JPS6147954A - Image forming method - Google Patents

Abstract

PURPOSE:To form an image having less tendency to generate fog and a good dotted image quality by developing photosensitive material contg. a hydrazine compd. with a developer contg. an amino compd., a dihydroxy compd., a specific amount of a sulfurous acid ion and a specific amount of a carbonate. CONSTITUTION:The photosensitive material is prepared by compounding silver iodide and silver bromide etc., with the hydrazine compd. such as 1-formyl-2- {4-[2-(2,4-di-t-butylphenyoxy)butylamide]phenyl}hydrazine. The developer is prepared by mixing the developing agent of the dihydroxybenzene such as hydroquinone and an agent having an excellent additivity such as 1-phenyl 4,4-dimethyl- 3-pyrazolidone and >=0.3mol/l sulfurous acid ion and <=0.2-0.9mol/l carbonate. Since the photosensitive material is developed with the developer at >=10.8pH in the presence of the amino compd. such as dimethylaminopropane-1,2- diol, the image having high contrast and less tendency to generate fog is rapidly obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a T& tone silver image by processing a silver halide photographic light-sensitive material, and in particular to a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material) used in the field of graphic arts. The present invention relates to a high-contrast image forming method in which a rapid developing solution containing sulfite at a higher concentration than a so-called lithium developing solution is used.

(Prior art) Lith developer contains a dihydroxybenzene compound as a developing agent, and has a pli of 9 to 11, usually 9.5 to 10.5.
It is characterized by containing a low concentration of sulfite (usually 0.1 mol/l or less) and an adduct of formalin and bisulfite (sulfite ion buffing agent) as a preservative. be.

The method for forming such high-contrast photographic images and the developing solution are described in GNI, Journal of the Seven Ranklin Institute (J
, A., O., Yule, “ J. of
The Franklin Engineers, J) 239
Vol., p. 221 (1945). Incidentally, lithographic development is sometimes called contagious development because development occurs contagiously.

In the case of Lith development processing, high-contrast and high-quality halftone dots can be obtained, but as can be inferred from the above-mentioned characteristics of the Lith developer, there are problems in terms of air defeat, storage stability, and rapid processability. be. In this sense, stabilization and acceleration are old and new themes in the field of graphic arts.

Rapid processing means development time of less than 1 minute, usually 40 minutes.
Refers to processing within seconds.

As a means from the developer side for rapid processing, high pH 1 high ifA images, a combination of a dihydroxyben-based agent and a developing agent exhibiting superadditivity (for example, a 1-phenyl-3-pyrazolidone-based developing agent, etc.) are listed. However, when taken alone, these methods conflict with stability or contrast enhancement, which is currently the biggest problem when rapidly processing photosensitive materials.

As a method to improve the above problems, JP-A-53-117
No. 20, No. 54-92235, No. 56-106244
There are numerous technical disclosures, such as issues.

However, neither of them reached a satisfactory level, and @! There is a strong desire for regulation, stabilization, and speed-up.

In particular, when increasing p)I is used as part of the means for speeding up the process, when the pH increases to around 10.8 or higher, there is a shortage of suitable pH buffering agents, which poses a problem in designing the developer. for example,
For developers with a pH of 11.5, phosphates are the most well-known pH buffering agent, or when using developers using them, fixers containing acidic hardeners are usually used. I can't. This is because the acid fixing hardener A18+ reacts with the poi- in the developer brought in with the film, causing scuttling stains on the film surface and rollers of automatic processors, making it unusable for practical use. .

8 for fixer! If a film agent is not used, problems such as deterioration of film properties and drying properties are likely to occur, which is very inconvenient in terms of handling.

(Object of the Invention) The present invention has been made to improve these drawbacks, and a first object of the present invention is to provide a high-contrast image forming method with rapid processing.

A second object of the invention is to provide a method for forming high quality halftone dots with low capri.A third object of the invention is to provide a method for forming high quality halftone dots with low capri.
A stable and rapid processing image forming method is provided.

A fourth object of the present invention is to provide an image forming method with excellent film properties and drying properties.

(Components of the Invention) The above-mentioned object of the present invention is to prepare a negative silver halide photographic light-sensitive material containing a hydrazine compound in the presence of a 7-mino compound, and which has a pH value of 10.8 or more and the following ( stomach)
This is achieved by an image forming method in which processing is performed with a developer containing the following components.

