JPS61259249A - High contrast developing method for photographic image - Google Patents

Abstract

PURPOSE:To obtain excellent dot image quality with a stable developing soln. by using a processing soln. from which an amino compd. harmful to the human body is removed by developing a silver halide photographic sensitive material applied with a latent image on the surface in the presence of the compd. expressed by the specific formula. CONSTITUTION:The ultra-high contrast image is formed by using the hydrazine compd. expressed by the formula in the stage of forming the photographic image using the silver halide photographic sensitive material. The silver halide photographic sensitive material applied with the latent image on the surface is developed in the presence of the compd. expressed by the formula. In the formula, R1 denotes an aryl group and R2 denotes an aryl group or alkyl group. The excellent dot image quality is expressed with the stable developing soln. by using the processing soln. from which the amino compd. harmful for the human body is removed.

Description

[Detailed Description of the Invention] Industrial Field of Application The present invention relates to a method for forming photographic images using a silver halide photographic light-sensitive material, and more particularly to a method for providing ultra-high contrast images using a hydrazine compound. be.

β) Prior art and its problems By adding a hydrazine compound to a silver halide photographic emulsion,
A method for obtaining sharp negative characteristics is disclosed in US Patent 2,
No. 419,975.

In this specification, a hydrazine compound is added to a silver chlorobromide emulsion and treated with a developer having a high pH (12,8).
Therefore, ultra-high contrast photographic properties with γ exceeding 10' (i) are obtained. However, due to the high pH, the developer is weak and unstable against air oxidation, and cannot be used for a long period of time.

In addition, the following components (1) to (4) ((1) dihydroxybenzene developer, (2) 3-pyrazolidone developer, (
3) Subsulfite [j! A method for quickly obtaining high-contrast negative images by processing a silver halide photographic emulsion with a developer containing a preservative and (4) an amino compound is also introduced. (Unexamined 5
6-106244) Since the treatment liquid contains amino compounds that are harmful to the human body, it must be considered that using the treatment liquid for a long period of time may cause some harm to the human body.

Therefore, there is a strong need for a high-contrast development method that provides halftone images of excellent quality, can be stored for a long time, and uses a processing solution that does not contain substances harmful to the human body.

(Q. Purpose of the Invention One of the objects of the present invention is to provide a method for developing silver halide photographic materials to obtain excellent halftone image quality using a stable developer.

Another object of the present invention is to provide a method for developing a silver halide photographic material to obtain excellent halftone image quality using a processing solution that removes amine compounds harmful to the human body. be.

(To) Structure of the Invention The present inventors have made extensive studies and found that a hydrazine compound represented by the following general formula (I) satisfies the above conditions.

General formula (1) %Formula% In the formula, R1 represents an aryl group (eg, phenyl group, naphthyl group, etc.).

(However, the aryl group may be substituted, and the substituents include, for example, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an aliphatic acylamide group, an aromatic acylamide group, an aliphatic sulfonamide group,
Aromatic sulfonamide group, alkoxycarbonyl group, halogen atom, nitro group, carboxyl group, sulfo group, cyano group, carbamoyl group, sulfamoyl group, semicarbazide group, thiosemicarbazide group, thioureido group, ureido group, alkylthio group, arylthio group, aliphatic thioacylamide group, aromatic thioacylamide group, etc.), and IL2 represents an aryl group [(for example, phenyl group, etc.)
represents. However, the aryl group may be substituted, and examples of the substituent include an alkyl group, a halogen atom, an alkoxy group, a cyano group, a nitro group, a carboxyl group, an alkoxycarbonyl group, etc.) or an alkyl group (however, an alkyl group is not substituted). ).

Specific examples of the hydrazine compound used in the present invention are described below, but the present invention is not limited thereto.

S CH.

CH.

CH.

The compound represented by the general formula (1) is generally synthesized by the reaction of hydrazines and sulfonyl halides, or the corresponding 1-sulfonyl-2-(4 or a3
-nitrophenyl)hydrazine is reduced by a conventional method to convert it into the corresponding amine compound, and then it can be synthesized by a general reaction using condensation, addition reaction, etc.

Next, a method for synthesizing the compound of the present invention will be specifically described.

