JPS5979244A - Formation of silver image - Google Patents

Abstract

PURPOSE:To stably obtain a high contrast photographic image by processing a photosensitive material contg. a tetrazolium compd. with a developing soln. contg. a specified compd. CONSTITUTION:A photosensitive material contg. a tetrazolium compd. is processed with a developing soln. contg. a compd. represented by general formula I , and a compd. represented by general formula II or III. In formulae I , II, and III, Y is N or methine; Z is N or C; W is S, O, or imino; V is H; (n) is 0 or 1; R12 is H, halogen, or nitro; Y is -COOM', -SO3M, -OH, or -CONH2; M' is H or 1-3C alkyl; (n) is 1 or 2; W' is as W, M1 is H, alkali metal, or ammonium; R13 is H, lower alkyl, lower alkoxy, -OH, -COOH, halogen, or -SO3H; M2 is as M1; X is -COOM'' etc.; M'' is H, alkali metal, -NH'4, R14 is H or lower alkyl; and (n) is 1 or 2.

Description

[Detailed description of the invention] related.

In general, in the photoengraving process, characters and halftone-resolved photographs 1ψ
In addition, a high-contrast photographic image is used to form an image of fine lines 1; It is known that silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

Conventionally, for example, a photosensitive material consisting of a silver chlorobromide emulsion with an average grain size of 0.2μ, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol%) has been processed using sulfite. Alkaline hydride p-quinone with low ion concentration
A method of obtaining a high contrast, high sharpness, and high resolution image, such as a halftone dot image or a fine line image, by processing with I liquid has been carried out.

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

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

For this purpose, the above-mentioned lithium-type photosensitive material is used to photograph a document through an intersection screen or a contact screen, and then develop it to form a halftone dot image. .

For this purpose, silver halide copy A containing a silver halide emulsion with fine grains and uniform grain size and grain shape is used.
Even when this type of silver halide photosensitive material is used, if it is processed with a general black and white developer, the highest density area and lowest density area (fog) necessary for halftone image formation will be affected. In addition, an intermediate density area is also reproduced, and this intermediate density area becomes a 1:% anti-gradient area, ie, a fringe, which is inconvenient in plate making, resulting in deterioration of dot performance.

Furthermore, squirrel-type photolithography has traditionally been used to reproduce line drawings or fine line images, and the same principle applies.

Therefore, when a general black and white photographic developer is used, the γ of the characteristic curve is at most 5 to 6 and Ii? As an iI image, no one with optical characteristics (γ of 7 to 9) was obtained.

In order to prevent this from happening, a special developing solution as mentioned above is used, and such a developing solution is called a contagious developer or a squirrel type developer.

Here, the contagious developer or Squirrel-type developer 1!11 modified means the following: J.C. Neil, Journal Okusa Franklin Φ Institute (J, A, C!).

Yule +J, Franklin In5t,)
As described in detail in Vol. 239, p. 221 (1945), hydroquinone is essentially the only developing agent.

Normally, in the photolithography process, a large amount of developer is used because the photolithography process is carried out continuously using an automatic developing machine or self-ink plate making machine, but Lith type developer is susceptible to auto-oxidation. However, since the stability of the developer is extremely poor, a control method to keep the developing quality constant even during continuous use is required as much as possible; great efforts are being made to improve the stability of this developer. is being done.

As a method to improve this, in order to maintain the stability of the above-mentioned Lith-type developer, there is a replenisher that compensates for the deterioration in activity due to development processing (processing fatigue replenishment), and a replenisher that compensates for the increase in oxidation power over time. The so-called two-liquid separation replenishment method, in which the 0-filled liquid is used to replenish the 0-filled liquid (temporal fatigue replenishment) and the 0-filled liquid separately, is generally widely adopted in automatic developing machines for photolithography and the like. However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

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

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

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

However, since the above method uses a special tetrazolium compound, when development processing is continued for a long period of time, black sludge containing silver is generated in the processing solution, and automatic processing equipment During processing, the dirt adheres to the rollers and belts and is not transferred to the processing film, and this dirt is not completely removed during the next processing steps, fixing and washing, and once dried, the remaining dirt is removed.
&< , the finishing quality of this photographic material is degraded,
A fully satisfactory antifouling agent has not yet been found.

