JPS5828570B2 - Direct positive image formation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for directly forming a positive photographic image using a silver halide photographic light-sensitive material. The present invention relates to a novel fogging agent used in a method of directly forming a positive image by processing with a liquid.

The present invention is a technology that can be applied to color diffusion transfer as well as ordinary black-and-white photography and color photography.

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 direct positive type methods used to create positive images using silver halide photographic light-sensitive materials, excluding special methods, are mainly of two types in consideration of practical usefulness. It can be divided into

The two types use a silver halide emulsion that has been fogged in advance and obtain a positive image after development by destroying fog nuclei (latent images) in exposed areas using solarization or shell effects. be.

The other type is the unfogged internal latent image type.
- A positive image is obtained by using a silver halogen emulsion and carrying out surface development after and/or while carrying out fogging treatment after image exposure.

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 using a fogging agent. It is being done.

The internal latent image type silver halide emulsion mainly refers to a silver halide emulsion that 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, U.S. Patent Nos. 2,592,250 and 24,569
No. 57, No. 2497875, No. 2588982, British Patent No. 1151363, Japanese Patent Publication No. 1977-2
No. 9405, JP-A No. 4-7-9434, JP-A No. 47-96
No. 77, No. 47-32813, No. 4732814,
The main ones include US Pat. No. 48-9727, US Pat. No. 48-9717, US Pat. No. 3,761,266, US Pat.

By using these known methods, it is possible to produce a relatively highly sensitive photographic material as a direct positive type.

Furthermore, although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, the theory of
The Photographic Process J
theory of the Photographic P
As discussed on page 161 of the 3rd edition of
It is possible to understand to some extent the process by which a positive image is formed due to the desensitization effect j caused by an internal latent image.

In other words, fog nuclei are selectively generated only on the surface of unexposed silver halide grains in non-image areas due to the surface desensitization effect caused by the so-called internal latent image created inside the silver halide grains by the initial image exposure. It is believed that 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, US Patent No. 2563785, US Patent No. 25889
82, naphthylhydrazine sulfonic acid described in US Pat. No. 2,604,700, or British Patent No. 140.
The sulfophthylhydrazines described in No. 3018 are used as fogging agents.

Further, Japanese Patent Publication No. 41-17184 describes that a color positive image can be obtained using a hydrazide or hydrazone compound.

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, so its development is considerably delayed.

Therefore, especially when applied to a multilayer color photographic light-sensitive material, non-uniformity of properties is likely to occur between the layers, resulting in the problem of X, -v'U.

In addition, the maximum final concentration obtained with conventional fogging agents is also relatively low.

Therefore, in order to obtain the desired fogging effect within a relatively short period of time, a relatively high concentration of the fogging agent is required. It has been found that, especially when a fogging agent is contained in the emulsion, a large amount of the fogging agent dissolves into the developer, resulting in undesirable non-uniformity.

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.

Also, in order to maintain a desirable degree of fogging, development has traditionally been carried out at high pH values of 12 to 13 or more.

However, developing under such high pH conditions is not at all desirable as it significantly accelerates the deterioration of the developing agent or deteriorates the film properties of the photographic light-sensitive material.

A first object of the present invention is to provide a novel fogging agent suitable for directly forming a positive image using an internal latent image type silver halide emulsion.

A second object of the present invention is to provide a method for directly forming a positive image by developing an internal latent image type silver-finished silver photographic emulsion in the presence of a novel fogging agent.

A third object of the present invention is to provide a photographic material having an internal latent image type silver halide photographic emulsion containing a novel fogging agent.

A fourth object of the present invention is to use a novel fogging agent which is effective at low fogging agent concentrations and at low pH values and which reduces the occurrence of non-uniform development and contamination due to the fogging agent and prevents film formation of photographic materials. The object of the present invention is to provide a means for improving the deterioration of physical properties.

A fifth object of the present invention is to provide a means for obtaining a good positive image with a high maximum density and a low minimum density with a relatively short fog development time by using a new fogging agent. .

A sixth object of the present invention is to provide a means to improve the other disadvantages of the prior art by using a new fogging agent.

Other objects of the invention will become apparent from the description below.

