JPS6333744A - High contrast negative image forming method - Google Patents

Abstract

PURPOSE:To form the negative image having high contrast by controlling a developer to a specific pH value, and by composing the developer of a main developing agent, an auxiliary developing agent, a sulfite, and a specific compd. CONSTITUTION:A silver halide photographic sensitive material is processed with the developing agent having a pH value of 11.0-12.3 and comprising 4 kinds of components composed of a dihydroxy benzene developing agent, the auxiliary developing agent of 1-phenyl-3-pyrazolidone and/or p-aminophenol, >=0.3mol/l the sulfite and at least one kind of the compd. shown by a general formula below. In the formula, X is a sulfur atom or an oxygen atom, L is -CONR2-, -NR2CO-, -SO2NR2-, etc., R1 and R2 are each a hydrogen atom, M is a hydrogen atom or an metal ion, etc., (n) is 0 or 1. The irregular development alkyl which is liable to occur in the case of forming negative images having high contrast by using a developer having a high pH value and jointly using an auxiliary developing agent, is effectively prevented by incorporating the compd(s). shown by the formula into the developing solution.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for developing silver halide photographic materials with high contrast, and in particular, a high contrast method suitable for the photolithography process for printing graphic arcs. The present invention relates to a method of forming a negative image.

BACKGROUND OF THE INVENTION In the field of graphic arcs, there is a need for an imaging system that exhibits high contrast photographic characteristics in order to provide good reproduction of continuous tone images with halftone images or reproduction of line images.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde to keep the concentration of free sulfite ions extremely low so as not to inhibit its infectious development properties. .

Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method for obtaining high contrast photographic properties using a stable developer, US Pat. Nos. 4,224,401 and 416
&977, same No. 4,166.742, same No. 431L
No. 781, No. 4272,606, No. 4,21L8
There is a method using a hydrazine derivative described in No. 57, No. 4243,739, and the like. This method provides photographic properties with high contrast and high sensitivity, and because it allows the addition of high concentrations of sulfite in the developing solution, the stability of the developer against air oxidation is reduced by the lithographic process. Dramatically improved compared to liquid.

(Problem to be Solved by the Invention) However, in the method using this hydrazine derivative, the pH of the developer is set higher than that of a normal lithium developer, so it is not commonly practiced in the industry. When processing silver halide photographic materials with automatic processors, they have the disadvantage that uneven development tends to occur.

The mechanism by which uneven development occurs is not clear, but the pH of the developer
If it is as low as a normal Lith developing solution, uneven development will not occur, but the contrast of the photosensitive material containing the P-radin derivative will not increase. Even with a high pH developer that causes high contrast, a developer containing only hydroquinone without an auxiliary developing agent will not cause uneven development. However, in the case of a developer containing only hydroquinone, the silver halide photosensitive material is continuously processed in an automatic processor, and when the halogen ions (mainly bromide ions) in the developer increase, the photographic sensitivity decreases. There is.

On the other hand, in a method for obtaining a high-contrast image without using a hydrazine derivative, the problem of uneven development is not so serious because the above-mentioned high pH value and auxiliary developing agent are not essential to the developer. However, even in systems that do not use hydrazine derivatives, it is possible to form high-contrast images using the above-mentioned high pH developer containing an auxiliary developing agent. When both non-hydrazine systems are used alternately, it is necessary to use a developer having a high pH and containing an auxiliary developing agent even in the non-hydrazine system. In this case, there is a drawback that development unevenness tends to occur, similar to the case of hydrazine type.

Even if a developer containing a high pH auxiliary developing agent is used to increase the contrast and the silver halide photosensitive material is continuously processed in an automatic processor, there is no change in photographic sensitivity and the performance is stable. However, it is necessary to use a compound that eliminates the defect of uneven development, but it has not been known at all as to what kind of compound is suitable from this point of view.