Incidentally, Japanese Patent Application Laid-Open No. 53-95618 discloses the addition of an inhibitor such as 1-phenyl-5-mercaptotetrazole. However, there is no mention of the use of a compound in which a water-soluble group is introduced into the benzene ring nucleus of a mercaptotetrazole compound, as in the present invention.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an image forming method for obtaining a high-contrast silver image with good halftone quality, in which staining of the film after processing is improved, and a developer with good stability is used to provide high contrast. The objective is to provide a method for forming images.

The above object of the present invention is to provide a photographic light-sensitive material containing at least one of the tetrazolium compounds represented by the following general formula [I], or 14, and at least one of the compounds represented by the following general formula 1. At least one general formula [0 General formula (3) of the compound represented by the following general formulas and/or ,
"10 and 几11 each represent an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an allyl group, a phenyl group (e.g. phenyl group, tolyl group,
hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group, etc.), naphthyl group (
(e.g., α-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic groups (e.g., thiazolyl group, benzothiazolyl group, oxacyl group, pyrimidinyl group, pyridyl group, etc.) It represents a group, and any of these may be a group that forms a metal chelate or a complex.

几2, R6 and R7 are allyl group, phenyl group, naphthyl group, heterocyclic group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group, mercaptoethyl group, etc.), hydroxyl group, carboxyl group, respectively. represents a group selected from a group or a salt thereof, a carboxyalkyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group), an amine group (e.g., amine group, ethylamine group, anilino group, etc.), a mercapto group, a 2)q group, and a hydrogen atom. , D represents a divalent aromatic group, E represents a group θ selected from an alkylene group, an arylene group, and an aralalkylene group, X represents a 7-ion group, and n represents 1 or 2. However, if the compound forms an inner salt, n is 1
It is.

In the general formula, Y represents a nitrogen atom or a methine group, Z represents a nitrogen atom or a carbon atom, W represents a sulfur atom, an oxygen atom or an imino group, and ■ represents a hydrogen atom. 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 represents 0 or 1; when 2 is a nitrogen atom, n is 0; when C, Z is a carbon atom, 11 is 1; ], 2 is a hydrogen atom,
Represents a halogen atom or a dil-I:1 group.

General formula 13 In the formula, X is -cooM', -so3M', -OB or -
OON represents each group of H□. M' represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms. n is 1 or 2, and W' represents a sulfur atom, an oxygen atom or an imino group. Ml represents a hydrogen atom, an alkali metal atom or an ammonium group. ``13 is a hydrogen atom, a lower 0 with a carbon number of 3 or less
Represents an alkyl group, lower alkoxy group, hydroxy group, carboxy group, halogen atom or sulfonic acid group.

In the general formula, M2 is a hydrogen atom, an alkali metal atom, or -NH4
represents a group, and X is 1000M", -so3M".

-01 (or -C0N1-I2, Nl'
represents a hydrogen atom, an alkali metal atom or an -NH4 group.几 and 4 represent a hydrogen atom or a lower alkyl group having 3 or less carbon atoms, and n is 1 or 2.

Next, specific examples of the tetrazolium compounds represented by general formulas 0], (4), and circles used in the present invention will be shown, but the compounds that can be used in the present invention are not necessarily limited to these.

