JP3016988B2 - Processing solution for silver halide photosensitive materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for a silver halide photosensitive material.

[0002]

2. Description of the Related Art A black-and-white light-sensitive material is processed by processes such as development, fixing and washing with water after exposure. In the developing and fixing steps, a developing solution and a fixing solution are used, respectively. The temperature of each processing solution is usually adjusted from 20 ° C. to 50 ° C., and the photographic material is immersed in these processing solutions for processing.

Similarly, a color light-sensitive material is subjected to processes such as color development after exposure, desilvering, washing with water, and stabilization. In each of these steps, a color developing solution, a bleaching solution, a bleach-fixing solution, and a fixing solution are used, respectively. Each processing solution is usually 2
The temperature is adjusted from 0 ° C. to 50 ° C., and the photosensitive material is immersed in these processing solutions for processing.

Further, a printing plate which is capable of using a silver image obtained by a silver complex salt diffusion transfer method, which is one of the silver halide photosensitive materials, as an offset printing original plate has already been disclosed in Japanese Patent Publication No. 46-43132 or Japanese Patent Publication No. JP-A-48-30562, and a positive-type printing original plate is disclosed in JP-A-49-5540.
No. 2, Japanese Patent Application Laid-Open No. Sho 52-106902 and Japanese Patent Application Laid-Open No. Sho 52-112 disclose negative type printing original plates.
No. 402 and the like.

After the printing plate is exposed, it is developed,
It is processed by a process such as washing with water. A developing solution is used for development, and a stabilizing solution is used for stabilization. The printing plate is immersed in these processing solutions for processing.

[0006] These treatment liquids are usually supplied as a concentrate or a powder, and the user dilutes or dissolves the concentrate or the powder with tap water before use.

However, tap water used for this dilution is not always suitable for a developer . For example, tap water contains minerals such as calcium ions and magnesium ions, inorganic compounds, chlorine ions, and various organic compounds. Among them, water containing a large amount of calcium ions and magnesium ions (so-called hard water) is used to dilute or dissolve a silver halide photosensitive material or a developer for a printing plate obtained by a silver complex salt diffusion transfer method. There is a need for an improvement in that a white precipitate is formed, which damages the surface of the photosensitive material or the printing plate or damages the rollers in the development processing apparatus.

In order to compensate for this disadvantage, ED is added to the developer.
It is known that aminopolycarboxylate-based sequestering agents such as TA (ethylenediaminetetraacetic acid) and DTPA (diethylenetriaminepentaacetic acid) are put in a developer. However, these chelating agents are not perfect when the pH is higher than 11, because calcium ions can be blocked but magnesium ions cannot be blocked. In addition, these chelating agents have a problem that they are not easily degraded by microorganisms and are not preferable in terms of environmental protection.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for processing a tap water used in a dilution or dissolving step with hard water without any problem in a developer for a silver halide photosensitive material. Another object of the present invention is to provide a developing solution for a silver halide photosensitive material containing a chelating agent which has good biodegradability and does not adversely affect the environment.

[0010]

The object of the present invention is to provide at least one compound represented by the formulas (4), (5) and (6) in a developing solution in an amount of 0.1 to 10 g / l, preferably 0.5 to 5 g / l in a working solution. l Solved by putting. ☆

Embedded image Here, X represents a hydrogen atom or an alkali metal atom, and R represents C
Represents H ₂ OH, CHO, COOX, and l represents 2, 3, 4
Represent . ☆

Embedded image Here, X represents a hydrogen atom or an alkali metal atom, and m represents 2, 3, or 4. ☆

Embedded image Here, X represents a hydrogen atom or an alkali metal atom, and n represents 2, 3, or 4.

[0011]

According to the present invention, no crystals or white precipitates are generated even when the concentrated or powdery developer is diluted or dissolved in tap water containing a large amount of minerals. Further, it can be used without problems even in a developer having a pH higher than 11. Further, since the compound has good biodegradability, it does not cause environmental problems in waste liquid treatment.

The developer used in the present invention may be supplied as it is, or may be a concentrated solution or a powder. Further, the compounds represented by Chemical Formulas 4, 5, and 6 are:
It may be dissolved in a developer concentrate in advance or, in the case of a powder developer , mixed as a powder. Further, the above compound may be separately packaged and added at the time of dilution, or may be dissolved in dilution water in advance.

The silver salt photosensitive material applied according to the present invention includes black-and-white and color photographic materials, photographic materials obtained by silver salt diffusion transfer method (DTR), and offset printing plates utilizing silver images. is there.

Hereinafter, in the present invention, chemical formulas 4, 5, and 6
Specific examples of the compound represented by are shown below, but it should not be construed that the invention is limited thereto.

[0015] ☆

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[0016] ☆

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[0017] ☆

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[0018] ☆

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[0019] ☆

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[0020] ☆

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[0021] ☆

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[0022] ☆

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[0023] ☆

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[0024] ☆

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The above compound may be added at 0.1 to 10 g / l, preferably 0.5 to 5 g / l in the working solution. If necessary, two or more kinds may be combined, or a chelating agent such as polyaminocarboxylic acid may be combined. .