Accordingly, an object of the present invention is to provide a photographic film image with less unevenness in development and with good performance such as sensitivity and halftone dot quality in a high contrast image forming method using a high pH developer.

(Means for Solving the Problems) The object of the present invention is to provide silver halide photographic materials as follows (1)
) to (4) and has a pH of 11.0 to 12.3
This was achieved by processing with a developer having a value of .

(11 dihydroxybenzene developing agent.

12) r-phenyl-3-pyrazolidone-based auxiliary developing agent and/or p-amino-phenol-based auxiliary developing agent.

, (3)...0.3 mol/day or more of sulfite.

(4) At least one compound represented by the following general formula (1).

General formula (1) N-N M8 Sue (Oh,.

In the formula, X represents a sulfur atom or an oxygen atom, and L
OO-, -NR2CONR3-, -NR2Coo-, -
0CONR2- or -NRSo NR- is R2
, R3 may be the same or different and each is a hydrogen atom,
(represents an alkyl group or aryl group), R represents a hydrogen atom, an aliphatic group, or an aromatic group, M represents a hydrogen atom, and 7 represents a kill metal ion, a quaternary ammonium ion, or a quaternary phosphonium ion. n represents O or 1.

In the present invention, by incorporating the compound represented by the general formula (1) into a developer, it is possible to form a high contrast negative image using a developer having a high pH value in combination with an auxiliary developing agent. This effectively prevents uneven development that tends to occur.

Therefore, the present invention is particularly effective in the case of a method using a hydrazine compound, which requires the combination of an auxiliary developing agent and a high pH in the developer as described above. (For example, gradation 4
Above) Even when forming a negative image, development unevenness can be effectively improved by the method of the present invention. Therefore, the present invention is also advantageous in that continuous operation is possible without replacing the developer, especially when both hydrazine-based and non-hydrazine-based systems are used alternately using the same developing machine. .

The compound represented by general formula (1) will be explained in detail.

The aliphatic group and aromatic group represented by R□ in general formula (1) are preferably an alkyl group having 1 to 20 carbon atoms (any linear, monobranched or cyclic alkyl group, such as a methyl group). , ethyl group, n7' thyl group, naphthyl group, t-amyl group, n-hexyl group, cyclohexyl group, etc.), alkenyl T5 having 2 to 20 carbon atoms (straight chain,
branched or cyclic alkenyl groups (e.g., vinyl, pro-pronyl, isopropenyl, etc.), aryl groups having 6 to 20 carbon atoms (e.g., phenyl, naphthyl, etc.), and R1 is These alkyl groups, alkenyl groups, and aryl groups are -8-, -0-, -N, and so on.

It may be further connected to the same or different alkyl group, alkenyl group, or aryl group via a connecting group composed of -, CO,, -So-9-802-, etc.