[Exemplary Compounds] (1) 2-(benzothiapour-2-yl)-3-phenyl-5-dodecyl-2H-tetrazolium chloride (2) 2,3-diphenyl-5-(4-t-octyloxyphenyl )-2H-tetrazolium-chloride (8) 2,3.5-tripheny, 211-tetrazolium chloride (4) 2,3.5-)su(p-carboxyethyl phenyl) -2H-tetrazolium chloride (5) 2
-(bencinaazol-2-yl)-3-phenyl-
5-(o-riμluphenyl)-2H-tetrazolium bromide (6) 2,3-diphenyl-2H-tetrazolium chloride (η 2,3-diphenyl-5-methyl-2H-te(
s) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium bromide (9) 2,3-diphenyl-5-ethyl-2H-tetrazolium bromide Q (12,3-diphenyl -5-It-hexyl-2
1-1-tetrazome bromide + ill 5'/7/-2,3-sifenyl 2H-tetrazolium bromide [2-(benzothiazol-2-yl)-5-phenyl-3-(4-tolyl)- 211-tetrazolium bromide 2-(benzothiazol-2-yl)-5-(4-
phenyl)-3-(4-di-1-phenyl)-
2H-tetrazolium chloride QJ 5-ethoxycarbonyl-2,3-di(3-ditophenyl)-2
11-teI lazolium chloride (1495-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium bromide (IG 2
．． 5-diphenyl-3-(p-)yl)-21(-
Tetrazolium chloride +17) 2.5-diphenyl-3-(p-iodophenyl)-2H-tetrazolium chloride +18
2.3-diphenyl-5-(p-diphenyl) -
2H-tetrazolium chloride aI 5-(p-bromophenyl)-2-phenyl-3-(2,4,6-1
-Rikplufenyl) -2) 1-tetrazolium chloride C! 1 3-(p-hydroxyphenyl)-5-(
p-ditho1phenyl)-2-phenyl-211-tetrazolium chloride C! 11 5-(3,4-9me)xyphenyl)-3
-(2-ethoxyphenyl)-2-(4-methoxyphenyl) -2H-tetrazolium chloride @ 5-(4-cyanophenyl)-2,3-diphenyl-2H-tetrazolium chloride (c) 3-(
p-7cetamidophenyl)-2,5-diphenyl-2H-tetrazolium bromide 1245-7cetyl-2,3-diphenyl-2H-tetrazolium bromide (ha) 5-(flu-2yl)-2,3- Diphenyl-2H-tetrazolium chloride @ 5-(tinyCno-2yl) -2,3-diphenyl-211-tetrazolium chloride @ 2,3-diphgonyl-5-(pyrid-4yl)-2
H-tetrazolium chloride @2,3-diphenyl-5-(quinol-2-yl)
-21(-tetrazolium bromide G!12.3-diphenyl-5-(benzoxazol-2yl) -
2H-tetrazolium bromide (to) 2.3-diphenyl-5-nido 2H
-tetrazolium bromide (102,2',3.3'-tetraphenyl-5,5
'-1゜4-butylene-di(2N-tetrazolium)
Bromide (a) 2,2',3,3'-tetraphenyl-5,5'-p-phenylene-di(2H-tetrazolium)zulomide (12-(4,5-dimethylazol-2yl)- 3,
5-diphenyl-2H-tetrazolium breamide (193,5-diphenyl-2-(triazin-2yl)-2H-tetrazolium czilide (a) 2-(benzothiazol-2yl)-3-(4-nod) xyphenyl)-5-7enyl-211-tetrazolium solmide (to) 1-methyl-2-phenyl-211-1,2
, 3-triazolium bromide (1'6l-n-bupyl-2-)x---ru2H
-1,2,3-triazolium bromide@2-(4-methoxyphenyl)-3-phenyl-2j(-naphtho-(1,2-d) -1,2,3-
Triazolium coulide (2) 1.5-(9,10-andraquinolino L)
-bis-(2-(3-phenyl)-2tl-naph I.
-(1,z-a)-1,2,3-)riazolium)ri-2,3-2(4-methoxyphenyl)-5-nitro2H-naphtho(1,2-d)- 1,2,3-triazolium chloride@t12-p-iodophenyl-3-p-nitrophenyl-5-phenyl-2H-tetrazolium chloride
9 θ Examples of the anion represented by X in the tetrazolium compound of the present invention include chloride ion, bromide ion,
Halogen ions such as boride 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, and anionic acids.

ion-based activators, specifically p-)lower alkylbenzenesulfonate anions of 7A4 luenesulfonic acid,
Higher alkyl benzene sulfonate anions such as p-dogylbenzene sulfonate anions, higher alkyl sulfur CIs such as lauryl sulfate 7 anions! Ester anions, boric acid anions such as tetraphenyl boron, G2
- Polymers such as dialkyl sulfosuccinate anions such as ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxysulfate 7 anions, higher 11-styl fatty acid anions such as stearate anions, and polyacrylate anions. Examples include those with acid roots.

Preferred properties can be obtained by using the tetrazolium compounds used in the present invention alone, but the preferred properties will not deteriorate even if a plurality of them are combined in any ratio.

In one preferred embodiment of the present invention, the tetrazolium compound of the present invention is added to the silver halide emulsion layer. In another preferred embodiment of the invention, it is added to a hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to a hydrophilic colloid layer adjacent via an intermediate layer.

