JPH0435058B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention uses a light source rich in ultraviolet light for exposure,
Regarding direct positive silver halide photographic light-sensitive materials of the type (for bright rooms) that can be handled using safe light with cut out ultraviolet light, more specifically, fogging is applied in advance and fogging is done by exposure using solarization or the Herschel effect. The present invention relates to a direct positive silver halide photographic light-sensitive material for use in a bright room, which destroys the silver halide to give a positive image, and a developing method thereof. (Prior art) A light source rich in ultraviolet light, such as xenon, metal halide, mercury lamp, ultra-high pressure mercury lamp, etc., is used for exposure, and a type of direct positive halogen for bright room use that can be handled under a fluorescent lamp for safety light with ultraviolet light cut out. In the case of plate making using a silver oxide photographic light-sensitive material, the reversal sensitivity of the photosensitive material decreases and becomes close to the re-reversal sensitivity, so that there is a strong tendency for re-reversal to occur in practice. This tendency for re-inversion to occur is particularly strong when using silver halide containing a large amount of silver chloride, and to improve this, it is necessary to increase the silver bromide content of silver halide. The present inventor has discovered that. However, this improved method has the disadvantage that as the silver bromide content increases, the gradation becomes noticeably softer, making it difficult to obtain satisfactory photographic performance. These drawbacks become particularly noticeable when processing with a rapid processing developer containing a superadditive developing agent (phenidone or metol), so this type of direct positive halogenation is hindering the trend towards rapid processing. This reduces work efficiency when using silver photographic materials. (Object of the Invention) The object of the present invention is to provide an image forming method using a direct positive silver halide photographic light-sensitive material for bright room use, which can suppress re-inversion due to exposure, has low Dmin, and provides photographic characteristics with high contrast and good so-called blurring. It's about doing. The above-mentioned "blankness" refers to the minimum density between the inverted part and the re-inverted part of the image obtained by wet-exposure and development of a direct positive photographic light-sensitive material.
This means that the minimum density is small, and is distinguished from fog caused by simply developing without exposure. (Structure of the Invention) The above object of the present invention is to provide at least one silver halide composition having a silver halide composition with a silver chloride content of 50 mol% or more.
a positive silver halide emulsion layer on a support, and a tetrazolium compound is present in the emulsion layer and/or in at least one hydrophilic colloid layer on the same side of the emulsion layer and the support. This can be achieved by an image forming method in which a direct positive silver halide photographic light-sensitive material for bright room use is processed with a developer containing at least one compound represented by the following general formula []. General formula [] In the formula, Y is a nitrogen atom or a methine group, and Z
is a nitrogen atom or a carbon atom, W is a sulfur atom, an oxygen atom or an imino group, and V is a hydrogen atom or a mercapto group. However, at least one of Y and Z is a nitrogen atom, and when Y represents a methine group, W is an imino group. n is 0 or 1, and when Z is a nitrogen atom, n is 0, and Z
When is a carbon atom, n is 1. R ₁ is a hydrogen atom,
A lower alkyl group, a halogen atom or a nitro group. The present invention will be explained in more detail below. The direct positive silver halide photographic light-sensitive material for bright room use of the present invention (hereinafter simply referred to as the light-sensitive material of the present invention) contains a tetrazolium compound and 50 mol% or more of silver chloride in a hydrophilic colloid layer provided on a support. It is characterized by a structure in which silver halides containing these are contained in the same layer or in separate layers. In the present invention, the above-mentioned tetrazolium compound contained in the hydrophilic colloid layer can preferably be represented by the following general formulas [] to []. General formula [] General formula [] General formula [] General formula [] General formula [] In the above general formulas [] to [], R ₂ -
