JPS624704B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a photographic image using a silver halide photographic light-sensitive material, and more particularly, it relates to a method for forming a photographic image using a hydrazine compound to produce an extremely high contrast negative image, in particular, good halftone quality and halftone gradation. The present invention relates to a stable activator-type developing method capable of forming a halftone image having . When printing a continuous tone original using an offset printing plate, the tone is reproduced by a collection of large and small dots called halftone dots. There are 80 to 200 or more halftone dots per inch, and each dot must be extremely small and must be sharp with no blur around it. For this reason, in the printing industry, a combination of a Lith-type photosensitive material and a Lith developer is used, which can obtain ultra-high contrast halftone images due to a special developing effect called the Lith effect. Lith developer is generally an alkaline solution in which the concentration of sulfite ions, which serve as a preservative, is kept extremely low and only hydroquinone is used as a developing agent. When developing a lithium-type photosensitive material with this solution, generally speaking, the lower the sulfite ion concentration, the higher the tone of the lithium-type photosensitive material. However, the general properties of lithium-type photosensitive materials are that they are greatly affected by the concentration of the developing agent and are also sensitive to changes in the bromide ion concentration, making it difficult to consistently obtain images of constant quality. Have difficulty. Furthermore, since the concentration of sulfite ion as a preservative in the Lith type developer is extremely low, the resistance to oxygen in the air after preparation is extremely low, and there are drawbacks such as severe deterioration. Furthermore, when a lithium-type light-sensitive material is continuously processed, bromide ions are released from the emulsion layer and the developing agent is consumed, just as with ordinary silver halide light-sensitive materials, so even if replenishment is performed, It is necessary to check and correct the activity of the developer every few hours, which causes troublesome daily management. Furthermore, when processing with such conventional methods, it is necessary to obtain sufficient blackening density and halftone dot quality.
A long development time of 1 to 2 minutes was required at a development temperature of 25°C to 35°C. Therefore, there has been a strong demand for a method that does not have the above-mentioned drawbacks and can provide ultra-high contrast and good halftone dot quality and halftone gradation. JP-A No. 51-22438 discloses that in order to avoid the use of unstable Lith developer, a hydroquinone type developing agent is contained in a silver halide emulsion, and an alkaline solution is added in the presence of a hydrazine compound such as hydrazine sulfate. A method for obtaining a high-contrast negative image by processing with an activator is disclosed. According to this method, the stability of the treatment liquid can be improved and the treatment speed can also be increased. However, although the method disclosed above can provide high-contrast characteristics similar to those of lithographic photosensitive materials, the halftone dot quality is inferior to that of current lithographic photosensitive materials, and the halftone dot characteristics are not suitable for plate-making applications using contact screens. It also has the disadvantage that the halftone gradation is too hard. In addition, when the hydrazine compound having an NH ₂ NH- group in the above-mentioned known example is incorporated into a light-sensitive material, it may be because the compound decomposes markedly over time.
It becomes difficult to maintain the high contrast characteristics obtained in the early stages of manufacturing photosensitive materials for a commercially necessary long period. Therefore, by incorporating these hydrazine compounds into a light-sensitive material, it is impossible to produce a light-sensitive material that is substantially capable of producing high-contrast images. Further, US Pat. No. 2,419,975 discloses a method of obtaining a high-contrast negative image by adding a hydrazine compound to a silver halide emulsion. The patent specification states that by adding a hydrazine compound to a silver chlorobromide emulsion and developing it with a developer with a high pH of 12.8, extremely high contrast photographic properties with a gamma (γ) exceeding 10 can be obtained. Are listed. However, many of the hydrazine compounds disclosed herein have poor stability in photosensitive materials and cannot be stored for long periods of time, and strong alkaline developers with a pH close to 13 do not allow the developing agent to be oxidized by air. It is easily damaged and unstable, and cannot withstand long-term storage or use. Furthermore, the development time is not much different from conventional lithography. Furthermore, γ
A photographic characteristic of high contrast of 10 or more alone is insufficient for use in plate-making applications such as those using contact screens, as the halftone dot quality is poor and the halftone gradation is too high. To discuss halftone quality and halftone gradation in detail, halftone quality refers to the performance of a dot when converting the level of blackening density into the size of a dot area through a contact screen, and generally the fewer fringes the better. Further, the halftone dot gradation represents the change in the halftone dot area with respect to the amount of exposure, and is theoretically a property determined by the density pattern of the contact screen used. Therefore, the above-mentioned Japanese Patent Application Laid-Open No. 51-22438
According to the method of the invention described in U.S. Pat. . However, as mentioned above, selecting a contact screen each time according to the photosensitive material used causes a great deal of trouble to those involved in the actual plate-making work, which is undesirable. Therefore, good halftone dots with few fringes can be obtained by using a stable processing solution, and there is no need for special operations such as selecting a contact screen, and the same contact screen can be used as when using conventional Lith development. For practical purposes, it has been strongly desired to create a photosensitive material that can provide the same halftone gradation. The present applicant previously solved the above-mentioned drawbacks by incorporating an acylhydrazine compound that is stable in a light-sensitive material and a hydroquinone developing agent into a silver halide light-sensitive material, and using an alkaline activator. We filed an application for a method to quickly obtain high-contrast negative images by processing