In another embodiment, the tetrazolium compound of the present invention is dissolved in a suitable organic solvent, for example, alcohols such as methanol and ethanol, ethers, esters, etc., and a silver fluoride photographic light-sensitive material is prepared by overcoating or the like. The photosensitive material may be incorporated into the photographic material by directly coating the outermost layer of the photosensitive material.

The tetrazolium compound of the present invention is contained in the photographic material of the present invention in an amount of 1 x 10 mol to 10 mol, particularly 2 x 10 mol to 2 x 10 mol, per 1 mol of silver halide contained in the photographic light-sensitive material of the invention.
It is preferable to use the range up to 100%.

The silver halide used in the /%q silver genide photographic light-sensitive material to which the present invention is applied includes silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloride, or a mixture thereof. Any of those used in conventional silver halide photographic emulsions such as, etc., are included. In particular, when using a light-sensitive material that is exposed using a printer using metalnolide or a high-pressure mercury lamp as a light source, the silver halide composition should be 70 mol% or more of silver chloride, especially 95 mol% or more of chloride. Silver-containing silver chlorobromide is preferred. These silver halides may be of coarse grain or fine grain and may be prepared by any known method, such as U.S. Pat.
, No. 877, No. 3,317,322, No. 2,22
No. 2,264, No. 3,320,069, No. 3,2
06,313 or [Journal of Photographic Science (J, Phot,
Sci, ) J gf (Volume 12, No. 5 (September, October issue), 4964, pp. 242-251, etc.)
It can be adjusted by the method etc.

It is also possible to use a mixture of silver halides prepared by different methods.

The silver halide contained in the silver halide emulsion layer of the photographic light-sensitive material used in the present invention has an average grain size of 0.05 to 1.5μ, preferably 0.1 to 0. .5μ and at least 75 of the total particle count
%, preferably 80% or more of said average particle size.
It is desirable to include silver halide having a grain size of 5 to 1.5 times, preferably 0.6 to 1.4 times.

According to the most preferred embodiment of the present invention, the silver halide of the present invention has an average grain size of 0.1 to 0.3 microns, and more than 80% of the total grains have an average grain size of 0.3 microns. 6
It is silver chloride or silver chlorobromide with a grain size of ~1.4 times.

In addition, iridium, rocum, osmium, bismuth, cobalt, nickel,
Atoms such as palladium, ruthenium, 'LM, zinc, lead, and cadmium may be contained. When these atoms are contained, the content is 10-8 to 1 O- per mole of silver halide.
It is preferable to contain 2 mol, especially 10-6 to 10-
It is suitable to contain 4 moles. Further, it may be of the surface latent image type or the internal latent image type, and silver halides prepared by various different methods may be mixed.

There are no restrictions on the shape of the crystal habit, such as hexahedron, octahedron, hexahedron, spherical, etc.

The silver halide and tetrazolium compounds used in the present invention are added to 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, such as phenylcarbamyl gelatin, acyl as described in U.S. Pat. Nos. 2,614,928 and 2,525,753, gelatin, phthalated gelatin, or U.S. Patent No. 2.548.52
Styrene acrylate, 7-acrylic ester, as described in the specifications of No. 0 and No. 2,831,767,
Hydrophilic colloids such as those obtained by graft polymerizing gelatin with polymerizable monomers having an ethylene group such as methacrylic acid and methacrylic acid ester can be mentioned.
It can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

The silver halide photographic light-sensitive material to which the present invention is applied is formed by coating a hydrophilic colloid layer containing the silver halide and tetrazolium compound of the present invention on a suitable photographic support. Examples of supporting bodies include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene. Films and the like are typically included, and each of these supports is appropriately selected depending on the intended use of the silver halide photographic material.

A silver halide photographic light-sensitive material to which the present invention is applied is as described in 1 above, a silver halide used in the light-sensitive material on a support,
At least one hydrophilic colloid layer containing a tetrazolium compound is coated on the silver halide photographic light-sensitive material to which the present invention is applied, and a protective layer having an appropriate thickness is preferably used. It is desirable that a gelatin protective layer of 0.1 to 10 μm, particularly preferably 2 μm to 2 μm, is coated.

The hydrophilic colloid used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners,
Surfactant, image stabilizer, ultraviolet absorber, antistain agent, pif adjuster, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development speed adjuster, Matting agents and the like can be used within a range that does not impair the effects of the present invention.