The object of the present invention is to prepare an internal latent image type silver halide emulsion after imagewise exposure in the presence of an amount of at least one compound represented by the following general formula [I], (II) or (III) that provides a fuming effect. It has been found that this can be achieved by developing.

General formula CI) In the formula, R1, R2, R3, R4, R5 and R6 are unsubstituted aryl groups (e.g. phenyl group, naphthyl group, etc.)
, substituted aryl groups (e.g. alkyl groups, alkoxy groups,
aryloxy group, ), rogene atom, hydroxy group, amino group, acylamino group, carboxy group, carbamoyl group, phenyl group substituted with a sulfo group, naphthyl group, etc.), heterocyclic group (e.g. 2-benzothiazolyl group, 2
-benzothiazolyl group, pyridyl group, quinolyl group, etc.)
and is preferably an unsubstituted phenyl group or a phenyl group substituted with the above substituent.

Xl, X and X3 represent a carbonyl group or a sulfonyl group.

Here, R7, R8 and R9 are a hydrogen atom, a lower alkyl group (preferably one having 1 to 4 carbon atoms), an unsubstituted aryl group (e.g. phenyl group, naphthyl group, etc.), a substituted aryl group (e.g. an alkyl group, Alkoxy group, aryloxy group, halogen atom, hydroxy group, amino group,
R7 represents a phenyl group substituted with an acylamino group, a carboxy group, a carbamoyl group, a sulfo group, a naphthyl group, etc.). It may form a ring.

Ll, L2 and L3 are divalent organic groups such as alkylene groups, phenylene groups, naphthylene groups, divalent heterocyclic groups (e.g. pyridinediyl groups, quinolinediyl groups, benzothiazolediyl groups, etc.), oxy groups, thio groups, Seleno group, 10 carbonyl group, -N- group (here RIO has 1 carbon atom
~4 alkyl groups), sulfinyl groups and/
or an alkylene group bonded to a sulfonyl group, or a group bonded to each other. , 21. May be substituted with occlusion, etc.

k, ■, m and n represent 0 or 1.

Among the compounds represented by the general formula [■], (II) or (II) of the present invention, the compound represented by the general formula C1,) in which Xl and X2 are carbonyl groups is particularly preferred.

The above general formula [■] useful as a fogging agent in the present invention
, [1■] or (III) (hereinafter referred to as the fogging agent of the present invention) include the following compounds, but the present invention is not limited to these. It's not something you can do.

The fogging agent of the present invention can be easily synthesized by a known method by reacting a compound having a carbonyl group or sulfonyl group at both ends of the molecule with a hydrazine compound.

As a hydrazine compound, for example, phenylhydrazine p
-sulfophenylhydrazine, p-chlorphenylhydrazine, p-7'' romphenylhydrazine, p-carboxyphenylhydrazine, p-methoxyphenylhydrazine, p-)lylhydrazine, 2-benzothiazolylhydrazine, 2-pyridylhydrazine, Included are 3-quinolylhydrazine and the like.

This reaction generally does not require a catalyst and a wide range of reaction temperatures can be used as long as both compounds remain in solution in the presence of a suitable solvent and are not heated above their decomposition temperatures.

Since the reaction products precipitate out of solution, pure compounds can be obtained simply by washing with a solvent.

If necessary, it can be purified by recrystallization using an appropriate solvent.

For example, the compound represented by the general formula CI) of the present invention is synthesized by reacting phosgene, sulfonyl chloride, carboxylic acid, carboxylic acid ester, carboxylic acid chloride, or sulfonic acid chloride compound with the above-mentioned hydrazine compound in ether at low temperature. can do.

Further, the compound represented by the general formula [■] of the present invention can be synthesized by reacting ochynecarboxylic acid or its chloride or oxosulfonic acid chloride compound with a hydrazine compound.

Further, the compound represented by the general formula [■] of the present invention can be synthesized by reacting a ketone or aldehyde compound with a hydrazine compound.

Next, a specific example of synthesis will be described.

Synthesis Example 1 (1) Synthesis of 5-diphenylcarbohydrazide (Compound Example 1) A toluene solution in which phosgene 231 was dissolved was gradually added dropwise to a cold ether solution in which phenylhydrazine of 501 was dissolved with stirring.

