JPS587985B2 - Lith developer parts solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a Lith developer used for processing high contrast silver halide photographic materials, and particularly to a Lith developer useful in the field of graphic arts.

More specifically, in a Lith developer solution that is divided into two or more parts liquids and stored, it is possible to provide a clear ability to distinguish between own and other parts by color, and at the same time to obtain good halftone dot quality. This article relates to a parts solution for Lith developer.

Photographic images required in the field of graphic arts are
It is desirable to have only the highest density part and the lowest density part, and not have an intermediate density part (so-called fringe).

Therefore, in order to create such photographic images, high contrast silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) are used.

) is often used in combination with Liss developer, which develops it contagiously.

A method of forming such a photographic image and a Lith developer are described in J.A. Koichi. C. Yule, Journal. of. The. Franklin. Institute (JAC.Yul)
e, “J. of the Franklin Inst.
” Vol. 239, p. 221 (1945).

A lithium developer in which development occurs contagiously in this way is also called a contagious developer.

The performance of Lith developer may deteriorate during storage over time.

Therefore, the Lith developer solution is generally stored divided into two or more parts solutions.

That is, for example, the parts solution containing a developing agent and the parts solution mainly containing an alkaline agent are stored separately.

By dividing the lithographic developer in this way, deterioration in the performance of the developer can be reduced, but on the other hand, new problems arise in terms of manufacturing and work.

In general, in the case of developing solutions that do not contain special compounds (such as dyes), the parts liquid of any new developing solution is colorless or pale yellow, and there is no clear distinction between them.

Therefore, when handling them, you must be extremely careful and careful to avoid mistakes.

For example, operations such as ■ checking by two or more people, ■ measuring various physical property values (e.g. pH) each time it is used, ■ pasting more labels than necessary, and ■ changing the shape of the container are required. This is a major drawback in terms of workability and productivity.

Regarding this point, it is possible to add special dyes etc. to clearly distinguish the component liquids of the developer, but in the case of lithium developer, adding such dyes etc. is extremely difficult in terms of photographic performance. This results in unfavorable results and is also unfavorable from the viewpoint of manufacturing costs.

On the other hand, the problem of fringing in photographic image formation methods using Lith developer is extremely important, and a number of so-called halftone dot improvers have been proposed to reduce fringing, but they are insufficient. At present, satisfactory results have not been obtained.

The present inventors have discovered that by incorporating a nitroindazole compound into a photosensitive material that is processed with a Lith developer,
Japanese Patent Application No. 50-156418 (Japanese Unexamined Patent Publication No. 52-808
It was proposed as Publication No. 36).

Therefore, the present inventors attempted to apply the nitroindazole compound, which is known to exhibit good results as a halftone improver, to the Lith developer as described above.

As a result, it was discovered that by selecting the pH conditions of the parts solution of the Lith developer, a completely new effect can be achieved.

That is, the first object of the present invention is to provide parts of a Lith developer that exhibits excellent performance in halftone dot quality and at the same time has the ability to visually distinguish one from the other when the part liquid is divided into two or more parts. It is to provide liquid.

The second object of the present invention is to improve development workability and production efficiency by eliminating the need for operations such as ① to ①, unlike conventional parts liquids, by coloring the parts so clearly that they can be judged at a glance. It is an object of the present invention to provide a parts solution for a Lith developer that can be expected to improve.

A third object of the present invention is to provide a parts solution for a Lith developer that does not have any adverse effects on photographic performance, such as those caused by the addition of dyes or the like.

The above-mentioned object of the present invention is achieved by using a parts solution of a Rizu developer divided into two or more parts, in which the parts solution contains a compound represented by the following general formula [I] and is adjusted to pH 12 to 15. be done.

That is, one of the features of the present invention is that one of the parts liquid, which was conventionally divided into two or more parts, contains a compound represented by the following general formula [1], and the pH value is adjusted to 12 to 15. , it is colored orange to reddish-orange or orange to yellow to distinguish it from the other parts liquid not according to the present invention.

General formula [I] In general formula [I], R represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms, and X represents a hydrogen atom, an alkali metal atom, or an alkali metal atom.

The compound represented by the general formula [■] used in the present invention (hereinafter referred to as the compound [I] of the present invention).

) Examples include 5-nitroindazole, 6-nitroindazole, alkali metal salts and alkali metal salts thereof, and these may be used in combination.