R ₁₈ is a substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, propyl group,
tert-butyl group, etc.), allyl group, phenyl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, alkoxyphenyl group, carboxyphenyl group, alkoxycarbonylphenyl group, aminophenyl group, mercaptophenyl group, sulfur group) hydroxyphenyl group, aminosulfoxyphenyl group, nitrophenyl group, halogenated phenyl group, etc.), naphthyl group (e.g. α-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.) ) and heterocyclic groups (for example, thiazolyl group, benzothiazolyl group, oxazolyl group, pyrimidine group, pyridine group, pyrazolyl group, etc.), all of which are groups that form metal chelates or complexes. But that's fine. In addition to the above groups, R ₄ , R ₇ , R ₁₀ , R ₁₂ and R ₁₄ are hydroxy groups, alkoxy groups, carboxy groups, alkoxycarbonyl groups, mercapto groups,
It may be an alkoxysulfide group or a cyano group. X represents an anion, and may be any generally known anion. D represents a divalent aromatic group such as a phenylene group, and E represents a divalent group selected from an alkylene group, an arylene group, and an aralkylene group. m represents 1 or 2. However, if the compound
When an inner salt is formed by the substituents of R ₄ , R ₇ and R ₁₀ , m is 1. Examples of the anion represented by X in the tetrazolium compound of the present invention include chloride ion,
Halogen ions such as bromide ions and iodide ions, acid radicals of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-toluene. Lower alkylbenzenesulfonic acid anions such as sulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, higher alkyl sulfate ester anions such as lauryl sulfate anions, boric acid anions such as tetraphenyl boron, - For polymers such as dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxysacylphate anions, higher fatty acid anions such as stearate anions, and polyacrylate anions. Examples include those with acid roots. The compounds that can be used in the present invention are not necessarily limited to the following specific examples of the tetrazolium compound used in the present invention. (Compound examples) (1) 1,5-dimethyl-4-phenyl-1H-tetrazolium chloride (2) 1,5-dimethyl-4-(3,5-xylyl)
-Tetrazolium chloride (3) 5-hydroxy-1,3-bis(p-nitrophenyl)-1H-tetrazolium chloride (4) 1,3,5-tri(p-carboxyethylphenyl-1H-tetrazolium chloride) (5) 1-(Benzthiazol-2-yl)-3-phenyl-5-(0-chlorophenyl)-2H-tetrazolium bromide (6) 4,5-dimethyl-1-phenyl-1H-tetrazolium chloride (7) 4,5 -dimethyl-1-(3,5-xylyl)
-1H-tetrazolium chloride (8) 3-(p-hydroxyphenyl)-5-methyl-1-phenyl-1H-tetrazolium bromide (9) 1,3-diphenyl-5-ethyl-1H-tetrazolium bromide (10) 1,3-diphenyl-5-n-hexyl-
1H-tetrazolium bromide (11) 5-cyano-1,3-diphenyl-1H-
Tetrazolium bromide (12) 1,4,5-triphenyl-1H tetrazolium chloride (13) 1-(benzothiazol-2-yl)-5-
(4-chlorophenyl)-3-(4-nitrophenyl)-1H-tetrazolium chloride (14) 5-hydroxy-1,3-diphenyl-
1H-tetrazolium hydroxide inner salt (15) 5-acetyl-1,3-di(p-ethoxyphenyl)-1H-tetrazolium bromide (16) 1,5-diphenyl-3-(p-tolyl)
-1H-tetrazolium chloride (17) 1,5-diphenyl-3-(p-iodophenyl)-1H-tetrazolium chloride (18) 1,3-diphenyl-5-(p-diphenyl)-1H-tetrazolium chloride (19) 5-[p-(p-acetamidoanilino)phenylazo]-1,4-dimethyl-1H-tetrazolium chloride (20) 5-(p-dimethylaminostyryl)-4-
Ethyl-1-phenyl-1H-tetrazolium chloride (21) 3,5-diallyl-1-(tetrazole-
5-yl)-1H-tetrazolium chloride (22) 1-cyclohexyl-4,5-dimethyl-
1H-tetrazolium chloride (23) 3-(p-acetamidophenyl)-1,5
-diphenyl-1H-tetrazolium bromide (24) 5-acetyl-1,3-diphenyl-1H
-Tetrazolium bromide (25) 1-(m-chlorophenyl)-4,5-dimethyl-1H-tetrazolium chloride (26) 1-cyclohexyl-4,5-dimethyl-
1H-tetrazolium chloride (27) 1-(0-chlorophenyl)-4,5-dimethyl-1H-tetrazolium chloride (28) 1-(p-bromophenyl)4,5-dimethyl-1H-tetrazolium chloride (29) 4, 5-dimethyl-1-p-tolyl-1H
-Tetrazolium chloride (30) 2-(benzothiazol-2-yl)-3-
Phenyl-5-dodecyl-2H-tetrazolium bromide (31) 2,3-diphenyl-5-(4-t-octyloxyphenyl)-2H-tetrazolium chloride (32) 2,3,5-triphenyl-2H-tetrazolium Chloride (33) 2,3,5-tri(p-carboxyethylphenyl-2E-tetrazolium-2,2-diethylhexylsuccinate (34) 2-(benzothiazol-2-yl)-3-
Phenyl-5-(0-chlorophenyl)-2H-
