JPS6212498B2 - - 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 sharp with no blur around the dot. 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 high contrast. 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 characteristics 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 high contrast photographic property of 10 or more is insufficient for use in platemaking 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 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,
Even with the method of the invention described in US Pat. No. 2,419,975, preferred gradations should be obtained if a contact screen with a density pattern suitable for the photosensitive material used is selected and used. 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 the same contact screen used in conventional lithography can be used without the need for special operations such as selecting a contact screen. Therefore, 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 over 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 (). Generally, a surface latent image type silver halide photographic light-sensitive material contains at least one thiocarbonyl group bonded to either a sulfur atom or an oxygen atom and a nitrogen atom, and the nitrogen atom is substituted with a hydrogen atom. This was achieved by treatment with an aqueous activator solution with a pH of 11.5 or higher in the presence of a compound with no oxidation. R ¹ NHNHCOR ² () [In the formula, R ¹ represents an optionally substituted aryl group or an optionally substituted alkyl group, and R ² represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted alkyl group. Represents an alkyl group. ] 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 layer. It is a latent 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 with 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 or an ethoxy group), a substituted amino group (preferably one substituted with an alkyl group having 1 to 20 carbon atoms, such as a dimethylamino group) , diethylamino group), aliphatic acylamino group (preferably one having an alkyl group having 1 to 21 carbon atoms, e.g. acetylamino group, heptylamino group), aromatic acylamino group (preferably a monocyclic or bicyclic aryl group). For example, a group represented by a 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, e.g. -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,

Groups represented by [Formula], heterocyclic residues, aralkyl groups (n=
1) means an alkyl group-substituted aryl 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 If so, preferably

[Formula] group,

[Formula] group,

[Formula] group,

[Formula] Examples include groups, and

[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 residue (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 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

In the group represented by [formula] Then, 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, an oxazoline ring, and a benzoxazoline ring. 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, etc. Can be mentioned. 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]. Among the groups represented by R ¹ in the general formula (), the optionally substituted alkyl group has 1 to 1 carbon atoms.
10 alkyl groups, which may be substituted with the groups listed above as substituents for the aryl group. As R ¹ in the general formula (), an optionally substituted aryl group is more preferable than an optionally substituted alkyl group. In the general formula (), the optionally substituted aryl group among the groups represented by R ² is a monocyclic or bicyclic aryl group, for example, a benzene ring containing a naphthalene ring, particularly preferably a benzene ring. This aryl group may be substituted with a group such as a halogen atom, cyano group, carboxy group, or sulfo group. Preferred examples of the aryl group represented by ^R2 include phenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3-chlorophenyl group, 4-cyanophenyl group, 4-carboxyphenyl group, 4-sulfophenyl group, 3, 5
-dichlorophenyl group, 2,5-dichlorophenyl group, etc. In the general formula (), the optionally substituted alkyl group among the groups represented by R ² is preferably an alkyl group having 1 to 4 carbon atoms, and may have the following substituents. . That is, halogen atoms, cyano groups, carboxy groups, sulfo groups, etc. Examples of particularly preferred alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups. Among these compounds represented by the general formula (), preferred compounds are those 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 () is preferably used in an amount of 10 _-8 to 10 _-1 mol/mol Ag, particularly preferably 10 _-6 to 10 _-2 mol/mol Ag, at least in the silver halide photographic light-sensitive material. It is contained in one layer. 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
-Dihydroxybenzenes such as butyl hydroquinone and hydroquinone monosulfonate, 1-
3-pyrazolidones such as phenyl-3-pyrazolidone, aminophenols such as N-methyl-p-aminophenol, and the like can be used alone or in combination. Among these, dihydroxybenzenes are practically preferred, and hydroquinones (among them, hydroquinone) are practically most preferred. 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
The amount is 0.1 to 2 moles. The compound represented by the general formula () and the 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 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 that the emulsion containing the compound represented by the general formula () used in the present invention and no developing agent is coated on a commonly used transparent support. When the material is exposed for 1 to 1/100 seconds and then developed using the methods of surface development A and internal development B shown below, the sensitivity obtained with surface development A is greater than the sensitivity obtained with internal development B. It is defined as. Here, sensitivity is defined as follows. S=100/Eh S is the sensitivity, and Eh is the density 1/2 (Dmax+Dmin), which is exactly between the maximum density (Dmax) and the minimum density (Dmin).
Indicates the amount of exposure required to obtain . Surface Development A Develop for 10 minutes at a temperature of 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 1l Internal development B Red blood salt 3g/l and phenol Safranin 0.0125g/l
Processed at 20℃ for 10 minutes in a bleaching 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 to 1l 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/π. 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 McMillan). 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, cellulose sulfates, etc.; polyvinyl alcohol, partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid,
polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymers can be used, such as single or copolymers such as polyvinylpyrazole. 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 method for forming a photographic image of the present invention involves combining the above-mentioned silver halide photographic light-sensitive material with either a sulfur atom or an oxygen atom and a thiocarbonyl group bonded to a storage atom (

