JPH01220973A - Picture forming method with high contrast - Google Patents

Abstract

PURPOSE:To form a silver picture with excellent dot quality by specifying the relation of potassium ion concentration and the potassium ion concentration shared in all cations. CONSTITUTION:A silver halide photographic material containing hydrazide compound is processed by a development liquid whose sulfite ion concentration is 0.20g ion/l or over, whose potassium ion is >=80g ion% of all cations and whose pH is 10-13. The hydrazide compound contained in the photosensitive material is the compound expressed is formulae I-III, where R1, R2 are allyl group, R is an organic bonding group, (n) is 0-6, (m) is 0 or 1, R21 is an aliphatic group, R22 is a hydrogen atom, P1, P2 are hydrogen atom, Ar is anti-diffusion group, and R31 is substituted alkyl group. Thus, the dot picture with excellent picture is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an image forming method, and particularly to a silver image forming method that stably provides a high contrast photographic image.

[Conventional technology]

In general, high-contrast photographic images are used in the photolithography process to form characters and halftone-resolved photographic images, and in the ultra-precision photolithography process to form fine line images. It is known that silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

Conventionally, for example, a photosensitive material consisting of a silver chlorobromide emulsion with an average grain size of 0.2 μm, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol %) has been processed using sulfite ions. A method of obtaining an image with high contrast, high sharpness, and high resolution, such as a halftone dot image or a fine line image, is carried out by processing with an alkaline hydroquinone developer having a low concentration.

This type of silver halide photosensitive material is known as a lithium-type photosensitive material.

The photolithography process involves converting a continuous-tone original into a halftone image, that is, converting the continuous-tone density changes of the original into a set of halftone dots with an area proportional to the density. There is.

For this purpose, a dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing an original through an intersection line screen or a contact screen, followed by development processing.

For this purpose, a silver halide photographic material containing a silver halide emulsion with fine grains and a uniform grain size and shape is used, but even when this type of silver halide photographic material is used, When processed with a general black and white developer, the quality of halftone dots, etc. is inferior to when a Lith type developer is used. Therefore, the sulfite ion concentration is extremely low.
It is processed with a developer called a developer using Lis, which is a single drug called hydroquinone, as a developing agent. However, Lith-type developer is susceptible to auto-oxidation and has extremely poor storage stability.Therefore, there is a strong need for a control method to maintain constant development quality even during continuous use. Significant efforts have been made to improve the.

As a method to improve this, in order to maintain the stability of the above-mentioned Lith-type developer, there is a replenisher (processing fatigue replenisher) that compensates for the deterioration in activity due to development processing, and a replenisher (processing fatigue replenisher) that compensates for the oxidative deterioration over time. A so-called two-liquid separation replenishment system, in which the replenisher (replenishment due to fatigue over time) and the replenisher (replenishment due to aging) are replenished using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like. However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

On the other hand, a method is known in which a high contrast image is obtained by processing with a developer having a high sulfite ion concentration.

The above method involves incorporating a hydrazine compound into a silver halide photographic light-sensitive material.

According to this method, it is possible to maintain a high concentration of sulfite ions in the developer, and it is possible to stably process with improved preservation.

However, the developer used for silver halide photographic light-sensitive materials containing hydrazine compounds requires a relatively high pH value in order to obtain good halftone dot quality, which tends to cause fog. In order to suppress fogging, the silver halide emulsion contains a fog suppressor, stabilizer, etc., so that the halftone dots are particularly defective (halftone dots near where the halftone dot area is 95%).
The condition of fringe, alignment, and blanking became poor, leading to a decline in the quality of halftone dots.

[Purpose of the invention]

An object of the present invention is to provide a method for forming a silver image with low fog and excellent halftone dot quality by developing with a developer having good stability.
An object of the present invention is to provide a method for forming a silver image with low fog and excellent halftone dot quality using a developer having good stability using a silver halide photographic light-sensitive material containing a metal.