Among the above-mentioned various additives, those which can be particularly preferably used in the present invention include, for example, thickeners or plasticizers described in US Pat.
Publication No. 39, West German Application Publication No. 1.904,604, Japanese Unexamined Patent Publication No. 48-63715, Japanese Patent Publication No. 45-154
Publication No. 62, Belgian Patent No. 762,833, U.S. Patent No. 3,767.410, Belgian Patent No. 558
, No. 143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, etelesoimine-based, active halogen-based, and vinyl sulfone. Various hardeners and ultraviolet absorbers such as inocyanate, incyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and 7-siloyl type, and ultraviolet absorbers include those described in US Patent No. 3.
253,921, British Patent No. 1,309,349, etc., especially 2-(2'-
Hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3/,51-di-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5' -butylphenyl)
-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5'-di-tertiary butylphenyl)-5-chlorobenzotriazole, etc.; , 072,908, German Patent No. 107.990, U.S. Patent No. 3.048°487
Compounds described in various specifications such as No. 1 and US Pat. No. 515,998 can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer, etc. 1 more
Coating aids, emulsifiers, permeability improvers for processing liquids, etc.
Antifoaming agents or surfactants used to control various physical properties of photosensitive materials include British Patent No. 543.532, British Patent No. 1,216,389, and U.S. Patent No. 3,026,202. , same No. 3,514,293
Specifications of each issue, Japanese Patent Publication No. 44-26580, Japanese Patent Publication No. 43-1
No. 7922, No. 43-17926, No. 43-1316
Publications No. 6, No. 48-20785, French Painting Patent No. 20
It is possible to use anionic, cationic, nonionic, or amphoteric compounds described in Patent No. 2,588, Belgian Patent No. 773.459, % Kokai No. 101118/1983, etc. can. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 48-89
No. 979, U.S. Patent No. 2,882,157,
Specifications of No. 2.972,535, JP-A-48-2
No. 0785, No. 48-43130, No. 4B-9039
No. 1, Special Publication No. 46-24159, No. 46-39312
There are compounds described in various publications such as No. 4B-43809 and JP-A No. 47-33627, and matting agents include, for example, British Patent No. 1,221,980 and U.S. Patent No. 2.992. .101, same No. 2,956,88
No. 4, the specifications of French Painting Patent No. 1.395゜544, Japanese Patent Publication No. 48-43125, etc., particularly polymers of polymethyl methacrylate having a particle size of 05 to 20μ. be able to.

Examples of the developer contained in the developer used in the present invention include the following.

Typical HO-(OH=OH)n-OH type active agents include catechol, pyrogallol and its derivatives, and ascorbic acid; Hydroquinone 7', methylhydroquinone, 2.3-dichlorono\hydroquinone, 2.5
-dimethylnoid p-quinone, 2゜3-dibromohydroquinone, 2.5-nino-hydroxyacetophenone,
2,5-diethylnohydroquinone, 2,5-di-p-
7-enenarno-1-hydroquinone, 2,5-dibenzoylamino/1-ido p-quinone, catechol, 4-PEcatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-7 cetyl-hirogapol , 4(2'-hydroxybenzoyl)pyrogallol, sodium ascorbate, etc.

Typical HO-(OH=OH)n-NH2 type developers are ortho and hihara 7 minophenol or 7 minopyrazopno, 4-7 minophenol, 2-7 minnow 6-phenylphenol. , 2-amino-4-ri I:Ic
y-5-phenylphenol 4-7minor 2-phenylphenol, 3.4-diaminophenol, 3-methyl-4,6-diaminophenol, 2.4-cyamylsorcinol, 2.4.6-dori7 Minophenol, N-
Methyl-p-7 minophenol, N-β-hydrooethyl-p-7mi/phenol, p-human σ-xyphenyl 7-minoacetic acid, 2-7 minonaphthol, and the like.

Examples of the 112N-(0=O)n-Nu□ type developer include 4-7 minnow 2-methyl-N, N-diethylaniline, 2,4-diamino-N, N-diethylaniline, N-(4 -amino-3-methylphenyl)-7ulfoline, p-7 enylenediamine, 4-amino-N,
N-dimethyl-3-human pxy7niline, 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-
methylsulponamidoethyl)-aniline, 4-amino-N-butyl-Nr-sulfobutylaniline, t-(
4-7minophenyl)-pyrrolidine, 6-amino-1-
ethyl, '1.2.3.4-tetrahydroquinoline, 9-aminoylolidine, etc.