No. 54-85660). According to this method, good halftone dot quality and good halftone gradation can be obtained, but further improvement in halftone dot quality is desired. Furthermore, it has been found that this method has a drawback in that the quality of halftone dots tends to vary depending on the stirring conditions during processing. Therefore, the first object of the present invention is to provide a method for obtaining extremely high-contrast negative images with a gamma (γ) of more than 10 using a stable processing solution and a stable photosensitive material. A second object of the present invention is to provide a method for obtaining halftone dot image quality more quickly and with better halftone image quality than the conventional Lith developer using a stable processing solution and a stable photosensitive material. A third object of the present invention is to use a stable processing solution and a stable photosensitive material to obtain substantially the same halftone gradation as when using a conventional lithium developer, and to use a special contact screen. It is an object of the present invention to provide a method for forming a squirrel image that does not require selection. A fourth object of the present invention is to provide a method for obtaining a halftone image having better halftone quality than the methods described in Japanese Patent Application Nos. 54-78338 and 54-85660. It is. A fifth object of the present invention is to provide a method for forming a halftone image in which processing liquid management and processing operations are simple, and the quality of halftone dots does not change due to changes in processing operations, especially changes in stirring conditions. It is. The above-mentioned objects have at least one silver halide emulsion layer, and at least one of the other hydrophilic colloid layers contains a hydroquinone developing agent and a compound represented by the following general formula (). A surface latent image type silver halide photographic light-sensitive material is imagewise exposed, and then the material contains a compound represented by the following general formula () and has a pH of
This was achieved by treatment with an aqueous activator solution of 11.5 or higher. R ¹ NNHHCOR ² () [In the formula, R ¹ represents an aryl group, and the aryl group may be substituted. R ² represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. ] [In the formula, R ³ represents a hydrogen atom or a lower alkyl group. R ⁴ represents a hydrogen atom, a lower alkyl group or a carbamoyl group. ] The compound represented by the general formula () exists stably in a silver halide emulsion, but is unstable in an alkaline aqueous activator solution. In addition, the compound represented by the general formula () exists stably in an aqueous activator solution, but in a silver halide emulsion it decomposes or changes over time, so it loses its property of providing a high-contrast negative image. I'll get lost. Therefore, in the present invention, the compound represented by the general formula () is used by being contained in a silver halide emulsion, and the compound represented by the general formula () is used by being added to an alkaline aqueous activator solution. . By using the method of the present invention, the method of Japanese Patent Application No. 78338/1978 and Japanese Patent Application No. 85660/1970 previously filed by the present applicant (containing the general formula () in a silver halide emulsion, This improves the disadvantage of the method of processing with an aqueous alkaline activator solution in which the quality of halftone dots tends to fluctuate due to changes in the stirring conditions during treatment, and further improves the quality of halftone dots. The light-sensitive material used in the present invention contains a compound represented by the general formula () and a hydroquinone developing agent in at least one of the silver halide emulsion layer and other hydrophilic colloid layer, and has a substantially surface-containing This is an image-type silver halide photographic material. The compound represented by the above general formula () will be explained in more detail. In the general formula (), among the groups represented by R ¹ , the optionally substituted aryl group is a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring or a naphthalene ring, particularly preferably a benzene ring. This aryl group may be substituted, and preferred substituents include linear, branched, and cyclic alkyl groups (preferably those having 1 to 20 carbon atoms; for example,
methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.), aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms).
For example, a benzyl group), an alkoxy group (preferably one having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group), a substituted amino group (preferably one having 1 to 20 carbon atoms),
substituted with an alkyl group. For example, dimethylamino group, diethylamino group), aliphatic acylamino group (preferably one with an alkyl group having 2 to 21 carbon atoms, e.g. acetylamino group, heptylamino group), aromatic acylamino group (preferably monocyclic or bicyclic (eg, benzoylamino group) or a group represented by X-(Y-) _o . In the group represented by X-(Y-) _o above, (1) n means 0 or 1; (2) Y is a divalent linking group, such as -CONH-, -R ¹¹
-CONH-, -O-R ¹¹ -CONH-, -S-R ¹¹ -
CONH−, −R ¹¹ −, −R ¹¹ −O−R ¹² −, −R ¹¹ −
S−R ¹² , −SO ₂ NH−, −R ¹¹ −SO ₂ NH−, −
NHCONH−, −CH ₂ −CH−N−, −R ¹¹ −NH
−, −R ¹¹ −O−R ¹² −CONH−, −NHCO−R ¹¹
−, −NHCO−R ¹¹ −CONH−, −R ¹¹ −R ¹² −, etc. Here, R ¹¹ and R ¹² may be the same or different, and each is a divalent saturated or unsaturated aliphatic group (e.g., ethylene group, butenylene group, 1-methylpropylene group, 1-methylmethylene group, etc.), or A divalent aromatic group (which may have a substituent such as an amino group; for example, a phenylene group, a naphthylene group, a 5-
(amino-1,2-phenylene group, etc.).
However, in the case of -R ¹¹ -R ¹² -, R ¹¹ and R ¹² are divalent groups different from each other. X is