Tetrazolium chloride (35) 2,3-diphenyl-2H-tetrazolium chloride (36) 2,3-diphenyl-5-methyl-2H-
Tetrazolium chloride (37) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium chloride (38) 2,3-diphenyl-5-ethyl-2H-
Tetrazolium chloride (39) 2,3-diphenyl-5-n-hexyl-
2H-tetrazolium chloride (40) 5-cyano-2,3-diphenyl-2H-
Tetrazolium diisopropyl naphthalene sulfonate (41) 2-(benzothiazol-2-yl)-3-
Phenyl-3-(4-tolyl)-2H-tetrazolium chloride (42) 2-(benzothiazol-2-yl)-5-
(4-chlorophenyl)-3-(4-nitrophenyl)-2H-tetrazolium chloride (43) 5-exitocarbonyl-2,3-di(3
-nitrophenyl)-2H-tetrazolium-1
-Methyl-benztriazole sulfonate (44) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium chloride (45) 2,5-diphenyl-3-(p-tolyl)-
2H-Tetrazolium-2-mercaptobenzoxazole sulfonate (46) 2,5-diphenyl-3-(p-iodophenyl)-2H-tetrazolium chloride (47) 2,3-diphenyl-5-(p-diphenyl)-2H- Tetrazolium chloride (48) 5-(p-bromophenyl)-2-phenyl-3-(2,4,6-trichlorophenyl)-
2H-tetrazolium chloride (49) 3-(p-hydroxyphenyl)-5-
(p-nitrophenyl)-2-phenyl-2H-
Tetrazolium chloride (50) 5-(3,4-dimethoxyphenyl)-3-
(2-Ethoxyphenyl)-2-(p-methoxyphenyl)-2H-tetrazolium chloride (51) 5-(4-cyanophenyl)-2,3-diphenyl-2H-tetrazolium chloride (52) 3-(p -acetamidophenyl)-2,5
-diphenyl-2H-tetrazolium chloride (53) 5-acetyl-2,3-diphenyl-2H
-Tetrazolium chloride (54) 5-(Flu-2-yl)-2,3-diphenyl-2H-tetrazolium chloride (55) 5-(Thien-2-yl)-2,3-diphenyl-2H-tetrazolium chloride ( 56) 2,3-diphenyl-5-(quinol-2
-yl)-2H-tetrazolium chloride (57) 2,3-diphenyl-5-(benzoxazol-2-yl)-2H-tetrazolium chloride The tetrazolium compound used in the present invention is:
For example, Chemical Review (Chemical
55, pp. 355-483. The tetrazolium compounds used in the present invention can obtain preferable characteristics when used alone, but when used in any ratio in combination,
No deterioration of desirable properties occurs. In one preferred embodiment of the present invention, the tetrazolium compound of the present invention is added to a silver halide emulsion layer. In another preferred embodiment of the present invention, it is added to a hydrophilic colloid layer directly adjacent to a hydrophilic colloid layer containing a silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer. In another embodiment, the tetrazolium compounds of the present invention are dissolved in a suitable organic solvent, such as methanol,
It may also be incorporated into the photosensitive material of the present invention by dissolving it in alcohols such as ethanol, ethers, esters, etc. and applying it directly to the outermost layer of the photosensitive material using an overcoating method or the like. The tetrazolium compound used in the present invention is preferably 1 x 10 ^-6 mol to 5 x 10 ^-1 mol, particularly 1 x 10 ^-5 mol to 1 x 10 mol, per mol of silver halide contained in the light-sensitive material of the invention. It is preferable to use the amount up to ^-2 mol. As the silver halide used in the light-sensitive material of the present invention, silver chloride, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide are used, and in each case, silver chloride is contained in an amount of 50 mol% or more. If the silver chloride content is less than 50 mol %, the high contrast effect of the present invention will be lost, which is not preferable. The silver halide emulsion according to the present invention having a silver chloride content of 50 mol% or more may be produced by any method such as an acidic method, a neutral method, or an ammonia method, and may be prepared by a commonly known method such as a simultaneous mixing method or a back mixing method. It can be produced by a method such as a method or a forward mixing method,
Additionally, optional addition flow rate, pH or EAg
It can also be manufactured under control. The silver halide contained in the silver halide emulsion layer of the present invention has, but is not limited to, an average grain size of 0.05 to 1.5 microns, preferably 0.1 to 0.5 microns, and at least 75% of the total grain number; Preferably 80% or more of the average particle size is 0.5 to 1.5
It is desirable to include silver halide having a grain size of 0.6 to 1.4 times, preferably 0.6 to 1.4 times. According to a most preferred embodiment of the present invention, the silver halide of the present invention has an average grain size of 0.10 to 0.3μ, and more than 80% of the total grains have a grain size of 0.6 to 1.4 times the average grain size. It is silver chlorobromide with An organic desensitizer can be added to the silver halide emulsion layer according to the present invention, and examples of the organic desensitizer include the seven-membered ring compound described in Japanese Patent Publication No. 43-14500, Fluorene derivatives having a nitro group described in No. 49-84432, JP-A No. 49-84639