As a heterogeneous developer, for example, 1-phenyl-3
-Pyrazolidone (phenidone), 1-phenyl-4-amino-5-pyrazolone, 1-(p-7minophenyl)-
3-amino-2-pyrazoline, 1-phenyl-3-methyl-4-amino-5-pyrazolone, 4,4'-dimethyl-1-phenyl-pyrazolidone (dimezone), 5-aminolaucil, 5-amino-2, 4,6-1-lihydroxyphyrimidene, etc.

Others include 'I', The Theory of the Photographic Process, 4th edition, by IL James.
Theory of the Photograpbi
cProcess *Fourth Edition
) pp. 291-334 and Journal of the
American Chemical Society (Journal)
of the American ChemicalS
73, page 3100 (1951)
Developers such as those described in the following can be effectively used in the present invention. Even if these developers are used alone, 2
Although Hi or more may be used in combination, it is preferable to use two or more in combination. A preferred combination is a combination of hydroquinone and phenidone or hydroquinone and dimezone, where hydroquinone is 5g to 50 t/t
, and phenidone or dimezone from 0.05g to 5g/
It is suitable to use within the range of l. Furthermore, even if a sulfite such as sodium sulfite, potassium sulfite, and sulfite is used as a preservative in the developer used in the present invention, the effects of the present invention will not be impaired, and the This can be mentioned as one of the characteristics. Sulfite concentration is 0.06-1
Gram ions/l is preferred.

Furthermore, hydroxycylamine and hydrazide compounds may be used as preservatives. Adjustment of pH with caustic alkali, alkali carbonate, or 7 mm/ml, which can be used in a general black and white developer, and provision of a buffer function; inorganic development inhibitors such as brompot; metal ion scavengers such as ethylenediaminetetraacetic acid; Development accelerators such as methanol, ethanol, benodyl alcohol, polyalkylene oxide, sodium alkylarylsulfonates, surfactants such as natural saponins, sugars or alkyl esters of the above compounds, glugulaldehyde, formalin, gluoxal, etc. It is optional to add a hardening agent, an ionic strength adjusting agent such as sodium sulfate, etc. -■ value is 9
Although the pH can be set arbitrarily between pH 10 and pH 12, it is preferable to use the pH within the range of pH 10 to 11 in terms of stability and photographic performance.

Examples of alkanolamines used in the present invention include evaporated monoethanolamine, diethanolamine, triethanolamine, etc., with triethanolamine being preferred. The preferred content of these alkanolamines is 20 to 5,002 per ton of developer, especially in the case of 1 ton of developer. 60 to 300 f per 1 t of lI liquid is preferable.

Examples of the glycols used in the present invention include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, and 1,5-pentanediol, with diethylene glycol being preferred. The preferred usage amount of these glycols is 20 to 500 per ton of developer.
t, particularly preferably 60 to 300 t per ton of developer.

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

Preferred exemplary compounds as compounds represented by the general formula used in the present invention are listed below.

(1): 5-nitroindazole (2): 6-nitroindazole (8): 5-methylbenztriazole (4): 6
-methylbenztriazole (51: 5-nitrobenzimidazole (6): 6-nitrobenzimidazole, etc.).

Next, examples of preferred compounds represented by general formula (2) are listed below, but the invention is not limited thereto.

Exemplary Compounds] (1) -IU31 αυ H3 Next, specific examples of the compound represented by the general formula (9) are shown below, but are not limited thereto.

Exemplary Compounds] (1) H (2) Na Na038 N =N N=N (4) kl N=N (5) 8 to 1 (6) H N=N Na N=, =N (8) II ( 9) 1-1 -N Ql) The compound represented by the general formula (concave) has a compound of 10 to 10% per developer.
10 moles, more preferably 10 to 10 moles, and the compound represented by the above and/or The preferred content of the inhibitor is 5 10 to 10 mol per ton of developer, particularly preferably = 4 10 to 10 mol i + "- per t of developer. The above development inhibitor is alkano!, amine and/or t It is preferable to bathe it in glycols and then add it to the developer.

