JPH06282046A - Processing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the method for processing the silver halide photographic sensitive material without any problem even if tap water used for a dilution or dissolution process is hard water. CONSTITUTION:A processing agent contains in an amount of 0.1-10g/l, preferably, 0.5-5g/E of the processing solution at least each one kind of compound each represented by formulae I-III in which X is an II or alkali metal atom; R is CH2OH, CHO, or COOX; and each of l, m, and n is 2, 3 or 4 Here, X represents H, potassium and sodium.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing solution for a silver halide light-sensitive material.

[0002]

2. Description of the Related Art Black-and-white light-sensitive materials are processed in processes such as post-exposure development, fixing, and water washing. In this developing and fixing process, a developing solution and a fixing solution are used respectively. The temperature of each processing solution is usually adjusted to 20 ° C. to 50 ° C., and the light-sensitive material is dipped in these processing solutions for processing.

Similarly, a color light-sensitive material is processed in steps 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. Each processing solution is usually 2
The temperature is adjusted to 0 ° C. to 50 ° C., and the light-sensitive material is dipped in these processing solutions and processed.

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

This printing plate was developed, stabilized, and exposed after exposure.
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 stability. The printing plate is dipped in these processing solutions for processing.

These treatment liquids are usually supplied as concentrates or powders, and the user dilutes or dissolves the concentrates or powders with tap water before use.

However, the tap water used for this dilution is not always suitable for the treatment liquid. For example, tap water contains minerals such as calcium ions and magnesium ions, inorganic compounds, chlorine ions, and miscellaneous organic compounds. Of these, water containing a large amount of calcium ions and magnesium ions (so-called hard water) produces crystals when diluted or dissolved with a silver halide photosensitive material or a developing solution for a printing plate obtained by a silver complex salt diffusion transfer method. Therefore, there is a need for improvement because it causes white precipitates and damages the surface of the light-sensitive material or the printing plate, and damages the rollers in the developing device.

In order to make up for this drawback, ED is added to the developer.
It is known to add an aminopolycarbocarboxylic acid type sequestering agent such as TA (ethylenediaminetetraacetic acid) or DTPA (diethylenetriaminepentaacetic acid) to a developer. However, these chelating agents are not perfect when the pH is higher than 11, because they can sequester calcium ions but not magnesium ions. Further, these chelating agents have a problem in that they are poor in degradability by microorganisms and are not preferable for environmental protection.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for treating a processing solution for a silver halide light-sensitive material, in which tap water used in a diluting or dissolving process can treat hard water without any problem. Another object of the present invention is to provide a processing solution for a silver halide light-sensitive material, which contains a chelating agent having good biodegradability and having no adverse effect on the environment.

[0010]

[Means for Solving the Problems] The above object is to provide at least one compound represented by Chemical formula 4, Chemical formula 5, and Chemical formula 6 in the treatment liquid, and 0.1 to 10 g / l, preferably 0.5 to 5 g / l in the used liquid. l solved by putting.

[Chemical 4] Here, X represents a hydrogen atom and an alkali metal atom, and R represents CH.
₂ OH, CHO, COOX, and 1 represents 2, 3, and 4.

[Chemical 5] Here, X represents a hydrogen atom, an alkali metal atom, and m is 2,
3 and 4 are represented.

[Chemical 6] Here, X represents a hydrogen atom or an alkali metal atom, and m represents 2, 3, or 4.

[0011]

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

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

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

Hereinafter, in the present invention, chemical formula 4, chemical formula 5, and chemical formula 6 will be described.
Specific examples of the compound represented by are shown below, but the invention is not limited thereto.

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16]

The above compounds may be added in a working solution in an amount of 0.1 to 10 g / l, preferably 0.5 to 5 g / l, and if necessary, two or more kinds may be combined or a chelating agent such as polyaminocarboxylic acid may be combined. .

Among the processing solutions for silver salt photosensitive materials, alkaline substances (sodium hydroxide, potassium hydroxide, sodium triphosphate, etc.) are used as developers, and sulfites (potassium sulfite, sodium sulfite, etc.) are used as preservatives. ) Is essential, but other compounds such as sulfates (sodium sulfate, ammonium sulfate, etc.), antifoggants (potassium bromide, etc.), developing agents (hydroquinone, 1-phenyl-3-pyrazolidone, metol, etc.), Development modifiers (polyoxyalkylene compounds, onium compounds, etc.)
Can be included.

Further, one or more kinds of surfactants (propylene glycol alginate, etc.), aminopolycarboxylic acid salts (sodium ethylenediaminetetraacetate, etc.) may be contained.

The stabilizer is a desensitizing accelerator, a buffer,
It is composed of conventionally known substances such as preservatives and wetting agents. For example, gum arabic, carboxymethyl cellulose, sodium alginate, vinylpyrrolidone, vinylimidazole, a copolymer of methyl vinyl ether and maleic anhydride, carboxymethyl starch, ammonium alginate, alginate oxydide cellulose, sulfates (sodium sulfate, ammonium sulfate, etc.), Tannic acid, polyol compounds having two or more hydroxyl groups (polyethylene glycol, propylene glycol, pentaerytriol, glycerol, diethylene glycol, hexylene glycol, etc.), weak organic acids (citric acid, succinic acid, tartaric acid, adipic acid,
Ascorbic acid, propionic acid, etc.), inorganic fine particles (colloidal silica, colloidal alumina, etc.), polyacrylic acid, ammonium dichromate, chrome alum, alginic acid propylene glycol ester, chelating agents (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyl) (1) Ethylenediamine triacetic acid, nitrilotriacetic acid, triethylenetetramine hexaacetic acid, etc.) Addition of one or more surfactants, etc., to obtain a printing plate processing stabilizer that more completely satisfies the object of the present invention. You can In addition to this, a minute amount of a colorant such as a phthalocyanine dye, malachite green, or ultramarine can be added in consideration of the distinguishability and appearance of water-miscible organic solvents such as methanol, dimethylformamide, and dioxane.