[Formula] a group having a unit,

[Formula] a group having a unit,

A group represented by [Formula], a heterocyclic residue, an aralkyl group (when n = 1), an alkyl group-substituted aryl group,

[Formula] means a group. Here, the heterocyclic residue is a 5- or 6-membered ring containing at least one heteroatom, which may be fused with an aromatic ring, especially a benzene ring, and is preferably a monovalent group of a heterocyclic compound ( For example, 1,2-benztriazol-5-yl, 5-tetrazoyl, indazol-3-yl, 1,3-benzimidazol-5-yl, hydroxytetrazainden-2
- or -3-yl), monovalent groups of heterocyclic quaternary ammonium salts (e.g. N-ethylbenzthiazolinium-2-yl, N-sulfoethyl-benzthiazonylium-2-yl, N.N -dimethylbenzimidazolinium-2-yl), monovalent groups of heterocyclic compounds having mercapto groups (e.g. 2-mercaptobenzthiazol-5- or -6-yl, 2-mercaptobenzoxazole-5- or -6-yl, etc.). The aralkyl group represented by X refers to a monocyclic or bicyclic aralkyl group in which the alkyl group has 1 to 3 carbon atoms, such as a benzyl group. Examples of the alkyl-substituted aryl group represented by X include 2,4-di-t-amyl-1-phenyl group. X means

[Formula] A group having a unit and Then, preferably

【formula】

【formula】

【formula】

[Formula] Examples include groups, and Ta

[Formula] As a group having a unit,

[Formula] Group or

[Formula] groups are preferred. Here, R ²¹ is an aliphatic group (e.g., an alkyl group,
cycloalkyl group, alkenyl group), aromatic group (e.g. phenyl group, naphthyl group) or heterocyclic group (e.g. thiazolyl group, benzothiazolyl group,
(imidazolyl group, thiazolinyl group, pyridinyl group, tetrazolyl group, etc.), R ²² represents a hydrogen atom, an aliphatic group exemplified for R ²¹ or an aromatic group exemplified for R ²¹ , R ²³ represents a hydrogen atom or R ²¹ represents the aliphatic group exemplified above, and R ¹¹ represents the same meaning as described above. However, at least one of R ²² and R ²³ is a hydrogen atom. Furthermore, R ²¹ and R ²³ may be combined with each other to form a ring, and a preferable example thereof is