(a) Dihydroxybenzene-based developing agent (b) Dihydroxybenzene-based developing agent and a developing agent that exhibits superadditivity (c) Developer 1! In a particularly preferred embodiment of the present invention, carbonate having a solubility of 0.2 mol or more and 0.9 mol or less per 1 z of the developing solution (to sulfite ion having a concentration of 0.3 mol or more per z) is a particularly preferred embodiment of the present invention. Salt concentration, 0.5 mol or more per developer 11
．． It is an embodiment in which the concentration is 7 mol or less, and more preferably an embodiment in which the μ value of the developer is 11 or more. Another preferred embodiment is an embodiment in which image processing is performed in the presence of an organic inhibitor.

More preferably, the organic inhibitor is represented by the general formula [:[], and even more preferably, the silver chloride composition is silver chloride, silver chlorobromide, silver chloroiobromide, and silver chloroiodide. silver oxide, and is treated with the above-mentioned developer in the presence of an organic inhibitor. represent.

The hydrazine compound used in the present invention is preferably a compound represented by the following general formula CI].

In the formula, R' represents a monovalent organic residue, V represents a hydrogen atom or a monovalent organic residue, and X represents an oxygen atom or a sulfur atom. Among the compounds represented by the general formula [I], compounds in which X is an oxygen atom and P is a hydrogen atom are more preferred.

The monovalent organic residues of R1 and R8 include aromatic residues, heterocyclic residues, and aliphatic residues.The aromatic residues include phenyl groups, naphthyl groups, and substituents thereof. (For example, alkyl group, alkoxy group, acylhydrazino group, dialkylamino group, alkoxycarbonyl group, cyano group, carboxyl group, nitro group, alkylthio group, dotetraxyl group, sulfonyl group, carbamoyl group, etc.) 10 gene atoms, 7 sylamide 7 groups, sulfonamide groups, thiourea groups, etc. Specific examples of those with substituents include 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylminophenyl group, etc. i, 4-octylaminophenyl group, 4-benzylaminophenyl group, 4-
7-7doamido-2-methylphenyl i, 4-(3-ethylthioureido)phenyl group, 4-[2-(2,4-di-tart-butylphenoxydyptylamide]7yl group, 4-[2- (2,4-di-tert-butylphenoxyptylamido]phenyl group, etc. can be mentioned.

The polycyclic ring residue is a membered or six-membered monocyclic or condensed ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, and a substituent may be attached thereto.

Specifically, for example, biroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, pendithiazole ring, naphthothiazole ring, selenazole ring,
Examples include residues such as a benzoselenazole ring and a naphthoselenazole ring.

These heterocycles include a methyl group and an ethyl group having 1 to 4 carbon atoms.
Alkyl group, methoxy group, ethoxy group, etc. carbon Z number 1 to 4
may be substituted with an aryl group having 6 to 1 carbon atoms such as an acyloxy group or a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, or a ryomido group. Aliphatic residues include straight-chain and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl groups and alkyl groups.

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably an alkyl group of 1 to 8, and specific examples include a methyl group, ethyl group, isobutyl group, l-octyl group, and the like. The straight chain and branched alkyl group for R4 is, for example, one having 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, and the like.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as a cyclopropyl group, a Schiftehexyl group, and an adamantyl group.

Examples of substituents for alkyl groups and cycloalkyl groups include acyloxy groups (e.g., methoxy, ethoxy, tetraboxy, butoxy, etc.), alkoxycarbonyl, carbamoyl, hydroxy, alkylthio, amide, acyloxy, Cyano group, sulfonyl group, halogen atom (e.g. chlorine, fA element, fluorine, iodine, etc.), aryl group (e.g. Gf phenyl group, halogen-substituted phenyl group,
Alkyl-substituted phenyl group) etc., and specific examples of substituted groups include 3-methoxypropyl group,
Tekyls include ethoxycarbonylmethyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, p-chlorobenzyl group, and the like.

In addition, examples of alkenyl groups include ally
Examples of the lJ group and the alkynyl group include a pronozergyl group.

Preferred specific examples of the hydrazine compound of the present invention are shown below, but the present invention is not limited thereto in any way.

