JPH04225346A - Photographic development processing method - Google Patents

Abstract

PURPOSE:To enhance contrast and sensitivity by developing an exposed photosensitive material with a developing solution specified in pH and containing each specified amount of developing agent, sulfite, an amino compound, and a lithium compound in the presence of a hydrazine derivative. CONSTITUTION:The exposed negative type silver halide photographic sensitive material is processed in the presence of the hydrazine derivative with the developing solution containing at least the developing agent, the sulfite in an amount of >=0.3mol/l, the contrast-enhancing amino compound, and the lithium compound in an amount of 7.5X10<-3>mol/l in terms of Li, and having a pH of 10.5-12.3. The lithium compound remarkably promotes rise of contrast in the development in the presence of the hydrazine derivative and the amino compound, thus permitting an amount of amino compound to be reduced by adding the lithium compound.

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

[Prior Art] In the field of photolithography for printing, image formation exhibiting high contrast (gamma value of 10 or more) photographic characteristics is used to reproduce continuous tone images using halftone images and to improve reproduction of line drawings. A system is needed. Traditionally,
A special developer called Liss developer has been used for this purpose, using "contagious development", but this developer has a very low concentration of sulfites (high concentrations of sulfites are It has the disadvantage that it is extremely susceptible to air oxidation (which inhibits infectious development) and that the stability of the developing solution over time is poor.

[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 contrast enhancement effect of the hydrazine derivative changes depending on the amount of the amino compound added, so it is 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 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 to be newly developed, causing "silver stains" and significantly impairing the quality of the image.

In order to reduce the occurrence of silver stains, it is desirable to use a compound that does not dissolve silver halide while having the property of promoting the high contrast effect of hydrazine derivatives, but at present it is comparable to amino compounds. At present, the compound has not been put into practical use. Therefore, in order to reduce the occurrence of silver stains, efforts have been made to minimize the amount of amino compounds used. Furthermore, since amino compounds are relatively expensive, it is desired to reduce the amount used in order to reduce the cost of developing solutions.

The first object of the present invention is to provide a developing method in which an exposed negative-working silver halide photographic light-sensitive material is developed in the presence of a hydrazine derivative and an amino compound to stably obtain the effects of high contrast and increased sensitivity. The goal is to provide the following. The second purpose is to provide photographic images with less silver stain in the above processing method.

[0009]

[Means for Solving the Problems] The above object of the present invention is to provide 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. Contains the main ingredient, ■ sulfite at least 0.3 mol/l, ■ an amino compound in an amount that promotes high contrast, and ■ lithium compound at 7.5 x 10-3 mol (in terms of lithium)/l, and from 10.5 to 12.3 p
This was achieved by processing with a developer having an H value.

The present inventors have discovered that a lithium compound significantly promotes the contrast enhancement effect of a light-sensitive material obtained by developing in the presence of a hydrazine derivative and an amino compound. Therefore, by adding a lithium compound to the developer, the amount of the amino compound added can be reduced.

The lithium compound of the present invention includes water-soluble inorganic and organic lithium salts, such as lithium nitrate,
Examples include lithium sulfate, lithium sulfite, lithium thiosulfate, lithium chloride, lithium hydroxide, lithium acetate, and lithium citrate. The amount of the lithium compound used must be 7.5×10 −3 mol/l or more in terms of lithium. Although it depends on the concentration of the processing agent, it can be added up to the solubility limit, preferably 2×10 −1 mol/l or less in terms of lithium.

The developing agent used in the developer used in the present invention is not particularly limited, but it preferably contains dihydroxybenzenes since 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,
Examples include methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, 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 to 0.5 mol/l, and the latter is 0.06 mol/l.
Preferably, it is used 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. Usage amount is 0
．． If the amount used is less than 3 mol/l, the stability cannot be practically maintained. The upper limit of usage amount is 1.0 mol/l
The following are desirable. 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

[0019] 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 having a dissociation constant of 1 x 10-11 to 3 x 10-13 of No. 433 can also be used.

Additives used in addition to the above components include sodium bromide, potassium bromide, sodium chloride, potassium chloride, potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, and JP-A-6
1-290448, mercapto compounds such as 1-phenyl-5-mercaptotetrazole, indazole compounds such as 5-nitroindazole, and sludge inhibitors as antifoggants and black spot inhibitors. 2-Mercaptobenzimidazole-5 described in JP-A-56-24347 as
- Sodium sulfonate and its derivatives, and 3-(5-mercaptotetrazole)benzenesulfonic acid and its derivatives described in JP-A No. 62-212651 as development unevenness preventive agents.

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

[0022] 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.

[0023] 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. 43734, No. 4,272,614, No. 4,3
No. 85,108, No. 4,269,929, No. 4,
No. 323,643, and JP-A No. 56-106244, No. 61-267759, No. 61-230145, No. 6
No. 2-270953, No. 62-178246, No. 62
-180361, 62-275247, 63-
No. 253357, No. 63-265239, Patent Application No. 1-
There are hydrazine derivatives described in specifications such as No. 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.