[Structure of the invention]

In view of the above-mentioned technical issues, the present inventors have conducted intensive studies on developer formulations, and have found that in developer formulations containing high concentrations of sulfite ions, the relationship between the potassium ion concentration and the potassium ion concentration in the total cations is The present invention was achieved by discovering an optimal range in which the halftone dot quality is extremely high.

An object of the present invention is to produce a silver halide photographic light-sensitive material containing a hydrazide compound with a sulfite ion concentration of 0.20 gram ions/12 or more and a potassium ion content of 8 of the total cations.
This is achieved by an image forming method in which processing is performed with a developer containing 0 gram ion % or more and having a pH of 10 to 13.

Note that the above cations refer to sodium ions, potassium ions, and lithium ions. (However, it is not necessary to contain all three types of ions.) The hydrazide compound contained in the silver halide photographic light-sensitive material (hereinafter referred to as light-sensitive material) used in the present invention has the following general formula [1], [ 2] and [3].

General formula (1) In the formula, RI and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is 0 to 6, and m is 0.
or represents l.

Here, examples of the aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc., but preferred as R1 and R2. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy, etc.), acylamino groups (e.g. acetylamino, pivallylamino, benzoylamino, tetradecanoylamino, a-C
(2,4-di-t-amylphenoxy)butyrylamino, etc.), sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (
(e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy groups, amino groups, alkylamino groups (e.g., methylamino, dimethylamino, etc.), carboxy groups, alkoxycarbonyl groups (e.g. , ethoxycarbonyl), carbamoyl group, sulfo group, etc. Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene groups (e.g.,
phenylene, naphthylene, etc.), aralkylene groups, etc., but alkylene groups include oxy groups, thio groups,
(representing a seleno group, a carbonialyl group), a sulfonyl group, etc. Various substituents can be introduced into the group represented by R.

Examples of the substituent include -C0NHNHR4 (R4 has the same meaning as R and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

Of the compounds represented by the general formula CI), preferably R3
and R2 is a substituted or unsubstituted phenyl group, and n=
A compound in which m=1 and R represents an alkylene group.

The following margin/〈Knee' Specific compound l -34 tC@H++ tcs11+ + Next, general formula [2] will be explained. The aliphatic group represented by R2+ preferably has 0 carbon atoms.
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 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 alkoxo group, or a sulfoxy group.

The aromatic group represented by R21 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a virolazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R21 is an aryl group.

The aryl group or I; of RZ+ may be substituted, and typical substituents include linear, branched, or cyclic alkyl groups (preferably those in which the alkyl moiety has 1 to 20 carbon atoms). monocyclic or bicyclic), alkoxy groups (preferably those having 1 to 20 carbon atoms), rIt-substituted aniamino groups or amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups ( Preferably 2 or more carbon atoms
30), a sulfonamide group (preferably having 1 to 30 carbon atoms), and a ureido group (preferably having 1 to 30 carbon atoms).

Among the groups represented by R22 in general formula [2], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R22 in general formula [21, the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, a cyano Among the groups represented by R22, preferred are an optionally substituted alkoxy group or an amino group.

A2 may be a cyclic structure containing an optionally substituted alkyl group, alkoxy group, or 10-1-S-1-N- group bond. However, R82 is never a hydrazino group.

R21 or R2□ in general formula [1] may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a fninoxy group,
It can be selected from alkylphenoxy groups, etc.

R2I or R2H in general formula [2] may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
Examples include groups described in US Pat. No. 4,355,105, such as a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. Among the compounds represented by the general formula [2], the compounds represented by the following general formula [2-al] are particularly preferred.

General formula [2-al In the above general formula [2-al, Ras and R2, are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, a-hydroxynaphthyl group, Cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-
2-pyrrolidyl group), R□ represents a hydrogen atom or an optionally substituted benzyl group, alkoxy group and alkyl group (e.g. benzyl group, p-methylbenzyl group, methoxy group, ethoxy group, ethyl group,
butyl group), and Ro and R27 represent a divalent aromatic group (
For example, phenylene group or I; represents naphthylene group), Y
represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -502CtlICI1.Nll-SO, Nl
R2a represents -NR'R" or -0R2, R',
R and R29 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), phenyl groups (e.g. phenyl group, p-methylphenyl group, p-
methoxyphenyl group) or a naphthyl group (for example, α-naphthyl group, β-7thyl group), and fil and n represent O or l. When R26 represents OR, , Y preferably represents a sulfur atom.