Compounds having a nitrophenylmercapto group described in No. 2, nitrostyryl compounds described in U.S. Patent No. 2,669,515, Pinacryptol Yellow, 5-m
-Nitrobenzylidene rhodanine and the like. The amount of these organic desensitizers added is in the range of 1.0 x 10 ^-6 mol to 1.0 x 10 -1 mol, preferably 1.0 x ^{10 -5 to} 1.0 x mol, per mol of silver halide.
10 ^-2 mol. In addition, iridium, rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, iron,
Atoms such as copper, zinc, lead, etc. may be contained.
When containing these atoms, silver halide 1
It is preferably contained in an amount of 10 ^-9 to 10 ^-2 mol, particularly preferably 10 ^-6 to 10 ^-3 mol. Further, it may be a surface latent image type or an internal latent image type. Additionally, silver halides prepared by a variety of different methods may be mixed. The crystal shape may be cubic, octahedral, or spherical without any limitations. The direct positive silver halide used in the present invention is fogged by conventionally known techniques before exposure. Fog may be imparted using a reducing agent alone or in combination with a reducing agent and a gold compound. Representative of such useful reducing agents include, for example, formalin, hydrazine, polyamines (e.g., triethylenetetramine, tetraethylenepentamine, etc.), thiourea dioxide, tetra(hydroxymethyl)phosphonium chloride, boron compounds ( Examples include amine borane, sodium borohydride, etc.), stannous chloride, etc., and are generally used in an amount of 2.0×10 ^-6 to 2.0×10 ^-3 mol per mol of silver halide. In particular, polyamine thiourea dioxide and boron compounds are preferably used. Typical examples of the above gold compounds include chloroauric acid, potassium chloroaurate, gold sulfide, gold selenide, etc., and generally 1.0% per mole of silver halide is used.
It is used in an amount of ×10 ⁻⁶ to 1.0×10 ⁻⁴ mol. The degree of fog imparted to the direct positive silver halide of the present invention is determined by the amount of fogging agent, the fogging temperature,
It can be suitably selected depending on time conditions. The silver halide and tetrazolium compounds of the present invention are contained in the hydrophilic colloid layer. The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but other hydrophilic colloids such as colloidal albumin, agar, acacia, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl Alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives,
For example, phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in U.S. Patent Nos. 2,614,982 and 2,525,753, or U.S. Pat.
Examples include those obtained by graft polymerizing gelatin with polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in the specifications of No. These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, interlayers, etc. The light-sensitive material of the present invention is formed by coating a hydrophilic colloid layer containing the silver halide and tetrazolium compound according to the present invention on a suitable photographic support. For example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate,
Typical examples include cellulose nitrate, such as polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material. Ru. As described above, the photosensitive material of the present invention is formed by coating on a support at least one hydrophilic colloid layer containing the silver halide and tetrazolium compound of the present invention. A protective layer having an appropriate thickness, preferably 0.1~
Preferably, a gelatin protective layer of 10μ, particularly preferably 0.8 to 2μ, is applied. The hydrophilic colloid used in the present invention may optionally contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, antistain agents, and pH adjusters. formulations, antioxidants, antistatic agents, thickeners, granularity improvers,
Dyes, mordants, brighteners, development speed regulators, matting agents, and the like can be used within the range that does not impair the effects of the present invention. Among the various additives mentioned above, those that can be particularly preferably used in the present invention include, for example, thickeners or plasticizers as described in US Pat.