Synthesis of compound (1): Phenylhydrazine 2.16 F (0.02 mol) and triethylamine 2.02 F (0.02 mol) were dissolved in 20 ml of dioxane, the internal temperature was kept below 20°C, and methanesulfonyl chloride was added under stirring. 2.29t (0,02
mol) dissolved in 5 m of dioxane was added over a period of about 4 minutes, stirred at the same temperature for 1 hour, then stirred in room koicha for 4 hours, and after removing the precipitated crystals, the p solution was dissolved in water under reduced pressure. The residue was recrystallized from water to give white crystals of 2.52
I got it. The melting point was 129.5°C to 131°0C.

Synthesis of compound (3): Phenylhydrazine 16.22F (0.15 mol) and triethylamine 15.18F (0.15 mol) were dissolved in methylene chloride 200-, keeping the internal temperature below 30°C, and adding trichloromethane while stirring. Methanesulfonyl chloride 32.6El (0.15 mol) methylene chloride 5
After adding the solution dissolved in 0- for about 25 minutes, stirring at the same temperature for 3 hours, stirring at room temperature for 3 hours, precipitate 'kF was collected and washed with methylene chloride to obtain white crystals 14f. . The melting point was 237.0°C to 238.5°C (decomposed).

These compounds used in the present invention can be used by being added to a processing agent or any layer on the emulsion side of a light-sensitive material.

The surface latent image type silver halogenide emulsion used in the present invention is
It may be produced by any method including an acid method, a neutral method, or an ammonia method. The present invention relates to the properties of silver halide photographic emulsions, such as the composition of silver halide (for example, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloride iodobromide), silver halide It can be carried out regardless of the crystal form or crystal habit size of bromine 3.
Silver chlorobromide emulsions containing 0 mole or less and 10 mole or less of iodine are particularly preferred.

The emulsion according to the invention can contain various additives. For example, chemical sensitizers (for example, sulfur sensitizers such as thiourea and hypo, noble metal sensitizers such as gold, platinum, and iridium compounds, and reduction sensitizers) can also be used in combination. In addition, spectral sensitizers, supersensitizers, stabilizers, anti-capri agents, surfactants, developers, development accelerators, hardeners,
It may contain a hardening accelerator, a coupler, a desilvering accelerator, a dye solution improver, a brightener, a thickener, a breaker thereof, and the like.

Protective colloids for the silver halide emulsion used in the present invention include gelatin, modified gelatin, albumin, agar, gum arabic, natural products such as alginic acid, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide, acrylic acid, and vinylimidazole. Examples include water-soluble synthetic resins such as copolymers.

The emulsions of the present invention are coated on a suitable support such as glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (e.g. polyethylene, polyglopylene, etc.) paper. . These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary.

The constituent layers of the present invention include compounds well known in the art, such as hardeners,
Matting agent, fluorescent whitening agent, antistatic agent, thickener, silver halide, physical development nucleus, antifoggant, spectral sensitizer, ultraviolet absorber, antihalation dye, coupler, developing agent,
These precursors and the like can be added.

The silver halide photographic emulsion according to the present invention is coated with a protective layer, an intermediate layer, an ultraviolet absorbing layer, an undercoat layer, or other silver halide emulsion as necessary.The aqueous alkaline developer used in the present invention is , well-known developing agents. As the developing agent, dihydroxybenzene developer (eg, hydroquinone) and 3-pyrazolidone developer (eg, 1-phenyl-3-pyrazolidone) are preferred.

The aqueous alkaline developer used in the present invention contains a sulfite preservative for the purpose of protecting the developer from air oxidation. Preferred are sulfites (eg sodium sulfite).

Generally, when a hydrazine compound is warmed into an emulsion or a processing solution to obtain an image with sufficient halftone quality, an amino compound is required to increase the contrast. This is not the case with the proposed chemical foods.

When an amino compound is required, a preferred compound is a compound represented by the following formula.

Here, R1 is a hydroxyalkyl group having 2 to 10 carbon atoms, R+ is a hydrogen atom, R is an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, benzyl group or a group represented by the following formula.

In the above formula, X and Y are each a hydrogen atom, 1 to 10
or a hydroxyalkyl group having from 2 to 10 carbon atoms.

Also preferred are amino compounds represented by the following formula.

R1 is an alkyl group having 1 to 10 carbon atoms, and R2 and R3 are each a hydrogen atom or 1 to 1 carbon atom.
An alkyl group having 0 carbon atoms.

Examples of preferred amino compounds include jetanolamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-dimethylamino-1,2-propanediol 3-diethylamino-1-/'lovanol, etc. .