【formula】

【formula】

Examples include [Formula]. The above R ²¹ or R ²² may further include an alkoxy group, an alkoxycarbonyl group, an aryl group, an alkyl group, a dialkylamino group, an alkylthio group, a mercapto group, a hydroxy group, a halogen atom, a carboxyl group, a nitro group, a cyano group, a sulfonyl group, It may be substituted with a carbamoyl group or the like. X means

Represented by [formula] In the base, Z is

A group of nonmetallic atoms that together with [Formula] form a 5- or 6-membered heterocycle, and the heterocycle specifically includes a thiazoline ring, a benzthiazoline ring, a naphthothiazoline ring, a thiazolidine ring,
Oxazoline ring, benzoxazoline ring, oxazolidine ring, selenazoline ring, benzselenazoline ring, imidazoline ring, benzimidazoline ring,
Tetrazoline ring, triazoline ring, thiadiazoline ring, 1,2-dihydropyridine ring, 1,2-dihydroquinoline ring, 1,2,3,4-tetrahydroquinoline ring, perhydro-1,3-oxazine ring, 2,4-benz [d]Oxazine ring, perhydro-1,3-thiazine ring, 2,4-benz[d]thiazine ring, uracil ring and the like. R ³¹ is a hydrogen atom or a saturated or unsaturated aliphatic group (e.g. an alkyl group, an alkenyl group,
(alkynyl group), which may be further substituted with an alkoxy group, an alkylthio group, an acylamino group, an acyloxy group, a mercapto group, a sulfo group, a carboxyl group, a hydroxy group, a halogen atom, an amino group, or the like. Among the groups represented by X mentioned above, particularly preferred are:

[Formula] a group having a unit,

A group represented by [Formula],

It is a group represented by [Formula]. In the general formula (), preferable compounds among the compounds represented by the general formula () of the group represented by R ² are disclosed in JP-A-53-10921 and JP-A-53-10921.
20922, 53-66732, patent application 1977-125602, 54-
82, JP-A-53-20318, Research Disclosure Magazine No. 17626 (No. 176, 1978), etc. Among these, particularly preferred is JP-A-53-
10921, 53-20922, and 53-66732. Examples of compounds represented by general formula () are shown below. The present invention is not limited to the following compounds. Synthesis methods for these compounds are described in JP-A-53-10921,
53-20922, 53-66732, patent application 1977-125602,
It is described in 54-82, etc. The compound represented by the above general formula () preferably has 10 ⁻⁸ to 10 ⁻¹ mol/mol Ag, preferably
It is contained in at least one layer of the silver halide photographic material in a range of 10 ^-6 to 10 ^-2 mol/mol Ag. In order to incorporate the compound represented by the general formula () into a photographic material, a method commonly used for adding additives to photographic emulsions can be applied. For example, water-soluble compounds should be prepared in an aqueous solution with an appropriate concentration, and compounds that are insoluble or poorly soluble in water should be prepared in an appropriate organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. It can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution to a photographic emulsion or a non-photosensitive hydrophilic colloid solution. It is also possible to use the well-known methods for adding water-insoluble (so-called oil-soluble) couplers to the emulsion in the form of a dispersion. The developing agent used in the present invention is contained in at least one of the silver halide emulsion layer or other hydrophilic colloid layer. As a developing agent,
Hydroquinone, chlorhydroquinone, bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, t
- Hydroquinones such as butyl hydroquinone and hydroquinone monosulfonate, but 1
3-pyrazolidones such as -phenyl-3-pyrazolidone, aminophenols such as N-methyl-p-aminophenol, etc. can also be used in combination with hydroquinones. Of these,
Hydroquinones are preferred from a practical standpoint, and hydroquinone is most preferred from a practical standpoint. Conventionally known methods can be used to incorporate the developing agent into the silver halide light-sensitive material. For example, a developing agent is dissolved in a suitable water-miscible organic solvent such as alcohols, glycols, ketones, esters, amides, etc. that do not adversely affect photographic properties, and the halogen It can be added to at least one of the silver oxide emulsion or a coating solution forming another layer for coating. It is also possible to use a method in which the developing agent is made into an oil dispersion and added to the emulsion as described in JP-A-50-39928. Alternatively, the developing agent may be dissolved in a gelatin solution, and the gelatin solution of the developing agent may be added and applied. Furthermore, as stated in Tokuko Sho 45-15461,
A dispersion in which a developing agent is dispersed in a polymer such as alkyl acrylates, alkyl methacrylates, or cellulose esters can be added and applied. The amount of hydroquinone developing agent contained in the silver halide photosensitive material is 0.1 to 5 mol per mol of silver halide, preferably
It is 0.2 to 3 moles. The compound represented by the general formula () and the hydroquinone developing agent may be added to any layer of the hydrophilic colloid of the silver halide photosensitive material. Examples include silver halide emulsion layers, overcoat layers, protective layers and other auxiliary layers. The compound represented by the general formula () and the hydroquinone developing agent may be added to separate layers, or may be added to the same layer. The silver halide grains used in the present invention are substantially of the surface latent image type. In other words, it is not substantially an internal latent image type. In the present invention, "substantially surface latent image type" means a photosensitive material made by coating a commonly used transparent support with an emulsion containing no developing agent and the compound represented by the general formula () used in the present invention. When the material is exposed for 1 to 1/100 seconds and then developed using the expression development (A) and internal development (B) methods shown below, the sensitivity obtained with surface development (A) is different from that obtained with internal development (B). It is defined as being greater than the obtained sensitivity. Here, sensitivity is defined as follows. S=100/Eh S represents the sensitivity, and Eh represents the exposure amount required to obtain a density 1/2 (Dmax+Dmin), which is exactly between the maximum density (Dmax) and the minimum density (Dmin). Surface development (A) Develop for 10 minutes at 20°C in a developer with the following formulation. N-Methyl-p-aminophenol (hemisulfate) 2.5g Ascorbic acid 10.0g Sodium metaborate tetrahydrate 35.0g Potassium bromide 1.0g Add water 1 Internal development (B) Red blood salt 3g/and Fe Nosafranin 0.0125g/
Processed at 20℃ for 10 minutes in a whitening solution containing
Develop for 10 minutes. N-methyl-p-aminophenol (hemisulfate) 2.5g Ascorbic acid 10.0g Sodium metaborate tetrahydrate 35.0g Potassium bromide 1.0g Sodium thiosulfate 3.0g Add water 1 If the emulsion of the present invention Unless it is substantially of the surface latent image type, positive gradations will be provided in addition to negative gradations, and the object of the present invention cannot be achieved. The silver halide in the silver halide photosensitive material used in the present invention is composed of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, or silver iodochlorobromide, and the silver halide grains are , the average particle size is preferably not larger than 0.7μ, more preferably not larger than 0.4μ. Average grain size is a term commonly used and easily understood by those skilled in the field of silver halide photographic science. Particle size means the particle diameter when the particles are spherical or can be approximated to a sphere. When the particle is cubic, the particle size is defined as the edge length x √4. The average is determined by an algebraic average or a geometric average based on the particle projected area.
For more information on how to determine average particle size, please refer to CE
By K. Mees and TH James: The theory of the
Photographic process, 3rded.p.36-p.43,