Furthermore, the argyl group, alkenyl group, and aryl group represented by R□ may have a substituent, and specific substituents include, for example, a halogen atom (fluorine, chlorine, bromine).
, an alkyl group (preferably one having 1 to 20 carbon atoms), an aryl group (preferably one having 6 to 20 carbon atoms), an alkoxy group (preferably one having 1 to 20 carbon atoms), an aryloxy group (preferably one having 1 to 20 carbon atoms), (6 to 20 carbon atoms), alkylthio group (preferably one with 1 to 20 carbon atoms),
ruthio group (preferably one with 6 to 20 carbon atoms), acyloxy group (preferably one with 2 to 20 carbon atoms), amine group (unsubstituted amine, preferably an alkyl group with 1 to 20 carbon atoms), or acyloxy group (preferably one with 2 to 20 carbon atoms), 2 substituted with ~20 aryl groups
or tertiary amino group), carbonamide group (preferably 9 alkylcarbonamide groups having 1 to 20 carbon atoms, 9 arylcarbonamide groups having 6 to 20 carbon atoms), 9 ureido groups (preferably 9 arylcarbonamide groups having 1 to 20 carbon atoms) an alkylureido group, an aryloxy group having 6 to 20 carbon atoms), a carboxy group, a carbonate group (preferably an alkyl carbonate group having 1 to 20 carbon atoms, an aryl carbonate group having 6S20 carbon atoms), an oxycarbonyl group ( Preferably carbon number 1~
20 alkyloxycarbonyl group, aryloxycarbonyl group having 6 to 20 carbon atoms), carbamoyl group (preferably an alkylcarbamoyl group having 1 to 20 carbon atoms, arylcarbamoyl group having 6 to 20 carbon atoms), acyl group (preferably Alkylcarbonyl group having 1 to 20 carbon atoms, arylcarbonyl group having 6 to 20 carbon atoms), sulfo group, sulfonyl group (preferably alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 2 o carbon atoms), sulfinyl g <Preferable alkylsulfinyl group having 1 to 20 carbon atoms, 7-arylsulfinyl group having 6 to 20 carbon atoms)
, S/l/7 amoyl group (preferably an alkylsulfamoyl group having 1 to 20 carbon atoms, an arylsulfamoyl group having 6 to 20 carbon atoms), a cyano group, and a nitro group. Particularly preferred are a carboxy group and a sulfo group, and when there are two or more substituents, they may be the same or different.

R2 and R3 are preferably hydrogen atoms, with 1 to 1 carbon atoms.
0 substituted or unsubstituted alkyl group, carbon number 6-10
is a substituted or unsubstituted aryl group, and the substituents include, for example, the same substituents as R1.

Preferred specific examples of the compounds used in the present invention are listed below.

-N N -N 2H5 ■ CH2C00H These compounds are per liter of developer! It is appropriate to use it at 710 g or less, preferably 39/f1 or less, and 20η/f1 or more. Furthermore, even when these compounds are used alone, 2
More than one type can also be used in combination.

The compound represented by the general formula (■) can be synthesized by a known method described in the following literature.

J, Am, Chem, Soc,, vol. 44, 15
02-1510゜U.S. Patent No. 017.270, British Patent No. 94Q, 169
Special Publication No. 494334. % Kaisho 55-59463Adv
anced in Heterocyclic
ChemIStr7+ L165-209 (1968
) West German Patent No. 2,716,707 In the present invention, high contrast refers more specifically to gradation γ of 4 or more.

As a method for obtaining such a negative image with basic contrast, known means can be used. For example, a method for monodispersing the grain size distribution of a silver halide emulsion (method
), a method in which the halogen composition of the silver halide emulsion is silver chloride or silver chlorobromide (method ■), a method in which development is carried out in the presence of a human 9 radine compound or a tetrazolium salt compound (method ■), a method ■ in which rhodium salts, etc. A method of incorporating a group metal compound into a silver halide emulsion (method ①) can be used.

In method (2), the degree of multiple fractions is preferably as described below.

In method (2), the silver chloride content is preferably 50 to 100 mol.

The method of using human 9-radine compound in Method 2 is described in detail in the above-mentioned US patent.

As the hydrazine used in this method, any known hydrazine can be used. Specific compound examples include U.S. Pat. No. 4,224,401, U.S. Pat. No. 416a977, U.S. Pat.
No. 72.606, No. 421L857, No. 4243
There is a hydrazine visiting conductor described in No. 739 and the like.

For details on the method using tetrazolium, see JP-A-52-18317 and JP-A-53-17719.
It is described in No. 53-17720.

Further, when this method (2) is used, a γ value of 10 or more can be obtained.

In method ①, for example, rhodium salt is added to 10-7 to 10
It is possible to contain about 1 mol of Ag by pressing the button.

In the image forming method of the present invention, it is preferable to use a dihydroxybenzene-based developing agent as a developing agent and a p-aminephenol-based developing agent or a 3-pyrazolidone-based developing agent as an auxiliary developing agent.