Publication No. 43-4939, West German Application Publication No. 1904604, Japanese Patent Publication No. 48-63715, Japanese Patent Publication No. 45-15462, Belgian Patent No. 762833, U.S. Patent No.
3767410 and Belgian Patent No. 558143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde, epoxy, and ethyleneimine hardeners. , active halogen type, vinyl sulfone type, isocyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc., and UV absorbers include, for example, U.S. Patent No. 3253921 and British Patent No.
Compounds described in each specification etc. of No. 1309349,
In particular, 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3 '-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-5'-3
butylphenyl)-5-chlorobenzotriazole, etc., and as the dye,
Compounds described in U.S. Patent No. 2072908, German Patent No. 107990, U.S. Patent No. 3048487, U.S. Patent No. 515998, etc. can be used. It may be contained in an intermediate layer or the like. In addition, coating aids, emulsifiers,
British Patent No. 548532, British Patent No. 1216389, and U.S. Patent No. 3026202 are used as permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials.
No., specifications of No. 3514293, Special Publication No. 1977-26580
No. 43-17922, No. 43-17926, No. 43-
Publications No. 13166 and No. 48-20785, French Patent No.
Anionic, cationic, nonionic or amphoteric compounds described in the specifications of No. 202588, Belgian Patent No. 773459, JP-A-48-101118, etc. can be used. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24158,
Publications No. 89979, U.S. Patent No. 2882157, U.S. Patent No.
Specifications of No. 2972535, JP-A-48-20785, JP-A No. 48
−43130, No. 48-90391, Special Publication No. 46-24159,
No. 46-39312, No. 48-43809, Japanese Patent Publication No. 4783627
There are compounds described in various publications, etc., and as matte agents, for example, British Patent No. 1221980,
Compounds described in the specifications of U.S. Patent No. 2992101, French Patent No. 2956884, French Patent No. 1395544, Japanese Patent Publication No. 48-43125, etc., especially silica gel with a particle size of 0.5 to 20μ, 0.5 to Examples include polymers of polymethyl methacrylate having a particle size of 20μ. The emulsion layer and other constituent layers in the light-sensitive material of the present invention can be coated by various known coating methods. Coating methods include dipping coating, air knife coating, roller coating, curtain coating, and extrusion coating. US Patent No. 2681294
The method described therein is one of the advantageous methods. Further, two or more layers may be applied simultaneously using methods such as those described in US Pat. No. 2,761,791 and US Pat. No. 3,526,528. The light-sensitive material of the present invention is processed with a developer containing at least one compound represented by the following general formula []. General formula [] In the formula, Y is a nitrogen atom or a methine group, Z is a nitrogen atom or a carbon atom, W is a sulfur atom,
It is an oxygen atom or an imino group, and V is a hydrogen atom or a mercapto group. However, at least one of Y and Z is a nitrogen atom, and when Y represents a methine group, W is an imino group. n is 0 or 1, n is 0 when Z is a nitrogen atom, and n is 1 when Z is a carbon atom. R ₁ is a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group. Typical specific examples of the compounds represented by the above general formula [] are shown below, but the present invention is not limited to the use of these compounds. (Compound examples) (a-1) Benzotriazole (a-2) 4-methylbenzotriazole (a-3) 5-bromobenzotriazole (a-4) 5-nitrobenzotriazole (a-5) 5-ethylbenzo Triazole (a-6) Benzimidazole (a-7) 5-chlorobenzimidazole (a-8) 5-nitroindazole (a-9) 6-nitroindazole (a-10) 5-methylbenzindazole The above general formula [ ] Compounds represented by these formulas are generally known as development inhibitors, and the preferred amount of these development inhibitors used is 10 ^-1 to ^{10 -5} mol per developer. Especially per developer
10 ⁻² to 10 ⁻⁴ mol is preferred. Further, it is preferable that the development inhibitor is dissolved in alkanolamine and/or glycol before being added to the developer. In the method of processing a direct positive photographic light-sensitive material of the present invention, the following may be mentioned as the developer contained in the developer. Typical HO-(CH=CH) _o -OH type developers include catechol, pyrogallol and its derivatives, and ascorbic acid, as well as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5
-dihydroxyacetophenone, 2,5-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4 -Phenyl-
Catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, 4(2-hydroxybenzoyl)pyrogallol, sodium ascorbate and the like. HO-(CH=CH) _o -NH Typical ortho- and para-aminophenols or aminopyrazolones are typical _2- type developers, including 4-aminophenol, 2-amino-6-phenylphenol, and 2-aminophenol.
