JPH0475490B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a direct positive silver halide photographic light-sensitive material, and more particularly to an internal latent image type direct positive silver halide photographic light-sensitive material containing a novel fogging agent. (Prior Art) It is well known that positive images can be formed directly using silver halide photographic materials without the need for reversal processing or negative photographic images. Conventionally known methods used to form positive images using direct positive silver halide photographic materials are mainly divided into two types in consideration of practical usefulness, excluding special methods. be able to. One type uses a pre-coupled silver halide emulsion and uses solarization or the Herschel effect to destroy fog nuclei (latent images) in exposed areas to obtain a positive image after development. . The other type uses an unfogged internal latent image type silver halide emulsion and performs surface development after and/or while performing fogging treatment after image exposure to obtain a positive image. . Here, the fogging treatment may be performed by exposing the entire surface to light, using a fogging agent, using a strong developer, heat treatment, etc., but usually a fogging agent is not used. It is carried out using The term "internal latent image type silver halide emulsion" refers to a silver halide emulsion which mainly has photosensitive nuclei inside the silver halide grains and forms a latent image inside the grains upon exposure. This latter type of method of directly obtaining a positive image using a silver halide emulsion generally has higher sensitivity than the former type of method, and is suitable for applications requiring high sensitivity. It is related to these. Various techniques are known to date in this technical field. For example, US Pat. No. 2,952,250,
Same No. 2456957, Same No. 2497875, Same No. 2588982,
British Patent No. 1151363, Japanese Patent Publication No. 43-29405, Japanese Patent Publication No. 47-9434, Japanese Patent Publication No. 47-9677, Japanese Patent Publication No. 47-32813,
No. 47-32814, No. 48-9727, No. 48-9717,
U.S. Patent No. 3,761,266, U.S. Pat. No. 3,796,577, Japanese Patent Application Publication No. 1973-
The main ones are No. 8524 and No. 50-38525. By using these known methods, it is possible to produce a relatively highly sensitive photographic material as a direct positive type. For details on the mechanism of direct positive image formation, see, for example, "The Theory of the Photographic Process" by Mies and James.
You can understand to some extent the process by which positive images are formed by the ``desensitizing effect of internal latent images'' as discussed on page 161 of the 3rd edition. In other words, due to the surface desensitization effect based on the so-called internal latent image type produced inside the silver halide grains by the initial image exposure, the surface of the unexposed silver halide grains in the non-image area is selectively affected. It is believed that fog nuclei are generated and then a photographic image is formed in the unexposed areas by normal development. A hydrazine compound is known as a useful fogging agent that exhibits such a selective fogging effect. For example, hydrazine compounds described in U.S. Patent No. 2563785 and U.S. Patent No. 2588982;
Naphthylhydrazine sulfonic acid, described in British Patent No. 2604700, or sulfomethylhydrazines, described in British Patent No. 1403018, are used as fogging agents. Also, special public service 17184-17184
The issue describes that color positive images can be obtained using hydrazide or hydrazine compounds. However, in order to apply the method of directly forming positive images using these compounds as fogging agents to various photographic fields, technical problems remain that must be further improved. For example, in such fog development, a fog reaction by a fog agent must occur prior to the development reaction, so the induction period until development starts is shorter than in normal latent image silver development. long,
Its development is therefore considerably delayed. Therefore,
Particularly when applied to multilayer color photographic materials, there are problems such as non-uniformity of properties between layers. In addition, the maximum final concentration obtained with conventional fogging agents is also relatively low. Therefore, with conventional fogging agents, a relatively high concentration of fogging agent is required to obtain the desired fogging effect within a relatively short period of time; Various shortcomings were found. For example, it has been found that when a fogging agent is contained in an emulsion, a large amount of the fogging agent dissolves into the developer, resulting in undesirable non-uniform development. Furthermore, if nitrogen gas bubbles produced by the decomposition of the fogging agent become trapped in the binder of the photosensitive material, the quality of the image will be significantly impaired. Furthermore, when development is carried out using a high concentration fogging agent, there is a tendency for background areas to become discolored due to contamination by the fogging agent. Furthermore, when performing color development, the fogging agent competes with the color former and reacts with the oxidized product of the color developing agent, so if a high concentration of the fogging agent is used, the concentration of the coloring dye will be significantly reduced. In order to solve these problems, fogging agents that adsorb to the surface of silver halide grains, such as acylhydrazinophenylthiourea compounds, have been proposed in US Pat. No. 4,030,925 and US Pat. It is disclosed that a good fogging effect can be achieved with a small amount of addition, and that it has the characteristics of having little dependence on the development processing temperature. However, it has been found that when these compounds are included in an emulsion, the storage stability of the emulsion and the light-sensitive material is significantly deteriorated. For example, if a photosensitive material is stored in an environment of relatively high temperature or humidity, the minimum density will significantly increase and the maximum density will also decrease, resulting in a significant loss in the quality of the positive image. Also, in U.S. Patent No. 4139387,