The dihydroxybenzene-based developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, z3-dichlorohydroquinone, a3
-Dibromohyde 90quinone, ZS-dimethylhydroquinone, etc., among which samurai prefers -'' quinone.

1-phenyl-3-pyrazolito as auxiliary developing agent
Examples of 1-phenylene or its derivatives include 1-phenyl-3-py7
zoI) V, 1-phenyl-44-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolito-1, l-phenyl-44-dimethyl-3- Hirasol 1))', 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-44-dimethyl-3-pyrazolito1, 1-p
-) 4-dimethyl-3-pyrazolidone and the like.

As the p-aminophenol auxiliary developing agent, N-methyl-p-aminephenol, p-aminephenol, N
-(β-human 90xethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminephenol, p-benzylaminophenol, etc., among which N-methyl-p -Aminphenols are preferred.

Dihydroxybenzene developing agent is usually 0.05 mol/
Preferably, it is used in an amount of j to 0.8 mol/l. In addition, when using a combination of dihydroxy (benzenes) and 1-phenyl-3-pyrazolyne compounds or p-amino-phenols, the former is used at 0.05 mol/fl to 0.5 mol/day, and the latter is Preferably, it is used in an amount of 0.06 mol/ft or less.

Sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium gravisulfate, potassium metabisulfite, formaldehyde sodium bisulfite, and the like. Sulfite is 0.3 mol/9. However, if too large a quantity is added, it will precipitate in the developing solution and cause solution contamination, so the upper limit is preferably 12 mol/fi.

In addition to the present solution of the present invention, pH buffers such as boric acid, borax, trisodium phosphate, and tribasic potassium phosphate may be used. development inhibitors such as potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamibi,
Organic solvents such as methyl cellosol, hexylene glycol, ethanol, and methanol; Capri such as indazole compounds such as 5-nitroindazole, benztriazole compounds such as sodium 2-mercaptobenzimidazole-5-sulfonate, and 5-methylbenztriazole; inhibitor or black peppe
r) Inhibitor; In particular, when using a compound such as 5-nitroindazole, it should be dissolved in advance in a separate area from the area containing the dihydroxybenzene developing agent and sulfite preservative. It is common to mix the parts and add water. Furthermore, if the part where 5-nitroindazole is dissolved is made alkaline, it will be colored yellow and will be convenient for handling.

Furthermore, as the color toning agent, surfactant, and hard water/soft fixer, those having compositions commonly used can be used as necessary. 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 contain a water-soluble aluminum salt such as aluminum sulfate, light bread, etc. as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0 to 3. (lAfi/N). Ethylenediaminetetraacetic acid F e (m) complex salt may also be used as the oxidizing agent.

The treatment temperature is usually selected between 18°C and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.

The method of the invention is particularly suitable for rapid processing using automatic processors. As the automatic developing machine, any of roller conveyance type, belt conveyance type, and other types can be used. The processing time may be short, and is sufficiently effective for rapid development within 2 minutes in total, particularly 100 seconds or less, within which the time allotted for development is 15 to 60 seconds.

There is no particular restriction on the halogen composition of the silver halide emulsion used in the present invention, and compositions such as silver chloride, silver chlorobromide, silver iodobromide, silver bromide, silver chloride, etc. may be used. .

The silver halide grains in the photographic emulsion used in the present invention are
Although it is possible to have a relatively wide grain size distribution, it is preferable to have a narrow grain size distribution, especially when the size of the grains that make up 90 cm of the total grain size in terms of weight or number of silver halide grains is ±40% of the average grain size. 2 (such emulsions are generally called monodisperse emulsions).

The silver halide grains used in the present invention are preferably fine grains (for example, 0.7 microns or less), particularly preferably 04 microns or less.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have crystals such as egular or a composite of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Two or more silver halide emulsions formed separately may be used in combination.

Silver halide emulsions used in the present invention include cadmium salts, sulfites, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, etc. during the formation of silver halide grains or during physical ripening. may coexist.