amino-4-chloro-6-phenylphenol,
4-amino-2-phenylphenol, 3,4-
Diaminophenol, -methyl-4,6-diaminophenol, 2,4-diaminoresorcinol, 2,4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol , p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc.

[Formula] type developers include, for example, 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-(4-amino-3-methylphenyl)- Morpholine, p-phenylenediamine,
4-amino-N,N-dimethyl-3-hydroxyaniline-N,N,N',N'-tetramethylparaphenylenediamine, 4-amino-N-ethyl-
N-(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-(β-methoxyethyl)-3 -Methyl-aniline, 4-amino-3-methyl-N-ethyl-N
-(β-methylsulfonamidoethyl)-aniline, 4-amino-N-butyl-N-r-sulfobutylaniline, 1-(4-aminophenyl)-pyridine, 6-amino-1-ethyl, 1,2, 3,4
-tetrahydroquinoline, 9-aminoyllolidine, etc. Examples of the heterocyclic developer include 1-phenyl-3-pyrazolidone (phenidone) 4,4'-
Dimethyl-1-phenyl-pyrazolidone (dimezone), 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2
-pyrazoline, 1-phenyl-3-methyl-4-
Amino-5-pyrazolone, 5-aminouracil,
5-amino-2,4,6-trihydroxyphyrimidene, etc. Other books include The Theory of the Photographic Process, 4th edition, by TH James.
Fourth Edition) paragraphs 291-334 and Journal of the American Chemical Society.
73, Section 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 it is preferable to use two or more types in combination. A preferred combination is a combination of hydroquinone and phenidone or hydroquinone and dimezone, and it is preferable to use hydroquinone in an amount of 5 to 50 g/, and phenidone or dimezone in an amount of 0.05 to 5 g/. Furthermore, even if sulfites such as sodium sulfite, potassium sulfite, and ammonium sulfite are used as preservatives in the developer used in the present invention, the effects of the present invention will not be impaired.
This can be mentioned as one of the features of the present invention.
Suitable sulfite concentration is 0.06 to 1 gram ion/g. Furthermore, hydroxyamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, 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. The pH value can be arbitrarily set within the range of 9 to 12, but a range of pH 10 to 11 is preferred from the viewpoint of storage stability and photographic performance. Alkanolamines or glycols may optionally be contained as an organic solvent in the developing solution according to the present invention. Examples of the alkanolamines include monoethanolamine, diethanolamine, triethanolamine, etc., and triethanolamine is preferably used. The amount of these alkanolamines used is preferably 20 to 500 g per developer, particularly preferably 60 to 300 g per developer. Examples of the glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, etc. Diethylene glycol is preferably used. The preferred usage amount of these glycols is per developer.
It is preferably 20 to 500 g, particularly 60 to 300 g per developer. The above alkanolamines and glycols may be used alone or in combination of two or more. In the method for processing direct positive photographic materials of the present invention, processing can be carried out under various conditions. Regarding the processing temperature, for example, the development temperature is preferably 50°C or less, particularly preferably around 30°C, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which gives good results. There are many. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, steps such as pre-hardening and neutralization, and these may be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development. The objects of the present invention can be completely achieved by the photosensitive material of the present invention and the processing method thereof detailed above. It was found that printing plates with excellent dot quality with good visibility and sharpness could be produced when printing was evaluated. EXAMPLES The present invention will be described in more detail below 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. Example 1 Rhodium chloride (Rhcl _{3.3H 2} O) dissolved in a sodium chloride solution was added in an amount of 3 x 10 ^-4 mol per mol of silver halide, and the silver chloride content was as shown in Table 1. Silver chlorobromide emulsions with varying amounts were prepared using the simultaneous mixing method at 45°C for 30 minutes. The emulsion prepared above was desalted and redispersed to obtain a monodispersed emulsion. The best performance is obtained by adding 10 mg of thiourea dioxide per mole of silver halide to this monodisperse emulsion, ripening at 60°C for 60 minutes, and then adding 3 mg of chloroauric acid per mole of silver halide. The wine was aged at 60°C until it became foggy. The fogged emulsion thus obtained was divided into five equal parts, and the coating solution formulation E ₁ was prepared as shown below.