(1-1l1-formyl-2-(4-['2-(2゜4
-di-tart-butylphenoxynoptylamidocophenyl)hydrazine (1-221-formyl-2-(4-diethyla,
Minophenylnohydrazine (1-321-formyl-2-(p-) Rylnohydrazine (1-4) 1-formyl-2-(4-ethylphenylnohydrazine (1-5) l-formyl-2-( 4-7 Cetamide 2
-Methylphenylnohydrazine (1-6) l-formyl-2-(4-oxyethylphenylnohydrazine (1-7) 1-formyl-2,-(4-N,N-dihydroxyethylamino 7ethylnohydrazine) (1-8) 1-formyl-2-[4-(3-ethylthioureido lambda phenyl]hydrazine (1-9) 1-thioformyl-2-(4-[2-(2,
4-tert-butylphenoxyptylamide]
phenyl)hydrazine (1-LO) 1-formyl-2-(4-pendylaminophenylnohydrazine (1-1121-formyl-2-(4-octylaminophenylnohydrazine (1-12) 1.-formyl- 2-(4-dodecylphenylhydrazine(1-13,11-acetyl-2-(4-[: 2-
(2゜4-di-tert-butylphenoxynoptylamido]phenyl)hydrazine (1-14) 4-carboxyphenylhydrazine The addition position tL of the hydrazine compound is the halogenated vA emulsion layer and/or
Alternatively, it is a non-light-sensitive layer on the side of the silver halide emulsion layer on the support, preferably the silver halide emulsion layer and/or its lower layer. The amount added is lO-'-IO-'%
, n, /1 mole of silver, preferably 1 mole of flies/m.

The amino compound used in the present invention includes all primary to quaternary amines. Examples of preferable compounds include alkanolamines. Preferred specific examples will be listed below, but the present invention is not limited to these in any way.

(2-'L) Diethylaminoethanol (2-2) Diethylaminobutanol (2-3) Diethylaminopropane-1,2-diol (2-4) Dimethylaminopropane-1,2-diol (2-5 Nodiethanolamine (2-'L) -6) Diethyl Minnow 1-Proper Tool (2-7
Notriethanolamine (2-8 Nodiprobylaminopropane-1,2-diol (2-9) Dioctyl minnow 1-ethanol (2-L
O) Dioctylaminopropane-1,2-diol (2-1L) Dobu-cylaminopropane-1,2-diol (2-42 Nododecylamino-1-propane-1-propatol (2-1L)
13) Dodecylamino-1-ethanol (2-44) Aminopropane-1,2-diol (2,15) Diethylamino-2-pronozenol (2-16) Dibrobanolamine (2-1l) Glycine (2 -1,8)) diethylamino (2-19)) lyethylenediamine compound is used to improve the hydrophilic properties of coating layers on the light-sensitive layer side of silver halide photographic light-sensitive materials (e.g., silver halide emulsion layer, protective layer, undercoat layer). It may be contained in at least one layer of the colloid layer (colloid layer) and/or in the developing solution.One preferred embodiment is a mode in which it is contained in the developing solution. The content of the amino compound varies depending on the target to be included, the type of amino compound, etc.
Contrast and enhancement are required.

Examples of the dihydroxybenzene-based developing agent used in the developer of the present invention include hydroquinone and chlorohydroquinone, and hydroquinone is preferable. The amount used is usually 1 developer! It is 11 to 60.9.

Examples of developing agents that exhibit superadditivity with dihydroxybenzene-based developing agents include 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, and 1-phenyl-4-meF-4- hydroxylmethyl-3
-pyrazolidones, etc., and/or amino/phenolic agents such as N-methyl-P-aminophenol.

The sulfite used in the present invention may be any salt as long as it liberates sulfite ion C5oi-t in the developer,
Examples include sodium sulfite, potassium sulfite, potassium bisulfite, and the like. The concentration range of sulfite ions in the developer is 1. It may be 0.3 mol or more per lf', but 1.2 mol/1 or more is not practical for production. Preferred concentrations are 0.4 mol/l-0, fumol/l.

In a concentration range lower than 0.3 mol, it is susceptible to air oxidation and is a practical problem in terms of stability, so it cannot be used.

The carbonate used in the present invention is usually sodium carbonate, potassium carbonate, sodium bicarbonate, etc. used in a developer, and the concentration range is 0.2 mol or more and 0.9 mol or less per developer 11. . Outside this concentration range, the object of the present invention cannot be achieved.

The role of the carbonate in the present invention is not just a pH buffer effect, but also an effect of improving halftone dot quality and increasing contrast, and is expected to be different from the usual pH buffer effect. This is because if the above photographic effect can be obtained only by a simple pH buffer effect, an even better effect can be obtained by increasing the amount added, but surprisingly, the desired effect is not obtained outside the above range. I can't do it. This has not been previously known, and is presumed to be due to a synergistic effect with the hydrazine compound, the amine compound, the cleaning of the developer, etc., and is completely new. however,
The present invention is not limited in any way by the above estimation.

