JPH04322248A - Photographic development processing method - Google Patents

Abstract

PURPOSE:To obtain a negative image high in contrast and free from silver sludge stains by using a developing solution specified in pH and containing a developing agent, a sulfite, an amino compound, and a specified mercapto compound in the presence of a hydrazine derivative. CONSTITUTION:An exposed negative type silver halide photographic sensitive material is developed in the presence of the hydrazine derivative by using the developing solution of 10,5-12.3 in pH, containing the developing agent, the sulfite in a concentration of >=0.3mol/l, the amino compound in an amount for promoting contrast, and the mercapto compound represented by formula I in which M is an H or alakli metal atom or an ammonium group. This mercapto compound has an especially remarkable effect on prevention of the silver sludge stains in the presence of the hydrazine derivative and a small effect on plnotographic performance.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a developing method for silver halide photographic light-sensitive materials, and particularly in the field of photolithography for printing, it is a developing method that can stably obtain useful high-contrast images. It is related to.

0002

[Background Art] In the field of photolithography for printing, images exhibiting high contrast (gamma value of 10 or more) photographic characteristics are used to reproduce continuous tone images using halftone images and to improve reproduction of line drawings. A forming system is required. Traditionally, a special developer called Liss developer has been used for this purpose, which utilizes "contagious development", but this developer has an extremely low concentration of sulfites (high concentration of sulfites). Salts are extremely susceptible to air oxidation (which inhibits "contagious development") and have the drawback of poor stability of the developing solution over time.

[0003] Recently, a high concentration of sulfite is used in the developer,
A method of developing a silver halide photosensitive 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,
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
A method using a hydrazine derivative described in No.
Japanese Patent Publication Nos. 56-106244 and 61-267
No. 759, No. 60-258537, No. 61-2301
No. 45, No. 61-230145, No. 62-21164
No. 7, JP-A No. 2-50150, etc., describe a method of developing with a developer to which an amino compound is added 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 developer, the stability of the developer against air oxidation is better than that of a lithium developer. This is a big improvement compared to .

Addition of an amino compound to a developer can increase the activity of the developer, promote the contrast-enhancing effect of the hydrazine derivative in a developer with a lower pH value than when it is not added, and stabilize the developer. This contributes to faster processing. The effect of promoting the high contrast effect of the hydrazine derivative changes depending on the amount of the amino compound added, and it is more advantageous to add a large amount of the amino compound.

[0006]

[Problem to be Solved by the Invention] However, amino compounds have the property of dissolving silver halide, and a developer containing a large amount of an amino compound may dissolve the silver halide in the photosensitive material during development. This causes a problem called "silver stain" or "silver sludge" in the industry. This "silver sludge stain" causes significant problems, especially when processed using an automatic processor. When processed for a long time in an automatic processor, the eluted silver halide adheres as silver to the tank walls of the automatic processor and the rollers that transport the film. This adhered silver is transferred to the surface of the film that is to be newly developed, causing "silver sludge stains" that significantly impair the quality of the image.

[0007] As an agent for preventing silver sludge and liquid stains, 2-
Mercapto-1,3,4-thiadiazoles (UK Patent No. 940169), 2-mercapto-1,3,
4-oxadiazoles or 1-phenyl-5-mercaptotetrazole (U.S. Pat. No. 3,173,789)
DL-6,8-dithiooctanoic acid (U.S. Pat. No. 3,318,701), O-mercaptobenzoic acid (British Patent No. 1,144,481), aliphatic mercapto Carboxylic acids (U.S. Pat. No. 3,628,9
55 specification), L-thiazolidine-4-carboxylic acid (
J. Photogr. Sci. , 13, 233 (196
5)), disulfide compound (JP-A-52-36029
Specification), 2-benzoxazolethiol, 2-benzimidazolethiol (Photogr.Sci.
Eng. , 20, 220 (1970)), acetylene glycols (JP-A-55-9594), 2-mercaptobenzothiazole-5-sulfonic acid (JP-A-55-9594),
6-72441), 2-mercaptobenzimidazole-5-sulfonic acid (JP-A-60-258537)
(No. 1, Specification), etc. are known.

However, these compounds cannot be used as sludge inhibitors in developing solutions that have a dissolving effect on silver halide, especially those containing high concentrations of sulfite (0.3 mol/L or more) and amino compounds. If hydrazine derivatives are used, the sludge prevention effect may be lost due to air oxidation, the sludge prevention effect may be weak and a large amount must be used, or the presence of hydrazine derivatives may adversely affect the effects of sensitization and high contrast during development. There were problems such as poor quality, soft tone, and fog, which could not be said to be completely satisfactory.