As the silver halide emulsion, a so-called immature emulsion (primitive emulsion) which is not chemically sensitized can be used, but it may also be chemically sensitized. For chemical sensitization, see Frieser's ``Dei Grundlagen der Fotographischen Prosetsse Mitsutoshi Silver Halogenidene'', Akademitsier Fuerlages Gesellschaft,
1968 (HeFrieser, Die Grund
-1agen der Photo-graphisc
hen Prozesse mit 5ilver h
aloge-niden, Akademische
Verlaggesselschaft.

1968) etc. can be used.

Namely, sulfur sensitization method using gold compounds (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines), reducing substances (e.g. stannous salts, amines, Hydrazine derivatives, formamidine sulfinic acid.

A reduction sensitization method using a silane compound), a noble metal sensitization method using a noble metal compound (for example, a gold compound or a complex salt of a Group I metal of the periodic table such as platinum, iridium, palladium, etc.) are carried out singly or in combination. be able to.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Various synthetic hydrophilic polymeric substances such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, acrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

In addition to lime-processed gelatin, acid-processed gelatin and Platin e of the Society of Scientific - Photographic Shalamin (
Bull, Soc, Cci, Phot.

Enzyme-treated gelatin as described in Japan) A, p. 16.30 (1966) may be used, and gelatin hydrolysates and 5F elementary decomposition products may also be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine color 2, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes may be used in combination to obtain a supersensitizing effect.

Along with the sensitizing dye, 1 is a dye that itself has a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostilbene compounds substituted in a nitrogen-containing heterogeneous environment (
For example, U.S. Pat. No. 2.9] 3390, U.S. Pat.
% cadmium salts, azaindene compounds, etc. U.S. Patent No. 3.61 a613, U.S. Patent No. 361-6
The combinations described in No. 41, No. 617.295 and No. 3635721 are particularly useful.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as indithiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes,
For example, triazaindenes, tetraazaindenes (
Especially 4-hydroxy substituted (1,:L 3ay 7)
tetraazaindenes), pentaazaindenes;
Many compounds known as antifoggants or stabilizers can be added, such as henzenethiosulfonic acid, benzenesulfinic acid, amibibenzenesulfonic acid, and the like.

Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehyde 9 (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (23-dihydroxydioxane, etc.), activated vinyl compounds (L35-triacryloyl-hexahydro) -8-triazine, L3-vinylsulfonyl-2-prohanol), active halogen compounds <24-dichloro-6-hydroxy-s-triazine), mucohalogen acids (mucochloric acid, mucophenoxychlor M, etc.), etc. Can be used alone or in combination.

In addition to the photographic emulsion layer of the light-sensitive material produced using the present invention, other hydrophilic colloid layers include coating aids, antistatic properties, slip property improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as enhancement, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, i'?
IJ ethylene glycol/polypropylene glycol condensate% polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, pv ethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide addition of silicone nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates , alkylbenzene sulfo/acid tL alkylnaphthalene sulfonate, alkyl sulfate esters, alkyl phosphate esters, N-acyl-N-alkyl taurines, sulfosuccinate esters, sulfoalkyl polyoxyethylene al middle layer phenyl ethers, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphate esters;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 8,600 or more and described in Japanese Patent Publication No. 58-9412.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate.

(meth)acrylamide 9, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid,
A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

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

Example 1 5-dichloro-9-ethyl-33-bis(3-sulfopropyl)oxacarbocyanine 90 was added to anhydro to a 0.3μ cubic silver iodobromide emulsion containing 2.5 mol of iodide. xyr sodium salt (sensitizing dye) at 230η/1 mole of silver, hydrazine derivative, ■-formyl-(2-4-(2-(Z4-di-t-pentylphenoxy)butyramide]phenyl)hibiradi) #1 .09
/ silver 1 mole, polyethylene glycol (molecular, quantitative 1
000) was added in 30011v/1 mole of silver, and further 5-methyl (nttriazole, 4-hydroxy-6-methyl-
Lλ3a.