The preferred concentration range of compound (I) of the present invention is the compound [
It varies depending on the concentration (thickness) of the parts solution of the Liss developer containing [I], and the solution to be used is 0.0.
The amount is 5 mg to 500 mg, preferably 1 mg to 100 mg, and 0.5 mg to 1000 mg, preferably 1 mg to 500 mg per liter of replenisher.

A density range other than this is unfavorable in terms of manufacturing cost and photographic performance.

There are no particular limitations on the developer components that can be coexisting in the parts solution containing the compound [I] of the present invention, except for compounds that partially liberate formalin, such as formalin sodium bisulfite adducts.

Compound [I] of the present invention may be added after being dissolved in an organic solvent, or may be added directly, and is not limited to its form.

Examples of the organic solvent include triethylene glycol, diethylene glycol, diethanolamine, triethanolamine, methanol, and ethanol.

The parts solution of the Lith developer according to the present invention has a pH value of 1
By adjusting the number to 2 to 15, the above object of the present invention can be achieved for the first time.

That is, at a pH of less than 12, the compound [
I] has poor color development, and above pH 15, pH 12 ~
Compared to the case of No. 15, no difference was observed in color development, and on the contrary, a problem occurred in the storage stability of compound [I], and a pH range of 12 to 15 was optimal.

At this time, the values of pH 12 to 14 are measured values with a pH meter, but the values of pH 14 or higher are calculated values.

It is already known that the compound [■] of the present invention is used as a halftone quality improver, but the compound [1] was used under the above conditions for the purpose of coloring the parts solution of the Lith developer. The examples used are hitherto completely unknown.

That is, the present invention is completely novel in that the parts liquid of the Lith developer is strongly and clearly colored and clearly distinguished from other parts liquids.

The pH of the parts solution of the Lith developer according to the present invention is set to 12 to 1.
To prepare No. 5, an alkaline agent is used.

Examples include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, etc., but the examples are not limited thereto, and any alkaline agent that can be adjusted to pH 12 to 15 may be used.

The lith developer referred to in the present invention is used in combination with a parts solution according to the present invention containing the compound [I] of the present invention and another parts solution not according to the present invention, and the final components thereof are , contains a developing agent, a sulfite ion buffer, and an alkaline agent in addition to the compound [I] of the present invention.

The developing agent can be appropriately selected from dihydroxybenzene-based developing agents well known in the field of photography.

Specific examples include hydroquinone, chlorohydroquinone, bromohydroquinone, isobrobylhydroquinone, toluhydroquinone, methylhydroquinone,
, 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone sulfonate.

Among these, hydroquinone is particularly practical.

These developing agents may be used alone or in combination.

The amount of the developing agent added is 5 to 50 g, preferably 10 to 30 g per liter of developer.

The sulfite ion bath is used in an amount effective to keep the sulfite ion concentration in the developer almost constant, and is used in amounts such as aldehyde hydrogen sulfite alkali adducts such as formalin sodium bisulfite adducts, and acetone sodium bisulfite adducts. Examples thereof include ketone bisulfite alkali adducts, carbonyl bisulfite-amine condensation products such as sodium-bis(2-hydroxyethyl)aminomethane sulfonate, and the like.

The amount of sulfite ion bathofer used is 15 per liter of developer.
~150g.

The alkaline agent is added to make the Lith developer alkaline, more preferably to pH 8 or higher (particularly pH 9 to 15).

Therefore, the amount added and the type of compound are not limited at all.

Alkaline agents may also act as pH buffers and development regulators.

The free sulfite ion concentration can be controlled by adding an alkali sulfite salt such as potassium sulfite to the lithium developer referred to in the present invention.

The amount of sulfite added is generally 10 g or less, but it may of course be 10 g or more.

In addition to the above-mentioned components, the Lith developer referred to in the present invention may optionally contain a water-soluble acid (e.g., acetic acid, boric acid), an alkali (e.g., sodium hydroxide), a pH buffering agent (e.g., potassium carbonate, borax), etc. ), development modifiers such as alkali halides.

Furthermore, preservatives such as alkorbic acid, ethylene urea, koji acid, benzotriazole, 1-phenyl-5-mercabutotetrazole, 4-hydroxy-6-methyl-
1.3.3a, Fog suppressants such as 7-tetrazaindene, chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, polyalkylene oxides, 1-3
grade alkanolamines (e.g. diethanolamine,
(triethanolamine), amine compounds and organic solvents such as triethylene glycol, diethylene glycol, dimethylformamide, and methyl alcohol.

In the present invention, the components of the Lith developer may be in any form as long as they contain the components necessary for use.