The silver halide emulsion of the silver salt light-sensitive material used in the practice of the present invention may be silver chloride, silver bromide, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide, and is preferably chloride. 5 silver
It is 0 mol% or more of silver halide. These silver halide emulsions are spectral sensitizers (spectral sensitizing dyes depending on the light source and application, such as camera type, laser light type, panchromatic type for color separation), gelatin hardening agents, coating aids, antifoggants. , A plasticizer, a developing agent, a matting agent and the like.

[0030]

The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited thereto. Example 1 The components of the developer for a lithographic printing plate by the silver complex salt diffusion transfer method used below are shown below.

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 developing solution was added to ion-exchanged water to obtain 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 prepare a comparative example.

Similarly to the above constituents, EDTA tetrasodium salt, NTA (nitrilotriacetic acid) trisodium salt, chemical formula 8, chemical formula 10, chemical formula 11, chemical formula 12, chemical formula 14, chemical formula 15, chemical formula 16
2g, and add calcium ion concentration of 30 to ion exchange water.
It was dissolved in 1 liter of water added with calcium carbonate and magnesium carbonate so that the concentration of 0 ppm and the concentration of magnesium ion would be 200 ppm. These are referred to as treatment liquid 1, treatment liquid 2, treatment liquid 3, treatment liquid 4, treatment liquid 5, treatment liquid 6, treatment liquid 7, treatment liquid 8, and treatment liquid 9.

Treatment agents 1, 2, 3, 4, 5, 6, 7, 8,
Table 1 shows the results of evaluating the liquid forms of 9 and Comparative Examples.

[0035]

[Table 1]

Example 2 Processing solutions 1, 2, 3, 4, 5, 6, 7, 8, 9 and Comparative Examples were exposed to Silver Master RII (trade name) and then processed by an automatic processor under the following conditions. Carried out. Treatment process time Temperature Development 30 seconds 30 ° C Stabilization 30 seconds 25 ° C

The stabilizer used had the following composition. Stabilizing solution Ethylene glycol 5 g (liquid) Colloidal silica (20% aqueous solution) 1 g (liquid) Citric acid 10 g Sodium citrate 35 g Water is made up to 1 liter.

Then, these samples were mounted on an offset printing machine, and the plate surface was sufficiently moistened with an etchant containing the following components,
Printing was performed using a dampening liquid having the following composition.

Etching solution Water 600 ml Isopropanol 400 ml Ethylene glycol 50 g

Humidifying water 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 judged by 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 50,000 sheets, and the number of sheets in which the silver image was blown out was evaluated. A 50,000 sheets or more B 25,000 C 10,000 D 50,00

[0042]

[Table 2]

Example 3 Stabilizer Ethylene glycol 5 g Colloidal silica (20% aqueous solution) 1 g Citric acid 10 g Sodium citrate 35 g

The above stabilizing solution was added to ion-exchanged water to obtain 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 prepare a comparative example.

Similarly to the above constituents, EDTA tetrasodium salt, NTA (nitrilotriacetic acid) trisodium salt, chemical formula 8, chemical formula 10, chemical formula 11, chemical formula 12, chemical formula 14, chemical formula 15, chemical formula 16
2g, and add calcium ion concentration of 30 to ion exchange water.
It was dissolved in 1 liter of water added with calcium carbonate and magnesium carbonate so that the concentration of 0 ppm and the concentration of magnesium ion would be 200 ppm. These are referred to as treatment liquid 10, treatment liquid 11, treatment liquid 12, treatment liquid 13, treatment liquid 14, treatment liquid 15, treatment liquid 16, treatment liquid 17, and treatment liquid 18.

Treatment liquids 10, 11, 12, 13, 14, 1
Table 3 shows the results of evaluating the liquids of 5, 16, 17, 18 and Comparative Example.

[0047]

[Table 3]

Treatment liquids 10, 11, 12, 13, 14, 1
After the silver master RII (trade name) was exposed to the treatment agent using 5, 16, 17, 18 and Comparative Example, the treatment was carried out by an automatic processor under the following conditions. Treatment process time Temperature Development 30 seconds 30 ° C Stabilization 30 seconds 25 ° C

As the developer, a developer having the same composition as in the comparative example of Example 1 dissolved in ion-exchanged water was used.

Then, these samples were mounted on an offset printing machine, the plate surface was sufficiently wetted with the etchant used in Example 1, and printing was performed using the dampening liquid of Example 1 to test for stains. went.

The printing results of the examples judged by the following criteria are shown in Table 4 together with the state of scratches on the plate surface. Print stains
It was judged by the following method. Printing was continued up to 5,000 sheets, and the print stain on the 5,000th sheet was evaluated according to the following three levels. A No stains B Slight stains C Entire surface stains

[0052]

[Table 4]

[0053]

The processing agent for silver salt sensitizers of the present invention does not cause clouding or precipitation when diluted or dissolved with water having high hardness, and even when the silver halide photographic material is treated with this processing agent, it is not damaged. Will not occur.

Claims (1)

[Claims] 1. A processing solution for a silver halide photographic material comprising at least one of the following general formulas 1, 2, and 3. [Chemical 1] Here, X represents a hydrogen atom and an alkali metal atom, and R represents CH.
₂ OH, CHO, COOX, and 1 represents 2, 3, and 4. [Chemical 2] Here, X represents a hydrogen atom, an alkali metal atom, and m is 2,
3 and 4 are represented. [Chemical 3] Here, X represents a hydrogen atom or an alkali metal atom, and m represents 2, 3, or 4.