In the present invention, the pH value of the developer may be %10.8 or higher, but is preferably in the range of 11 to 12, and 10.
．． If it is smaller than 8, a sufficiently high-contrast image cannot be obtained, and if it is 13 or more, it is not practical in terms of handling safety.

In a preferred embodiment of the present invention, "in the presence of an organic inhibitor" is the same as the above-mentioned "in the presence of an amino compound". Examples of organic inhibitors include 1-phenyl-
Examples include 5-mercaptotetrazole, 5-methylbenzotriazole, 5-nitrobenzimidazole, 5-sulfobenzotriazole, 2-mercaptobenzothiazole, and compounds represented by the general formula [I[I].

In the general formula [■], the alkyl group of Rs may be linear, branched, or cyclic, and preferably has 1 to 12 carbon atoms.
Examples thereof include a methyl group, an ethyl group, an isopropyl group, and the like. These alkyl groups may be substituted, and examples of the substituent include a hydroxyl group, a carboxyl group, and a mercapto group. General formula [IIr
] (hereinafter referred to as the compound of the present invention [Iff
]. Examples include 5-nitroindazole,
Examples include 6-nitroindazole and alkali metal salts thereof, and these may be used alone or in combination. The concentration range of the compound [] of the present invention when added to a developer is 1v to 1g of O,l per 11 of the developer, preferably 1
1n9~2001! When added to a photosensitive material, the amount is 0.0:LQ to 500 Da, preferably 1rI9 to 100 Da, per mole of silver halide. A density outside this range is unfavorable in terms of manufacturing cost and photographic performance.

The compound CTI[] of the present invention may be added after being dissolved in an organic solvent, or may be added directly, and does not take any of these forms. Examples of the organic solvent include triethylene glycol, diethylene glycol, jetanolamine, triethanolamine, methanol, and ethanol.

In addition, a preferred embodiment of the present invention includes an embodiment in which processing is performed with the developing solution of the present invention in the presence of a polyalkylene oxide compound (this meaning is the same as in the amino compound)◎In the present invention Specific examples of the polyalkylene oxide compounds preferably used are shown below, but the present invention is not limited thereto.

[Exemplary compound co(3-1) HO(C!H, CHloJnH[n =
35 Ko (3-2) 04H1OCOH@OH@
OnonH [n = 20 (3-3)] O,H
,,0(OH,OH,szzH[n=30](
3-4) a,,xffiso(am, o'a, snl
i [n == 30 (3-6) 0111. m5(
Oh! OH, SunHCn = 30 (s -7) 0
4H@5(OH1G1110JnOQOH10H10Q
OH[n=5o] (3-8) HO(OH, (Jl,
O]l(OHlJm(OHIGH,0)n00CH,C
HlooOH[1-)-n=70, m=5](3
-9) HO (OH, OH, O)1. C0HOHIQ
) rn (OH, O horse 0) nH gourd ON! .

[1+n=15. m=1v] (3-10)HO(OHtOH*su1(OHOH,sum
(CHIOHIO)n, H■ OH.

[1-)-H=3Q, m=35] (3-11)
1i0(OH,(H,0Jl(O)10H,sum(O
H10H20) nH1h [1-)-m=15, m=15] (3-12)
10(OH,OH,Sl(0HOH,O) m(OH
,OH! SunH■ O Goose H! [1+n=30. m=45] (3-13) [0(OH,OH,O]1(OH10
10H10)110)m(CHIC)11(1)nH
[1+Yutomiz;s, m=2x] (314) HO(OH*OH*su1(OH,0HIO
H@OH,O)m(CHIOHIO)nH[1+n=3
8. m=15] (315) HO<OH*OH1su1(OHOH,O)
m(01(,OH,0JnHI OH,OOH.

[1+n=15, m==15][1+n=3o
] The amount of the polyalkylene oxide compound optionally used in the present invention is 0.0111 to 11 per developer.
There is 40 g, preferably HaO,l! The addition method of 0, which is i to 5I, may be added by dissolving in water or triethylene glycol or the like, or may be added as is. When a polyalkylene oxide compound is added to a light-sensitive material, the amount is preferably in the range of 0.01 to 1Op, preferably 9 to 3y, per mole of silver halide. The addition position may be either the silver halide emulsion layer and/or the non-photosensitive layer, but preferably t L < Gt and the silver halide emulsion layer and/or its lower layer.

