JPH06118581A - Method for processing photographic development - Google Patents

Abstract

PURPOSE:To obtain a replenishing method to stably maintain photographic characteristics for a long time by using a developer having higher concn. of sulfite as a replenishing liquid than the concn. of sulfite in the developer used in the initial state of development. CONSTITUTION:A silver halide photographic sensitive material containing a hydrazine deriv. is developed in an automatic developing machine. In this process, reduction of concn. of sulfite due to oxidation with air in the developing machine is compensated with a developer containing higher concn. of sulfite as the replenishing liquid. Thereby, the concn. of sulfite is stably maintained equal or almost equal to the concn. in the developer of the initial state of development. The higher the concn. of sulfite in the replenishing liquid the replenishing amt. can be decreased, however, the concn. is determined according to the solubility and replenishing amt. of sulfite. By this method, stable photographic performance can be obtd. for a long time and the replenishing amt. can be reduced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a silver halide photographic light-sensitive material containing a hydrazine derivative, and particularly in the field of photolithography for printing, a high-contrast image can be obtained by using an automatic processor. The present invention relates to a development processing method which can be stably obtained.

[0002]

2. Description of the Related Art In the field of photoengraving for printing, an image showing photographic characteristics of high contrast (gamma value of 10 or more) for good reproduction of continuous tone images by halftone dot images and reproduction of line drawings. A forming system is needed. Conventionally, for this purpose, a special developer called "lith developer" utilizing "infectious development" has been used, but this developer has an extremely low sulfite concentration (high concentration of sulfite). Salts are extremely susceptible to aerial oxidation, which hinders "contagious development", and has the disadvantage that the stability of the developer over time is poor.

Recently, a high concentration of sulfite has been used in a developer,
A method of developing a silver halide light-sensitive material in the presence of a hydrazine derivative and an amino compound to obtain a high-contrast image has been put into practical use. For example, U.S. Pat. No. 4,224,224
No. 401, No. 4,168,977, No. 4,166,7
No. 42, No. 4,311,781, No. 4,272,60
No. 6, No. 4,221,857, No. 4,243,739
Method using a hydrazine derivative described in No.
JP-A-56-106244 and 61-267759.
No. 60-258537 and 61-230145.
No. 61-230145 and No. 62-211647.
JP-A No. 2-50150 and the like describe a method of developing with a developer containing an amino compound in the presence of a hydrazine derivative.

According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since a high concentration of sulfite can be added to the developing solution, the stability of the developing solution against air oxidation is high. Greatly improved compared to.

Generally, in a developing process using an automatic processor,
In order to enable stable processing for a long time, a method of replenishing the developing solution is adopted according to the processing amount of the light-sensitive material and the elapsed time. Japanese Unexamined Patent Publication (Kokai) No. 62-91939 describes a replenishing method in the development processing of a silver halide photographic light-sensitive material containing a hydrazine derivative.

In this specification, p by the air oxidation of the developing solution
A replenishment method for compensating for an increase in H value and a decrease in pH due to processing of a light-sensitive material is described, and a method for obtaining stable photographic performance for a long time by keeping the pH constant during processing. Is. However, as a result of detailed examination by the present inventors, it is necessary to control only the pH value (although it is necessary to control the pH value as well).
It has been found that stable photographic characteristics cannot always be maintained.

[0007]

Generally, the amount of sulfite contained in a developing solution is reduced by aerial oxidation of hydroquinone and oxidation by a developing treatment (hereinafter referred to as "treatment oxidation"). Reduction of sulfite causes deterioration of photographic characteristics, especially in a high contrast developer system using a hydrazine derivative (γ value of 10 or more).
Is significantly affected by the concentration of sulfite as compared to a developer system that does not use a hydrazine derivative. In particular, the photographic sensitivity is remarkably increased, which causes trouble in long-term processing.

In the development processing by the automatic developing machine, since the air contact area of the developing tank is large, the reduction of sulfite by the air oxidation of hydroquinone is overwhelmingly larger than the reduction of sulfite by the oxidation of the processing. The air oxidation causes an increase in the pH of the developer, but the decrease in sulfite has a greater effect on the photographic characteristics than the effect on the photographic characteristics (particularly the sensitivity) due to the increase in the pH. Therefore, the concentration of sulfite in the developing solution must be controlled in order to perform stable development processing in the developing solution system using the hydrazine derivative.