Representative ゝ, □-1+ Specific example of general formula [2] IllI0CF represented by the above general formula [2] and [2-al.

■ *-NHNHCCOCH, CI! So! CH
! CH! Oi1*-NHNHCCOCHzCH
zSCHiCHzOHCH.

II.

Heso* -N)INHccN)Ic, □11□Next, a method for synthesizing the compound 2-45°2-47 will be shown as an example from among the above-mentioned specific compounds.

Synthesis of compound 2-45 Synthesis scheme (A) (B) Compound 4-nitrophenylhydrazine 153g and 500g
Mix mQ of diethyl oxalate and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50 of the obtained crystals (A)
9 was heated and dissolved in 1000 mff of methanol, and pd/
Reduction is carried out under a C (palladium/carbon) catalyst in a H2 atmosphere pressurized at 50 Psi to obtain compound (B).

22 g of this compound (B) was dissolved in a solution of 200 mQ of acetonitrile and 169 pyridine, and the compound (C) 24 was dissolved at room temperature.
g of acetonitrile solution was added dropwise. After filtering out insoluble matter,
The filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

Compound (D) 309 was hydrogenated in the same manner as above to obtain Compound (E) 209.

Compound (E) 109 was dissolved in 100+nQ of acetonitrile, 3.09% of ethyl inthiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound CF)7 was purified by crystallization.
．． Obtained 0g. Compound (F) 5.09 methanol 5
Methylamine (40% aqueous solution 8ra
Q) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme CB) 1'lA (C) (D) (E) Compound 2-47 Compound (B) 229 was dissolved in 200 mL of pyridine, and 22 g of p-nitrobenzenesulfonyl chloride was added to a stirring vessel. added. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). This compound (C) was subjected to the same reaction as compound 2-45 according to the synthesis scheme to obtain compound 2-47.

Next, general formula [3] will be explained.

General formula [3].

Ar NIINH C Rs+ In the general formula [31, A" represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done.

Examples of silver halide adsorption promoting groups include a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group, as disclosed in US Pat. No. 4.

Examples include the groups described in No. 385, No. 108.

R31 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (for example, methoxy, ethoxy, etc.), aryloxy (for example, phenoxy, p-chlorophenoxy, etc.), peterocyclic oxy (for example, pyridyloxy, etc.), mercapto, alkylthio (methylthio, etc.). , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl ( For example, benzenesulfonyl, etc.), peterocyclic sulfonyl (for example, pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (for example, acetyl, benzoyl, etc.), cyano, chlor, bromine, alkoxycarbonyl (for example, ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl ( (e.g., phenoxycarbonyl), carboxy, carbamoyl, alkylcarbamoyl (e.g., N-methylcarbamoyl, N,N-
dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-phenylcarbamoyl, etc.), amino, alkylamino (e.g., methylamine, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino,
naphthylamino, etc.), acylamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy), ), alkylaminocarbonyloxyaminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g., phenylami7carponyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), arylsulfamoyl (For example, phenylsulfamoyl, etc.).

The hydrogen pi molecule of hydrazine is a sulfonyl group (e.g., methanesulfonyl syl group (e.g., acetyl, trifluoroacetyl, etc.))
, oxalyl group (eg, ethoxalyl, etc.)).

Representative compounds represented by the above general formula [3] include:
There are the following.

-I6 υ Shirishi t3 *-Nl! N1(CCH20CII2CH□0C11□
CH□011 Next, a synthesis example of compound 3-5 will be described.

Synthesis of compound 3-5 Synthesis scheme Compound 3-5 was obtained according to the synthesis method of compound a 2-45.
child .