The silver halide composition of the silver halide photographic light-sensitive material (hereinafter referred to as light-sensitive material) used in the present invention is silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, and silver chloride. It can be any silver. In particular, in the case of silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride, it is preferable to process in the presence of an organic inhibitor. More preferably, the general formula [[l
It is preferable to carry out the treatment in the presence of a compound represented by:

The silver halide composition used in the photosensitive material used in the present invention has an average grain size of 0.05 to 1.5 μm.

Preferably 0.1 to 0.8 μm, more preferably 0.1
5 to 0.5 μm, and at least 75% of the total number of particles, preferably 80% or more of the average particle size of said stage is also preferably 0.
．． It contains silver halide grains having a grain size of 6 to 1.4 times, preferably 0.7 to 1.3 times, and preferably meets the above grain size and grain size distribution conditions.

As a method for preparing the emulsion used in the present invention, forward mixing, back mixing, manual mixing, and simultaneous mixing are all possible, and the most preferred method is simultaneous mixing.

Further, methods for preparing emulsions include an ammonia method, a neutral method, and an acid method.

The halogenated aS agent used in the photosensitive material used in the present invention can be sensitized with various chemical sensitizers.

Examples of sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, phosphorylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (H,H-dimethyl heptadurea, selenourea, etc.). etc.), reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooolite, potassium aurithiocyanate,
Various noble metal sensitizers represented by potassium chloroaurate, 2-oresulfobenzothiazole methyl cupride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc., each singly or in combination Can be used in combination. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.

Silver halide emulsions are disclosed, for example, in U.S. Pat.
No. 7, No. 2,716,062, No. 3,512.9B2
No. 1,189,380, West German Application Publication No. 2.05
No. 8.626, No. 2,118,411, Special Publication No. 1973-
No. 4133, U.S. Patent No. 3.342.596, Special Publication No. 4
No. 441l, West German Application Publication No. 2,149. '7 -
No. 89, Special Publication No. 3G-2825 and Special Publication No. 49-13
No. 566, preferably compounds such as 5.6-)rimethylene-7- and 6-droxys-)riazolo(1,5-a)pyrimidine, 5.6-titramethylene-7-hydroxy-8-triazolo( 1,5-, nopyrimidine, 5-methyl-7-hydroxy-8-triazolo(1,5-a nopyrimidine, 7-hydroxy-8-triazolo(1,5-a)pyrimidine, 5-methyl-6-
Promomer hydroxy-g-)riazolo(1゜5-&
nopyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, furovir gallate, sodium gallate, mercaptan@(1-7enyl-5-
It can be stabilized using mercaptotitotisol, 2-mercaptobenzthiazole λ, benztriazoles (5-brobenztriazole, 5-methylbenttriazole, benzimidazoles (6-nitrobenzimidazole), etc.). Other silver halide emulsions include, for example, West German Application Publication No. 2.21l゜153;
2.21l. A latent image stabilizer such as a sulfur-containing amino acid compound described in No. 895 or the like may also be used. Particularly preferably, l-''yenyl-5-mercaptotetrazole is used in combination, and the amount added is 1.5 mm per mole of silver halide.
~5g, preferably 1.0In9~5001n9.

In addition to the above additives, the silver halide emulsion can be optically sensitized to a desired wavelength range by using optical sensitizers such as cyanine dyes and merocyanine dyes alone or in combination.

The hydrophilic colloid particularly advantageously used in the emulsion layer of the light-sensitive material used in the present invention is gelatin, but hydrophilic colloids other than gelatin include, for example, fluid albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose - acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, such as British Patent No. 523.6451, West German Publication No. 2,255,711, West German Application No. 2.046
．． 682, U.S. Pat. No. 3,341,332, etc., gelatin derivatives, such as U.S. Pat. No. 2.614.92 E1, U.S. Pat.
Phenylcarno (mil gelatin, sylated gelatin, phthalated gelatin) as described in U.S. Pat. No. 753, etc., or U.S. Pat.
Examples include gelatin graft-polymerized with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, and methacrylic ester as described in No. 67, etc., and these hydrophilic The colloid can also be applied to hydrophilic colloid layers that do not contain silver halide, such as anti-tulsion layers, protective layers, interlayers, etc.

In the photosensitive material used in the present invention, fi% of the emulsion layer
-1ti is usually 0.111 to Og/m as silver,
Preferably II~5,! iI/rrt. In that case gelatin as the preferred hydrophilic colloid is 0
．． The amount is 1 g to 10 g/g, particularly preferably 1 g to 5 g/g.