[Formula] The biggest feature is that it is treated with the above activator aqueous solution. A preferred thiocarbonyl compound used in the present invention is represented by the following general formula (). In the formula, X represents a sulfur atom or an oxygen atom.
R ⁰ and R ¹ may be the same or different, and each represents the number of carbon atoms substituted with an aliphatic group [for example, unsubstituted or a substituent such as a carboxy group, a sulfo group, a hydroxy group, an aryl group (preferably a phenyl group), etc. 1 to 4 alkyl groups, more specifically, for example, methyl group, ethyl group, propyl group, butyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, hydroxyethyl group , benzyl group, phenethyl group, etc.]; aryl group [e.g., unsubstituted or alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), sulfo group, alkoxy group (preferably an alkyl group having 1 to 4 carbon atoms); alkyl group), an aryl group (preferably phenyl group) substituted with a substituent such as a halogen atom, more specifically, for example, phenyl group, 2-methylphenyl group, 4
-sulfophenyl group, 4-ethoxyphenyl group,
4-chlorophenyl group, etc.]; heterocyclic residue [e.g., 5- to 6-membered nitrogen-containing heterocyclic residue, more specifically, e.g., 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc.]; or amino group [Preferably a substituted amino group, such as an arylamino group (an aryl group is preferably an unsubstituted phenyl group or a phenyl group substituted with a substituent such as an alkyl group, a sulfo group, or a carboxy group), more specifically a 4- sulfophenylamino group, etc.). R ⁰ and R ¹ are bonded to each other to form a 5- or 6-membered heterocycle (e.g. piperidine ring, morpholine ring,
piperazine ring, etc.) may be formed. R ² is an aliphatic group [e.g., unsubstituted or carboxy group, sulfo group, hydroxy group, aryl group,
(e.g., phenyl group) and other substituents, and more specifically, for example, methyl group, ethyl group, propyl group, butyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group. group, sulfoethyl group, sulfopropyl group, sulfobutyl group, hydroxyethyl group, benzyl group, phenethyl group, etc.]; aryl group [for example, unsubstituted or alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), sulfo group, an alkoxy group (preferably an alkoxy group whose alkyl moiety has 1 to 4 carbon atoms), an aryl group (preferably a phenyl group) substituted with a substituent such as a halogen atom, more specifically, for example, a phenyl group, 2-methylphenyl group, 4-sulfophenyl group, 4-ethoxyphenyl group, 4-chlorophenyl group, etc.). Furthermore, R ¹ and R ² may be combined with each other to form a 5- or 6-membered heterocycle. The compound represented by the following general formula () formed in this way is more preferable. In the formula, Q is a heterocyclic ring (including those fused to at least one unsaturated ring having 5 to 6 carbon atoms, such as a benzene ring or a tetrahydrobenzene ring; the same applies hereinafter). It represents a necessary atomic group, and X and R ⁰ have the same meanings as in the general formula (). To explain the general formula () in more detail, Q is a heterocycle (the "heterocycle" itself is preferably a 5-membered ring), for example, a thiazolidine-2-thione ring (for example, a thiazolidine-2-thione ring).
2-thione ring, 5-methylthiazolidine-2-thione ring, 4-carboxythiazolidine-2-thione ring, etc.), 4-thiazoline-2-thione ring (e.g. 4-methyl-4-thiazoline-2-thione ring,
4-carboxymethyl-4-thiazoline-2-thione ring, 4-carboxy-4-thiazoline-2-
thione ring, etc.), 1,3,4-thiadiazolin-2
-thione ring (e.g. 5-ethylthio-1,3,4
-thiadiazoline-2-thione ring, etc.), benzthiazoline-2-thione ring (e.g. benzthiazoline-2-thione ring, 5-carboxybenzthiazoline-2-thione ring, 5-sulfobenzthiazoline-2-thione ring, 5 -methylbenzthiazoline-2-thione ring, etc.), benzoxazoline-2-
Represents an atomic group necessary to complete a thione ring (eg, benzoxazoline-2-thione ring, 5-sulfobenzoxazoline-2-thione ring, 5-methylbenzoxazoline-2-thione ring, etc.), etc. R ⁰ has the same meaning as R ⁰ in general formula (). In the nuclear substituent of the heterocycle completed by R ⁰ or Q, the cation that forms a salt of a sulfo group or a carboxy group is preferably one that forms a water-soluble salt, and specifically, an alkali metal ion, especially an alkali metal ion.
Na ₊ and K ₊ are preferred. The nitrogen-containing heterocyclic compound represented by the general formula () includes compounds represented by the following general formulas (a) to (c), and the compound represented by the general formula (a) is particularly preferred.

