JPH0395549A - Method for developing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce fog density and to enhance image quality by developing a photosensitive material with a developing solution containing a compound selected from a group of indazole, benzimidazole, and benzotriazole derivatives, and a specified compound. CONSTITUTION:The photosensitive material is processed with a developing solution containing at least one compound selected from a group of indazole, benzimidazole, and benzotriazole derivatives, and the compound represented by general formula I in which n is an integer of 2 - 6; each of R1 and R2 is H or 1 - 6C alkyl; and M is H or an alkali metal, thus permitting fog density to be reduced without undergoing any effect on other performances, such as aptitude to rapid processing and handling easiness, and image quality to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a developing method for silver halide black-and-white photographic light-sensitive materials, and more particularly to a developing method capable of producing high-quality images with high density and less fog. .

(Prior art) In recent years, commonly used black and white photosensitive materials (X-ray,
(for plate making, micro, negative, etc.) are developed in an automatic developing machine (hereinafter referred to as automatic developing machine) in a short time of about 1 minute to 3 minutes. In recent years, the demand for rapid processing has become increasingly strong. For rapid processing, the developing temperature must be set to a high temperature (30
It is often maintained at a temperature of 40°C to 40"C and developed using a highly active developer. For this purpose, various additives such as a development accelerator and an anti-capri agent are used in the developer.

In particular, when a photosensitive material (such as an X-ray photosensitive material) that has not been sufficiently pre-hardened to produce high image density with a small amount of silver is processed with an automatic processor, the emulsion film of the photosensitive material is developed. In order to strengthen the mechanical strength during processing, dialdehyde hardeners and antifogging agents such as indazoles, benzyl ξdazoles, benzo I-lyazoles, and anthraquinone sulfonic acids are used in the developer. It is common knowledge in the industry to add

In addition, there has recently been a demand for faster processing of such X-ray photosensitive materials, and it takes about 45 minutes from the start of processing to the end of drying.
Processing times ranging from seconds to 90 seconds are increasingly being used.

Now, in response to the demand for rapid processing, hardening of the photosensitive material may be considered in order to achieve high image density, but this method is not preferred because it has disadvantages in terms of drying properties in automatic processor processing.

On the other hand, an increase in the amount of silver is also undesirable since it causes problems in drying properties and increases in cost. In order to increase the development activity of the developer, it is possible to increase the amount of developing agent and raise the pH, but the problems of the developer being easily oxidized by air and the problem of increasing the volume of the concentrated solution make it difficult to handle. , which is not desirable.

(Problems to be Solved by the Invention) An object of the present invention is to provide a developing solution with improved photographic properties in order to achieve rapid processing.

Specifically, the objective is to obtain high-quality images with high image density and low contrast and capri density without sacrificing other performances such as processability and handleability.

(Means for Solving the Problems) The above problems have been solved by the present invention described below. That is, a silver halide photosensitive material is processed with a developer containing at least one compound selected from the group consisting of indazoles, benzimidazoles, and benzotriazoles and at least one compound represented by the following general formula [I]. It is characterized by

General Formula [I] In the general formula (1) used in the present invention, examples of the alkali metal represented by M include sodium, potassium, and the like.

Examples of the alkyl group represented by R+ and R2 include a methyl group, an ethyl group, and a probyl group.

Specific examples of the compounds are shown below, but the invention is not limited thereto.

SH These compounds can be synthesized by the method described in JP-A-51-1475 and JP-A-53-50169.

Among the compounds of the general formula CI) of the present invention, compounds in which R1 and R2 in the general formula have an ethyl group are particularly effective.

-6- In the present invention, the amount of the compound of general formula [I] added to the developer is about 0.005 to 5.0% per 142 of the developer.
g, more preferably in the range of about 0.01 to 1.0 g.

In the present invention, indazoles are used as antifoggants.
At least one compound among benzigodazoles and henzotriazoles is used.

Specific compound examples are shown below.

Examples include 5-nitrointasole, 5-nitrobenzydazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, and the like. The amount added is 11 of the developer! ．． about 0.005-5g, more preferably about 0.01-1
．． It is in the range of 0g.

As the developing agent used in the developer used in the present invention, a combination of dihydroxybenzenes and 1-phenyl-3-virazolidones is preferred.

This is because the super-additive effect is large, the development activity is high, and it is suitable for rapid processing.