For example, a parts liquid in which these components are dissolved in separate forms or a concentrated parts liquid may be used.

These parts liquids can be dissolved in water or diluted with water to obtain a working liquid, if necessary.

The photographic light-sensitive material referred to in the present invention contains a silver halide emulsion as a light-sensitive component.

Silver halides include silver chloride, silver bromide, silver iodide, and the like.

A particularly effective silver halide composition in the present invention includes 5 silver chloride.
Contains 0 mol% or more, preferably 60 mol% silver chloride
The above composition contains silver bromide at 40 mol% or less and silver iodide at 5 mol% or less.

These silver halide emulsions are also described in "The Theory of the Photographic Process" by James, 4th edition, Macmi 11an Publishing (1977), 88-1.
Neutral method, acidic method, ammonia method, forward mixing method, back mixing method, Shinklechet method, which are described in literature such as 04 tools,
double jet method, controlled double jet method,
It can be manufactured by a method such as a convergence method or a core-shell method.

Furthermore, although there are no particular limitations on the grain size, grain size distribution, crystal habit, morphology (normal crystal twinning, etc.) of the silver halide grains used, silver halide grains with relatively uniform grain sizes of 1 μm or less are preferred.

Further, these silver halide grains or silver halide emulsions may contain an iridium salt and/or a rhodium salt in order to improve flash exposure characteristics and the like.

These silver halides generally include sulfur sensitizers such as sodium thiosulfate, thiourea, etc.; noble metal sensitizers such as gold sensitizers, specifically palladium sensitizers such as chloraurate, gold trichloride, etc. Examples include palladium chloride, palladate chloride, platinum compounds, iridium compounds, etc.; selenium sensitizers such as selenite, selenium urea, etc.; reduction sensitizers such as stannous chloride, polyamine sulfites such as diethylenetriamine, It can be chemically sensitized by using a chemical sensitizer such as silver nitrate alone or in combination, and it can be optically sensitized to a desired wavelength range by using an optical sensitizer such as cyanine dye or merocyanine dye alone or in combination. can be done.

As the silver halide vehicle, gelatin, gelatin derivatives, synthetic hydrophilic polymers, etc. can be used.

The silver halide photographic emulsion used in the light-sensitive material of the present invention can contain various photographic additives.

For example, antifoggants include azaindenes, specifically 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene, triazoles, thiazoles, tetrazoles, and other antifoggants known in the art. You can use either one.

Examples of halftone quality improvers include polyalkylene oxides and amine compounds.

Further, as the hardening agent, aldehyde compounds, ketone compounds, halogen-substituted acids such as mucochloric acid, ethyleneimine compounds, etc. can be used.

As the spreading agent, saponin, lauryl or oleyl monoether of polyethylene glycol, etc. are used.

There are no particular restrictions on the development accelerator, but for example,
Compounds such as those described in Publication No. 9-24427, 4
Grade ammonium salts and the like can be used.

As a physical property improver, a polymer latex made of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, etc. can be contained.

For the silver halide emulsion layer or other constituent layers of light-sensitive materials, for example, JP-A-52-104940, JP-A-51-
An antistatic agent can be added as described in publications such as No. 56220 and JP-A No. 49-46733.

Examples of the support used in the light-sensitive material of the present invention include any support such as polyethylene terephthalate film, polycarbonate film, polystyrene film, and cellulose acetate film.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 The degree of coloring was investigated when 5-nitroindazole was added to the following Lith developer parts solution.

The results were as shown in Table-1.

Liss developer Parts liquid Parts liquid A Triethylene glycol 40g Formaldehyde Sodium bisulfite addition compound 50g Hydroquinone 16g Diethanolamine
16g potassium sulfite 4
g Add water to make 167 ml.

Parts Solution B Add 3 to 30% of 5-nitroindazole to Parts Solution A.

Parts liquid C Triethylene glycol 2g Ethylenediaminetetraacetic acid disodium 2g Potassium bromide
2.5g potassium carbonate
2.0g Sodium carbonate monohydrate 10g
Add water to make 167ml.

Furthermore, the pH is adjusted to 13 with sodium hydroxide.

Parts liquid D Add 3% of 5-nitroindazole to parts solution C.

Parts liquid E The pH of parts liquid D was adjusted to 1 by adding boric acid.
Adjust to 2.

Parts liquid F The pH of parts liquid D was adjusted to 1 by adding boric acid.
Adjust to 0.

Parts Solution G The pH of Parts Solution D is adjusted to 15 by adding sodium hydroxide.