General formula [
The amount of the compounds 1], [2], and [3] is from 5 x 10-7 to 5 x 10-' mol per mol of silver halide contained in the silver halide photographic material of the present invention. is preferred, and more preferably in the range of 5 x 10-' to I x 10-'' moles.

The hydrazide compound used in the present invention can be contained in the silver halide emulsion layer, the layer adjacent to the emulsion layer, and any other layer coated on the emulsion layer side of the support, but preferably It may be contained in a coating layer provided on the emulsion layer side of the support and diffused into the silver halide emulsion layer. The effect of a hydrazide compound having an adsorption group can be increased by adding a smaller amount than a hydrazide compound having no adsorption group.

The amount of the hydrazide compound used in the photosensitive material of the present invention is suitably in the range of 10-6 to 1O-1 mol per mol of silver halide, preferably 10-1 mol per mol of silver halide.
-4 to 1 O-2 moles. The appropriate amount can be arbitrarily determined by considering the composition of silver halide, particle size, chemical ripeness, amount of hydrophilic colloid as a binder, and balance with additives such as stabilizers, suppressors, and accelerators. .

The silver halide emulsion of the light-sensitive material used in the present invention includes:
Various silver halides can be used. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. In particular, the effect of the present invention on silver bromide and silver iodobromide is remarkable, and the silver iodobromide type (A9I
(5 mol% or less) is particularly effective for high-sensitivity silver halide photographic materials.

The silver halide emulsion of the light-sensitive material used in the method of the present invention may be prepared by a silver halide emulsion suspended in a hydrophilic colloid by a known method, such as a neutral method, a single jet method using an ammonia method, etc. Emulsion preparation methods such as , double jet method, etc. are used.

The silver halide contained in the silver halide emulsion layer of the light-sensitive material used in the present invention preferably has an average grain size of 0.1 to 1.0 μm, particularly preferably 0.1 to 0.7 μm.
It is preferred that at least 75%, particularly preferably 80% or more of the total number of grains contain silver halide having a grain size in μm and from 0.7 to 1.3 times the average grain size.

Furthermore, polyvalent metal ions (e.g. iridium, rhodium, etc.)
However, silver halide emulsions in which 10-'-10-' moles are occluded per mole of silver halide can also be used. The silver halide emulsion is preferably of the surface latent image type, and can be sensitized by conventional chemical sensitization using a gold compound such as a sulfur compound, chloroauric acid salt, gold trichloride, or the like.

Further, an iridium salt or a rhodium salt may be present during chemical sensitization.

The silver halide emulsion of the light-sensitive material used in the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Sensitizing dyes include cyanine, hemicyanine,
Commonly used methine dyes and styryl dyes such as logocyanine, merocyanine, oxanol, and hemioxanol can be used.

The above dye is disclosed in U.S. Pat. No. 2,742.833 and U.S. Pat.
56.148, 3,567.458, 3,61
5.519, 3,632゜340, 3,155
．． 519, 3,384.485, 4,232°115, 3,796.580, 4,028.1
No. 10, No. 3,752゜673, JP-A-55-450
The description in No. 15 etc. can be referred to.

A polymer latex consisting of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is applied to the silver halide emulsion layer and other layers coated on the support to improve the dimensional stability of photographic materials. , may be included for the purpose of improving the physical properties of the film.

4-Hydroxy-6-methyl-1,3,3a, 7-titrazaindene, l-phenyl-5-mercaptotetrazole, hydroquinone, resorcinol oxime, hydroquinone aldoxime, etc. are used as stabilizers or anti-capri agents in silver halide emulsions. Many compounds can be added in amounts of 10-4 to 10-' moles per mole of silver halide.

The silver halide emulsion of the light-sensitive material used in the present invention has a hardening agent usually used in its coating solution, such as aldehydes (formaldehydes, glyoxals, glutaraldehydes, mucochloric acid, etc.), N-methylol compounds (dimethylol urea, etc.). , methyloldimethylhydantoin derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1.3.5-1-lyacroyl-hexahydro/S-triazine, bis(vinylsulfonyl)
Methyl ether, etc.), active halides (2,4-cyclo-6-hydroxy-S-) riazine, etc.) can be used alone or in combination, and they are also commonly used as thickeners, matting agents, coating aids, etc. You can use whatever is used.

Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Furthermore, in the present invention, substances commonly used as couplers, ultraviolet absorbers, optical brighteners, image stabilizers, antioxidants, lubricants, metal ion sequestrants, emulsifying dispersants, etc. may be added to photosensitive materials depending on the purpose. It can be included.

The light-sensitive material used in the present invention has layers other than the silver halide emulsion layer, such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a subbing layer, an auxiliary layer, an irradiation prevention layer, and a backing layer. The support to be used may be appropriately selected from baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. depending on the intended use of the photosensitive material. - As the developing agent of the developer used in the present invention, HO-
(CH-CH)n-OH type developer, t(O-(C)I-
CI()n-NHz type developer, H,N-CC-C)n-
Nl(, mold developer, etc. are included.

As the lo-(CH=CH)n-OH type developer, a compound represented by the following general formula [4] is useful.

General formula [4] In the formula, R41+ R42 and R43 are each a hydrogen atom,
Halogen atoms (e.g. Cff, Br), substituted or unsubstituted alkyl groups (e.g. methyl, ethyl, phenethyl, etc.), substituted or unsubstituted aryl groups (e.g. phenyl), substituted or unsubstituted heterocyclic groups, ORaa
or -5Raa, and R44 represents a substituted or unsubstituted alkyl group (eg, methyl, ethyl), a substituted or unsubstituted aryl group (eg, phenyl), or a substituted or unsubstituted heterocyclic group. DI represents O or l, and when n+-0 represents a hydrogen atom.

A typical example of this type of developer is hydroquinone.

Typical HO-(CH=0H)n-NHz type developers are ortho- and para-aminophenols or aminopyrazolones, such as 4-aminophenol, 2-aminophenol,
Amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2,4・Cyamylsorcinol, 2.4.6・Triaminophenol, N
Examples include -methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol.

In the case of binding with a hetero developer, a compound represented by the following general formula [5] is useful in the present invention.

General formula [5] In the above formula, R51 represents a phenyl group or a phenyl group substituted with a group such as a methyl group, a chloro group, an amino group, a methylamino group, an acetylamino group, or a methoxy group, and Rs, Rss and R□ each represent an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an alkyl group substituted with a substituent such as a hydroxy group, a carboxy group, or a sulfo group (e.g., methyl, ethyl, propyl, hydroxymethyl, etc.). represent.

Specifically, the following compounds may be mentioned.

l-Phenyl-3-pyrazolidone (phenidone) l-phenyl-4-amino-5-pyrazolone 1-(p-aminophenyl)-3-amino-pyrazolone l-phenyl-3
-Methyl-4-amino-5-virazolontophenyl-4
．． 4 ・Dimethyl-3-pyrazolidone (dimezone) l-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone (dimezone 5) 1-72-4,4-dihydroxymethyl-3-pyrazolidone -Phenyl-5-methyl-3-pyrazolidone 1-p-
Aminophenyl-4-methyl-4-propyl-3-pyrazolidone ip-chlorophenyl-4-methyl-4-ethyl-3-
Virazolidone 1-p・acetamidophenyl-4,4・diethyl-3
-Pyrazolidone 1-p-hetahydroxyethylphenyl-4,4-dimethyl-3-pyrazolidone 1-p-methoxyphenyl-4,4-diethyl-3-pyrazolidone 1-p-)dyl-4,4-dimethyl-3- Pyrazolidone etc.

Other books include T. H. James, The Theory Op.
The Photographic Process 4th Edition
ory of the Photographic P
rocess, Fourth Ed'1tion) 2nd
pp. 91-334 and Journal of the American Chemical Society.
American Chemical 5ociet
y) The developer described in Vol. 73, p. 3100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but a method of using two or more types in combination is preferred.

A preferred combination is hydroquinone and dimezone or hydroquinone and phenidone or hydroquinone and dimezone-5, where hydroquinone is 5 g
It is preferable to use phenidone, dimezone, or dimezone-5 in a range of 0.05 g to 5 g/12.