[0028]

[Chemical formula 1]

[0029]

[Case 2]

[0030]

[Chemical formula 3]

[0031]

[C4]

[0032]

[C5]

[0033]

[C6]

[0034]

[C7]

[0035]

[Chemical formula 8]

[0036]

[Chemical formula 9]

[0037]

[Chemical formula 10]

[0038]

[Chemical formula 11]

[0039]

[Chemical formula 12]

[0040]

[Chemical formula 13]

[0041]

[Chemical formula 14]

[0042]

[Chemical formula 15]

[0043]

[Chemical formula 16]

[0044]

[Chemical formula 17]

[0045]

[Chemical formula 18]

[0046]

[Chemical formula 19]

[0047]

[C20]

[0048]

[C21]

[0049]

[C22]

[0050]

[C23]

[0051]

[C24]

[0052]

[C25]

[0053]

[C26]

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, and 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 pigments 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 and antifoggants include azoles, nitroimidazoles, nitroindazoles, nitrobenzimidazoles, benzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, mercaptobenzimidazoles) , aminotriazoles, benzotriazoles, mercaptotetrazoles, mercaptotriazoles, azaindenes, and the like.

Layers of the photosensitive material of the present invention (emulsion layer, intermediate layer,
The overlayer 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)acrylates, (meth)acrylamides, vinyl acetate, styrene, acrylonitrile, acrylic acid, styrene sulfonic 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 purposes such as a coating aid, antistatic properties, improved slipperiness, and prevention of adhesion.

[0064]

EXAMPLES The present invention will be explained in more detail by way of examples below.

[0065]

[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. 4mg per gram of silver nitrate
In addition, 1-phenyl-5-mercaptotetrazole, polyethyl acrylate latex, 2-hydroxy-
After adding 4,6-dichloro-1,3,5-triazine sodium salt and sodium dodecylbenzenesulfonate, coat on polyethylene terephthalate film so that the amount of silver (in terms of silver nitrate) is 5 g/m2 and the amount of gelatin is 3 g/m2. I did it. On top of this is a protective layer of gelatin.
8 g/m2 of a yellow dye having a maximum absorption wavelength of 400 to 450 nm (for example, Oxonol Yellow from Hoechst) and a surfactant were applied. This film will be referred to as film A.

After exposing this film to light through a sensitometric wedge using a bright room printer (manufactured by Dainippon Screen Manufacturing Co., Ltd., P-627FM), a developer containing the lithium compound of the present invention having the composition shown in Table 1 was applied. The film was developed with a comparison developer at 38° C. for 20 seconds, fixed, washed with water, and dried. An automatic processor (LD-221QT, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used for this treatment.

[0067]

[Table 1]

[0068]

Example 2 A film was produced using the hydrazine derivative of Chemical Formula 2 instead of the hydrazine derivative described in Example 1. This film will be referred to as film B. Film B was also treated in the same manner as in Example 1. Table 2 shows the results of the processing.

[0069]

[Table 2]

In Table 2, the sensitivity is determined by the developer of the present invention (B
) and (C), use the comparative developer (A); for the developer of the present invention (E), use the comparative developer (D); and for the developer of the present invention (G) and (H), use the comparative developer (F) is expressed relative to the reciprocal of the exposure amount required to obtain a transmission density of 3.0 as 100. γ is the concentration 0.1 and 3.0 on the characteristic curve
represents tanθ, which is connected by a straight line.

[0071] For silver stains, use the developing solutions (F) and (G) shown in Table 1.
, For (H), film B was processed continuously at 2 m2/l without replenishment, the automatic processor was stopped, and after being left for 24 hours, several sheets of film B were processed to remove silver stains on the film and the development of the automatic processor. The silver stain was evaluated by observing the stain in the tank.

[0072] 3 and 4 are practically unacceptable levels.

When the comparative developer (F) was inspected for stains on the developing tank and roll after processing, a considerable amount of silver sludge was found to have adhered thereto. In the developing solutions of the present invention (G) and (H), some silver sludge was attached, but it was much less than in (F).

[0074]

Effect of the invention: As shown in the results in Table 2, (B), (C), (E), (G) of the present invention to which a lithium compound was added
), (H) are the comparative developers (A), (D), (F
) has faster sensitivity and higher γ.

From the results of the developers (G) and (H), by adding a lithium compound, the amount of the amino compound added can be reduced and silver stains can also be eliminated.

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
Developing agent, ■ Sulfite 0.3 mol/l or more, ■ Amino compound in an amount that promotes high contrast, ■ Lithium compound at 7.5 x 10
-3 moles (in terms of lithium)/l or more, and 10
．． A photographic processing method characterized by using a developer having a pH value of 5 to 12.3.