It is disclosed that thiocarbohydrazide compounds have effective fogging properties and are also relatively highly water soluble. However, it has been recognized that these compounds also have the following practical drawbacks. That is, it has been found that because the gradation of the highlight part of the obtained positive image, that is, the leg part on the photographic characteristic curve, is significantly softened, so-called toe-cutting tends to become worse. Such characteristics have a high contrast with background parts such as characters and line drawings, and are extremely disadvantageous when creating photographic images with sharp outlines. Various other fogging agents have been proposed, but all of them lack the ability as a fogging agent,
There are drawbacks such as deterioration of performance due to heat, humidity, etc. during storage, and there is a desire to develop a further improved fogging agent. (Object of the Invention) Therefore, the first object of the present invention is to provide a direct positive photosensitive material with good storage stability. A second object of the present invention is to provide a direct positive light-sensitive material that provides sharp and clear images. A third object of the present invention is to achieve a good fogging effect by using a new fogging agent suitable for directly forming a positive image with an internal latent image type silver halide photographic emulsion, and to prevent uneven development or It is an object of the present invention to provide a direct positive light-sensitive material which does not cause contamination, has little variation due to development processing temperature or storage over time, and has excellent stability. (Structure of the Invention) The above object of the present invention is to provide a photographic material having on a support at least one hydrophilic colloid layer containing internal latent image type silver halide grains. At least one hydrophilic colloid layer on the colloid layer side is achieved by a direct positive silver halide photographic light-sensitive material containing a compound represented by the following general formula. In the formula, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen-substituted alkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an aryl-substituted alkyl group, an unsubstituted phenyl group, or an alkyl, halogen- or alkoxy-substituted phenyl group. , R ¹ and R ² may be the same or different, and each is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen-substituted alkyl group, an alkoxyalkyl group, an aryl-substituted alkyl group, an aryl group, or a group represented by the following formula: It is. Incidentally, R used here has the same meaning as R described above. A is an unsubstituted phenylene group, an alkyl-, halogen- or alkoxy-substituted phenylene group, or a group represented by the following formula.

[expression] or

[Formula] The alkyl groups of R, R ¹ and R ² are linear or branched alkyl groups consisting of 1 to 10 carbon atoms, and specifically include methyl group, ethyl group, n-butyl group, n- Examples include dodecyl group, isopropyl group, t-pentyl group, and the like. Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as cyclopropyl group, cyclohexyl group, and adamantyl group. The halogen-substituted alkyl group is preferably an alkyl group having 1 to 10 carbon atoms substituted with a fluorine atom, chlorine atom, bromine atom, or iodine atom, such as trifluoromethyl group, ω-trifluoroethyl group, α-bromopropyl group. group, ω-bromobutyl group, and the like. The alkoxyalkyl group consists of 1 to 10 carbon atoms, and specifically includes a methoxyethyl group, a methoxymethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethoxy group, and the like. The aryloxyalkyl group has 7 to 12 carbon atoms, and includes, for example, phenoxymethyl, phenoxyethyl, tolyloxymethyl, methoxyphenyloxymethyl, chlorophenyloxymethyl, and the like. The aryl-substituted alkyl group is an alkyl group having 1 to 4 carbon atoms substituted with a phenyl group or a naphthyl group, and each of the phenyl group and the naphthyl group may have a substituent. Examples of substituents include lower alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, etc.), lower alkoxy groups having 1 to 3 carbon atoms (e.g., methoxy group, propoxy group, etc.), and halogen atoms. (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), substituted amino groups (eg, N,N-diethylamino group, N,N-dimethoxyethyl group, etc.). Therefore, specific examples of aryl-substituted alkyl groups include benzyl group, p-triethyl group,
2,4-dichlorophenylmethyl group, p-N,N
-diethylaminophenylethyl group, p-methoxyphenylmethyl group, and the like. R
The halogen atom, alkoxy group, and alkyl group substituted on the phenyl group are shown in the examples of the halogen atom, lower alkoxy group, and lower alkyl group, respectively, and specific examples of the substituted phenyl group include p-chlorophenyl group. , p-methoxyphenyl group, p-tolyl group, 2,4-dichlorophenyl group, 2-chloro-4-methylphenyl group, and the like. The aryl groups for R ¹ and R ² include phenyl groups, naphthyl groups, and substituents thereof (for example, lower alkyl groups, lower alkoxy groups, halogen atoms, cyano groups, sulfo groups, sulfonamide groups,
Substituted and unsubstituted carbamoyl groups, acylamido groups, alkoxycarbonyl groups, carboxyl groups,
Substituted and unsubstituted sulfamoyl groups, etc.) are included. Specific examples of substituted groups include p-chlorophenyl group, p-methoxyphenyl group, p-tolyl group, p-sulfophenyl group, p-morpholinosulfophenyl group, p-acetamidophenyl group,
Examples include p-cyanophenyl group and p-carboxyphenyl group. Specific examples of the unsubstituted phenylene group and the alkyl-, halogen-, or alkoxy-substituted phenylene group of A include those shown below,

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Among these, p-phenylene group is particularly preferred. Typical compounds represented by the above general formula (hereinafter referred to as the fogging agent of the present invention) useful as a fogging agent in the present invention are illustrated below, but the present invention is not limited thereto. The fogging agent of the present invention can generally be synthesized by the following method. 1-Acyl-
2-(4-nitrophenyl)hydrazine.