Prepared as ~ _E5 . Preparation of coating solution E ₁ ; 1 g of 5-nitrobenzimidazole per mole of silver halide as a suppressor in one of the 5 equally divided emulsions and p-nitrophenol-di-phenylphosphonium chloride halogenated. 1 g per mole of silver, a 20% aqueous solution of saponin as a coating aid, 4 g per mole of silver halide, a styrene-maleic acid copolymer as a thickener, 5 g per mole of silver halide, and formaldehyde as a hardening agent. A finishing coating solution was prepared at 1.5 by adding glyoxal. Preparation of coating solution E ₂ : Same as the preparation of coating solution E ₁ , but in addition to the additives in E ₁ , exemplified compound (32) was added to silver halide 1 in an aqueous solution.
5×10 ^-4 per mole plus silver halide per mole
1.5 to prepare an _E2 coating solution. Preparation of Coating Solution E ₃ : Same as Coating Solution E ₂ , except that Exemplified Compound (12) was used as a 1% methanol solution in place of Exemplified Compound (32), and the concentration was 5× per mole of silver halide.
10 ^-4 mol was added. Preparation of Coating Solution E ₄ : Same as Coating Solution E ₃ , but the same mole amount of (39) as a tetrazolium compound was added instead of Exemplified Compound (12). Preparation of Coating Solution _E5 : Same as Coating Solution _E4 , but the same mole amount of (45) as a tetrazolium compound was added in place of Specific Example (39). Next, the following P ₁ was used as a coating solution for a protective film for emulsion.
A liquid was prepared. Preparation of P ₁ solution: Add 10% of pure water to 1Kg of gelatin, swell at 40℃
1% aqueous solution of sodium diethylsulfosuccinate sulfonate as a coating aid.
A 10% aqueous solution ₁ of the following structural formula f1 was added as a filter dye, 40 g of fine silica gel powder with an average particle size of 4 μ was added as a matting agent dispersed in gelatin, and formaldehyde was added as a hardening agent to give a final product of 20. (filter dye f ₁ ) Next, back coating liquid _B1 was prepared as follows. Preparation of B ₁ solution: Add 20% of pure water to 1Kg of gelatin, swell at 40℃
Then, 800 cc of the above dye F ₁ 10% aqueous solution used in P ₁ liquid was added as an additive, 16 g of styrene-maleic acid copolymer was added as a thickener, and dipropylnaphthalene was added as a coating aid. Add 16g of sodium disulfonate and make up to 30% with pure water. Preparation of backside protective film liquid: A P2 liquid was prepared in the same manner as the preparation of the emulsion protective film liquid, except that the dye _f1 was removed from _{the P1} liquid. Preparation of a silver halide photographic light-sensitive material: Combine the back coating liquid B ₁ and its protective film liquid P ₂ on polyethylene terephthalate that has been undercoated, and apply gelatin in an amount of 2 g/m 2 for the former and 2 g/m ² for the latter. After simultaneous multilayer coating with a silver content of 1 g/m ² , the emulsion coating solution and its protective film solution were combined on the opposite side in the same way, and the amount of silver was 3 g/m ²
(Amount of gelatin applied is 2 g/m ² ), and the amount of gelatin applied to the protective film was 1 g/m ² . At the time of coating, the protective film was hardened using a combination of three hardeners: formaldehyde, mucochloric acid, and ethyleneimine. Each of the above test samples was printed using an ultraviolet light room printer (ORC Manufacturing Co., Ltd.) that uses an ultra-high pressure mercury lamp as the light source.