(1966, published by Mc Millan). Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, 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; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N - A wide variety of synthetic hydrophilic polymers can be used, such as single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. In addition, chemical sensitizers for silver halide emulsions such as gold, platinum, palladium, iridium, and thiosulfate, sensitizing dyes such as cyanine dyes and merocyanine dyes, oxanol dyes, hemioxanol dyes, and merocyanine dyes, etc. anti-irradiation dyes, chromium salts, aldehydes, N-methylol compounds, dioxane derivatives, activated vinyl (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl))
Hardeners such as methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.) can be used. Details of these compounds can be found in Research Disclosure, publication number 17643 (December 1978).
Or as described in Japanese Patent Application Nos. 54-78338 and 54-85660. The main feature of the method for forming a photographic image of the present invention is that after the above-mentioned silver halide photographic light-sensitive material is imagewise exposed, it is treated with an alkaline activator aqueous solution containing a compound represented by the general formula () and having a pH of 11.5 or higher. shall be. Image exposure can be performed in a conventional manner. Furthermore, it is also possible to perform so-called halftone exposure in which the original image is exposed through a contact screen in the same way as the exposure of conventional lithium-type photosensitive materials. The method of the present invention differs from the known lithium-type photosensitive material substitutes disclosed in Japanese Patent Application Laid-open No. 51-22438 or US Pat. There is no need to specially select a contact screen for use in the photosensitive material, and it is advantageous that the same contact screen used for conventional lithium-type photosensitive materials can be used to obtain the same halftone gradation. The exposed photosensitive material is treated with the activator aqueous solution of the present invention. This activator aqueous solution preferably contains the compound represented by the general formula () in an amount of 10 ^-4 to 1 mol/, particularly 10 ^-3 to 5×10 ^-1 mol/, and has a pH of 11.5 or more, preferably is adjusted to be 12.0 or higher, especially 12.5 or higher. General formula () will be explained in more detail. Preferred alkyl groups represented by R ³ in the general formula () have 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl. The alkyl group represented by R ⁴ is preferably a lower alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an allyl group. These alkyl groups may be substituted with substituents such as hydroxy groups. The lower alkenyl group represented by R ⁴ preferably has 1 to 3 carbon atoms and is, for example, a vinyl group or an allyl group. The alkoxycarbonyl group represented by R ⁴ preferably has 2 to 4 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, and isopropoxycarbonyl group. The acyl group represented by R ⁴ preferably has 1 to 4 carbon atoms, such as formyl group, acetyl group, propionyl group, n-butyryl group, and isobutyryl group. The heterocyclic group represented by R ⁴ is preferably a 5- or 6-membered nitrogen-containing heterocyclic group, and a 6-membered ring may be fused to these rings. Examples include pyrrolyl group, imidazolyl group, pyridyl group, benzothiazolyl group, quinolyl group, and indolyl group. The alkyl group which may be substituted with the phenyl group represented by R ⁴ is preferably a lower alkyl group having 1 to 3 carbon atoms, such as a methyl group or an isopropyl group. Among the compounds represented by the above general formula (), preferred are compounds in which R ³ and R ⁴ are both hydrogen atoms, compounds in which at least one of R ³ and R ⁴ is a lower alkyl group, or R ³ is a hydrogen atom and R ⁴ is a phenyl group which may be substituted with a lower alkyl group. Among them, particularly preferable ones are R ³ and
This is a compound (hydrazine) in which both R ⁴ are hydrogen atoms. The compound represented by the general formula () of the present invention is
Contained in activator. Examples of compounds are shown below, but the present invention is not limited to these compounds. The above exemplified compounds include, for example, sulfates, hydrochlorides,
It may be a salt such as a bromate or a phosphate, or it may be a hydrate. The alkaline activator aqueous solution used in the present invention can contain, in addition to the hydrazine compound represented by the above general formula (), any components used in ordinary lithium-type developers (excluding the developing agent). That is, alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), carbonates (e.g., sodium carbonate, potassium carbonate, etc.), phosphates (e.g., monobasic sodium phosphate, tribasic potassium phosphate, etc.), Alkaline agents such as borates (e.g., boric acid, sodium metaborate, borax, etc.), or PH buffers, bromides, iodides, antioxidants (e.g., sodium sulfite, potassium metabisulfite, etc.), etc. can be included. . Furthermore, organic solvents (e.g. diethylene glycol,
triethylene glycol, diethanolamine,
triethanolamine, etc.), water softeners (e.g., sodium tetrapolyphosphate, sodium hexametaphosphate, sodium nitrilotriacetate, ethylenediaminetetraacetic acid or its sodium salt, etc.), hardening agents (e.g., glutaraldehyde, etc.), viscosity-imparting agents (e.g. (carboxymethyl cellulose, hydroxyethyl cellulose, etc.), color toning agents, surfactants, antifoaming agents, etc.
The amounts of these additives may be the same as for conventional aqueous activator solutions and are well known to those skilled in the art. Conditions for treatment with the activator aqueous solution of the present invention can be determined as appropriate. Normal processing temperature is 18℃~50℃
℃ range, but the treatment may be performed at other temperatures. The treatment with the activator aqueous solution of the present invention is usually carried out by immersing the above-mentioned photosensitive material in the activator aqueous solution, and at this time it is preferable to stir the activator aqueous solution. Various known means (for example, means for rotating a stirring blade, means for blowing inert gas, etc.) can be used for this stirring. According to the method of the present invention, the quality of halftone dots does not vary due to changes in stirring conditions such as changes in stirring means or changes in stirring speed as described above. When a halftone image is formed by the method of the present invention, an even better result can be obtained by performing the treatment with the above activator aqueous solution in the presence of a polyalkylene oxide compound or its derivative as described in JP-A No. 54-37732. It is possible to obtain halftone dot quality. The polyalkylene oxide or derivative thereof used in the present invention has a molecular weight of at least