This is hydrogenated using a catalyst in ethanol as a solvent to reduce it to the corresponding 4-amino compound.
The asymmetric N-acylhydrazinophenyl-1,2-hydrazinecarbothioamide (including N'-substituted and non-substituted) compounds of the present invention can be obtained by converting the 4-aminophenyl hydrazide obtained as described above into 1 -Acyl-2-(4-isothiocyanate phenyl)hydrazine can be derived as a precipitate by heating and refluxing it with a desired thiosemicarbazide in an ethanol solvent. Here 1-
Acyl-2-(4-isothiocyanate phenyl)
Hydrazine is 1-acyl-2-(4-aminophenyl)hydrazine and thiophosgene or 1,
By reacting with 1'-thiocarbonyldiimidazole in an inert solvent (e.g. benzene, chloroform, acetonitrile, acetone),
or 1-acyl-2-(4-aminophenyl)
It can be obtained by converting hydrazine and carbon disulfide into a dithiocarbamate in the presence of triethylamine, followed by reaction with ethyl chloroformate. Thiosemicarbazide can also be obtained by reacting equimolar amounts of isothiocyanate and hydrazine in an alcohol solvent. On the other hand, the symmetric N,N'-bis(acylhydrazinophenyl)-
1,2-hydrazinecarbothioamide can be synthesized by reacting 2 equivalents of acylhydrazinophenyl isothiocyanate with hydrazine according to the method for producing thiosemicarbazide described above. Further, the compound of the present invention having a carboamidophenyl group or a sulfoamidophenyl group as a linking group can be prepared by using the above-mentioned 1-acyl-2-(4-aminophenyl)hydrazine with aminobenzoic acid chloride or aminobenzenesulfonyl chloride. and the corresponding 1-acyl-2-(aminophenyl acidophenyl)hydrazine,
Furthermore, it can be synthesized by a method of deriving this into isothiocyanate and reacting it with thiosemicarbazide. Next, a specific example of synthesis will be described. Synthesis Example 1 Synthesis of 1-formyl-2-(4-nitrophenyl)hydrazine (raw material) 19.2 g of 4-nitrophenylhydrazine and 8.5 g of sodium formate were mixed with 80 ml of ethanol and formic acid ester.
Heat under reflux for 2 hours in a mixed solvent of 400 ml of formic acid and 60 ml of formic acid. Thereafter, the solvent is distilled off and concentrated, and the mixture is cooled. The precipitated crystals were collected by filtration, washed with ethanol, and dried. Yield 13.1g Synthesis Example 2 Synthesis of 1-formyl-2-(4-aminophenyl)hydrazine (raw material) 8g of 1-formyl-2-(4-nitrophenyl)hydrazine was mixed with 200ml of ethanol and 100ml of ethyl acetate.
Suspend and stir with 1.5 g of palladium-carbon in a mixed solvent to absorb hydrogen. The reaction solution is filtered, the filtrate is distilled off, and the residue is washed with a mixed solvent of ethanol/n-hexane and dried. Yield: 3.6g Synthesis Example 3 Synthesis of 1-acetyl-2-(4-nitrophenyl)hydrazine (raw material) 15.3g of 4-nitrophenylhydrazine and 10.2g of acetic anhydride are dissolved in 100ml of benzene and heated under reflux for 2 hours. Cool on ice, collect the precipitated crystals by filtration, wash with ethanol, and dry. Yield 16.0g Synthesis Example 4 1-benzoyl-2-(4-nitrophenyl)
Synthesis of hydrazine (raw material) 15.3 g of 4-nitrophenylhydrazine and 22.6 g of benzoic anhydride were reacted in the same manner as in Synthesis Example 3 with 100 ml of benzene. Yield 19.6g Synthesis Example 5 Synthesis of 1-(2-formylhydrazine) phenyl isothiocyanate 1.5g of 1-formyl-2-(4-aminophenyl)hydrazine was dissolved in 100ml of dry acetone and placed in a dry ice-acetone bath (-78°C). ) to cool.