HMW-215) using a step wedge, and a half-tone original with a blackening rate of approximately 50% was used for reprinting, and the test sample was exposed to light so that the blackening rate was approximately 50%. The exposed test sample was processed under the following processing conditions by applying a developing solution with the following formulation and a commercially available fixer to a roller conveyance type automatic developing machine (developing solution tank capacity: 40). The developing solution used was prepared by dissolving 500 ml of the stock solution of the following developing solution in 500 ml of pure water to make 1. (Processing conditions) Development: Temperature: 30°C, 30 seconds Fixation: 〃 20 seconds Water washing: 〃 20 seconds [Developer solution (undiluted solution)] Potassium bromide 2.5g EDTA-2Na 1g Potassium sulfite (55% aqueous solution) 90ml Potassium carbonate 25g hydroquinone 10g 5-methylbenzotriazole 100mg 5-nitrobenzotriazole 100mg 1-phenyl-5-mercaptotetrazole
30mg 5-nitroindazole 50mg 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.5g diethylene glycol 60g Adjust the pH to 10.6 with sodium hydroxide and make up to 500ml by adding water. The photosensitive material prepared as described above is placed in a calibrator for calibration.
After printing on the PS plate SPP with a 2KW metal halide lamp and processing it with a PS plate automatic developing machine (using Sakura PS plate developer), visual evaluation of re-inversion, missing halftone dots, and sharpness is shown in Table 1. The results were obtained. The criteria for characteristic evaluation in the table is as shown below. A: Best B: Good C: Somewhat inferior D: Inferior

[Table] As is clear from the results shown in the above table, samples of the present invention (sample No. 6, 8, 9, It can be seen that samples 10, 11, and 13) suppressed re-inversion compared to the comparative samples, and produced an excellent finish with good sharpness. Example 2 A photosensitive material was prepared in the same manner as in Example 1, but the developer used in this example was 5-methylbenztriazole, 1-
Phenyl-5-mercaptotetrazole and 5
- A developing solution was prepared by adding the compounds shown in Table 2 below in place of nitroindazole according to the amounts shown in the table. Next, the test sample created in Example 1
No. 8 was exposed to ultraviolet light in the same manner as in Example 1 using a bright room printer (ORC Seisakusho HMW-215) using an ultra-high pressure mercury lamp as a light source. Next, development was performed using a developer containing the compounds shown in the table below.

【table】

[Table] Evaluation of the sample after development processing was performed according to Example 1. The results are shown in Table 3.

[Table] As is clear from the above table, by using a developer containing the development inhibitor according to the present invention, re-inversion can be suppressed and a silver image with excellent halftone dot omission and sharpness can be obtained. I solved it. Example 3 An emulsion was prepared as in Example 1 without the addition of rhodium chloride and ripened to produce fog. Divide this emulsion into 5 equal parts and apply coating liquid formulations E ₁ to E _5.
Prepared according to. However, pinacryptol yellow was added as a desensitizer to each coating solution in the form of a methanol solution of 1 g per mole of silver halide. The images were evaluated after exposure and processing in the same manner as in Example 1. It was found that the sample using the emulsion containing the tetrazolium compound according to the present invention suppressed re-inversion and produced an excellent finish with good sharpness. I understood. (Effects of the Invention) The photographic material of the present invention achieves the above-mentioned objects of the present invention, thereby making it possible to improve the omission of halftone dots and the sharpness of images. Furthermore, the above effect can be obtained by the general formula []
This is further promoted by processing with a developer containing the compound represented by.

Claims (1)

[Scope of Claims] 1. At least one direct positive silver halide emulsion layer having a silver halide composition with a silver chloride content of 50 mol % or more on a support, and in the emulsion layer and/or A direct positive silver halide photographic light-sensitive material for bright room use containing a tetrazolium compound in at least one of the emulsion layer and the hydrophilic colloid layer on the same side of the support is a compound represented by the following general formula [] 1. A method for forming an image using a direct positive silver halide photographic light-sensitive material for bright room use, which comprises processing with a developer containing at least one type of. General formula [] [Wherein, Y is a nitrogen atom or a methine group,
Z is a nitrogen atom or a carbon atom, W is a sulfur atom, an oxygen atom or an imino group, and V is a hydrogen atom or a mercapto group. However, at least one of Y and Z is a nitrogen atom, and when Y represents a methine group, W is an imino group. n is 0 or 1, and when Z is a nitrogen atom, n is 0,
When Z is a carbon atom, n is 1. R ₁ is a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group. ]