【formula】 【formula】

[Formula] In the general formulas (a) to (c), X represents a sulfur atom or an oxygen atom. X is preferably a sulfur atom. A and B may be the same or different, and each represents a hydrogen atom, a carboxy group, an aliphatic group, an aryl group,
Atoms necessary to complete an alkoxycarbonyl group or an unsaturated ring having 5 to 6 carbon atoms (these rings are preferably substituted with a substituent such as a sulfo group or a carboxy group) by bonding with each other represents a group. However, when A and B combine with each other to complete an unsaturated ring having 5 to 6 carbon atoms, the compound represented by (a) has a group consisting of a hydroxy group, a sulfo group, and a carboxy group in its molecule. Contains at least one group selected from Y represents a hydrogen atom, a carboxy group, an aliphatic group or an aryl group. R ⁰ has the same meaning as R ⁰ in general formula (). E and G may be the same or different and each represents a hydrogen atom, an aliphatic group, or a carboxy group. To explain general formulas (a) to (c) in more detail, A and B are each a hydrogen atom, a sulfo group, a carboxy group, an aliphatic group [e.g., an unsubstituted or hydroxy group, a halogen atom, a carboxy group, a sulfo group] , an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) substituted with a substituent such as an aryl group (preferably a phenyl group), more specifically a methyl group, an ethyl group, a butyl group, a hydroxy group, etc. ethyl group, sulfopropyl group, carboxymethyl group, benzyl group, etc.); aryl group [for example, unsubstituted or substituted aryl group with alkyl group, hydroxy group, halogen atom, carboxy group, sulfo group, etc., more specifically For example, phenyl group, 4-
Methylphenyl group, 4-hydroxyphenyl group,
3- or 4-chlorophenyl group, 4-carboxyphenyl group, 4-sulfophenyl group, etc.]; alkoxycarbonyl group (preferably an alkoxycarbonyl group whose alkyl moiety has 1 to 5 carbon atoms, such as an ethoxycarbonyl group); or A group of atoms necessary to complete a ring having 5 to 6 carbon atoms that is bonded to each other and has only one double bond (these rings are preferably substituted with a substituent such as a sulfo group or a carboxy group) , for example, a trimethylene group, a tetramethylene group, etc., or a necessary group that bonds with each other to form an unsubstituted or substituted benzene ring. Substituents for this benzene ring include an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, etc.), an aryl group (such as a phenyl group, etc.), an alkoxy group (preferably a carbon an alkyl group substituted with a halogen atom (e.g. chlorine atom, bromine atom, etc.), a carboxy group (preferably the alkyl moiety has 1 to 3 carbon atoms); Examples include a carboxymethyl group), an arylamino group (preferably the aryl group is a phenyl group, such as an aniline group), a carboxy group, and a sulfo group. Y is a hydrogen atom, a carboxy group, an aliphatic group [for example, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) that is unsubstituted or substituted with a substituent such as a hydroxy group, a sulfo group, or a carboxy group; For example, methyl group, ethyl group, carboxymethyl group,
Carboxyethyl group, hydroxyethyl group, etc.];
or represents an aryl group [for example, an unsubstituted aryl group (preferably a phenyl group) substituted with a substituent such as a sulfo group or a carboxy group, such as a phenyl group or a p-sulfophenyl group]. E and G are each a hydrogen atom, an aliphatic group [for example, an unsubstituted or substituted alkyl group with a carboxy group (preferably an alkyl group having 1 to 4 carbon atoms), more specifically a methyl group, a carboxymethyl group, carboxyheptyl group] or a carboxy group. Specific examples of the thiocarbonyl compounds used in the present invention include the following. compound number Next, a synthesis example of the thiocarbonyl compound of the present invention will be shown. Compound - (2) Synthesis Morpholine 21.8g (0.25 mol), potassium hydroxide
Dissolve 14g (0.25 mol) in 200ml of alcohol and add 19g of carbon disulfide while stirring under cooling (below 5℃).
After stirring for 2 hours, 35.5 g (0.25 mol) of methyl iodide was added and heated under reflux for 30 minutes, then cooled and the precipitated crystals were collected. Recrystallize from ethanol. Yield: 22g (50%) Melting point: 86-7°C Synthesis of compound-(4) Dissolve 25g (0.2 mol) of taurine in 200 ml of an aqueous solution of 22.4 g (0.4 mol) of caustic potassium, and add disulfide while stirring under cooling (below 5°C). Add 100 ml of ethanol containing 15.2 g (0.2 mol) of carbon and stir at room temperature for 2 hours to complete the reaction. Add 18.5 g (0.2 mol) of monochloroacetone while stirring again under cooling (below 5°C).
It drips for about 30 minutes or so. After reacting at room temperature for 3 hours, it is concentrated, and the precipitated crystals are separated and dried.
The crystals are suspended in ethanol and heated under reflux for 30 minutes in acidic sulfuric acid (PH 3-4), then cooled and the precipitated crystals are collected. Recrystallize from dilute aqueous caustic potassium solution. Yield: 10 g (20%) Melting point: 300°C or higher Synthesis of compound - (7) Add carbon disulfide to 250 ml of methanol solution containing 44 g (0.5 mol) of β-aminopropionic acid and 28 g (0.5 mol) of caustic potassium under cooling (below 5°C) After adding 30 ml (0.5 mol) and stirring for 2 hours, a methanol solution of 100 g (0.5 mol) of phenacyl bromide was added dropwise while cooling to below 5°C, and after the dropwise addition was completed, the mixture was stirred at room temperature for 2.5 hours. After adding 220 ml of water, the alcohol was distilled off under reduced pressure. This was acidified with hydrochloric acid (PH 3-4) while stirring under cooling, and the precipitated crystals were collected and washed with water to form 4-phenyl-3-(2-carboxyethyl)-4-hydroxythiazolidine-2-thione.
Obtain 116 g (melting point 132°C). Add 500% of glacial acetic acid to these crystals.
ml and heat under reflux for 30 minutes. After cooling,
Add 1 part of water and collect the precipitated crystals. Yield 89g (65%) Melting point 134~6℃ Compounds −(5), −(6), −(8), −(9), −
(10), −(11), −(12), (13), −(14) and