As a source of sulfite ions in the developer used in the present invention, sulfites such as sodium sulfite and potassium sulfite can be used.

Furthermore, hydroxylamine, hydrazine, and hydrazide compounds may be used as preservatives. As a source of potassium ions, potassium sulfite, potassium carbonate, potassium bromide, etc., which are commonly used in developing solutions for photosensitive materials, can be used. In addition, pH adjustment and buffering functions should be provided using caustic alkali, alkali carbonate, or amines used in general black and white developers, inorganic development inhibitors such as brompotali, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, natural saponins, surfactants such as sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, and glyoxal, sodium sulfate. It is optional to add ionic strength adjusting agents such as. p) (The value can be set arbitrarily from 10 to 13, but from the viewpoint of preservative and photographic performance, it is especially 1.
It is preferable to use it in the range of 1-12.

The developer used in the present invention preferably contains an alkanolamine, and examples of the alkanolamine include monoethanolamine, jetanolamine, and triethanolamine, with triethanolamine being preferred.

The preferred content of these alkanolamines is 2 to 500 g per developer lα, particularly preferably 5 to 100 g per developer IQ.

The developer used in the present invention preferably contains glycols, and examples of the glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, and 5-bentane. Examples include diol, 2-methoxyethanol, etc., and diethylene glycol is preferred. The preferred usage amount of these glycols is 10 to 500 g per developer IQ, particularly 20 to 500 g per developer IQ, especially 20 to 500 g per developer IQ.
-1009 is preferred.

The above alkanolamines and glycols may be used alone or in combination of two or more.

The developer used in the present invention may contain an organic fog inhibitor. Preferred organic fog inhibitors include the following formula ['61. Compounds represented by [71 or [8] are mentioned, and it is preferable to contain at least one of these compounds, and at least two or more of the above compounds may be used in combination.

General formula [6] In the formula, G represents a nitrogen atom or a methine group, H represents a nitrogen atom or a carbon atom, J represents a sulfur atom, an oxygen atom or an imino group, and F represents hydrogen when H is a carbon atom. Represents an atom or an alkyl group.

However, at least one of G and H is a nitrogen atom, and when G represents a methine group, J is an imino group.

n represents O or l; when H is a nitrogen atom, n is 0; when H is a carbon atom, n is l;

R1 represents a hydrogen atom, a halogen atom, a lower alkyl group having 3 or less carbon atoms, a lower alkoxy group having 3 or less carbon atoms, a hydroxy group, a carboxy group, a sulfonic acid group, or a nitro group.

General formula [71 In the formula, X is a hydrogen atom, a halogen atom, an alkyl group, a nitro group -COOM', -303M', -OH or -C
ONH, M/ represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms, n is 1 or 2, and W
'represents a sulfur atom, an oxygen atom, or an imino group, MI represents a hydrogen atom, an alkali metal atom, or an ammonium group, and R7, represents a hydrogen atom, a lower alkyl group having 3 or less carbon atoms, or a lower alkoxy group having 3 or less carbon atoms. group, hydroxy group, carboxy group, halogen atom or sulfonic acid group.

General formula [8] In the formula, M2 is a hydrogen atom, an alkali metal atom, or -NH4
represents a group, and X is 1000M", -So, M", -O
Represents a polygroup of H or -CONH2, M" is a hydrogen atom,
represents an alkali metal atom or -NH, group, R8 represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms, n
is 0.1 or 2.

Preferred examples of the compound represented by the above general formula [6] include the following.

(1) 5-nitroindazole (2) 6-nitroindazole (3) 5-methylbenzotriazole (4) 6-methylbenzotriazole (5) 5-nitrobenzimidazole (6) 6-nitropenzimidazole-11
Next, examples of preferable compounds represented by the general formula [7] are listed below.