The photosensitive material used in the present invention is coated on a suitable photographic support, and examples of the support used in the present invention include baryta paper, polyethylene double-covered paper, polypropylene synthetic paper, glass plate, cellulose acetate, etc. Typical examples include cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films, and these supports can be selected as appropriate depending on the intended use of the photosensitive material. be done.

The photosensitive material used in the present invention is typically formed by coating G-i on a support with at least one hydrophilic colloid layer containing silver halide (according to the present invention). The photosensitive material used in the invention includes a protective layer having an appropriate thickness,
That is, preferably 0.1 to 10 μm, preferably 0.1 to 10 μm.
Preferably, a gelatin protective layer of 8 to 2 μm is applied.

In the hydrophilic colloid layer including the emulsion layer of the photographic material used in the present invention, various photographic additives such as hardeners, surfactants, image stabilizers, ultraviolet absorbers, antistain agents, pH Conditioners, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. are used within the range that does not impair the effects of the present invention. be able to. For example, as a thickening agent or a malleable agent, U.S. Pat.
-4939, West Germany-Application Publication No. 1.904.604,
JP 48-63715, JP 45-15462, Belgian Patent No. 762,833, U.S. Patent No. 3.76
7.410, Belgian Patent No. 558,143, etc., such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardening agents include aldehyde-based, epoxy-based, and ethyleneimine-based , active halogen type, vinyl sulfone type, isocyanate type,
Various hardening agents such as sulfonic acid ester type, carbodiimide type, mucochloric acid type, and siloyl type can be used in the hydrophilic colloid layer including the emulsion layer of the light-sensitive material used in the present invention.

In addition to the above-mentioned materials, the developer according to the present invention includes solvents such as triethylene glycol, diethylene glycol, triethanolamine, ethanol, benzyl alcohol,
Jetanolamine, dimethyl sulfoxide, dimethylformide, etc., inorganic inhibitors such as potassium bromide and potassium iodide as inhibitors, silicates, borates, sodium hydroxide, and alkaline agents as anti-buffing agents. Salts such as potassium hydroxide, sodium chloride, sodium sulfate, acetate, citrate, ethylenediaminetetraacetic acid) IJ
A water softener such as a salt or nitrotriacetic acid, an &I agent such as glutaraldehyde, a development accelerator such as methylimidacillin, methylimidazole, or a quaternary amine can be added.

(Example) Example 1 A 0.2 μm cubic monodisperse silver iodobromide emulsion was prepared according to a conventional method and sensitized with sulfur. 3,3'-bis(3
- Sulfoprobyl nooxalic acid lupocyanine hydroxide sodium salt (250 μ/silver 1 mol 2, 2% saponin as a coating aid, polyethyl acrylate (150 wt%/Ge1) as a softening agent, polyalkylene compound <3
-4 (320In9/silver 1 mole, 2-4 as stabilizer)
Methyl-4-hydroxy-1,3,3&,? - Tetrazaindene (3 p/ml 1 mol), l-phenyl-5-mercaptotetrazole (1501n9/silver 1 mol), and hydrazine compound (1-1) (1,5 g/silver 1 mol) were added, and the following protection was added. Coating was carried out simultaneously on a polyethylene terephthalate base together with a layer solution.At this time, the amount of gelatin attached to the emulsion layer was L5,!9/G, and the silver amount was 39/G.

The protective layer liquid contains gelatin as a coating aid; octyl octyl ester as a matting agent; 4μI11L silica as a matting agent; 2-hydroxy-4,6-dichloro-o-1 as a hardening agent;
It consists of 3,5-triazine sodium salt and has a gelatin content of 21! /trj on the emulsion layer and dried.

The above sample was cut into an appropriate size, exposed to light through a wedge using a photo camera, and developed with the developer described below.

When evaluating the halftone dot quality, the dot quality was evaluated by exposing it to light using a conventional contact lens. The developing conditions were 38°C and 20 seconds. For fixing, an ordinary fixer solution with an acidic hardener was used.

Developer (1) Hydroquinone 30.91-phenyl-4-methyl-4-human-roxymethyl-3-pyrazolidone 005g Potassium sulfite
0.6mol sodium carbonate
0.5M potassium bromide
3I5-Methylbenztrizole
0.3g Sodium ethylenediminetetraacetate 1l 2g
Amino compound (2-4) 11 with 20g water
Finish it.

