion used in the present invention can contain a water-soluble rhodium salt or a water-soluble iridium salt. A well-known method for incorporating these metal salts is to add them during the preparation of the emulsion, particularly preferably during the formation of silver halide grains.

Examples of water-soluble rhodium salts include rhodium dichloride, rhodium trichloride, potassium rhodium chloride (I[[), ammonium rhodium hexachloride (I[)), and the like.

As a water-soluble iridium salt, iridium hexachloride (Il
l) Potassium chloride, potassium chloride iridate (TV), ammonium chloride iridate (III), and the like.

The amount of the water-soluble rhodium salt and water-soluble iridium salt added is preferably in the range of 1X10-' to 1x10-3 mol per mol of silver halide.

The silver halide emulsion used in the present invention may or may not be chemically sensitized.

In the case of silver halide emulsions used in reversible photographic materials intended to be handled in bright working environments, emulsions that have not been chemically sensitized are preferably used. It is also used for line drawings and halftone images. j
In the case of silver halide emulsions used for m-sensitive materials, emulsions that have not been chemically sensitized may be used, and sulfur sensitizers, selenium sensitizers, reduction sensitizers, gold sensitizers, etc. An emulsion chemically sensitized using .

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

That is, azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted-
1,3,3a,7-tetraazaindene, pentaazaindene, etc.; Azoles such as nitroimidazole, nitrobenzimidazole, chlorobenzimidazole, mercaptothiazole, mercaptobenzothiazole, mercaptobenzimidazole Classes, mercaptothiadiazoles, aminotriazoles, benzotriazoles! ll (especially 5-bromobenztriazole, 4-methylbenztriazole), nitrobenztriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), pyrimidines, triazines, mercaptopyrimidines,
Stabilizers such as mercaptotriazines, thioketo compounds, gallic acid esters, benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfinamides, phosphonimes, oximes, aldoximes, etc.
Compounds known as antifoggants can be included.

The photographic light-sensitive material of the present invention comprises a silver halide emulsion layer and/or
Alternatively, various surfactants may be added to other hydrophilic colloid layers for the purposes of coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (e.g., accelerating development, increasing contrast, sensitization, etc.). It can be included. Surfactants include nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, and fluorine-containing surfactants, which can be used alone or in combination depending on the purpose. .

Gelatin is primarily used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids may also be used, for example in U.S. Pat. No. 3,341,332.
Water-soluble polymers and gelatin derivatives described in British Patent No. 523.661, U.S. Patent No. 2.548, etc.
, 520, 2.831.767, etc. Polymers obtained by graft polymerizing gelatin with polymerizable monomers having an ethylene group such as styrene acrylate and acrylic ester, and cellulose derivatives (hydroxyethyl cellulose). , carboxymethyl cellulose, cellulose sulfate, etc.), synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyacrylic acid, and polyacrylamide, and proteins such as albumin and casein.

In the photographic light-sensitive material of the present invention, an inorganic or organic hardening agent can be contained in the silver halide emulsion layer and other hydrophilic colloid layers.

For example, chromium salts (such as chromium alum) aldehyde M
(formaldehyde, geltaraldehyde, etc.), active vinyl compounds (I,3,5-)lyacryloyl-hexahydro-3-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halides (2, 4
-dichloro-6-hydroxy-3-triazine, etc.),
Mucohalogenic acid! lI (mucochloric acid, etc.), N-carbamoylpyridinium salts ((I-morpholinocarbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (I-(I-chloro-1-pyridinomethylene)pyrrolidium-2-naphthalene) sulfonates, etc.) can be used alone or in combination. Among them, JP-A No. 53-41゜221, No. 53-57, 25
7, 59-162°546, 60-80846 and U.S. Pat. No. 3,325,28
The active halides described in No. 7 are preferably used.