While stirring this cooling liquid under a nitrogen gas atmosphere,
A solution of 1.8 g of 1,1'-thiocarbonyldiimidazole dissolved in 100 ml of acetone was added dropwise for reaction.
After the dropwise addition is completed, the temperature is gradually returned to room temperature, and the solvent is distilled off under reduced pressure at a low temperature. The residue is washed in a cold aqueous solution with stirring, and the crystals are filtered and dried. Yield: 0.95g Synthesis Example 6 Synthesis of 4-(2-acetylhydrazine) phenylisothiocyanate 1-acetyl-2- obtained by reducing 1-acetyl-2-(4-nitrophenyl)hydrazine in the same manner as in Synthesis Example 2. (aminophenyl)hydrazine 1.65
g and 1,1'-thiocarbonyldiimidazole 1.8
g and are reacted in the same manner as in Synthesis Example 5. Yield 1.0g Synthesis Example 7 Synthesis of 4-{4-(2-formylhydrazino)phenylcarbamoyl}phenylisothiocyanate 2.5g of 1-formyl-2-{4-(4-aminobenzamido)phenyl}hydrazine and Mix and stir 1.4 g of calcium carbonate in 15 ml of water and 15 ml of dioxane. Add 1.27 g of thiophosgene under ice-cooling and react for 3 hours, and precipitate crystals are collected by filtration, washed with water and cold ethanol, and dried. Yield 1.8g Synthesis Example 8 Synthesis of 4-(2-benzoylhydrazino)phenyl isothiocyanate 1-benzoyl-2-(4-nitrophenyl)
1- obtained by reducing hydrazine in the same manner as in Synthesis Example 2
2.3 g of benzoyl-2-(4-aminophenyl)hydrazine and 1.8 g of 1,1'-thiocarbonyldiimidazole are reacted in the same manner as in Synthesis Example 5.
Yield 1.4g Synthesis Example 9 Synthesis of N-{4-(2-formylhydrazino)phenyl}-1,2-hydrazinedicarbothioamide (Compound Example 1) 4-(2-formylhydrazino)phenyl isothiocyanate 1.9 g and thiosemicarbazide 0.91
g in 100 ml of ethanol, heated to reflux for 10 minutes, and cooled. The precipitated crystals are collected by filtration, washed with cold ethanol and ether, and dried. Yield 2.2g Synthesis Example 10 Synthesis of N-{4-(2-benzoylhydrazino)phenyl}-1,2-hydrazinedicarbothioamide (Compound Example 7) 4-(2-benzoylhydrazino)phenyl isothiocyanate 2.7 g and thiosemicarbazide
0.91g was reacted in the same manner as in Synthesis Example 9. Yield 2.8g Synthesis Example 11 Synthesis of N-ethyl-N'-{4-(2-formylhydrazino)phenyl}-1,2-hydrazinedicarbothioamide (Compound Example 11) 4-(2-formylhydrazino) 1.9 g of phenylisothiocyanate and 1.2 g of 4-ethylthiosemicarbazide are reacted in the same manner as in Synthesis Example 9.
Yield 1.86g Synthesis Example 12 Synthesis of N,N'-bis{4-(2-formylhydrazino)phenyl}-1,2-hydrazinedicarbothioamide (Compound Example 27) 4-(2-formylhydrazino)phenyl 3.8 g of enyl isothiocyanate is added dropwise to 100 ml of an ethanol solution of 0.32 g of hydrazine, followed by heating under reflux for 20 minutes. After cooling, the crystals precipitated are collected by filtration, washed with ethanol, and dried. Yield 3.2g Synthesis Example 13 Synthesis of N-cyclohexyl-N'-4-{4-(2-formylhydrazino)phenylcarbamoyl}phenyl-1,2-hydrazinedicarbothioamide (Compound 29) 4-{4- (2-formylhydrazino)phenylcarbamoyl}phenylisothiocyanate 3.3
g and 1.73 g of cyclohexylthiosemicarbazide are reacted in the same manner as in Synthesis Example 9. Yield: 2.2 g The fogging agent of the present invention can be applied to a support of a direct positive photographic light-sensitive material having at least one silver halide emulsion layer containing internal latent image type silver halide grains. At least 1 on the emulsion layer side
The hydrophilic colloid layer of the layer, preferably the internal latent image type silver halide photographic emulsion layer and/or the hydrophilic colloid layer adjacent thereto (e.g. silver halide photosensitive layer, interlayer, filter layer, protective layer, antihalation layer) It is made to contain. When using two or more types of fogging agents of the present invention,
It is preferable that they coexist in the same layer in a silver halide emulsion layer or a layer adjacent thereto, but they may be contained in separate layers. The amount of the fogging agent used in the present invention can vary over a wide range depending on the characteristics of the silver halide emulsion used, the type of fogging agent, and the development conditions. After image exposure, it is sufficient that the amount provides enough fogging to obtain a positive image when developed with a surface developer.