In addition, p-aminophenols can be used as the developing agent.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5 dimethylhydroquinone, and hydroquinone is particularly preferred.

The 3-virazolidone diameter developing agent used in the present invention is 1
-phenyl-3-virazolidone, l-phenyl-4,4
-dimethyl-3-virazolidone, ■-phenyl-4-methyl-4-hydroxymethyl-3-virazolidone, 1-
Phenyl-4.4-dihydroxymethyl-3-virazolidone, 1-phenyl-5-methyl-3-virazolidone,
ip-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-}lylu-4,4-dimethyl-3-virazolidone, 1-p-}lylu-4-methyl 4-hydroxymethyl-3-virazolidone, etc. be.

In addition, as a P-anophenol developing agent, N-
Methyl-p-aminophenol, p-anophenophenol, N-(β-hydroxyethyl)p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, p-benzyl ξ Among them, N-methyl-p-aminophenol is preferred.

The developing agent is usually 0.001 mol/I! ．． ~1.2 mol/
Preferably, an amount of i is used.

Examples of the sulfite preservative used in the developer in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite.

The amount of sulfite is preferably 0.2 mol/l or more, particularly 0.4 mol/l or more. Further, the upper limit is preferably up to 2.5 mol/2.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably pH 10 to 12
The range is up to

Alkaline agents used to set pH include pHtA moderating agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A No. 62-186259 (Borate), JP-A No. 6-186 (Borate)
)-93433 (for example, buffers such as saccharose, acetoxime, 5-sulfosalcylic acid, phosphate, carbonate, etc.) may be used.

Further, a hardening agent may be used in the developer.

As the hardening agent, dialdehyde hardeners or their bisulfite adducts (these are referred to as aldehyde hardeners) are preferably used, and specific examples include glutaraldehyde or its bisulfite adducts. There is.

The amount of aldehyde hardener used in the developer is 1g/
n~15g/j! , preferably 2 g/1 to 10 g/
It is l.

In addition, potassium iodide may be used as an antifoggant or a development inhibitor in the developer.

Additionally, the developer contains organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformagode, methyl cellosolve, hexylene glycol, ethanol, and methanol; 1-phenyl-5-mercaptotetrazole; It may also contain an antifoggant such as a mercapto compound such as imidazole 5-sulfonic acid sodium salt;
EARCH DISCLOSURE Vol. 176, No.
1 7 6 4 3, Section XXI (December issue, 197
Development accelerators listed in 1988), color toning agents, surfactants, antifoaming agents, water softeners, and JP-A-1986-
It may also contain the amino compounds described in No. 106244.

In the development process of the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 and European Patent Publication No. 0136582 can be used.

In addition, L. F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent No. 2,
193,015, 2,592,364, JP-A-48-64933, etc. may be used.

The fixing solution used in the present invention is an aqueous solution containing thiosulfate as a fixing agent, and has a pH of 3.8 or more, preferably 4.2 to 7.0. More preferably PH4.2
~5.0.

As the fixing agent, it is preferable to use thiosulfate,
Examples include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixative used can be changed as appropriate.
Generally from about 0.1 to about 6 mol/l.

The fixer may also contain water-soluble anoleanium salts that act as hardeners, such as aluminum chloride, aluminium sulfate, potassium chloride, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or derivatives thereof can be used alone or in combination of two or more. 0.005 of these compounds per liter of fixer
Those containing mol or more are effective, especially 0.01 mol/l to 0
．． 0.3 mol/nin is particularly effective.

The fixing solution may optionally contain preservatives (e.g., sulfite, bisulfite), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents with water softening ability, and The compounds described in Publication No. 62-78'551 can be included.

The method for developing the photosensitive material of the present invention is not particularly limited as a photographic material, and general black and white photosensitive materials are mainly used, as well as color photosensitive materials that undergo reversal processing, such as black and white development of color reversal film or paper. It can also be used in liquids.

In particular, photographic photosensitive materials for laser printers for medical images, scanner photosensitive materials for printing, medical direct photography X-ray photosensitive materials, medical indirect photography X-ray photosensitive materials, CRT image recording photosensitive materials, microphotosensitive materials, It is preferable to use it for general black and white negative film, black and white photographic paper, etc.