600, and the polyalkylene oxide or its derivative may be contained in a silver halide photosensitive material or in an alkaline activator. The polyalkylene oxide compound or derivative thereof that can be used in the present invention has 2 to 4 carbon atoms.
a polyalkylene oxide consisting of at least 10 units of an alkylene oxide, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, preferably ethylene oxide, and water, an aliphatic alcohol, an aromatic It includes condensates with compounds having at least one active hydrogen atom, such as alcohols, fatty acids, organic amines, and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. Specific examples of polyalkylene oxide compounds or derivatives thereof include: polyalkylene glycols polyalkylene glycol alkyl ethers polyalkylene glycol aryl ethers polyalkylene glycol (alkylaryl) ethers polyalkylene glycol esters polyalkylene glycol fatty acid amides poly Alkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, etc. can be used. The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In that case, the individual polyalkylene oxide chains may consist of fewer than 10 alkylene oxide units, but
The total number of alkylene oxide units in the molecule must be at least 10. If there is more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound or derivative thereof used in the present invention preferably contains 14 or more and up to 100 alkylene oxide units. The amount of the polyalkylene oxide compound or its derivative added is in the range of 5 x 10 ^-4 g to 5 g, preferably 1 x 10 ^-3 g to 1 g, per mole of silver halide in the silver halide photosensitive material. range. In the activator aqueous solution, 1×10 ^-2
g/ or more, preferably 5×10 ^-2 g/ to 40
It can be used at concentrations in the range of g/g/g. Following the treatment with the above activator aqueous solution, a fixing treatment is performed in accordance with a conventional method. As the fixer, one having a commonly used composition can be used. 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 as a hardening agent. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. In addition to the above-mentioned activator treatment and fixing treatment, treatment with known auxiliary baths (eg, stop bath, hardening bath, etc.) can be carried out in black-and-white processing. The timing, conditions, etc. of application of the treatment with these auxiliary baths may be in accordance with conventional methods. According to the photographic image forming method of the present invention, a compound represented by the general formula () is added to a photosensitive material together with a developing agent, thereby using a conventionally used lithium-type photosensitive material and an infectious developer. Compared to conventional methods, it is possible to significantly improve the stability of the processing solution and reduce management costs. It can be obtained by processing time. In addition, this method can improve not only the stability of the processing solution but also the stability of the photosensitive material, compared to the known method of using a photosensitive material containing a hydrazine compound and a developer with a high pH. In addition to producing extremely high-contrast negative images with significantly superior halftone dot quality and halftone gradation compared to the method using a photosensitive material containing only hydroquinone and an activator containing a hydrazine compound, it is also possible to obtain an exceptional contact screen. There is no need to make a selection, and it is possible to obtain practically the same halftone gradation for the lithium-shaped photosensitive material using the contact screen used when exposing the lithium-shaped photosensitive material. Furthermore, according to the photographic image forming method of the present invention, in order to treat a photosensitive material containing a developing agent and a compound represented by the general formula () with an alkaline activator containing the compound represented by the general formula (), a simple alkaline activator is used. This has the great advantage that the halftone dot quality is further improved compared to the case where the halftone dot quality is not changed even if the stirring conditions of the activator are changed. The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. Example: Silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously added over 50 minutes to a gelatin aqueous solution kept at 50°C.
By keeping pAg at 7.9, the average particle size
A 0.25μ silver bromide emulsion was prepared. After removing soluble salts in a conventional manner, this emulsion contains
43 mg of sodium thiosulfate was added and chemically aged at 60°C for 60 minutes. This emulsion contains 120 g of gelatin per mole of silver bromide. 10 to this bromide emulsion
% hydroquinone dissolved in an aqueous gelatin solution and 5-methylbenzotriazole as an antifoggant, and a hardener 2-hydroxy-
After adding 4,6-dichloro-1,3,5-triazine sodium salt, it was coated on a cellulose triacetate film at a silver content of 45 mg per 100 cm ² . The amount of hydroquinone applied is per ^100cm2 .
It was 22 mg (52.8 g/mol Ag). Let this film sample be No. 1. For comparison, when preparing a sample using the same method as No. 1, compound-2 of the general formula () of the present invention,
−12, −22, −23, −24, −27, −
30, -31, -35, -40, -43, -45 and -46, each at 1.0 per mole of silver halide.
×10 ^-3 mol, 1.2 × 10 ^-3 mol, 5 × 10 ^-5 mol, 7.5
×10 ^-5 mol, 5 × 10 ^-5 mol, 4 × 10 ^-5 mol, 7.5 ×
10 ^-5 mol, 5.5 x 10 ^-5 mol, 6 x 10 ^-5 mol, 5 x
10 ^-5 mol, 2 x 10 ^-5 mol, 5 x 10 ^-5 mol, 8 x
Thirteen types of film samples containing 10 ^-4 moles were prepared, and these were respectively film No. 2, No. 3, No. 4, No. 5,
No.6, No.7, No.8, No.9, No.10, No.11,
They were named No.12, No.13, and No.14. these films
After exposure through a sensitometric exposure wedge using a 150-line magenta contact screen, an alkaline activator (A) with the following composition:
and alkaline activators (B ₁ , B ₂ ) containing the general formula () (Specific Examples 1 and 3) with and without stirring the activators, respectively.
It was developed at ℃ for 10 seconds, stopped, fixed, washed with water, dried, and examined for photographic properties. To stir the activator, place a nitrogen blowing pipe with small holes on the side at the bottom of the activator bath 1 and use a constant amount (100 c.c./cm) during development.
This was done by blowing the activator with nitrogen (minutes).