After stirring was continued for about 1 hour after the completion of the dropwise addition, a lot of the precipitated crystal product was collected, washed with water, and then dried.

Melting point: 169-170°C Synthesis Example 2 Synthesis of succinic acid bisphenyl hydrazide (Compound Example 8) Succinic acid 118z was dissolved in water 11, and 216 g of phenylhydrazine was further added and reacted by heating on a boiling water bath for about 5 hours. Thereafter, the mixture was cooled with water, and a lot of the precipitated crystalline product was collected, washed with methanol, and then dried.

Melting point: 230-232°C Synthesis Example 3 Phenylhydransoacetoacetic acid phenylhydrazide (Compound Example 53) Diketene 421 was gradually added dropwise to a benzene solution in which phenylhydrazine 1081 was dissolved while stirring.

Since the reaction was exothermic, stirring was continued for about 3 hours while keeping the internal temperature around room temperature by occasionally cooling with water.

After the reaction was completed, the precipitated crystalline product was collected and recrystallized from ethyl alcohol.

Melting point: 152-153°C Synthesis Example 4 α・β-Bisphenylhydransopropionic acid (Compound Example 68) 123 g of dibromopyruvic acid was added to an aqueous solution in which 145 P of phenylhydrazine hydrochloride was dissolved, and the mixture was heated on a boiling water bath while stirring. After reacting for about 5 hours, the precipitated crystal product was collected and recrystallized in chloroform.

Melting point: 217-219°C At least one of the fogging agents of the present invention may be present in the internal latent image type silver halide emulsion layer during the development process after image exposure.

That is, after exposing a photographic material having an internal latent image type silver halide emulsion, it may be developed in the presence of the fogging agent of the present invention.

In a preferred embodiment, at least one of the fogging agents of the present invention is added to a silver halide emulsion layer or a layer adjacent thereto (for example, a silver halide photosensitive layer, an intermediate layer, a filter layer, a protective layer, an anti-ration layer, etc.). ), or in a developer solution (or developer) or a processing bath, such as a fog bath, which is processed prior to development.

When two or more types of fogging agents of the present invention are used together, 7. It is preferable that they coexist in the same layer or in the same solution in the silver ugenide emulsion layer or its adjacent layer, or in the developer or bath prior to development. 91JL layer or another processing solution, one side is a silver halide photographic light-sensitive material constituent layer,
The other compound may be contained separately in the treatment liquid, and both compounds may work together in the treatment process.

The fogging agent of the present invention can also be used in combination with the previously known fogging agents mentioned above.

The amount of the fogging agent used in the present invention can vary widely depending on the characteristics of the silver halide emulsion used, the type of fogging agent, and the development conditions. After image exposure, the amount should be enough to provide enough blurring effect to obtain a positive image when developed with a surface developer (and the amount should be enough to provide a sufficient maximum density (e.g., 2.0 or more) after development). is desirable.

When the fogging agent of the present invention is incorporated into a silver halide emulsion and at an appropriate time after the completion of ripening, about 10-4 mol - 1O-1 mol of the fogging agent is added to a developing solution ( or developer) or a processing bath prior to development, the amount is preferably about 10 -5 mol - 10 -2 mol.

In addition, when applied to color diffusion transfer method,
It can be incorporated into the image receiving layer or sheet.

In this case, the content of the fogging agent may be the same as in the case where it is contained in the silver halide emulsion layer.

Common silver halide developers that can be used in the developing composition of the present invention include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc. or a mixture thereof.

It is also possible to include these developers in advance in the emulsion 11J and allow them to act on the silver halide during immersion in the high pH aqueous solution.

The developing composition used in the present invention can further contain specific antifoggants and development inhibitors, or these compositions can be optionally incorporated into the layers of the silver halide photographic light-sensitive material. It is possible.

Commonly useful antifoggants include, for example, benzotriazoles, benzothiazoles such as 5-methylbenzothiazole; 1-phenyl-5-mercaptotetrazoles, 5-methylbenzotriazole, etc.;
-Dicyclic thiones such as -tetrazoline-5-thione; aromatic, aromatic and aliphatic mercapto compounds, and the like.