A silver halide photographic material to which the processing method of the present invention can be applied comprises a support and at least one silver halide emulsion coated thereon. In addition, the silver halide emulsion layer is
It is possible to coat not only one side of the support but also the whole screen.

Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary.

Silver halide emulsions are silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide dispersed in a hydrophilic colloid.

In this case, silver bromide or silver iodobromide is preferred, and silver iodide is preferably 10 mol% or less, particularly 0.2 to 5 mol%, more preferably 0.2 to 5 mol%. It is preferable to use silver iodobromide containing 5 to 4 mol%, which provides high sensitivity and high gamma, and is suitable for the X-ray photosensitive material used in the present invention.

Silver halide emulsions are typically prepared by methods well known in the art (
For example, a water-soluble root salt (e.g., silver nitrate) and a water-soluble halogen salt are mixed in the presence of water and a hydrophilic colloid by a single-jet method, double-jet method, controlled jet method, etc., and a physical mastery and gold increase method is used. feeling and/
Alternatively, it is manufactured through chemical training such as sulfur sensitization. The emulsions thus obtained include cubic, octahedral, spherical, and other shapes.Research Disclosure 2 2
5 3 4 (January 1983) can be used, and the internal latent image type silver halide grains and surface latent silver grains described in Japanese Patent Publication No. 41-2068 can be used. It can also be used in combination with image-shaped silver halide grains.

In particular, in the present invention, it is preferable to use tabular silver halide grains.

In the case of the above-mentioned tabular grains, the preferred grain form is an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Further, the thickness of the particles is preferably 0.3μ or less, particularly preferably 0.2μ or less.

Here, the aspect ratio of a tabular grain is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each individual tabular grain to the average value of the grain thickness of each tabular grain.

It is preferred that the tabular grains are present in an amount of preferably 80% by weight or more, more preferably 90% by weight or more of the total grains.

Tabular silver halide emulsions are prepared by adding spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-6-methyl-1.3) during the manufacturing process or immediately before coating. , 3a,7-tetrazaindene), sensitizers (e.g., U.S. Pat. No. 3,619,198
(compounds described in the specification), antifoggants (e.g. benzotriazole, 5-nitropenzimidazole, polyethylene oxide, hardeners, coating aids (e.g. saponin, sodium lauryl sulfate, dodecylphenol polyethylene oxide ether, Hexadecyltrimethylammonium bromide) etc. can be added.

The tabular silver halide emulsion thus produced is coated and dried on a support such as cellulose acetate film or polyethylene terephthalate film by a dipping method, air knife method, bead method, extrusion doctor method, double-sided coating method, etc. be done.

(Example) Next, the present invention will be specifically explained.

Example 1 (1) Preparation of tabular grains 1 Potassium bromide 5 g, potassium iodide 0.05 g, gelatin 30 g 1 thioether IO(CHI) 2S(CH.) ZS(CH2) 2
Add 2.5 cc of a 5% aqueous solution of 01{ and keep at 73°C, and add an aqueous solution of 8.33 g of silver nitrate, 5.94 g of potassium bromide, and 0.726 g of potassium iodide while stirring. was added in 45 seconds using a double jet method.

Subsequently, after adding 2.5 g of potassium bromide, 8.3 g of silver nitrate was added.
An aqueous solution containing 3 g was added over 26 minutes so that the flow rate at the end of the addition was twice that at the beginning of the addition.

After this, 20cc of 25% ammonia solution, 50% NH
After adding 10 cc of 4NO3 and physically ripening for 20 minutes, 240 cc of IN sulfuric acid was added to neutralize.

Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a controlled double jet method while maintaining the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate after the addition was completed was nine times the flow rate at the start of the addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 25 cc of 1% potassium iodide aqueous solution was added over 30 seconds. After this, increase the temperature to 35
After lowering the temperature to ゛C and removing soluble salts by the sedimentation method,
The temperature was raised to 40°C, 30 g of gelatin and 2 g of phenol were added, and the pH of the caustic soda was adjusted to pH with potassium bromide. 6.40, p.
The wording has been adjusted to Ag8.10.

After raising the temperature to 56°C, 600 μg of a sensitizing dye having the following structure and 150 mg of a stabilizer were added.

After 10 minutes, 2.4 mg of sodium thiosulfate pentahydrate, 140 µm of potassium thiocyanate, and 2.1 µm of silver chloride were added to each emulsion, and after 80 minutes, the emulsions were rapidly cooled and solidified to form an emulsion. In the resulting emulsion, 98% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 1.4μ.
m, standard deviation 22%, average thickness 0.187 μm, and aspect ratio 7.5.