The photographic light-sensitive material of the present invention comprises a silver halide emulsion layer and/or
Alternatively, other hydrophilic colloid layers may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester,
Polymers containing as monomer components acrylonitrile, olefin, styrene, etc. alone or in combination, or combinations thereof with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, etc. can be used.

Acetic acid, citric acid, salicylic acid, ascorbic acid, polyacrylic acid, a copolymer of acrylic acid and divinylbenzene, etc. can also be used as the membrane surface pH adjusting agent.

The silver halide emulsion layer and hydrophilic colloid layer according to the present invention can contain photographic additives such as matting agents, plasticizers, thickeners, optical brighteners, and ultraviolet absorbers. For information on these additives, please refer to Re5earch D
isclosure Volume 176 Item 1764
3 p, 23-p, 28 (I978, 12).

Examples of the support used in the photosensitive material of the present invention include transparent or opaque synthetic resin films such as polyethylene terephthalate, polycarbonate, polystyrene, and polypropylene, and paper supports coated with polyethylene resin.

In the processing of the silver halide photographic light-sensitive material of the present invention, black and white processing solutions used in the photolithography industry can be used, but dihydroxybenzenes and 1-phenyl-3-pyrazolidone are particularly preferably used as developing chemicals. or a combination of dihydroxybenzenes and p
-PH using a combination of aminophenols and containing 0.15 mol/1 or more of sulfite ions as a preservative
A developer solution of 10.5 to 12.3 is used.

When the silver halide photographic material of the present invention is processed with this developer, a negative image having sufficient ultra-high contrast characteristics can be obtained.

Dihydroxybenzenes used as developing agents in the above processing include hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone,
．． Examples include 3-dichlorohydroquinone, 2.5-dichlorohydroquinone, and 2.5-dimethylhydroquinone, with hydroquinone being particularly preferred.

Further, as developing agents for l-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, 1-phenyl-4゜4-dihydroxymethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-
Examples include 3-pyrazolidone.

In addition, p-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, N
-(β-hydroxyethyl)-p-aminophenol,
Examples include 2-methyl-p-aminophenol and p-benzylaminophenol.

The developing agent is preferably used in an amount of usually 0.05 mol/1 to 0.8 mol/l.

In addition, when dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols are used in combination, the former is used in a range of 0.05 mol/l to 0.5 mol/l.
2. Preferably, the latter is used in an amount of 0.06 mol/l or less.

A compound that provides free sulfite ions as a preservative is added to the developer, such as sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is 0.15 mol/1 or more, especially 0.3
It is preferably mol/17 or more. Also, the upper limit is 2.5 mol/l
It is preferable to set it up to.

To set the developer pf (sodium hydroxide,
Alkaline agents such as potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate, pH adjusters, and buffers are used.

In addition to the above components, additives added to the developer include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide, and mercapto compounds (for example, 1-phenyl-
5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc.), imidazole compounds (5-nitroimidazole, 5-nitrobenzimidazole, etc.), triazole compounds (
(5-methylbenzotriazole, etc.), antifogging agents, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, ethanol, methanol, surfactants, chelating agents, water softeners. Examples of the additives include sulfuric acid, a development accelerator, an antifoaming agent, a color toning agent, a hardening agent, a silver stain preventive agent (for example, 2-mercaptobenzimidazole sulfonic acids), and an amine compound described in JP-A-56-106244.

When the silver halide photographic material according to the present invention is developed with the developer described above, the development temperature is usually selected between 18°C and 50°C, preferably between 20°C and 40°C. Further, the development time is preferably 5 seconds to 200 seconds.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may also contain aluminum hydroxide or the like as a hardening agent.

When processing the photographic material according to the present invention using an automatic developing machine that continuously performs development, fixing, washing, and drying, favorable results with uniform finishing quality can be obtained.

When using an automatic developing machine, the developing time is 10 seconds to 100
Rapid processing of seconds is preferably used.

(Example) The present invention will be explained in more detail with reference to Examples below.