In the present invention, the silver halide emulsion is an internal latent image type silver halide emulsion, that is, a halogen emulsion that mainly forms a latent image inside the silver halide grains and has most of the photosensitive nuclei inside the grains. milk containing silver oxide grains], and any...
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 grain is substantially free of silver halide solvent. When developed for 4 minutes at 20°C using the surface developer A described below which develops only the image, the internal developer described below develops the image inside the grain by exposing another part of the same emulsion sample in the same way. It shows a maximum density not greater than 115, which is the maximum density obtained when developing with B for 4 minutes at 20°C.

Preferably, the maximum density obtained with surface developer A is not more than 1/10 of the maximum density obtained with internal developer.

Surface developer A Metol L-Ascorbic acid NaBO2.4N (20 Br Add water to make internal developer B 2.5 g 10'? 20 g 1'y' l m Sodium sulfite (anhydrous) Hydroquinone carbonate soda water Salt B r I Add water to give 2.0 g 90.0 g 8.0 i 52.5 P 5, OL? 0.51 l In addition, internal latent image type silver halide emulsions can be prepared by various methods. Includes

For example, the conversion type silver halide emulsion described in US Pat. No. 2,592,250, or the conversion type silver halide emulsion described in US Pat. No. 3,206,316, US Pat. Silver halide emulsions having internally chemically sensitized silver halide grains, or U.S. Pat.
No. 71157, No. 3447927, No. 35312
From a silver halide emulsion having silver halide grains containing polyvalent metal ions as described in the specification of No. 91, or grains having a layered structure as described in JP-A-50-8524. or a silver halide emulsion containing silver iodide prepared by the ammonia method described in Japanese Patent Application No. 51-74062.

Furthermore, the silver halide emulsion used in the present invention contains a compound having an azaindene ring, a nitrogen-containing heterocyclic compound having a mercapto group, etc. in an amount of 1 to 1 mole of silver halide.
By containing 1 to 11', more stable results with a lower minimum concentration can be given.

As the compound having an azaindene ring, 4hydroxy-6-methyl-■.3.3a.7-titrazaindene is preferred.

Examples of the nitrogen-containing heterocyclic compound having a mercapto group include a pyrazole ring, l, 2, 4-triazole ring, ■, 2, 3
-triazole ring, ■・3,4-thiadiazole ring, 1
・2,3-thiadiazole ring, l・2,4-thiadiazole ring, ■・2,5-thiadiazole ring, 1,2,3・
4-tetrazole ring, pyridazine ring, 1.2.3-triazine ring, Examples include a riazolotriazole ring, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, a pentazaindene ring, and a phthalazinone ring, an interduryl ring, and 1-phenyl-5-mercaptotetrazole is preferred.

In addition, in the silver halide emulsion applied to the present invention, antifoggants or stabilizers such as mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds, and zinc compounds may be used.

Various photographic additives may optionally be added to the silver halide emulsion applied to the present invention.

For example, optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, *lobolacyanines, hemicyanines, oquinols, etc. These optical sensitizers include basic groups such as thiazoline and thiazole, or rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, and thiobarbyl as part of their structure as a nitrogen-containing heterocyclic nucleus. Those containing nuclei such as acid and pyrazolone are preferred;
Such nuclei can be alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen phenyl, cyano, alkoxy substituted and optionally fused with carbocycles or heterocycles.

Applied to the present invention... □Silver germide can be supersensitized.

Regarding the method of supersensitization, see, for example, "Review of the mechanism of supersensitization J.
tization) PSE Vol, 18, 厘4
418 (1974).

In addition, various additives can be used in the silver halide emulsion applied in the present invention depending on the purpose. Examples of wetting agents include dihydroxyalkanes, and film property improvers include , for example, a copolymer of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid, styrene-maleic acid copolymer, styrene-maleic anhydride half-alkyl ester copolymer, etc. Polymeric substances in the form of fine particles are suitable, and coating aids include, for example, saponin, polyethylene glycol lauryl ether, and the like.

Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of conditioning agents, matting agents, etc. is optional.

Furthermore, it is useful to apply the method of the present invention for color purposes; in this case, it is preferable to include cyan, magenta, and yellow coloring agents in the silver halide emulsion; however, these coloring agents include phenols. , 5-pyrazolones, and ketomethylene compounds are effective, and it is preferable to use them in combination with active site substitution type color formers, colored color formers, and development inhibitor release type color formers.