It is desirable that the amount provides a sufficient maximum density (for example, 1.5 or more) after development. Usually, the amount of fogging agent per 1 mol of internal latent image type silver halide is preferably about 10 ^-6 mol to ^{10 -2} mol, more preferably
It ranges from 10 ⁻⁶ mol to 10 ⁻³ mol. Further, when applied to a color diffusion transfer method, it can be mixed into the image-receiving layer or sheet. In this case, the content of the fogging agent may be the same as when it is contained in the silver halide emulsion layer. Further, the fogging agent of the present invention can also be used in combination with the conventionally known fogging agents mentioned above. Specific examples of useful known fogging agents include hydrazine, hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4
-methylphenyl)hydrazine, 1-acetyl-
2-phenylhydrazine, 1-acetyl-2-
(4-acetamidophenyl)hydrazine, 1-
methylsulfonyl-2-phenylhydrazine,
1-benzoyl-2-phonylhydrazine, 1-
Hydrazine compounds such as methylsulfenyl-2-(3-phenylsulfonamidophenyl)hydrazone, formaldehyde phenylhydrazine; 3-(2-formylethyl)-2-methylbenzothiazolium bromide, 3 -(2-formylethyl)-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzoselenazolium bromide, 3-(2-
Acetylethyl-2-benzyl-5-phenyl-
Benzoxazolium bromide, 2-methyl-
3-[3-(phenylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-
[3-(p-Tolylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-[3
-(p-sulfophenylhydrazono)propyl]
Benzothiazolium bromide, 2-methyl-3
-[3-(p-sulfophenylhydrazono)pentyl]benzothiazolium iodide, 1,2-dihydro-3-methyl-4-phenylpyrido[2,
1-b] Benzothiazolium bromide, 1,2
-dihydro-3-methyl-4-phenylpyrido[2,1-b]-5-phenylbenzoxazolium bromide, 4,4'-ethylenebis(1,2-
dihydro-3-methylpyrido[2,1-b]benzothiazolium bromide), 1,2-dihydro-3-methyl-4-phenylpyrido[2,1-
b] N-substituted quaternary cycloammonium salts such as benzoselenazolium bromide; 5-[1-ethylnaphtho[1,2-b]thiazolin-2-ylideneethylidene]-1-(2-phenylcarbazoyl ) Methyl-3-(4-sulfamoylphenyl)
-2-thiohydantoin, 5-(3-ethyl-2
-benzothiazolinylidene)-3-[4-(2-formylhydrazino)phenyl]rhodanine, 1
-[-(2-formylhydrazino)phenyl]3
-phenylthiourea, 1,3-bis[4-(2-
Examples include formalylhydrazino)phenyl]thiourea. The internal latent image type silver halide photographic light-sensitive material of the present invention directly forms a positive image by developing in the presence of a fogging agent after imagewise exposure. Although any development method can be adopted as the development method, a surface development method is preferable. This surface development processing method means processing with a developer substantially free of silver halide solvent. Common silver halide developers that can be used in the developer of the present invention include polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, and phenylenediamine. or a mixture thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, N,N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, Examples include 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline. These developers can also be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution. The developer used in the present invention may further contain specific antifoggants and development inhibitors, or these developer additives may be optionally incorporated into the layers of the silver halide photographic light-sensitive material. is also possible. Commonly useful antifoggants include:
Benzotriazoles such as 5-methylbenzotriazole; benzothiazoles; 1-
Included are heterocyclic thiones such as phenyl-5-mercaptotetrazole; aromatic and aliphatic mercapto compounds, and the like. Further, the developer can also contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound. The internal latent image type silver halide photographic light-sensitive material according to the present invention comprises at least one layer of internal latent image type silver halide emulsion. The internal latent image type silver halide emulsion according to the present invention is an emulsion having silver halide grains that mainly form a latent image inside the silver halide grains and has most of the photosensitive nuclei inside the grains. Silver halides such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like are included. Particularly preferably, the emulsion is prepared by exposing a portion of a sample coated on a transparent support to a light intensity scale for a defined period of time up to about 1 second so that the surface of the grains is substantially free of silver halide solvent. When developed for 4 minutes at 20°C using surface developer A as described below, which develops only the image, internal development as described below, in which another part of the same emulsion sample is exposed in the same way and develops the image inside the grain. It shows a maximum density not greater than 1/5 of the maximum density obtained when developing with solution B at 20° C. for 4 minutes. Preferably, the maximum density obtained with surface developer A is not more than 1/10 of the maximum density obtained with internal developer B. Surface developer A Metol 2.5g L-ascorbic acid 10g NaBO ₂・4H ₂ O 35g KBr 1g Add water 1 Internal developer B Metol 2.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate hydrate 52.5g KBr 5.0g KI 0.5g Add water 1 Further, the internal developer silver halide emulsion according to the present invention includes those prepared by various methods.