The thus prepared coating solution containing 7-titrazaindene, a dispersion of polyethyl acrylate, and 2-hydroxy-L&5-triazine sodium salt was coated on a polyethylene terephthalate film support at a silver coverage of 4.09/m2.
The amount of gelatin cloth is 2. ．． 511)/rrL2 to obtain a film. Furthermore, gelatin was coated as a protective layer on top of the gelatin at a concentration of 19/m 2 to obtain a film. This is referred to as film/l61.

The films were exposed through a sensitometric exposure wedge using a 150 line magenta contact screen.

Further, a film/l62 was prepared in the following manner.

Solution I: Water 1000g, 11 gelatin 20g, pH=4.0 ■Liquid: AgNO2200g, water 600- ■Liquid: KB
r 4.29, NaC 1759ph (4320~, water 600°C - Solution 2 was added simultaneously to an aqueous gelatin solution of IQ kept at 45°C at a constant rate for 30 minutes.

After removing soluble salts from this emulsion using a conventional method well known in the art, gelatin was added as a stabilizer without chemical ripening.
-Methyl-4-hydroxy-L313a, 7-thitraazaindene was added. The average grain size of this emulsion was 0.28 μm, the yield of the emulsion was II kg, and the amount of gelatin contained was 709.

A hardener 2-hydroxy-46-dichloro-1 was added to this emulsion.
,3,5-) silver per ITrL2 on polyethylene terephthalate film after addition of riazine sodium salt! It was applied in an amount of 4.5 g. Furthermore, gelatin was applied as a protective layer on top of the gelatin at a concentration of 1 liter/m 2 to obtain a film. This film is called Fu2.

This film sample was brought into close contact with a dot film original and exposed using a P607 printer manufactured by Dainippon Screen.

Further, film/I63 is prepared as follows.

Silver nitrate aqueous solution and potassium bromide potassium iodide aqueous solution,
A monodispersed cubic silver iodobromide emulsion A (2 mol of silver iodide, 2 mol of silver iodide,
silver bromide (98 molti) was prepared. Separately, a silver nitrate aqueous solution and a potassium bromide aqueous solution were prepared at %pA in the presence of ammonia.
Mixing by double jet method while keeping g at 7.9,
A monodisperse cubic silver bromide emulsion B with an average grain size of 0.3 s microns was prepared. Emulsion A was sulfur sensitized with sodium thiosulfate.

Furthermore, in both emulsions A and B, the sensitizing dye ras'-dichloro-33'-di(3-sulfopropyl)-9-ethyl-
oxacarbocyanine sodium salt, 6 x 10 mol per mol of silver for emulsions A and B, respectively, 4
．． Spectral sensitization was performed by adding 5×10 mol.

Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,
33a,7-chitrazaindene was added.

These emulsions A and B were mixed at a silver halide weight ratio of 6:4, and then the following compound was added at a ratio of 0.40 to 4.
'j/m2.

Furthermore, a human 9-radine derivative represented by the following formula was added at 4×10 6 mol per mol of silver.

Furthermore, an alkylbenzene sulfonate was added as a surfactant to adjust the pH of the emulsion to 5.8, and each emulsion prepared above was coated on a polyethylene terephthalate support with a film thickness of 100 microns. 3. Og
/rrL2, and further coated as a protective layer on top of the gelatin at a ratio of 1 g/rrL2 to prepare a film /163. A tungsten light at 3200' was passed through a sensitometric optical wedge using a 150-line magenta contact screen and blinded for 5 seconds.

Further, a film/l64 was prepared as follows.

Silver nitrate aqueous solution and 1 mole of silver! An aqueous sodium chloride solution containing D5XlO mol of anthonium rhodium hexachloride (m) was mixed in a gelatin solution at 40°C by a double jet method while controlling the pH to 2.3 to obtain an average particle size. A monodisperse silver chloride emulsion with a size of 0.2 microns was prepared.