-(19) can be synthesized according to the method for synthesizing compounds -(4) and -(7). Synthesis of Compound (17) 18.1 g (0.1 mol) of 2-methylthiobenzothiazole and 18 g (0.15 mol) of propane sultone were reacted without solvent at 130°C in an oil bath for 1 hour. After the reaction, add 50ml of xylene and decant.
Next, add 50 ml of acetone and decant. Add 50ml of water to this and add 28.8g of soda sulfide.
Add an aqueous solution of (0.12 mol) and stir at room temperature, then collect the crystals. Recrystallize with 20% aqueous isopropyl alcohol. Yield: 10g (32%) Melting point: 312°C (decomposed) Other thiocarbonyl compounds can also be synthesized by referring to the following literature. KCKennard and JAVan Allen, “J.Org.
Chem.” Vol. 24, pp. 470-473 (1959); R.W. Lamon and W. J. Humplett, “J.
"Heterocycl.Chem." Vol. 4, pp. 605-609 (1967); M. Ohara's Special Publication Sho 39-26203; M. Morita, "Yakushi" Vol. 82, pp. 36-45 (1962). In order for the thiocarbonyl compound of the present invention to be present during treatment with an aqueous activator solution, the thiocarbonyl compound of the present invention is added to at least one of the constituent layers of the above-mentioned photographic material, or the thiocarbonyl compound of the present invention The thiocarbonyl compound may be added to the activator aqueous solution. The amount of the thiocarbonyl compound of the present invention used when added to a constituent layer of a photographic light-sensitive material is in the range of 10 ^-4 mol to 2 mol, particularly 5 x 10 ^-4 mol to 0.2 mol, per mol of silver halide. Ru. The added layer is preferably a photographic emulsion layer or an adjacent layer. When added to an aqueous activator solution, the amount of the thiocarbonyl compound of the present invention used is preferably in the range of 5 mg to 15 g, particularly 10 mg to 10 g, per 1 aqueous activator solution. The alkaline activator aqueous solution used in the present invention includes alkali metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), carbonates (e.g., sodium carbonate, potassium carbonate, etc.), phosphates (e.g., monobasic sodium phosphate, potassium hydroxide, etc.), In addition to alkaline agents such as potassium triphosphate, etc.), borates (e.g., boric acid, sodium metaborate, borax, etc.), PH buffers, brominating agents, iodides, and antioxidants (e.g., sodium sulfite, metaborate, etc.). potassium bisulfite, etc.). Furthermore, as necessary, 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 (such as glutaraldehyde), viscosity-imparting agents (such as carboxymethyl cellulose, hydroxyethyl cellulose, etc.),
It may also contain a toning agent, a surfactant, an antifoaming agent, and the like. The amounts of these additives used 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 aqueous activator 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. 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. 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 alkylene oxide, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2 oxide, preferably ethylene oxide, and water, an aliphatic alcohol,
It includes condensates with compounds having at least one active hydrogen atom such as aromatic alcohols, fatty acids, organic amines, and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. Examples of polyalkylene oxide compounds or derivatives thereof include polyalkylene glycols polyalkylene glycol alkyl ethers polyalkylene glycol aryl ethers 〃 〃 (alkylaryl) ethers polyalkylene glycol esters polyalkylene glycol fatty acid amides polyalkylene Glycolamines, 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 g/