For example, the compound silver halide emulsions described in U.S. Pat. No. 2,592,250, or U.S. Pat.
Silver halide emulsions with internally chemically sensitized silver halide grains as described in US Pat. No. 3,367,778 or polyvalent metal ions as described in US Pat. A silver halide emulsion having built-in silver halide grains, or a silver halide emulsion in which the grain surface of silver halide grains containing a dopant as described in U.S. Pat. No. 3,761,276 is weakly chemically sensitized, or Silver halide emulsions comprising grains having a layered structure as described in JP-A-50-8524, JP-A-50-38525 and JP-A-53-2408, and other JP-A-52-156614 and JP-A-55- These include silver halide emulsions described in No. 127549. Further, in the internal latent image type silver halide emulsion according to the present invention, commonly used stabilizers, such as compounds having an azaindene ring and nitrogen-containing heterocyclic compounds having a mercapto group (typical examples include 4-hydroxy- 6-methyl-1,3,3a,
7-tetrazaindene and 1-phenyl-5-
By containing 1 mg to 10 g of mercaptotetrazole per mole of silver halide, a more stable result with a lower minimum concentration can be obtained. In addition, in the present invention, as antifoggants or stabilizers, for example, mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds, zinc compounds, etc. may be used. Various photographic additives may optionally be added to the internal latent image type silver halide emulsion according to the present invention. For example, optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear meloncyanines, trinuclear or tetranuclear cyanines, styryls, homopolar cyanines, hemicyanines, oxonols, etc. These optical sensitizers include basic groups such as thiazoline and thiazole, or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid,
Those containing a nucleus such as thiobarbituric acid or pyrazolone are preferred, and such a nucleus can be substituted with alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, or alkoxy, and can be fused with a carbocyclic or heterocyclic ring. It is optional to do so. The internal latent image type silver halide emulsion according to the present invention can be supersensitized. Regarding the method of supersensitization, see, for example, "Review of the mechanism of supersensitization" (Review
of Supersensitization);
Photographic Science and Engineering
Vol. 18, page 4418 (1974). Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylate. Water-dispersible particulate polymeric substances obtained by emulsion polymerization such as copolymers with acids, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc. are suitable; Examples of the auxiliary agent include saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, PH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of conditioning agents, matting agents, etc. is optional. The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to obtain an internal latent image type silver halide photographic light-sensitive material. It is useful to use the silver halide photographic light-sensitive material of the present invention for color applications, and in this case it is preferable to include cyan, magenta and yellow dye image-forming couplers in the silver halide photographic emulsion. Yellow dye-forming couplers include benzoylacetanilide type, pivaloylacetanilide type, or substituents whose carbon atoms at the coupling position can be separated during the coupling reaction;
Two-equivalent type yellow couplers substituted with so-called split-off groups are useful. As magenta dye-forming couplers, pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type couplers, or two-equivalent type magenta couplers having a split-off group are useful. As the cyan dye-forming coupler, phenolic, naphthol, pyrazoquinazolone, or two-equivalent cyan couplers having a split-off group are useful. In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent fading of dye images due to short-wavelength actinic rays. 327, same
328 (all manufactured by Ciba Geigy) alone or in combination is advantageous. Any support can be used for the silver halide photographic material according to the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, and polypropylene, which are subbed-treated as necessary. Film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc. In addition to gelatin, the silver halide photographic material according to the present invention may contain a suitable gelatin derivative depending on the purpose. Examples of suitable gelatin derivatives include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin. In addition, in the present invention, other hydrophilic binders can be included depending on the purpose. In addition to gelatin, suitable binders include colloidal albumin, agar, gum arabic, dextran, alginic acid, acetyl-containing 10- Cellulose derivatives such as cellulose acetate hydrolyzed to 20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol.