An object of the present invention is to provide a replenishing method for keeping photographic characteristics stable when a silver halide photographic light-sensitive material containing a hydrazine derivative is processed for a long time (3 to 6 months) using an automatic processor. Is to provide.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to develop a silver halide photographic light-sensitive material containing a hydrazine derivative by using an automatic processor, rather than the sulfite concentration of the developer used at the start of development. It is achieved by a developing method characterized in that a developer having a high sulfite concentration is replenished as a replenisher.

The reason for controlling the sulfite concentration in the developing solution during the processing period is as described above, but the sulfite concentration is the same as or close to the sulfite concentration of the developing solution used at the start of development (at least It is desirable to keep it at 80% or more of the sulfurous acid concentration at the start).

The gist of the present invention is to reduce the concentration of sulfite due to air oxidation of an automatic developing machine by using a developer containing a high concentration of sulfite as a replenisher, so that the sulfite concentration of the developer used at the start of development can be improved. In order to obtain stable photographic characteristics by maintaining the same density as or close to.
A method of using the developer used at the start of development, which is a conventionally used method, as a replenisher is also considered, but since the sulfite concentration of the developer at the start and at the time of replenishment is the same,
Sulfurous acid concentrations cannot be maintained at the same level at the beginning and during the treatment period. Further, in order to keep the sulfurous acid concentration at the beginning and during the treatment period close to each other, the replenishing amount of the replenisher must be extremely large. Therefore, the present invention has an advantage that stable photographic performance can be obtained over a long period of time and the replenishment amount can be reduced as compared with the conventional method.

The concentration of sulfite in the replenisher of the present invention is preferably 5% or more higher than the concentration of sulfite in the developer used to start development. The higher the sulfite concentration of the replenisher, the smaller the replenishment amount, but the concentration may be determined in consideration of the solubility of the sulfite, the replenishment amount, and the like.

In the present invention, the amount of replenisher to be replenished is approximately determined by measuring the decrease in sulfite concentration due to air oxidation and treatment oxidation. The decrease in sulfite concentration changes depending on the type of automatic processor (difference in the air contact area of the developing tank) and the development processing amount of the photosensitive material. If such conditions are determined, replenishment that meets the conditions can be easily performed in advance. You can decide the amount. For example, the reduction amount of sulfite peculiar to an automatic processor per day may be measured and the reduction of sulfite concentration due to processing oxidation of the development processing amount of the light-sensitive material per day may be measured and supplemented. The method of replenishment may be replenishment after one day of treatment or on the next day, or during treatment, the replenishment may be divided into time units and treatment amounts.

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint that a good halftone dot quality can be easily obtained. Preferred is the combination of compounds with 1-phenyl-3-pyrazolidones or the combination of dihydroxybenzenes with p-aminophenols.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone,
Brom hydroquinone, isopropyl hydroquinone,
Methyl hydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone,
There are hydroquinone monosulfonate and the like, but hydroquinone is particularly preferable.

As a developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4- Methyl-4-
Hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1-
Phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone,
1-p-tolyl-4,4-dimethyl-3-pyrazolidone and the like. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, N
-(Β-hydroxyethyl) -p-aminophenol,
There are N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.

The developing agent is usually preferably used in an amount of 0.1 mol / L to 0.8 mol / L. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.1 mol / L to 0.5 mol / L and the latter is 0.06.
It is preferably used in an amount of not more than mol / L.

The developing solution used at the start of development and the developing solution used as the replenishing solution may have the same developing agent amount, but preferably, the developing solution used as the replenishing solution should be increased in amount. Examples of sulfites used at the start of development and in the replenisher of the present invention include potassium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The amount used is 0.3 mol / L or more. If the amount used is less than this, the homeostasis cannot be practically maintained. The upper limit of the amount used is preferably 1.0 mol / L or less.
If it is used in excess of this amount, it will precipitate in the developing solution or worsen silver sludge.

The concentration of sulfite in the developer used as the replenisher must be higher than the concentration of sulfite in the developer used at the start of development. The degree is not particularly limited, and may be arbitrarily determined based on the type of automatic processor, the processing amount of the photosensitive material, and the replenishing amount. Usually, it should be higher than the concentration of sulfurous acid in the developer used at the start of development by 5% or more.