(1) 2-mercaptobenzimidazole-5-sulfonic acid (2) 2-mercaptobenzimidazole (3) 2
-Mercapto-7-methylbenzimidazole-5-sulfonic acid (4) 2-mercapto-7-acetylbenzimidazole-5-sulfonic acid sodium salt (5) 2-mercapto-5-methylbenzimidazole (6) 2- Mercapto-5-nitropenzimidazole (7) 2-mercapto-6-acetylbenzimidazole-5-sulfonic acid ammonium salt (8) 2-mercapto-7-chlorobenzimidazole-5-sulfonic acid (9) 2-mercapto- Sodium 7-promobenzimidazole-5-sulfonate (10) 2-mercapto-5-sulfonic acid-7-carboxylic acid henzimidazole (11) 2-mercapto-7-hydroxybenzimidazole-5-sulfonic acid (12) 2.Mercapto-7-ethylbenzimidazole-5-sulfonic acid Specific examples of the compound represented by the general formula [8] are shown below.

(1) l-phenyl-5-mercaptotetrazole (2) l-(3-sulfonate-4-methyl)phenyl-5-mercaptotetrazole sodium (3)
1-(3-sulfonic acid-7-chloro)phenyl-5-mercaptotetrazole sodium salt (4) l(p-
Sulfonic acid) phenyl-5-mercaptotetrazole sodium salt (5) 1-(Tochloro4-sulfonic acid) phenyl-5-mercaptotetrazole sodium salt (6)
1-(3-sulfonic acid-4-methyl)phenyl-5-mercaptotetrazole potassium salt (7) 1-(p
-sulfonic acid) phenyl-5-mercaptotetrazole potassium salt (8) 1-(p-methoxy)phenyl 5-mercaptotetrazole (9) 1-(p-hydroxy)phenyl-5-mercaptotetrazole (10) 1-( p-hydroxyethoxy)phenyl-5-mercaptotetrazole (11) 1-(3,5-dicarbamyl)phenyl-
5-Mercaptotetrazole (12) l-(p-carbamyl)phenyl-5-mercaptotetrazole - The compound represented by the above formula [6] is used in an amount of 1 per 11 developer solutions.
0-' to lO-1 mole, more preferably lO-4 to IO
-2 mol, the compound represented by [7] or [8] above is 10-6 to 1 mol, more preferably 10
-' to lO-2 mol, and in total the preferred content of these development inhibitors is from 10-' to lO-2 per lO of developer solution.
-1 mol, especially 1O-4 to 1O- per Nl of developer solution.
2 mol is preferred. Further, it is preferable that the development inhibitor is dissolved in alkanolamine and/or glycol before being added to the developer.

Processing with a developer in the present invention can be carried out under various conditions, but the development temperature is preferably 50°C or lower, particularly around 40°C, and the development time is generally completed within 3 minutes. However, preferably within 2 minutes often brings about good results. Processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening, neutralization, etc. may optionally be employed, and these may be omitted as appropriate. Furthermore, these processes may be so-called manual development processes such as plate development and frame development,
Mechanical development such as roller development or hanger development may be used.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. The technical scope of the present invention is not limited in any way by the following examples, and various embodiments are possible.

In particular, embodiments of the present invention will be explained using a high-sensitivity silver halide photographic light-sensitive material, a so-called darkroom type silver halide photographic light-sensitive material, but the present invention is not limited thereto in any way.

Example 1 A silver iodobromide emulsion (2 mole % silver iodide per mole silver) was prepared using the simultaneous mixing method. The average grain size was 0.08 μm. The emulsion was washed with water and desalted in a conventional manner, and then sensitized with sulfur in the presence of an iridium salt and a rhodium salt of 2×10 −@mol/mole of silver. After sensitization, a stabilizer was added. 1 g of hydroquinone, 2 g of resorcinaldoxime and 4
-Hydroxy-6-methyl-1,3.3a,7-titrazaindene compound (1.5 g each per mole of silver) was added, and the above-mentioned 1-(hydroxyethoxyethyl)-3-(pyridine-2) was added as an ortho-sensitizing dye.・Iru)-5-
((3-sulfobutyl-5-chloropenzoxazolinylidene) ethylidene-2-thiohydantoin compound was added at 2.19% per mole of silver, and as fog suppressants adenine, 5-methylbenzotriazole, l-phenyl -5-mercaptotetrazole 2-mercaptobenzimidazole-phonic acid at 0.19 per mole of silver, respectively;
0.05g per mole of silver of polyethylene glycol with 30 ethylene oxide chains (one of the end groups is dodecylbenzene) was added as a development regulator, and sodium fluorinated dodecylbenzene sulfonate and sahonin were added as coating aids, and as a thickener. An emulsion was prepared by adding a styrene-maleic acid copolymer. This emulsion was divided into 10 parts, and hydrazide compounds shown in Table 2 were divided into 10 parts per mole of silver.
Each mole was added to prepare an emulsion coating solution.