After particle formation, soluble salts were removed by flocculation methods well known in the art, and 4-human90x-6-methyl-L 3.3a was added as a stabilizer.

7-thitraazaindene and 1-phenyl-5-mercaptotetrazole were added. Emulsions 1 and 9 contained 559 g of gelatin and 105 g of silver.

Using this emulsion, the following compound was added at a concentration of 70"W/m2, and 2.4-dichloro-
A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support by adding 6-hydro90x-La5-triazine sodium salt to give a silver amount of 3.59 per meter, and the upper layer was further coated with a silver halide emulsion layer. Film/164 was prepared by applying a gelatin layer as a protective layer. This film/464 was exposed through an optical wedge using a Dainippon Screen Co., Ltd. WP6t7DQ printer (light source 100V KW quartz halogen lamp).

Film scraps 1, 2, /I exposed as above, respectively
63, Rin 4 was developed at 34°C for 30 seconds with a developer having the following composition, fixed, washed with water, and dried (an automatic processor FG660F manufactured by Fuji Photo Film Co., Ltd. was used for this process).

The results obtained are shown in Table 2. The reciprocal of the exposure amount required to obtain a density of 1.5 when processed with developer A is expressed relative to 100. G represents tanθ, which is a straight line connecting concentrations 0.3 and 3.0 on the % sex curve.

The halftone dot quality is visually evaluated on a five-level scale, with "5" being the best and "l" being the worst. Halftone products 'fIi "5" and "4" are practical as halftone original plates for plate making, and "3"
” is of such poor quality that it can barely be put to practical use, while “2” and “l” are of an impractical quality.

The development unevenness was evaluated on a five-point scale, with a score of "5" indicating that no development unevenness occurred on the film, and a score of "1" indicating that development unevenness occurred on the film surface. "4"
Although development unevenness occurs in a very small portion of the film, it is at a practically acceptable level, but a rating of "3" or lower is not practical.

As is clear from the results in Table 2, developer B of the present invention.

In the case of C, the development unevenness is good.For comparison, the general formula (1
In the case of developer A which does not contain the compound (), there is a lot of uneven development and it is not practical. Furthermore, for comparison, in the case of a developer containing l-phenyl-5-mercaptotetrazole, which is well known to be added to developers as a mercapto-based compound, development unevenness is good, but sensitivity is low and halftone quality is poor. bad.

(Effects of the Invention) According to the present invention, uneven development that tends to occur when forming a high contrast image using a high pH developer can be effectively suppressed without compromising performance such as sensitivity and halftone dot quality.

Claims (1)

[Scope of Claims] A method for forming a high contrast negative image in which a silver halide photographic light-sensitive material is processed with a developer, wherein the developer is
-12.3, and the following (1) to (4) (1) dihydroxybenzene-based developing agent, (2) 1-phenyl-3-pyrazolidone-based auxiliary developing agent and/or p-amino- A high-contrast negative image characterized by containing a phenol-based auxiliary developer, (3) 0.3 mol/l or more of sulfite, and (4) at least one compound represented by the following general formula (I). Formation method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a sulfur atom or an oxygen atom, and L is -CO
NR_2-, -NR_2CO-, -SO_2NR_2-
, -NR_2SO_2-, -OCO--COO-, -S
--NR_2-, -CO-, -SO-, -SO_2-,
-OCOO-, -NR_2CONR_3-, -NR_2
COO-, -OCONR_2- or -NR_2SO_2
NR_3- (where R_2 and R_3 may be the same or different and each represents a hydrogen atom, an alkyl group, or an aryl group), R_1 represents a hydrogen atom, an aliphatic group, or an aromatic group, and M represents hydrogen. It represents an atom, an alkali metal ion, a quaternary ammonium ion, or a quaternary phosphonium ion, and n represents 0 or 1.