Any support can be used to coat the silver halide emulsion to which the present invention is applied.

In addition to gelatin, the silver halide emulsion to which the present invention is applied 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, other hydrophilic binders may be included depending on the purpose. In addition to gelatin, suitable binders include colloidal albumin, agar, gum arabic, dextran, alginic acid, and hydrolyzed to an acetyl content of 19 to 20%. cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylamino acetate copolymers,
Emulsions include polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc. It can be added to the layers constituting the silver halide photographic material, such as layers, intermediate layers, protective layers, filter layers, backing layers, etc., depending on the purpose. Plasticizers, lubricants, etc. can be contained.

In addition, the photographic light-sensitive material having a silver halide emulsion layer to which the present invention is applied includes, in addition to the emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, an antihalation layer, etc. on a support. It is possible to arrange a large number of different layers of.

The method of forming a direct positive image according to the present invention includes a colloid transfer method, a silver salt diffusion transfer method, and US Pat. No. 3,087 to Rogers.
No. 817, No. 3185567 and No. 29836
No. 06, U.S. Pat. No. 3,253,915 to Weyarts et al., U.S. Pat. No. 3,227,550 to Whitemore et al., U.S. Pat. No. 3,227,551 to Pearl et al., U.S. Pat.
No. 415644, No. 3415645 and No. 34
It is also applicable to the color image transfer method, color diffusion transfer method, absorption transfer method, etc. described in each specification of No. 15646.

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 the conversion method according to the method described in Example 1 of US Pat. No. 2,592,250.

The above-mentioned compound example 1, which is a fogging agent of the present invention, is added to this emulsion.
7 and coated on a cellulose triacetate support with a coated silver amount of 35 μ/100 crA, dried, and exposed with a wedge to develop the following formulation: Phenidone Sodium Sulfite (Anhydrous) Hydroquinone Sodium Carbonate (-Salt) ) Add Br 5-methylbenztriazole water (pH adjusted to 1,25KJI with NaOH) 0.4? 75g10g40g4y'01n9l was developed at 20°C for 4 minutes, fixed, washed with water and dried according to conventional methods.

The results of the positive inverted images obtained are shown in Table 1.

The results in the above table indicate that the fogging agent compound of the present invention has an effective fogging effect.

Example 2 A cyan coupler, 1-hydroxy-N-, which was dissolved in tri-cresyl phosphate and dispersed in an aqueous gelatin solution, was added to the internal latent image type silver chloroiodobromide emulsion prepared in Example 1. Cδ-(2.4-t-amylphenoxy)butyl-2-naphthamide was added, and further, among the fogging agents of the present invention, Compound Examples 8 and 21 were added.

In addition, as a conventionally known fogging agent, Japanese Patent Publication No. 41-1718
Comparative samples were prepared by adding 1-acetyl-2-phenylhydrazine (Compound A) described in Publication No. 4 and sulfosuccinic acid dihydrazide (Compound B) described in US Pat. No. 2,588,982.

Each emulsion was coated on a cellulose triacetate support to a coated silver amount of 2 omV'100 crA, dried, and exposed using a wedge.
β-Hydroxyethyl)aniline sulfate Sodium sulfite (anhydrous) 21 Trisodium phosphate 40 Gbenzimidazole 50 ■Add water and adjust the pH value as shown in Table 2 with NaOH.

) at 20° C. for 1 to 5 minutes, then bleached, fixed, washed with water and dried.

The results of each cyan positive image are compared and shown in Table 2.

As is clear from the above results, when the fogging agent compound of the present invention is contained in an emulsion, a good direct reversal positive image can be obtained in a smaller amount and at a lower pH of the developer than in the case of known fogging agents.

Incidentally, if we compare the results of sample-3 using compound A and sample-1 using fogging agent compound 8 of the present invention for comparison, we find that by using the fogging agent of the present invention, a smaller amount of A sufficient fogging effect was obtained within a short period of time by the addition of , and comparison of the results of Comparative Compound B and Compound 21 shows that the fogging agent compound of the present invention has a better fogging effect. .