Next, a coating solution for a protective film was prepared as follows. That is, 100% pure water in gelatin I Ky. 4 after swelling.
The gelatin was heated to 0°C, and 20 g of dodecylbenzenesulfonic acid as a spreading agent and 30 g of amorphous silica gel with an average particle size of 3 μm as a matting agent were dispersed in gelatin and finished to 20Q to prepare a coating solution for a protective film.

Preparation of silver halide photosensitive material The emulsion coating solution prepared above and coating for protective film are coated on a polyethylene terephthalate support with a thickness of 100 μm that has been subjected to subbing processing (see Example 1 of JP-A-59-19941). The liquids were combined and simultaneously coated in multiple layers so that the amount of silver was 1.8 g/m, the amount of gelatin applied in the emulsion layer was 1.g/I112, and the amount of gelatin applied in the protective layer was 0.8 g/m.
Photosensitive material sample No. 2 shown in FIG. l-No. I created lQ. During multilayer coating, formaldehyde, mucochloric acid, and three types of compounds with the following structure are added to the coating solution for the protective film. After stepwise exposure to light, the samples were developed using nine kinds of developer samples shown in Table 1.

The fixing solution used was a rapid fixing solution having the following composition. The development processing conditions were development at 40°C for 10 seconds and fixing at 35°C for 10 seconds.
washing with water at 30°C for 10 seconds and drying at 50°C for 10 seconds.

Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 240I! IQ Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid

6g Sodium citrate dihydrate 2g (
Composition) Pure water (ion exchange water) 17mQ
Sulfuric acid (50% W/V aqueous solution) 4.
7g aluminum sulfate (A12.0. converted content is 8.1% wiv) aqueous solution)
When using 26.5 g of fixer solution, it was dissolved in 500 mQ of water in the order of composition 1 above and finished to IQ. Below this certain margin, the halftone dot area of the sample processed above is 10%, 50%, 95%.
The quality of each halftone dot was visually observed using a 100x magnifying glass and evaluated on a five-point scale. Regarding the evaluation points, rlJ has the lowest quality, and the quality improves sequentially, with rank "5" indicating the best level. The measurement results are shown in Table-2.

Table 2 As is clear from Table 2), the S silver halide photographic light-sensitive material contains the hydrazide compounds represented by the general formulas [1], [2], and [3], and the potassium ion concentration of the developer and the sulfite It can be seen that favorable results are obtained when the ion concentration and pH are within the range of the present invention.

〔Effect of the invention〕

According to the present invention, a halftone dot image of excellent quality can be formed using a developer with good stability.

In addition, the occurrence of fog, which is a drawback when forming images using a silver halide photographic light-sensitive material containing hydrazine, and the fringing, uniformity, and missing halftone dots (particularly defects) are improved.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material containing at least one hydrazide compound represented by the following general formulas [1], [2], and [3] is prepared so that the sulfite ion concentration is 0.20 g ion. Image formation characterized by processing with a developer having a potassium ion concentration of 0.35 gram ions/l or more, a potassium ion concentration of 80 gram ions/l or more of the total cations, and a pH of 10 to 13. Method. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_1 is an aliphatic group, aromatic group, or heterocyclic group, and R_2_2 is a hydrogen atom, an optionally substituted alkoxy group, or a heterocyclic group. It represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.)