The pH is adjusted to 11.4 with caustic soda or boric acid.

(The same applies hereinafter) Developer (2) Developer solution (1) except that sodium carbonate was 0.2 mol
Same as .

Developing solution (3) Developing solution (1) except that sodium carbonate was O, 1 mol.
Same as .

Developer (4) Developer (1) except that sodium carbonate was 0.9 mol
Same as .

Developer (5) Same as developer (1) except that sodium carbonate was 1 mol.

Developer (6) Same as developer (1) except that 0.5 mol of sodium metaborate was used instead of sodium carbonate.

Developer (7) Same as developer (1) except that 1 mol of sodium metaborate was used instead of sodium carbonate.

Developer (8) Same as developer (1) except that sodium carbonate was 0 mol.

The results are shown in Table-1. In Table 1, sensitivity is evaluated based on the point showing a concentration of 3.0 on the aqueous curve, and is expressed in relative terms. Capri is listed including base concentration. vJF1 is expressed by the slope of the straight part on the aqueous curve. The halftone dot quality was visually determined using a 100x magnifying glass and evaluated on a scale of 10 (lotJS is the best).

Table 1 From Table 1, &l, &2 and rin4 according to the present invention
It is clear that the case gives excellent results.

In addition, when developing, fixing, washing and drying with these developing solutions (1) to (8), the drying properties were good in all cases, and unlike in the case of phosphates, scuttling stains did not occur.

Example 2 The photosensitive material prepared in Example-1 was developed with the following developer. The processing conditions, evaluation method, etc. are the same as in Example-1.

Developer solution (around (collection) Hydroquinone 40 g Potassium sulfite 0.5 mol Sodium carbonate 0.6 mol 5-Methylbenztrisol 0.2 g 1-phenyl-5-mercaptotetrazole 0.03 g Sodium bromide 2 g Ethylenediamine tetra It was finished to %200- with sodium acetate pure water.

The pH was adjusted to 11.5 using #J'NK using caustic soda.

(M-format diethylene glycol 50g Sodium ethylenedi7minetetraacetate o, osp Acetic acid 0.31 5-p indazole o, 1.y l-phenyl-3-trizolidone 0.5IN Potassium sulfate 0.51 Amino compound (2 -7] 15.p Finish to 7514 with pure water.

When using the developer, the composition and composition were mixed and made up to 1 liter with water.

Developer solution (lυ Developer solution Cl0 except that sodium carbonate was O, 1 mol)
).

Developer (12) Same as developer (10) except that sodium carbonate was 1 mol.

Developer (13) Same as developer (10) except pH was changed to 10.8.

Developer (14) p) Same as developer (w) except that I was changed to 10.2.

Developer (15) The developer (1O) does not contain amine compounds.

Developer (16) The developer (11) does not contain an amine compound.

Developer (1l) The developer (12) does not contain an amine compound.

The results are shown in Table-2.

Table 2 It is clear from Table 2 that only &10 (development (10)) according to the present invention is superior.

Example 3 Cubic silver chloroiodobromide (Ag0J:
AgBr:Ag engineering=80:19. M: 0.3 C molar ratio)) After sulfur sensitization of the emulsion, 2-methyl-4-hydroxy-1°3.3a, ? -Tetrazaindene (1,5g
/31!1% I'y), 1-722-5-mercaptotetrazole (from 100/1 mol of silver and 5-methylbenztriazole (from 200/1 mol of silver was added), and further a color sensitizer. As 1-(β-hydroxyethyl)-3-phenyl-5-[(3-γ-sulfopropyl-2-penzoxazolinylidene]-ethylidene cothiohydantoin (200~/1 mole of silver, hydrazine compound ( 1-11) (3001n9/silver 1 mole), 3% saponin as a coating aid, metal 7 acrylate as a softener, 2-acrylic acid, 2-methylpropanesulfonic acid, and 2-acetoacetoxyethyl methacrylate. Copolymer (l OOwt%/gelatin, polyalkylene compound (3-s) (zoomy/silver 1 morph,
Gelatin was added so that the emulsion layer had a gelatin coverage of 277/m and a silver coverage of 3.8, il/m, and was coated on a polyester base simultaneously with the protective layer solution described below and dried.

The protective layer liquid is gelatin C11! 3% saponin as a coating aid and bisvinylsulfonyl methyl ether as a hardening agent.

The above photosensitive material was processed in the same manner as in Example 1 using the following developer.

The results are shown in Table-3.