Example 3 As described in Example 2, the fogging agent compound of the present invention was added as shown in Table 3 to an internal latent image type silver chloroiodobromide emulsion containing an oil-protected dispersed cyan coupler. After coating triacetate on support and drying,
Wedge exposure was performed and development was performed in the same manner as in Example 2.

However, a developer having the same formulation as in Example 2 was adjusted to pH 11.5 with NaOH, and then developed at 20° C. for 4 minutes.

The results of the obtained inverted color image are shown in Table 3.

The above results show that by using the fogging agent of the present invention, a good reversal image with a high maximum density and a low minimum density is formed.

Example 4 A photographic film was prepared by the method described in Example 2 without containing a fogging agent in the emulsion.

That is, a protected dispersed cyan coupler was added to an internal latent image type silver chloroiodobromide emulsion, and the amount of coated silver was 20m9/100c.
4 on a cellulose triacetate support, dried, wedge exposed, and developed with the developer used in Example 2 at 20° C. for 5 minutes.

However, the developing solution contained the fogging agent of the present invention.

Also, for comparison, as a known fogging agent, U.S. Patent No. 2
Phenylhydrazine (Compound C) described in Japanese Patent Publication No. 563785, 1-formyl-2-phenylhydrazine (Compound D) described in Japanese Patent Publication No. 17184/1984, and 1-acetyl-2-phenylhydrazine (
Compound A) was added to the calcined mixture.

The results of the obtained positive images are shown in Table 4.

This result also shows that when a fogging agent is contained in a developer, the compound according to the present invention exhibits an excellent fogging effect in a small amount and at a lower developer pH than conventionally known fogging agents. Example 5 It is shown that a good positive image with a high maximum density and a low minimum density can be obtained.The method of forming a positive image using the fogging agent according to the present invention can also be applied to an image transfer method. .

A sample film was prepared by coating a silver halide emulsion with the following composition on a cellulose triacetate support.

Using the internal latent image type silver chloroiodobromide emulsion prepared in Example 1 (coated silver amount: 15cm/100c77f), the cyan image transfer coupler 2-(3,5-disulfobenzamide)- 4-(3-octadecylcarbamylphenylthio)-5-methylphenol dipotassium salt (10,8
P/silver 1 mol) and 2,5-dihydroxy-4-octatecylbenzenesulfonic acid potassium salt (6 g/silver 1 mol) and the fogging agent of the present invention (Compound Example 6) as shown in Table 5 and the known An emulsion containing a fogging agent (compound A) was coated on a transparent triacetate support and dried.

Next, after wedge exposure of the sample film, a viscous developer with the following formulation ascorbic acid 0.424-
Amino-N-ethyl-N-(β 10 ?-hydroxyethyl)aniline benzotriazole 0.3 g * Soluium hydroxide 4% Highly viscous carboxymethyl cell 700 ml Loin aqueous solution Add water 1. Develop by putting a viscous developer between the sample film and the image-receiving sheet containing a cationic mordant and compressing it at 20°C for 3 minutes, then peel off the image-receiving sheet and prepare as shown in Table 5. A positive image of the second image receiving sheet was obtained.

This result also shows that by using the fogging agent of the present invention, an image with a higher maximum density and a lower minimum density can be formed and an image can be obtained compared to the conventionally known fogging agent 1-formyl-2-phenylhydrazine. .

Good position rotation too

Claims (1)

[Scope of Claims] 1. An internal latent image type silver halide emulsion that has been imagewise exposed is treated with at least one compound represented by the following general formula [I], [■] or (III) to provide a diluting action. 1. A method for forming a direct positive image, characterized by carrying out development processing in the presence of a certain amount. General formula CI) [In the formula, R1, R2, R3, R4, R5 and R6 are each aryl group or heterocyclic group, Xl, X2 and X3 are each a carbonyl group or sulfonyl group, Yl is a C-group, and Y2 is -C- group, Y3 is -C- group, R7, R8
and R9 each represent a hydrogen atom, a lower alkyl group or an aryl group, Ll, Rui and L3 represent a divalent organic group,
R7 may be combined with L2 and R8 may be combined with L3 to form a 5- or 6-membered ring, and k, l, m and n each represent O or l. ].