[Table] Table 1 shows the halftone quality results. In Table 1, the halftone dot quality is visually evaluated in five stages, with "1" representing the best quality and "5" representing the worst quality. As a halftone original plate for plate making, only halftone quality "1" and "2" are practical, and "3"
"4" and "5" are halftone dots of practically unsatisfactory quality. From the results in Table 1, it can be seen that the halftone dot quality was kept constant regardless of the stirring conditions of the treatment, and the halftone dot quality was also improved.

【table】

【table】

Claims (1)

[Scope of Claims] 1. It has at least one silver halide emulsion layer, and contains a hydroquinone developing agent and a compound represented by the following general formula () in this layer and at least one of the other hydrophilic colloid layers. A silver halide photographic light-sensitive material of substantially surface latent image type is imagewise exposed, and then treated with an activator aqueous solution containing a compound represented by the following general formula () and having a pH of 11.5 or higher. A method for forming a photographic image. R ¹ NNHHCOR ² () [In the formula, R ¹ represents an aryl group. R ² is a hydrogen atom, a phenyl group, or a carbon number of 1 to 3
represents an alkyl group. ] [In the formula, R ³ represents a hydrogen atom or a lower alkyl group. R ⁴ represents a hydrogen atom, a lower alkyl group, or a carbamoyl group. ]