It can be used at concentrations in the range of . Following the treatment with the above activator aqueous solution, a fixing treatment is performed in accordance with a conventional method. As the fixing solution, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate thiocyanate, organic sulfur compounds known to be effective as a fixing agent 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, by adding a compound represented by the general formula () to a photosensitive material together with a developing agent, it can be used in a method using a conventionally used lithium-type photosensitive material and an infectious developer. In comparison, it is possible to significantly improve the stability of the processing solution and reduce management costs, and it is also possible to produce ultra-high contrast negative images with halftone dot quality and halftone gradation equivalent to those produced by conventional methods in an extremely short time. can be obtained by processing. 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, since the photosensitive material containing a developing agent and a compound represented by the general formula () is treated with an alkaline activator in the presence of a thiocarbonyl compound, the halftone quality is further improved. At the same time, the halftone dot quality does not change even if the stirring conditions of the activator change.
This is a big advantage. 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: By adding a silver nitrate aqueous solution and a potassium bromide aqueous solution simultaneously for 50 minutes to a gelatin aqueous solution kept at 50°C, and maintaining PAg at 7.9 during that time, the average particle size was
A 0.25μ silver bromide emulsion was prepared. After removing the soluble salts from this emulsion in a conventional manner, silver bromide was added to this emulsion.
Add 43 mg of sodium thiosulfate per mole and heat at 60°C.
Chemically aged for 60 minutes. In this silver bromide emulsion, hydroquinone dissolved in a 10% aqueous gelatin solution, 5-methylbenzotriazole as an antifoggant,
3-carboxymethyl 5-[(3-
Ethyl 2-thiazolidinylidene)ethylidene] rhodanine was added and coated on a cellulose triacetate film at a silver content of 40 mg per 100 cm ² , and this film was designated as No. 1. The amount of hydroquinone applied is 20 mg per 100 ^cm2 . When preparing a sample in the same manner as in this film number 1, compounds belonging to group () and group () of the present invention, -
2, −22, −43 and −(1), −(4), −
(11) and -(18) were added to the emulsion as shown in Table 1, and their film numbers were numbered 2 to 16 as shown in Table 1. These films were exposed through a sensitometric exposure wedge using a 150-line magenta contact screen, developed for 10 seconds at 20°C with and without agitation in an alkaline activator with the following composition, stopped, The photographic properties were examined after fixing, washing, and drying. Stirring of the activator is carried out by placing a nitrogen blowing pipe with small holes on the side at the bottom of the activator bath 1 and feeding a constant amount of nitrogen (100 c.c./min) during development to cause the activator to bubble. Ivy. Activator formulation Na ₂ SO ₃ 15.0 (g/) NaOH 44.0 (g/) NaBr 7.0 (g/) Add water 1 The results of halftone dot quality are shown in Table-1. 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】

Claims (1)

[Scope of Claims] 1. A substance having at least one silver halide emulsion layer, and containing a 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 surface latent image type silver halide photographic light-sensitive material containing at least one thiocarbonyl group bonded to either a sulfur atom or an oxygen atom and a nitrogen atom, and the nitrogen atom is not substituted with a hydrogen atom. A method for forming a photographic image, comprising processing with an aqueous activator solution having a pH of 11.5 or higher in the presence of a compound. R ¹ NNHHCOR ² () [In the formula, R ¹ is an optionally substituted aryl group,
or represents an alkyl group that may be substituted, and R ²
represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted alkyl group. ]