? CHz) 3(Cll■)3 SOx e SOJa/gelatin
Silver/binder ratio (gelatin + polymer) is 0.7
Adjust the amount added so that ・Water-soluble polyester 20χ (wtX vs. gelatin)・
Polymer latex (poly(ethyl acrylate/methacrylic acid)-97/3) 25.0g/Hardening agent 1,2-bis(sulfo8moremol/nylacetamide) Surface protective layer tan
The following chemicals were added per mole of silver halide to the emulsion of 2 g of phenoxyethanol per 100 g of ge of the emulsion layer to prepare a coating solution.

1 9-2,6-bis(hydroxyacuno)-4-diethylamino-1,3.5-20 Riazine 80 ■ Sodium polyacrylate (average molecular weight 41,000) 4.0 g Polystyrene sulfone Potassium acid (average molecular weight: 600,000) 1.0g
Coated on a support.

The total amount of coated silver on both sides was 3.2 g/nf.

The surface protective layer was prepared so that each component had the following coating amount.

Appearance: 1 target: 1 volume Covering amount: Gelatin 1.15 g/Polyacrylic acid (average molecular weight: 45,000) '0.25: Sodium polyacrylate (average molecular weight: 400,000) 0.02・pt
-Sodium salt of octylphenoxy diglyceryl butyl sulfonate 0.02? Poly(degree of polymerization 10) oxyethylene cetyl ether/poly(degree of polymerization 10) oxyethylene-poly(degree of polymerization 3) Oxyglyceryl p-octyl phenoxy ether/C8FI? S03K C3H.・C,F. 7so■N{CFlzMCHz-}rsO
JaC3H? 0. 035 0. 01 0.003 0. 001? CsF I 7SO■N{CHzCHzOh-oiC
l zcHcI{ go}zHO. 003 ・Proxel polymethyl methacrylate (average particle size 3.5 μm) ・Poly(methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size 2.5 μm) 0.001 0.025 0.020 (2) Preparation of developer The following developer was prepared using the above developer.

The pH was then adjusted to 10.25.

Capri values were measured as the net concentration increase corrected for the base concentration. The gradation G is expressed as the slope of a straight line connecting the density point of fog +0.25 and the density point of fog +2.0.

Sensitivity is fog value +1. It was determined as a relative value of the reciprocal of the exposure amount required to obtain a blackening density of 0. Dm represents the maximum concentration.

From the photographic results, the following can be said. Sample No. without antifoggant. -1 (comparative example), sample N added with 5-methylbenzotriazole
o. -2 (comparative example) has less fog to some extent, but D+n. No increase in G is observed. On the other hand, sample Nα-3 (comparative example) to which only exemplary compound 1-1 of the present invention was added had a Dm. Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used for fixing.

Next, the following development process was performed using a roller conveyance type automatic processor.

Next, the photographic results will be shown. In addition, in terms of photography. 5-
Sample No. 1, which is an embodiment of the present invention, added methylbenzotriazole and Exemplary Compound I-1. -4 (present invention)
Dm. An increase in C; was observed, and the object of the present invention could be achieved.

Example 2 The photosensitive material used in Example 1 was subjected to the same development process as in Example 1 using the following developer.

(1) Preparation of developer Using the above developer, the following developer was prepared.

The pH was then adjusted to 10,25.

Sample No. which is an aspect of the present invention. 4, it was possible to reduce the capri and effectively increase <Dm and G without sacrificing sensitivity.

(Effects of the Invention) According to the present invention, in rapid processing, there is no burden on the preparation method of photosensitive materials and developing solutions, there is no adverse effect on photographic properties or other performance, there is little fog, and there is high concentration. High-quality images with excellent gradation can be obtained.

Claims (2)

[Claims] (1) A silver halide photographic light-sensitive material is prepared using a developer containing at least one compound selected from the group consisting of indazoles, benzimidazoles, and benzotriazoles and at least one compound represented by the following general formula [I]. A development processing method characterized by processing. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, n represents an integer from 2 to 6. R_1 and R_2 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. M represents a hydrogen atom or an alkali metal. (2) The development processing method according to claim (1), wherein the developer further contains an aldehyde hardener.