The aqueous alkaline developer used in the present invention contains a benzo)IJ azole antifoggant, in order to minimize the formation of fog, and also contains the necessary organic antifoggants for the purpose of obtaining favorable halftone dot quality. It is common to use 5-methylbenzotriazole, preferably 5-methylbenzotriazole.

The aqueous alkaline developer used in the present invention contains a hydrazine compound represented by the general formula. It is desirable that the optimum amount of the hydrazine compound mixed into the developer be selected depending on the amount of Type 81, amino compound, antifoggant, etc. of the silver halide photographic emulsion. For compounds of the invention, concentrations of io-' to 1o-5 mol/I Ag are most preferred.

<Example 1> A silver iodobromide emulsion containing 97.4 g of Br and 2.6 g of silver was coated on a 100 μm thick polyester film with a coating weight of 3.7 g of silver, and Xenon PIash was applied.
'ir: A 10 second wedge exposure was applied as a light source. The exposed samples were processed in an aqueous alkaline developer having the composition shown in Table 1.

Table-1; Formula of aqueous alkaline developer 0.8M +) 7 Shun solution 500w
4/lNa 2 So 3
60 f/LEDTA-2Na
1. Of/L5 Methyl IH Benzotriazole 0.1
FM'/l Hydroquinone 30
f/11 phenyl-4-methyl-hydroxymery-
″'-3z Razor Nod' 0.4t/1KBr
3.5 f/L diethylethanolamine 201/l and 1 compound of the present invention (2), (3), (6), (
7) was added at a concentration of 0.1 f/l to prepare four types of developing solutions. The pH of the developer was 11.8. The development temperature was 20°C and the development time was 150 seconds. After development, fixing, washing, and drying were carried out according to conventional photographic processing methods. The developed samples were evaluated for dot quality DK. The results are shown in Table 2.

Table 2 From Table 2, it was found that the compounds of the present invention have a contrast enhancing effect on silver iodobromide at a pH of 12 or less in the processing solution.

<Example 2> From Example 1, the compound in the present invention has a p of 12 or less.
H was found to be effective against the contrast-enhancing effect on silver iodobromide emulsions, but in order to investigate whether the photographic properties of obtaining sufficient halftone dot quality could be obtained even at lower pH, the following We conducted an experiment.

A silver iodochlorobromide emulsion containing 31% Br and 0.07% Co was coated on a 100μ thick polyester film at a coating weight of 3.6PAg.

Exposure was given under the same conditions as in Example 1, and photographic processing was performed using the developer in Example 1. In addition, the pH of the developer
In order to investigate the sound effect that it has on the photographic characteristics, the pH was adjusted to several levels from 1 to 14 times. The developed samples were evaluated for t-dot performance. The results are shown in Table-3.

(The following is a blank space) Table 3 From Table 3, it was found that the compound of the present invention can obtain a high contrast effect even at a processing solution pH lower than that of silver iodochlorobromide. This result is extremely important for improving the stability of the processing solution.

<Example 3> From Examples (1) and (2), the compound in the present invention is 1
It has been found that a silver halide photographic light-sensitive material can have a high contrast effect at a pH of 2 or less, but we are interested in finding a way to achieve the high contrast effect necessary for sufficient halftone dot quality without containing amino compounds that are harmful to the human body. It depends on whether you can get it or not. Therefore, we conducted the following experiment. A developer was prepared by removing diethylethanolamine from the formulation shown in Table 1 of Example 1, and a sample was prepared in the same manner as in Example 2.

The hydrazine compound used is the compound (3) of the present invention. Developer f) pHFllll, 0,11.5.12.0
+7) Scored 3 points. Table 4 shows the halftone dot performance of sandals.

As shown in Table 4, the compounds proposed in the present invention (
3) It has been found that even when a developer removed with tlj: diethylethanolamine' is used, sufficiently good halftone dot quality can be given to silver halide photosensitive materials.

This result is extremely important when considering the storage stability of the treatment liquid or its toxicity to the human body.

Claims (1)

[Scope of Claims] A method for forming a photographic image, which comprises developing a silver halide photographic material having a latent image on its surface in the presence of a compound represented by the following general formula (I). General formula (I) R_1-NHNH-SO_2R_2 (In the formula, R_1 represents an aryl group, and R_2 represents an aryl group or an alkyl group.)