It is therefore an object of the present invention to provide a method for forming high contrast negative images with hydrazine derivatives that is free of "silver sludge stain".

0010

[Means for Solving the Problems] The above objects of the present invention are as follows:
In a method of forming a high-contrast negative image by developing an exposed negative-working silver halide photographic light-sensitive material in the presence of a hydrazine derivative, at least (1) a developing agent (2) 0.3 mol/L or more of sulfite ( 3) An amino compound in an amount that promotes high contrast (4) Processing with a developer containing a mercapto compound represented by Chemical Formula 1 and having a pH value of 10.5 to 12.3. This was achieved by

The mercapto compound represented by the formula 1 is a compound disclosed in Japanese Patent Application No. 2-83106, and the mercapto compound represented by the formula 1 is particularly suitable for development containing an amino compound in the presence of a hydrazine derivative. The effect of preventing sludge in liquids is particularly remarkable, and the effect on photographic properties is also small. The amount of the mercapto compound of the present invention added to the developer solution is effective if it is added in an amount of 0.01 g or more per liter of the developer solution, but it is preferably used in a range of 0.1 g to 1 g. Representative compounds represented by Chemical Formula 1 of the present invention include the following.

0012

[Case 2]

[0013]

[Chemical formula 3]

The developing agent used in the developer used in the present invention is not particularly limited, but it preferably contains dihydroxybenzenes because it is easy to obtain good halftone dot quality, and dihydroxybenzenes are preferred from the viewpoint of developing ability. and 1-phenyl-3-pyrazolidones or dihydroxybenzenes and p-aminophenols are preferred.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone,
Examples include hydroquinone monosulfonate, and hydroquinone is particularly preferred.

The developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-pyrazolidone. 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,
Examples include 1-p-tolyl-4,4-dimethyl-3-pyrazolidone. The p-aminophenol developing agents used in the present invention include N-methyl-p-aminophenol, N
-(β-hydroxyethyl)-p-aminophenol,
Examples include N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol, and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.1 mol/L to 0.8 mol/L. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols, the former is 0.1 mol/L to 0.5 mol/L, and the latter is 0.06 mol/L.
It is preferable to use it in an amount of mol/L or less.

Sulfite preservatives used in the present invention include sulfites such as 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 stability cannot be practically maintained. The upper limit of the amount used is preferably 1.0 mol/L or less. If the amount used is more than this, it will precipitate in the developer or deteriorate the silver sludge.

The amino compound used in the present invention has an effect of promoting high contrast in the presence of a hydrazine derivative. Regarding this amino compound, JP-A-56-1062
No. 44, No. 61-267759, No. 61-23014
No. 5, No. 62-211647, JP-A-2-50150
No. 2-208652, etc. can be used.

Typical examples 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-dipropylamino-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-
Butylethanolamine 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-2
0) 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

[0021] The amount added may be an amount that promotes high contrast, but
Generally, it can be added in an amount of 0.005 to 1.0 mol/L. The pH of the developer of the present invention is set in the range of 10.5 to 12.3. Alkaline agents used to set pH include pH adjusters and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium silicate, and potassium silicate. Contains an agent. In addition, as a buffering agent, JP-A-6
Boron compound of No. 2-186259, JP-A-60-93
Compounds of No. 433 having dissociation constants of 1 x 10-11 to 3 x 10-13 can also be used.

Additives used in addition to the above components include sodium bromide, potassium bromide, sodium chloride,
Examples include potassium chloride, potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol described in JP-A-61-290448, and 1-phenyl-5-mercaptotetrazole as an antifoggant and black spot inhibitor. mercapto compounds such as 5-nitroindazole, indazole compounds such as 5-nitroindazole, 2-mercaptobenzimidazole, which is described in JP-A-56-24347 as a sludge inhibitor.
Examples include sodium 5-sulfonate and its derivatives, and 3-(5-mercaptotetrazole)benzenesulfonic acid and its derivatives described in JP-A-62-212651 as an agent for preventing uneven development.

Compounds having sulfonic acid groups or carboxyl groups as solubilizing agents for amino compounds, such as sodium p-toluenesulfonate, sodium benzenesulfonate, sodium 1-hexanesulfonate, sodium p-toluate, sodium isobutyrate, Sodium benzoate, sodium n-caproate, sodium n-caprylate, sodium n-caprate, etc. can be added.