Processing with a developer in the present invention can be carried out under various conditions.The development temperature is preferably 50°C or lower, particularly preferably around 30°C, and the development time is generally completed within 3 minutes. However, preferably within 2 minutes often brings about good results. Processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening, neutralizing, etc. may optionally be employed, and these may be omitted as appropriate. Furthermore, these processes may be mechanical development such as so-called theory (p'? process, roller development, etc.) such as plate development and frame development, and negative image development.

The present invention will be explained in more detail by referring to Example f'lI below. The technical scope of the present invention is not equally limited by the following examples, and various embodiments are possible.

In particular, embodiments of the present invention are suitable for use in so-called bright-room type silver halide photography for low-sensitivity low-speed photography.
Although the materials will be explained, the present invention is not limited thereto in any way.

Example-1 While keeping liquid A of the following formulation at 42°C, liquid B and liquid C?
The average particle size is 0.0000000000000000000000000000000000000000000.
A 18 μm filled silver emulsion (composition: 98 mol% chloride, 2 mol% bromide) was priced at ¥Aa. 5 minutes after the end of physical ripening, 4-hydroxy-6-methyl-1,3,3a + 7-ttrazaindene 32 was added, marketed to prevent particle growth, and washed with desalted water three times, then gelatin for dispersion was added and the mixture was washed with water for 50 minutes. ℃30
After obtaining an emulsion dispersed for minutes, 0.162 of sodium thiosulfate was added as a chemical sensitizer, and the mixture was further aged for 60 minutes. At the end of aging, 4-hydroxy-6-methyl-1,3゜3a,
After adding 3 f of 7-chitrazaindene and 160 l of 10% gelatin water bath solution, pure water was added to the obtained emulsion to make it to 5 t.

Solution A Solution B Solution 2 6 6 t49 Solution C A coating solution was prepared as follows using the above-mentioned 5t emulsion.

[Preparation of Coating Solution E1] 500 ml of the above emulsion was sampled in 1 portion, and 300 ml of a 1% aqueous solution of 2.3.5-triphenyl-2H-tetrazolium chloride as a compound represented by the general formula (2) was used as a coating aid. 30 ml and 101 ml of styrene-maleic acid copolymer as a thickener.
A coating solution Eyu finished in t was obtained.

[Preparation of coating iP1 for protective film for emulsion] Add 10 L of pure water to I kg of gelatin, swell, and then warm to 40°C. Add 1% aqueous solution of sodium diethylsulfosuccinate sulfonate as a coating aid to 31 kg of gelatin, filter. A 10% aqueous solution gxt of the following compound f1 was added as a dye, and a methyl methacrylate copolymer 30f having an average particle size of 1 to 0.3 microns was dispersed in gelatin and added as a matting agent to obtain 201.

Compound f, (dye): [Preparation of back coating liquid B1] Add pure water 201 to gelatin L Kq, and after swelling, heat at 40°C.
10% each of the above compound f1 and the following compound f2 used in the emulsion-holding film liquid as an additive.
Add 800% aqueous solution and add styrene as a thickener.
Maleic acid copolymer 16? , saponin was added to 162 as a coating aid and finished to 301 with pure water.

Compound f2 (dye): 803N a [Preparation of back protective film 7IIB2] This was prepared in the same manner as the pupil retention film liquid for emulsion, except that the dye f1 was removed.

[Creation of halogenated photographic material]

Coating liquid B1 for the back surface and its protective film liquid B2 were simultaneously coated on polyethylene terephthalate that had been subbed using a multilayer coating machine, and the amount of gelatin applied was 22/-1 for the former and 12/-1 for the latter.
Become sluggish. L was applied to the sea urchin. In the same way, combine the emulsion coating solution and its protective film solution on the opposite side of the support, and then apply the gelatin coating solution to 2.5? I wrapped it so that it would look like this.

In addition, when coating the back coating liquid and its protective film liquid on the support, and furthermore the emulsion layer and its protective film liquid on the opposite side, formalin hardener and ethyleneimine hardener are added to the protective film liquid. was added and hardened.

The above test sample was applied to an ultraviolet bright room printer (1:) RO Seisakusho BMW-215) that uses an ultra-high pressure mercury lamp as a light source.
It was then exposed to light by performing a back-burning process with a light intensity of 10 mJ. The original used for the exposure was a halftone original with a blackening ratio of about 50%, and the test sample that was reprinted had a ratio of approximately 1:1. The exposed test sample was placed in a roller conveyance type automatic developer 1a (developer tank capacity: 115 tons) using a developer (1) having the following formulation and a commercially available fixer, and processed under the following processing conditions.