Developer (20) Hydroquinone 2591-7 Yellow 4,4-dimethyl-3-pyrazolidone
0.4J sodium bromide
2g5-methylbenztriazole O,1g6-nitroindazole
0.05g amino compound (2-4) 10
J9 Sodium sulfite 0.7 mol Sodium carbonate 0.5 mol Sodium ethylenediaminetetraacetate 2g O Adjusted to 11 with water. pH was adjusted to 11.5 with caustic soda.

Developer (21) A developer (zO) containing 0.1 mol of sodium carbonate.

Developer (22) Add 1 mol of sodium carbonate to the developer (20).

Table 3 From Table 3, it is clear that &2o (Development (20)) according to the present invention is superior.

Example 4 0.1 μm monodispersed silver chlorobromide (kgol: AgBr
= 99:1C%) emulsion was mixed with rhodium chloride (1(
5" in the presence of 4 mol/M 1 mol, and after sulfur sensitization, 2-methyl-4-hydroxy-1,3,3a,7-
Citrazaindene (2g/1 mole of silver), l-phenyl-
5-Mercaptotetrazole (150~/1 mol silver)
Hydrazine compound (1-3) (400~/1 mole of silver,
2% saponin as a coating aid, polyethyl acrylate (IQQ wt%/gelatin as a softening agent), and gelatin was added so that the amount of gelatin in the emulsion layer was 1.8 g/m and the amount of silver was 39/m. Then, the following protective layer solution was simultaneously coated on top of the polyester paste and dried.

Homoku 111 liquid contains gelatin, phthalated gelatin, 2%
It consists of saponin, 3μ polymethyl methacrylate, 2-hydroxy-4,6-cyclol:L, 3.5-triazine sodium salt, etc., and the amount of gelatin attached is 29 /
It was simultaneously coated on the emulsion layer so that the color was m'.

The above photosensitive material was processed with the above developer. The results are shown in Table-4. Note that the halftone dot quality is the returned halftone dot quality, and is not the camera photographed halftone dot quality. Exposure was performed using a bright room printer.

Table 4 It can be seen from Table 4 that A30 according to the present invention is superior.

(Effects of the Invention) According to the present invention, it is possible to stably obtain a high-contrast, low-capri silver image and a high-quality halftone silver image by rapid development, and it also avoids the problem of deterioration of film properties and drying properties. hard.

Claims (10)

[Claims] (1) A negative silver halide photographic light-sensitive material containing a hydrazine compound has a pH value of 10.8 or more in the presence of an amino compound, and the following (a), (b), and (c) are used. An image forming method characterized by processing with a developer containing the component (d). (a) Dihydroxybenzene-based developing agent (b) A developing agent that exhibits superadditivity with dihydroxybenzene-based developing agent (c) Sulfite ion with a concentration of 0.3 moles or more per liter of developer (d) 0 per liter of developer Carbonate with a concentration of .2 molar or more and 0.9 molar or less (2) The image forming method according to claim 1, wherein the hydrazine compound is a compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 is a monovalent organic residue, R^2 is a hydrogen atom or a monovalent organic residue, X is an oxygen atom or a sulfur represents an atom. ] (3) The method for forming both images according to claim 2, wherein the compound represented by the general formula [I] is a compound represented by the following general formula [II]. General formula [II] R^1-NH-NH-CHO [wherein, R^1 has the same meaning as R^1 in general formula [I]. ] (4) The image forming method according to claim 1, 2 or 3, wherein the amino compound is contained in a developer. (5) The image forming method according to claim 1, 3, or 4, wherein the concentration of the carbonate is 0.3 mol or more and 0.7 mol or less per liter of developer. (6) Claim 1 in which the above pH value is 11 or more.
The image forming method according to item 2, item 3, item 4, or item 5. (7) The image forming method according to claim 1, 2, 3, 4, 5, or 6, wherein the above treatment is carried out in the presence of an organic inhibitor. (8) The side image forming method according to claim 7, wherein the organic inhibitor is a compound represented by the following general formula [III]. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^3 is a hydrogen atom or an alkyl group, R^4 is a nitro group at the 5th or 6th position, and M is a hydrogen atom or a metal atom. represent ] (9) Claim 7, wherein the silver halide is any one of silver chloride, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide.
The image forming method according to item 8 or item 8. (10) Claims 1, 2, 3, 4, 5, 6, 7, and 8, wherein the above treatment is carried out in the presence of a polyalkylene oxide compound. Section or No. 9
Image forming method described in section.