Vinyl alcohol polymers containing urethane carboxylic acid groups or cyanocetyl groups, such as vinylaminoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerization of proteins or saturated acylated proteins with monomers having vinyl groups. , polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be added to constituent layers of silver halide photographic materials such as emulsion layers, intermediate layers, protective layers, filter layers, backing layers, etc. depending on the purpose. Furthermore, the hydrophilic binder may contain appropriate plasticizers, lubricants, etc. depending on the purpose. Further, the constituent layers of the silver halide photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent. These hardeners include chromium salts, zirconium salts, aldehyde-based hardeners such as formaldehyde and mucohalogen acids, halotriazine-based hardeners, polyepoxy compounds, ethyleneimine-based hardeners, vinyl sulfone-based hardeners, and acryloyl-based hardeners. Can be mentioned. Further, the silver halide photographic light-sensitive material according to the present invention includes an emulsion layer, a filter layer, an intermediate layer, an emulsion layer, a filter layer, an intermediate layer,
It is possible to provide a large number of various photographic constituent layers such as a protective layer, a subbing layer, a backing layer, an antihalation layer, etc. The silver halide photographic material according to the present invention can be effectively applied to various uses such as black and white general use, X-ray use, color use, medium color use, printing use, infrared use, micro use, and silver dye bleaching use. You can also
U.S. Patent No. 3087817, U.S. Patent No. 3185567, U.S. Patent No.
No. 2983606, No. 3253915, No. 3227550, No. 3227551, No. 3227552, No. 3415644,
Same No. 3415645, Same No. 3415646, Same No. 3594164,
Same No. 3594165, Same No. 3573043, Same No. 3647437,
Same No. 3928312, No. 4135929, No. 4198235,
It is also applicable to color image transfer methods, color diffusion transfer methods, etc. as described in British Patent No. 4,336,322 and British Patent No. 1,496,363. (Examples) The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 An internal latent image type silver chloroiodobromide emulsion was prepared by a conversion method according to the method described in Example 1 of US Pat. No. 2,592,250. Separately, the magenta coupler 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylsuccinimideanilino)-5-pyrazolone 40g, 2,5-di-
Mix and dissolve 1 g of tert-octylhydroquinone, 75 g of dioctyl phthalate, and 30 g of ethyl acetate,
It was added to an aqueous gelatin solution containing sodium isopropylnaphthalene sulfonate and emulsified and dispersed. Pigments including this dispersion: and Emulsion 1 (silver chloroiodobromide) spectrally sensitized by
(contains 0.35 mol), and further contains 4-hydroxy-6
An emulsion was prepared by adding 1 g of -methyl-1,3,3a,7-tetrazaindene and 1 g of potassium 2,5-dihydroxy-4-sec-octadecylbenzenesulfonate. Among the fogging agents of the present invention, the above-mentioned compound examples 1, 2, 5, 6, 7, 8, 9, 11, 15, 16,
20, 26, 27, 29, 30, 31 and 32 respectively in Table-1
A methanol solution was added to the emulsion in the amount shown in , and a sample was prepared by coating on a resin-coated paper support and drying. In addition, as a comparative fogging agent, the compound [A] described in JP-A-53-20318 and US Pat. No. 4,139,387: Compound [B]: A sample was prepared with the addition of Each of these samples was stored for 1 day at a temperature of 23°C and a relative humidity of 55% (conditions -
1), stored for 2 days at a temperature of 55°C with no humidity control (condition-2), and stored for 2 days at a temperature of 40°C and a relative humidity of 80% (condition-3), and then subjected to imagewise exposure. , the following processing was performed. Processing: Color development (3 minutes 30 seconds) - Stop (30 seconds) - Bleach fixing (1 minute 30 seconds) - Washing (1 minute 30 seconds) The processing temperature was 30°C for each processing step, and the composition of each processing solution showed that. Color developer: Potassium carbonate 25g/ Potassium bromide 1g/ Benzyl alcohol 10g/ Potassium sulfite 2.5g/ 5-methylbenzotriazole 10mg/ 4-amino-3-methyl-N-ethyl-
N'-(β-methanesulfonamidoethyl)aniline sulfate 4.5g/PH (adjusted with potassium hydroxide) 12.0 Stop solution: Sodium acetate 6.7g/Acetic acid 18.5g/Sodium sulfite 4.5g/PH 4.1 Bleach-fix solution: Ammonium thiosulfate 110g/ Sodium hydrogen sulfite 10g/ Iron ammonium ethylenediaminetetraacetate
60g/diammonium ethylenediaminetetraacetate
5g/bis-thiourea 2g/PH (adjusted with aqueous ammonia) 6.5 The obtained results are shown in Table-1 and Table-2.