Example 1 A silver nitrate aqueous solution and a sodium chloride aqueous solution containing ammonium rhodium(III) hexachloride were mixed by a double-jet method to prepare a silver chloride emulsion containing rhodium equivalent to 5×10 −' moles per mole of silver.

The resulting emulsion was a cubic emulsion with an average grain size of 0.18 microns. 4-Hydroxy-6-methyl-1,3,3a,? as a stabilizer without chemical ripening after particle formation.
- 2X10-'' moles of tetrazaindene per mole of silver, 11 moles of 1-phenyl-5-mercaptotetrazole
5×10 −4 mol was added per mol.

The emulsion was divided into 14 parts, hydrazine derivative compounds (I)-5, (I)-13, and hydroxamic acid compound (II)-7 were added as shown in Table 1, and a polymer latex was prepared using US Pat. No. 3,525. A polyethylene terephthalate film-based support was prepared by adding the latex described in Production Recipe 3 of No. 620 in an amount equivalent to 20 g per mole of silver, and adding 1,3-divinylsulfonyl-2-propanol as a hardening agent. (thickness: 100 microns) so that the amount of silver per tr was 2.8 g. Furthermore, a protective layer consisting of 1.2 g of lime-treated gelatin per 1 d was applied as a protective layer on top of the sample number (I).
) ~ (Foundation) created photosensitive materials.

The prepared samples (I) to (Foundation) were conditioned at 25°C relative humidity of 40% for 3 hours, then airtightly packaged and kept in a constant temperature room at 25°C for 20 hours.
Storage for 20 days (A condition) and 20 days in a constant temperature room at 50°C.
It was stored for days (set as B condition).

After storage, each sample was transferred to P-61TDQ manufactured by Dainippon Screen Co., Ltd.
It was exposed to light through an optical wedge using a type printer (light s1o ov, tKw quartz halogen lamp), and developed for 20 seconds at 38°C using a developing solution (I) with the following composition using an automatic developer aFG-660F manufactured by Fuji Photo Film Co., Ltd. I did it.

The results obtained are shown in Table 1.

Relative sensitivity is expressed as a relative value of the reciprocal of the exposure amount that gives a density of 3.0, and contrast (γ) is expressed as an average gradation level from density 0.3 to 3.0. Also, the fog density is 4 in the unexposed area.
The density is shown in stacked sheets (including support).

Sample (21+51+7) 01 according to the present invention showed almost no increase in fog density under storage conditions (A) and CB under storage conditions (changes in photographic performance were also small) compared to comparative examples.
It can be seen that it has good storage stability.

Developer prescription (I) Hydroquinone 45.0g N-methyl-p-aminophene 0.8g Norl 1/2 sulfate Sodium hydroxide 18.0g Potassium hydroxide 55.0g 5-sulfosalicylic acid 45.0g Boric acid
25.0g potassium sulfite
110.0g Ethylenediaminetetraacetic acid 1
．． 0g thorium potassium bromide 6.0g 5-methylbenzotriazole 0.6gn-butyljetanolamine 15.0g Add water
11 (pH-11,6) Example 2 Samples 1 to 14 of Example-1 were processed using a developer having the following composition, and the same results as Example-1 were obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer consisting of a silver chloride emulsion or a silver chlorobromide emulsion having a silver bromide content of 30 mol% or less, A silver halide photograph characterized in that at least one emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative represented by the following general formula (I) and a hydroxamic acid represented by the following general formula (II). photosensitive material. General formula (I) R_1-NHNHCHO In the formula, R_1 represents an aliphatic group or an aromatic group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula (II), R_2 is a hydrogen atom, an alkyl group,
Aryl group, amino group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, sulfamoyl group,
Represents an acyl group, carboxy group, hydroxyamino group, or hydroxyaminocarbonyl group. X represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a sulfonyl group. At this time, R_2 and X may be connected to form a ring structure. Y represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.