The replenishing developer may be prepared separately from the developer used at the start of development, or may be a concentrated solution of the developer at the start of development and may be of a type diluted at the time of use. For example, it may be used as a replenisher with a dilution ratio lower than that at the start of development.

The amino compound used in the present invention has an effect of promoting a high contrast in the presence of a hydrazine derivative. This amino compound is described in JP-A-56-1062.
No. 44, No. 61-267759, No. 61-23014.
5, No. 62-211647, and JP-A No. 2-50150.
No. 2,208,652 and the like can be used.

The typical ones are listed below. (Representative Example) I-1) N-n-butyldiethanolamine I-2) 3-Diethylamino-1,2-propanediol I-3) 2-Diethylamino-1-ethanol I-4) 2-Diethylamino-1-butanol I-5) 3-Diethylamino-1,2-propanediol I-6) 3-Diethylamino-1-propanol I-7) 3-Diethylamino-1-propanol I-8) Triethanolamine I-9) 3-Di Propylamino-1,2-propanediol I-10) 2-Dioctylamino-1-ethanol I-11) 3-Amino-1,2-propanediol I-12) 1-Diethylamino-2-propanol I-13) n-Propyldiethanolamine I-14) 2-Di-isopropylaminoethanol I-15) N, N-di-n-butylethanol Amine I-16) 3-Di-propylamino-1,2-propanediol I-17) 2-Methylamino-1-ethanol I-18) 3-Dimethylamino-1,2-propanediol I-19) 4 -Dimethylamino-1-butanol I-20) 1-dimethylamino-2-butanol I-21) 1-dimethylamino-2-hexanol I-22) 5-dimethylamino-1-pentanol I-23) 6- Dimethylamino-1-hexanol I-24) 1-Dimethylamino-2-octanol I-25) 6-Dimethylamino-1,2-hexanediol

The amount of addition may be any amount as long as it promotes contrast enhancement,
Generally, an amount of 0.005 to 1.0 mol / L can be added. The pH of the developer of the present invention is set in the range of 10.5 to 12.3. The alkaline agents used to set the pH are sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains pH adjusting agents and buffers such as potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate, and potassium silicate. Further, as the buffering agent, a boron compound disclosed in JP-A-62-186259, JP-A-60-9
A compound having a dissociation constant of 3433 No. 1 × 10 ^{−11 to} 3 × 10 ⁻¹³ can also be used.

As additives used in addition to the above components, sodium bromide, potassium bromide, sodium chloride,
There are potassium chloride, potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol and the like, and as antifoggants and black spot inhibitors, mercapto compounds such as 1-phenyl-5-mercaptotetrazole and indazoles such as 5-nitroindazole. 2-mercaptobenzimidazole-5 described in JP-A-56-24347 as a system compound and an anti-sludge agent
-Sodium sulfonate and its derivatives, and 3- (5-mercaptotetrazole) benzenesulfonic acid and its derivatives described in JP-A No. 62-212651 as development unevenness preventing agents.

A compound having a sulfonic acid group or a carboxyl group as a dissolution aid for an amino compound, for example, sodium p-toluenesulfonate, sodium benzenesulfonate, sodium 1-hexanesulfonate, sodium p-toluate, sodium isobutyrate, Sodium benzoate, sodium n-caproate, sodium n-caprylate, sodium n-caprate and the like can be added.

As the fixing liquid, those having a generally used composition can be used. The fixer includes sodium thiosulfate, ammonium thiosulfate, etc. as a fixing agent, water-soluble aluminum (eg, aluminum sulfate, aluminum chloride, potassium alum, etc.) as a hardening agent, and a dibasic acid (eg, tartaric acid, as a precipitation inhibitor of aluminum). Potassium tartrate, sodium tartrate, sodium citrate, lithium citrate, potassium citrate, etc.), sulfites, bisulfites as preservatives, acetic acid, boric acid, etc. as pH buffering agents. The pH of the fixing solution is preferably 3.8 or more, and more preferably 4.5 to 5.0 in view of the stability of the solution.

The developing treatment temperature is usually selected from 18 ° C to 50 ° C, more preferably 25 ° C to 40 ° C.
The developing method of the present invention is particularly suitable for rapid processing using an automatic developing machine, and as the automatic developing machine, any one of roller-conveying type and belt-conveying type can be used. The processing time may be short, the total processing time is within 3 minutes, and the development processing time is within 15 to 60 seconds, preferably within 20 to 40 seconds.