Among the developing solutions for silver salt photosensitive materials, examples of the developing agent include alkaline substances (such as sodium hydroxide, potassium hydroxide and sodium tertiary phosphate), and sulfites (such as potassium sulfite and sodium sulfite) as preservatives. ) Is essential, but other compounds such as sulfates (such as sodium sulfate and ammonium sulfate), antifoggants (such as potassium bromide), developing agents (such as hydroquinone, 1-phenyl-3-pyrazolidone, and methol); Development modifiers (polyoxyalkylene compounds, onium compounds, etc.)
Can be included.

Furthermore, one or more surfactants (eg, propylene glycol alginate), aminopolycarboxylates (eg, sodium ethylenediaminetetraacetate) and the like may be contained.

The silver halide emulsion of the silver halide light-sensitive material used in the practice of the present invention can be silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide. 5 silver
0 mol% or more of silver halide. These silver halide emulsions include spectral sensitizers (spectral sensitizing dyes according to the light source and application, for example, camera type, laser light type, panchromatic type for color separation, etc.), gelatin hardener, coating aid, antifoggant , A plasticizer, a developing agent, a matting agent, and the like.

[0029]

The present invention will be described in more detail with reference to the following Examples, which, of course, are not intended to limit the scope of the present invention. Example 1 The components of a lithographic printing plate developer according to the silver complex salt diffusion transfer method used below are shown.

Developer A Sodium hydroxide 24 g Potassium hydroxide 8 g Anhydrous sodium sulfite 50 g 2-Methyl-amino-1-propanol 30 g Uracil 0.2 g

The above developer was added to ion-exchanged water with a calcium ion concentration of 300 ppm and a magnesium ion concentration of 200 ppm.
Was dissolved in 1 liter of water to which calcium carbonate and magnesium carbonate were added to obtain a comparative example.

Similarly, the above-mentioned constituents include EDTA 4 sodium salt, NTA (nitrilotriacetic acid) trisodium salt, Chemical formula 8, Chemical formula 11, Chemical formula 12, Chemical formula 14, Chemical formula 15, Chemical formula 16, Chemical formula 16
Is added to the ion-exchanged water to obtain a calcium ion concentration of 30.
It was dissolved in 1 liter of water to which calcium carbonate and magnesium carbonate were added so that the concentration became 0 ppm and the magnesium ion concentration became 200 ppm. These are developer 1, developer 2, developer 3, developer 4, developer 5, developer 6, developer 7, developer 8, and developer 9.

Developers 1, 2, 3, 4, 5, 6, 7, 8,
Table 1 shows the results of evaluating the liquids of No. 9 and Comparative Example.

[0034] ☆

[Table 1]

Example 2 For the developing solutions 1, 2, 3, 4, 5, 6, 7, 8, 9 and the comparative example, the silver master RII (trade name) was exposed and processed by an automatic developing machine under the following conditions. Carried out. Processing time Time Temperature 30 seconds 30 ° C Stabilization 30 seconds 25 ° C

The stabilizer used had the following composition. Stabilizer Ethylene glycol 5 g (liquid) Colloidal silica (20% aqueous solution) 1 g (liquid) Citric acid 10 g Sodium citrate 35 g Make up to 1 liter with water.

Next, these samples were mounted on an offset printing machine, and the plate surface was sufficiently wetted with an etchant of the following components.
Printing was performed using a humidifying solution having the following composition.

Etch liquid Water 600 ml Isopropanol 400 ml Ethylene glycol 50 g

Humidification liquid Water 8 l Succinic acid 6 g Sodium sulfate 25 g Ethylene glycol 100 g Colloidal silica (20% solution) 28 g

The printing results of the examples determined according to the following criteria are shown in Table 2 together with the state of scratches on the plate surface. The printing durability of printing was determined by the following method. 1,000 or more 5
Printing was continued up to 000 sheets, and evaluation was made on the following four levels according to the number of ink skips of the silver image. A 50,000 sheets or more B 25,000 C 10,000 D 5,000

☆

[Table 2]

[0042]

The developer for a silver salt photographic material of the present invention is prepared by diluting or dissolving with a water having high hardness without developing turbidity or sedimentation.
No damage is caused by treating with a liquid .

Claims (1)

(57) [Claims] 1. A developing solution for a silver halide light-sensitive material, comprising at least one of the following general formulas 1, 2 and 3. ☆ [Formula 1] Here, X represents a hydrogen atom or an alkali metal atom, and R represents C
Represents H ₂ OH, CHO, COOX, and l represents 2, 3, 4
Represent . ☆ [Formula 2] Here, X represents a hydrogen atom or an alkali metal atom, and m represents 2, 3, or 4. ☆ [Formula 3] Here, X represents a hydrogen atom or an alkali metal atom, and n represents 2, 3, or 4.