[0024] As the fixer, one having a commonly used composition can be used. The fixing solution contains sodium thiosulfate, ammonium thiosulfate, etc. as a fixing agent, water-soluble aluminum (e.g., aluminum sulfate, aluminum chloride, potassium alum, etc.) as a hardening agent, and dibasic acids (e.g., tartaric acid, (potassium tartrate, sodium tartrate, sodium citrate, lithium citrate, potassium citrate, etc.), sulfites, bisulfites as preservatives, acetic acid, boric acid, etc. as pH buffers,
can include. The pH of the fixing solution is preferably 3.8 or higher, more preferably 4.5 to 5.0 from the viewpoint of stability of the solution.

[0025] The developing treatment temperature is usually selected between 18°C and 50°C, more preferably between 25°C and 40°C. The developing method of the present invention is particularly suitable for rapid processing using an automatic developing machine, and any automatic developing machine such as a roller conveyance type, a belt conveyance type, or others can be used. The processing time may be short, and 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.

The hydrazine derivatives used in the development processing method of the present invention include hydrazine sulfate, hydrazine hydrochloride, etc., and US Pat. Nos. 4,224,401 and 4,2
No. 43,734, No. 4,272,614, No. 4,
No. 385,108, No. 4,269,929, No. 4
, No. 323,643, and JP-A No. 56-106244, No. 61-267759, No. 61-230145,
No. 62-270953, No. 62-178246, No. 62-180361, No. 62-275247, No. 6
There are hydrazine derivatives described in specifications such as No. 3-253357, No. 63-265239, and Japanese Patent Application No. 1-92356 and No. 1-99822, which can be used in the present invention.

The above-mentioned hydrazine derivative may be contained in the developer or in the emulsion layer and/or its adjacent layer of the light-sensitive material. When included in developer, 5mg to 5g per liter
, when contained in a photosensitive material, 10 per mole of silver.
-6 to 5 x 10-2 mol preferably 10-5 to 2 x 10
-2 moles.

In a preferred embodiment of the present invention, the hydrazine derivatives described in the above-mentioned patent specifications are preferably incorporated into the light-sensitive material.

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

[0030]

[C7]

[0031]

[Chemical formula 8]

[0032]

[Chemical formula 9]

[0033]

[Chemical formula 10]

[0034]

[Chemical formula 11]

[0035]

[Chemical formula 12]

[0036]

[Chemical formula 13]

[0037]

[Chemical formula 14]

[0038]

[Chemical formula 15]

[0039]

[Chemical formula 16]

[0040]

[Chemical formula 17]

[0041]

[Chemical formula 18]

[0042]

[Chemical formula 19]

[0043]

[C20]

[0044]

[C21]

[0045]

[C22]

[0046]

[C23]

[0047]

[C24]

[0048]

[C25]

[0049]

[C26]

[0050]

[C27]

[0051]

[C28]

[0052]

[C29]

[0053]

[C30]

[0054]

[Chemical formula 31]

[0055]

[C32]

The silver halide emulsion of the light-sensitive material used in the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Any of those used in conventional silver halide emulsions, such as silver halide and silver chloride, can be used. The silver halide grains used in the silver halide emulsion may be produced by any of the acid method, neutral method, and ammonia method. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. The average particle diameter of the silver halide grains used may be in the range of 0.05 to 1.5 microns. Although the particle size distribution is not particularly limited, it is preferable to have a narrow distribution. In particular, monodisperse emulsions (when the standard deviation of the grain size distribution is divided by the average grain size, the value is 0.
20 or less) is preferred.

The silver halide emulsion used in the present invention contains metal salts such as cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, and rhodium salts during the formation or growth process of silver halide grains. can be done.

The silver halide emulsion may or may not be chemically sensitized. Chemical sensitization includes sulfur sensitization, reduction sensitization, noble metal sensitization, or a sensitization method that combines these, and sensitization can be performed using any of these methods.

The binder (or protective colloid) for the photosensitive material of the present invention includes gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers. A wide variety of synthetic hydrophilic polymeric materials can be used, such as. Specific examples of the above include albumin, casein, hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate, sodium alginate, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic acid, polyvinylimidazole. , polystyrene sodium sulfonate, styrene-maleic anhydride copolymer,
Examples include copolymers of sodium styrene sulfonate and sodium maleate.

The silver halide emulsions of the present invention can be spectrally sensitized using dyes known in the photographic industry as sensitizing dyes. These dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holophoric cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol dyes.