Developer Solution (Processing Conditions) Compounds shown in Table 1 below were added to the above developer solution to prepare respective developer solutions.

Below is the margin: 300 m of the exposed test sample was prepared using this developer.
1. 200- was processed while replenishing with a replenisher having the same composition as the starting solution at a ratio of /rrl, and the film was visually observed and evaluated for stains. It is shown in Table 2 below.

Table 2 From the above results, it is clear that the treatment according to the present invention improves staining.

Furthermore, when the rollers of the automatic processor were observed after processing, it was also observed that the rollers were less stained when the developer formulation was used to cause less smearing of the film.

Further, the returned halftone dot values obtained during processing were of high quality with high edge contrast in the combination of the present invention.

Procedural amendment (voluntary) December 3, 1980 Director General of the Japan Patent Office Wakasugi Hao 1, Indication of the case 1989 Special Patent Application No. 189117 3, Relationship with the case of the person making the amendment Patent issue 1. '11 Artificial 4 inscriptions)
(1, 2, 7,) Konishi Rokuryoku Shin Kogyo Co., Ltd. 4, Agent 〒105 6, Number of inventions that will increase from the amendment 7, Subject of the amendment A11l f (Details of the invention i: II) Explanation 4 part 1
) 8, Contents of correction As shown in the attached sheet O Contents of correction 1 Meiyudenaka No. 4114 dry 1ii', formula (8) N =
ゞ"ゞ="" To correct the statement, continuation amendment (automatic) (August 13, 1980, Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office) Display of the case 1989 Patent Application No. 189117 2 Invention Name Silver image forming method 3 Relationship with the case of the person making the amendment Applicant name (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent 105 5 Date of amendment order Initiation 6 Number of inventions increased by amendment 7 Supplemental Subject specification (detailed description of the invention column) 8 Contents of amendment (1) Page 48 of the specification, bottom line number B: “Potassium bromide 2.5 g

Claims (1)

[Scope of Claims] A photographic light-sensitive material containing at least one type of tetrazolium compound represented by the following general formula Or, CtO or Circle,
At least one compound represented by the following general formula and/or the general formula represented by the following general formula and/or (2) [in the formula, 几5, 几3, R4%''5 , R8, 几9, IL
,. and R□1 each represent a group selected from a furkyl group, an allyl group, a phenyl group, a naphthyl group, and a heterocyclic group, and any of these may be a group capable of forming a metal chelate or a complex. R2, ■t6 and ■
(Respectively, allyl group, phenyl group, naphthyl group, heterocyclic group, alkyl group, hydroxyl group, carpoxyl group or its salt, carboxyalkyl group, amino group, mercapto group,
represents a group selected from a nitro group and a hydrogen atom, D represents a divalent aromatic group, E represents a group selected from an alkylene group, an arylene group, and an aralkylene group, Q represents an anion, and n represents 1 or Represents 2. However, when the compound forms an inner salt, n is 1. ] General 2U [In the formula, Yii represents a nitrogen atom or a methine group, Z represents a nitrogen atom or a carbon atom, W represents a sulfur atom, an oxygen atom or an h imino group, and ■ represents a hydrogen atom. However, at least one of Y and 2 is a nitrogen atom, and Y
When represents a methine group, W is an imino group. n represents 0 or 1; when Z is a nitrogen atom, n is 0;
When is a carbon atom, n is 1. R1□ represents a hydrogen atom, a halogen atom or a nitro group. ] General formula [In the formula, X is 1000M', -803M', -
represents each group of OH or -0ONH2, M' represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms, n is 1 or 2, W' represents a sulfur atom, an oxygen atom or an imino group, Ml represents a hydrogen atom, an alkali metal atom, or an ammonium group, and 3 represents a hydrogen atom, a lower alkyl group having 3 or less carbon atoms, a lower alkoxy group, a hydroxy group, a carboxy group, a halogen atom, or a sulfonic acid group. ] General formula [In the formula, M2 is a hydrogen atom, an alkali metal atom, or -N
l-! 4 groups, X is 1000M", -8o3M
". represents each group -OH or -a ON H□, and λ4" represents a hydrogen atom, an alkali metal atom or a -NH4 group.
R''14 represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms, and n is 1 or 2.]