Examples of the hydrazine derivative used in the development processing method of the present invention include hydrazine sulfate and hydrazine hydrochloride, and US Pat. Nos. 4,224,401 and 4,2,4.
43,734, 4,272,614, 4,
385,108, 4,269,929, 4,323,643, and JP-A-56-106244.
No. 61-267759 and No. 61-230145.
No. 62-270953, 62-178246.
No. 62-180361, No. 62-275247.
No. 63-253357, No. 63-265239.
There are hydrazine derivatives described in the specifications such as Japanese Patent Application No. 1-92356, Japanese Patent Application No. 1-92356, and Japanese Patent Application No. 1-99822, which can be used in the present invention.

The hydrazine derivative described above may be contained in the emulsion layer and / or the layer adjacent thereto. It is contained in the developing solution and is from 10 ^{−6 to} 5 × 10 ⁻² mol, preferably 1 per mol of silver.
It is 0 ^{-5 to} 2 × 10 ^-2 mol.

As a preferred embodiment of the present invention, it is preferred to incorporate the hydrazine derivative described in the above patent specifications into the emulsion layer.

Representative examples of the hydrazine derivative are shown below, but the invention is not limited to these representative examples.

[0033]

[Chemical 1]

[0034]

[Chemical 2]

[0035]

[Chemical 3]

[0036]

[Chemical 4]

[0037]

[Chemical 5]

[0038]

[Chemical 6]

[0039]

[Chemical 7]

[0040]

[Chemical 8]

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

[0056]

[Chemical formula 24]

[0057]

[Chemical 25]

[0058]

[Chemical formula 26]

The silver halide emulsion of the light-sensitive material used in the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
And any of those used for ordinary silver halide emulsions such as silver chloride can be used. The silver halide grains used in the silver halide emulsion may be produced by any of the acidic method, the neutral method and the ammonia method. The silver halide grains may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. The silver halide grains having an average grain size of 0.05 to 1.5 microns can be used. The particle size distribution is not particularly limited, but preferably has a narrow distribution. In particular, a monodisperse emulsion (when the standard deviation of the grain size distribution is divided by the average grain size, the value is 0.
20 or less) is preferable.

The silver halide emulsion used in the present invention includes a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt, during the formation or growth of silver halide grains.
A metal salt such as a rhodium salt can be contained.

The silver halide emulsion may or may not be chemically sensitized. Chemical sensitization includes sulfur sensitization, reduction sensitization, noble metal sensitization, or a combination of these sensitization methods, and any of them can be sensitized.

Examples of the binder (or protective colloid) for the light-sensitive material of the present invention include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, homopolymers or copolymers. Various synthetic hydrophilic polymer substances such as can be used. Specific examples of the above include albumin, casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sodium alginate, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic acid, polyvinyl imidazole. , Sodium styrene sulfonate, styrene-maleic anhydride copolymer, styrene sulfonate sodium-maleic acid copolymer, and the like.

The silver halide emulsion of the present invention can be spectrally sensitized with a dye known as a sensitizing dye in the photographic industry. These dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholer cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.

A stabilizer, an antifoggant and the like for keeping the photographic characteristics stable can be added to the silver halide emulsion during the manufacturing process. These additives (stabilizers, antifoggants) include azoles, nitroimidazoles, nitroindazoles, nitrobenzimidazoles, benzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, mercaptobenzimidazoles. , Aminotriazoles, benzotriazoles, mercaptotetrazoles, mercaptotriazoles, azaindenes and the like.

The layers of the light-sensitive material of the present invention (emulsion layer, intermediate layer,
The over layer and other hydrophilic colloid layers) can be hardened. As these hardeners, inorganic and organic hardeners already known in the art can be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a synthetic polymer latex in order to improve dimensional stability. These include, for example, alkyl (meth) acrylate, (meth) acrylamide, vinyl acetate, styrene, acrylonitrile, acrylic acid, stellenesulfonic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, etc., alone or in combination. There is a synthetic polymer latex.

The light-sensitive material used in the present invention is coated on a suitable photographic support. These supports include baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
There are polyethylene terephthalate films and the like.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a surfactant for the purpose of coating aid, antistatic, improving slipperiness, preventing adhesion and the like.