Stabilizers, antifoggants and the like can be added to the silver halide emulsion during the manufacturing process in order to maintain stable photographic properties. These additives (stabilizers, antifoggants) include azoles, nitroimidazoles, nitroindazoles, nitrobenzimidazoles, benzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, mercaptobenzimidazoles. , aminotriazoles, benzotriazoles, mercaptotetrazoles,
Examples include mercaptotriazoles and azaindenes.

Layers of the photosensitive material of the present invention (emulsion layer, intermediate layer,
Overlayers, 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)acrylates, (meth)acrylamides, vinyl acetate, styrene, acrylonitrile, acrylic acid, sterenesulfonic acid, α,β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, etc. alone or in combination. There are synthetic polymer latexes.

The light-sensitive material used in the present invention is coated on a suitable photographic support, and these supports include baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
Examples include polyethylene terephthalate film.

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

[0066]

【Example】

Example 1 A gelatin-silver chloride emulsion consisting of cubic crystals with an average grain size of 0.1 micron was prepared by the double jet method, desalted by the flocculation method, washed with water, and redissolved.The hydrazine derivative of Chemical Formula 8 was added to the emulsion with 1 g of silver nitrate. Add 4mg per serving, and add 1
- After adding phenyl-5-mercaptotetrazole, polyethyl acrylate latex, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt and sodium dodecylbenzenesulfonate, the amount of silver (1 square meter with silver nitrate) was added onto a polyethylene terephthalate film. The amount of gelatin was 3 g (per square meter). On top of this, as a protective layer, 0.8 g of gelatin (per 1 square meter) and 80 mg of yellow dye with maximum absorption wavelength from 400 to 450 nm (
per square meter), a surfactant, and a hardening agent to obtain a film. This film was processed with a developing solution (A to F) containing the compounds of the present invention shown in Compounds 2 and 3 and the following comparative compounds, Compounds 4, 5, and 6.

[0067]

[C4]

[0068]

[C5]

[0069]

[C6]

Composition of developer Developer (A) Sodium ethylenediamine diacetate
1g
Sodium hydroxide

48g potassium sulfite

108g hydroquinone

55g N-methyl-P-aminophenol 1/2 sulfate
0.8g 5-sulfosalicylic acid

40g 5-methylbenztriazole

0.4g 3-(-5-mercaptotetrazole)
Benzene sulfonic acid 0.2g Potassium bromide

4g
N-n-butyldiethanolamine
Add 12g of water to make 1L and adjust the pH to 11.8.

Developers (B) to (F) were prepared as follows. In the process, the produced film was passed through a sensitometric wedge and exposed to light using a bright room printer (manufactured by Dainippon Screen Manufacturing Co., Ltd., P-627FM), and then exposed to light at 38°C for 20 seconds with a developer having the above composition (A to F). It was developed, fixed, washed with water, and dried. An automatic processor (LD221QT, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used for this treatment. For silver sludge, use the developer (
A to F) as a complete film (20 inches x 24 inches)
2 square meters per liter was continuously treated. The developer was not replenished during processing. After processing, the automatic developing machine was stopped, and after 24 hours, 5 sheets of the entire film were processed and the stains on the film and the developer tank were observed. Table 1 shows the results of the treatment. In Table 1, the sensitivity is expressed as a relative value, with the reciprocal of the exposure amount required to obtain a transmission density of 3.0 using developer (A) as 100.

[0072]

[0073]

Effect of the invention: As shown in Table 1, Japanese Patent Application No. 2-8310
Silver sludge stains in the developer (F) containing the compound disclosed in No. 6 occur without any practical problem, but silver sludge stains in the developer (B, C) containing the compound of the present invention The occurrence of stains was even better than that, with no stains occurring at all, and the change in photographic sensitivity was extremely small. Furthermore, there was a large difference in effectiveness from other developing solutions (A, D, E).

Claims (1)

[Claims] 1. A method for forming a high-contrast negative image by developing an exposed negative-working silver halide photographic light-sensitive material in the presence of a hydrazine derivative, comprising at least
(1) Developing agent (2) Sulfite 0.3 mol/L or more (3) Amino compound in an amount that promotes high contrast (4) Chemical formula 1
A photographic processing method characterized by using a developer containing a mercapto compound represented by the formula and having a pH value of 10.5 to 12.3. [Chemical formula 1] (In the formula, M represents a hydrogen atom, an alkali metal atom, or an ammonium group)