【table】

【table】

【table】

[Table] From the results in Tables 1 and 2, the use of the fogging agent of the present invention provides good fogging effects and also has excellent storage stability in a high temperature and high humidity atmosphere. That is clear. That is, sample 1
(Comparison) When stored at high temperature (condition-2), the minimum concentration (Dmin.) increases significantly, and when stored in a high humidity atmosphere (condition-3), the maximum concentration (Dmax.) decreases significantly. . Moreover, when compound [B] is used, (comparison -
2) The gradation (γ ₂ ) of the legs is soft, and when stored under high temperature and high humidity, the tone becomes even softer and the legs become more difficult to cut. On the other hand, the direct positive light-sensitive materials of the present invention (Samples Nos. 3 to 19) are extremely stable even after aging under high temperature and high humidity conditions, and have good resistance to foot breakage. Example 2 The method of forming a positive image using a fogging agent according to the present invention can also be applied to a diffusion transfer method. A photosensitive sheet was prepared by sequentially coating the following layers on an opaque film support made of polyethylene terephthalate. (1) A gelatin layer containing the following magenta dye image-forming compound. (2) A green-sensitive internal latent image direct positive silver bromide emulsion (prepared similarly to Emulsion C described in Example 1 of U.S. Pat. No. 3,761,276, containing an internal latent image spectrally sensitized with a sensitizing dye) (type emulsion), potassium 2,5-dihydroxy-4-sec-octadecylbenzenesulfonate, and the fogging agent of the present invention (Compound Example 2) in the amount shown in Table 3. (3) Gelatin protective layer. Furthermore, in place of the fogging agent in layer (2) above, Table 3
Exactly the same photosensitive sheet was prepared except that the fogging agent shown in 1 was used. A dye image receiving sheet was then prepared by coating the following layers in the order listed onto an opaque paper support. (1) Copolymer of styrene, N,N-dimethyl-N-benzyl-N-p-(methacroylaminophenyl)methylammonium chloride and divinylbenzene, gelatin and 1-phenyl-4
- An image-receiving layer made of hydroxymethyl-4-methyl-3-pyrazolidinone. (2) Gelatin interlayer containing UV absorbers. (3) Gelatin protective layer. After processing the above photosensitive sheet under the storage conditions described in Example 1, it was subjected to imagewise exposure, immersed in an activator solution having the following composition for 15 seconds, and then passed between a pair of pressure rollers to form the above image receiving sheet. Superimposed on. Treatments were performed at 18°C, 24°C, and 33°C. (Activator composition) Potassium hydroxide 56.2g/5-methylbenzotriazole 7.2g/11-aminoundecanoic acid 2.0g/potassium bromide 2.0g/After 3 minutes, the photosensitive sheet and image-receiving sheet were peeled off. Table 3 shows the maximum density and minimum density of the magenta dye transfer image obtained on the image-receiving layer.

[Table] In Table 3, the compound [A] used in Example 1 and the following were used as conventionally known fogging agents for comparison. Compound [C]: From these results, it is clear that the fogging agent of the present invention acts as a good fogging agent and has excellent storage stability even in light-sensitive materials produced by the diffusion transfer method. That is, when using the fogging agent of the present invention,
Compared to the case of using compound [A], fluctuations during storage over time under high temperature and high humidity (decrease in Dmax. and
Dmin. increase) is small. In addition, compared to the case where compound [C] is used, the concentration (Dmax.) fluctuation due to processing temperature is significantly smaller, and compound [C]
There was no occurrence of bubbles or uneven development that was observed when using .

Claims (1)

[Scope of Claims] 1. A photographic material having on a support at least one hydrophilic colloid layer containing internal latent image type silver halide grains, on the side of the hydrophilic colloid layer on the support. A direct positive silver halide photographic material, characterized in that at least one hydrophilic colloid layer contains a compound represented by the following general formula. [In the formula, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen-substituted alkyl group, an alkoxyalkyl group, an aryloxyalkyl group, an aryl-substituted alkyl group, an unsubstituted phenyl group, or an alkyl, halogen- or alkoxy-substituted phenyl group. , R ¹ and R ² may be the same or different,
Each hydrogen atom, alkyl group, cycloalkyl group,
Represents a halogen-substituted alkyl group, an alkoxyalkyl group, an aryl-substituted alkyl group, an aryl group, or [Formula]. A is an unsubstituted phenylene group, an alkyl, halogen or alkoxy substituted phenylene group,
Represents [formula] or [formula]. ]