[0069]

【Example】

Example 1 Light-sensitive material (A) A gelatin-silver chloride emulsion consisting of cubic crystals having an average grain size of 0.1 micron was prepared by the double jet method, and desalted, washed with water and redissolved by the flocculation method. 6
4 mg per 1 g of silver nitrate was added, and 1-phenyl-5-mercaptotetrazole, polyacrylic acid ethyl latex, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt and dodecylbenzenesulfonic acid were added. After sodium was added, it was coated on a polyethylene terephthalate film so that the amount of silver (per one square meter of silver nitrate) was 5 g and the amount of gelatin was 3 g (per one square meter). On top of this, as a protective layer, 0.8 g of gelatin (per 1 square meter) and 80 mg of a yellow dye having an absorption maximum wavelength in 400 to 450 nm.
(Per 1 square meter), a surfactant and a hardener were added and coated to obtain a light-sensitive material (A).

0.4 mol% AgCl, 0.4 mol%
An emulsion consisting of cubic crystals of AgI and a halogen composition of 99.2 mol% AgBr having an average particle size of 0.25 μ was prepared by the double jet method, desalted by the flocculation method, washed with water and redissolved. After chemically sensitizing with sodium sulfate, anhydro-5,5-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt (sensitizing dye) was added to silver nitrate. 2 mg per 1 g, 5 mg of the hydrazine derivative of Chemical formula 2 per 1 g of silver nitrate were added, and 5-methylbenztriazole, 4-hydroxy-6-methyl-1,3,3a,
After adding 7-tetrazaindene, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt and sodium dodecylbenzenesulfonate, the amount of silver (as silver nitrate) on the polyethylene terephthalate film.
It was coated so that the amount of gelatin was 4.8 g / m ² and the amount of gelatin was 3 g / m ² .

On this emulsion layer, a gelatin layer containing a surfactant (sodium dodecylbenzenesulfonate) and a hardener (sodium 2-hydroxy-4,6-dichloro-1,3,5-triazine) was formed. Gelatin was coated at 1 g / m ² to obtain a light-sensitive material (B).

For the processing, the light-sensitive material (A) was exposed through a sensitometric exposure wedge with a bright room printer (P-627FM manufactured by Dainippon Screen), and the light-sensitive material (B) was subjected to sensitometry. After exposure with a tungsten light source through an exposure wedge, both were developed with a developer having the following composition (Table 1) at 38 ° C. for 20 seconds, fixed, washed with water, and dried. LD221QT was used). The conditions such as the determination of the replenishment amount and running were carried out by the following method.

[0073]

[Table 1]

Determination of Replenishing Amount The replenishing amount when the replenishing liquid B was used with respect to the development starting liquid A in Table 1 was determined as follows. Large size (50.8 cm x
After processing 50 sheets of the light-sensitive material A exposed to a half area of 61.0 cm), after operating for 1 day and stopping overnight,
Next morning, measure the sulfite concentration in the developer. The number of liters of replenisher B required to make up for the decreased sulfite concentration was experimentally determined to be 2.5 liters.

Running Conditions Under the experimental conditions 1 and 2, the developing solution A was used, and
50 for each film processed with an exposed area of / 2
Replenished by ml. As the replenishing solution, the development starting solution A was used under the experimental condition 1, and the replenishing solution B was used under the experimental condition 2. Every day, 50 sheets of each size were processed and the running processing was repeated for 3 weeks. The photosensitive material A was used for running.

The results of photographic characteristics (change in sensitivity) and sulfite concentration after running are shown in Table 2. In Table 2, the light-sensitive materials (A) and (B) were mixed at 38 ° C. with the development initiating solution A.
The reciprocal of the exposure amount required to obtain a blackening density of 3.0 when processed for 0 seconds was set to 100, and the change in sensitivity during running was relatively shown.

[0077]

[Table 2]

[0078]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide photographic light-sensitive material containing a hydrazine derivative can be stably processed by an automatic processor over a long period of time with little fluctuation in sensitivity.

Claims (1)

[Claims] 1. A method for developing a silver halide photographic light-sensitive material containing a hydrazine derivative using an automatic developing machine, wherein a developer having a sulfite concentration higher than that of the developer used at the start of development is replenished. A development processing method comprising replenishing as a liquid.