As is clear from Table 1, parts liquids D and E have a pH in the range of 12 to 15 and contain 5-nitroindazole.
and G are other parts liquids A, B, and C not according to the present invention.
The degree of coloring of the liquid is very strong compared to Samples and F, and can be easily distinguished by visual judgment, demonstrating the excellent characteristics of the present invention.

Example 2 A silver halide emulsion containing 85 mol% silver chloride, 0.2 mol% silver iodide, and the remainder silver bromide was subjected to gold sensitization and iom sensitization, and then 3-carboxymethyl-5-[ 2-(3-ethylthiazolinidene)ethylidene] polyoxyethylene nonyl phenyl ether optically sensitized with rhodamine and further containing 50 ethylene oxide groups, and the development described in Japanese Patent Publication No. 40-23465. Lith film prepared by adding an accelerator, mucochloric acid, and mixing polybutylmethacrylate polymer and coating it on a film base was exposed through a sensitometric exposure wedge using a 150-line magenta contact screen. After that, the following Lith developer was prepared using the Lith developer parts solution used in Example 1, and developed.

Developer Solution 1 Mix parts solution A and parts solution C, and add water to make 1 liter.

Developer solution 2 Mix parts solution B and parts solution C and add water to make up to 1 liter Developer solution 3 Mix parts solution A and parts solution D and add water to make up to 1 liter.

Development was performed at 26° C. for 1 minute and 40 seconds using an automatic developing machine.

Table 2 shows the results of photographic properties after development.

Regarding Table 2, the halftone quality is determined visually, with 10 being very good and 1 being very poor.

It is evaluated using a 10-point scale.

Furthermore, the sensitivity is expressed in relative terms, with the sensitivity obtained when the photosensitive material is developed with developer 1 as 100.

As is clear from Table 2, in the case of developer 3 according to the present invention, 5-nitroindazole, which was used for the purpose of coloring the developer parts solution, significantly improved the halftone dot quality in terms of photographic performance and yielded good results. It will be done.

On the other hand, in the case of developer 2 not according to the present invention, the photographic performance is equivalent to developer 3, but the visual distinction between parts liquid B and parts liquid C is not clear, and there is a large difference between the parts liquid B and parts liquid C. There are differences.

Example 3 The degree of coloring when 6-nitroindazole was added to the following Lith developer parts solution was investigated.

The results are shown in Table-3.

Liss developer Parts liquid Parts liquid H Triethylene glycol 50,9 Polyethylene glycol (average molecular weight 1500) 0.2g Formaldehyde sodium bisulfite addition compound 40,9 Diethanolamine 20g Hydroquinone
16.9 Add water to make up to 167 ml Parts Solution ■ Add 5 ■ of 6-nitroindazole to Parts Solution H.

Parts Liquid J To Parts Liquid H, add 10~6-1 ditroindazole.

Paan liquid K triethylene glycol 3g ethylenediaminetetraacetic acid disodium 2g boric acid
2g potassium sulfite 4g potassium bromide
3g potassium carbonate
Add 50g of water to make 167ml.

Further, adjust the pH to 13 with sodium hydroxide.

Parts Liquid L Add 5 mg of 6-nitroindazole to Parts Liquid K.

Parts liquid M To parts liquid K, 6-nitroindazole 10~ is added.

Parts Solution N Adjust the pH of Parts Solution L to 15 with sodium hydroxide.

Parts liquid 0 Adjust the pH of parts liquid L to 12 with sodium hydroxide.

parts liquid P Adjust the pH of parts solution L to 10 with boric acid.

As is clear from No. 3, the parts liquids M, N, and O according to the present invention, which contain 6-nitroindazole and have a pH in the range of 12 to 15, have a lower pH than other parts liquids not according to the present invention. The degree of coloring of the liquid is very strong, visually
Very easy to distinguish.

That is, by adding 6-nitroindazole to the Lith developer parts solution whose pH is adjusted to 12 to 15,
It can be seen that it is strongly colored and can be clearly distinguished from other nearly colorless developer parts solutions.

Claims (1)

[Scope of Claims] 1. A parts solution of a Liss developer used for processing high contrast silver halide photographic light-sensitive materials, the parts solution containing a compound represented by the following general formula α] and having a pH of
A parts solution for a Liss developer, characterized by being adjusted to 1.2 to 15. General Formula [I] [In the formula, R represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms, and X represents a hydrogen atom, an alkali metal atom, or an alkali metal atom. ]