KR100567778B1 - Washing accelerating composition for radiographic or black film and paper - Google Patents

Abstract

The present invention relates to a water-promoting composition used before or after washing a black-and-white film or photo paper before performing washing, and is used instead of water in the post-development water washing, preventing discoloration of the film or photo paper, improving image clarity, staining of sanitary clothing. The purpose of the present invention is to provide a water-promoting composition for preventing, prolonging the service life of the fixative, shortening the washing time, reducing swelling and softening of the gelatin, and reducing water and waste water / sewage during the washing process.

Photo paper, black-and-white film, flush washing, developer, fixer, film discoloration, washing

Description

Washing accelerating composition for radiographic or black film and paper}

The present invention relates to a flush promoting composition of a black and white film and photo paper (Baryta paper), the flush promoting composition of the present invention is characterized by consisting of a builder, a preservative, a hard water softener and purified water.

The flushing process of black and white film or photo paper is done by removing the remaining silver halides which have not been reduced or unsensitized into soluble complex salts (silver salts) and removing them from the membrane. This step is performed to completely remove the fixer. Lack of water treatment leads to discoloration or fading of the film in storage. This is because the stored film reacts with moisture or carbon dioxide gas in the air to produce thiosulfate, and the thiosulfate degenerates silver sulfide into silver sulfide. If sufficient settling and washing are not carried out, the silver salt of the photo paper or film slowly decomposes to yellowish silver sulfide and sulfuric acid during storage of the photo paper or film. Therefore, to prevent discoloration of the film, fatigued fixer should not be used, and complete fixation should be performed using new fixer.

Conventional washing methods include physical and chemical methods. Physical methods for washing water treatment include oxygen generators, and chemical methods include water and hydrogen peroxide as an oxidant. Washing treatment is a process in which the thiosulfate contained in the emulsion of the film or photo paper after fixing has been removed using double salt and some fixing solution circulated for 20 to 30 minutes. The washing time depends on the flow rate of the water.
At present, there are the following types of flushing accelerators for the films and photo papers on the market.

Eastman Kodak's hypo clearing agent is a powdered drug consisting of sodium sulfite, sodium metabisulfite, sodium citrate, and EDTA sodium salts. It has the effect of shortening and saving water. In addition, Eastman Kodak's stop bath serves to stop the development by neutralizing the developer of the film or photo paper.

Agfa's Soda Interim Bath consists of a 1% sodium carbonate solution, which is used between the fixation and final wash steps to reduce the final wash time by 30%, increase the retention time of the photos, and fix the photo paper. It has the effect of removing ingredients completely. In addition, Sistan has been used for the permanent preservation treatment of photo paper because it has an effect of preventing the phase change of the film by the external environment or harmful chemicals.

US Patent No. 5,910,397 discloses a method for removing excess fixative using oxidizing and wetting agents. In the above, the oxidizing agent was used as peroxide, perborate, persulfide, and the wetting agent was cationic, anionic, nonionic, amphoteric surfactants alone or in a mixture.

However, the prior arts have the following problems.

During the fixing of the film or photo paper (if necessary) and at the end of washing, some developing solution or fixing solution is not completely washed, and the developing solution or fixing solution falls on clothing and sanitary clothing, leaving stains on the cloth, and the film or photo paper stored for a long time There is a problem of discoloration.

Silver halide crystals remain in the emulsion of the film or photo paper, resulting in a fog, resulting in poor film clarity.

There is a problem that the silver salt is precipitated in the water used in the washing process after settling, causing environmental problems by waste water / waste water.

There is a problem in that the effectiveness of the fixer decays while repeating the washing process after the development of the film or photo paper and the washing process after the fixing.

Water washing after the development of the film or photo paper using the conventional method has a problem that the service life of the fixing solution is shortened because the developer cannot be completely removed.

There is a problem that water stains may occur on the film and photo paper.

In addition, the swelling and softening of the emulsion of the film or photo paper due to the extension of the washing time, there is a problem that fingerprint traces or scratches occur on the surface of the film or photo paper.

The present invention provides a flushing promoting composition which is used during the fixing process or before performing a final washing process for removing some developer chemicals and fixing solution of the film and photo paper after the fixing is completed to solve the above problems.

It is another object of the present invention to provide a flushing composition for removing silver halide crystals remaining in an emulsion of a film or photo paper.

Still another object of the present invention is to provide a water-promoting composition for precipitating silver salt by performing washing-promoting in the first step of the washing process after fixing the film or photo paper.

Still another object of the present invention is to provide a flushing promoting composition which is extended in the efficacy of the fixer even after repeated washing of the film or photo paper after development or pre-fixing of the pre-washing process.

It is still another object of the present invention to provide a flushing composition which shortens the washing time and prevents swelling of the emulsion.

Still another object of the present invention is to provide a flushing promotion composition in which a flushing effect is enhanced by adding hydrogen peroxide to a builder.

It is another object of the present invention to provide a water-promoting composition which prevents water staining of films and photo papers by adding a surfactant as a humectant if necessary.

Hereinafter, the present invention will be described in detail.

The present invention relates to a flush promoting composition of a black and white film and photo paper, the flush promoting composition according to the present invention is characterized by consisting of a builder, a preservative, a hard water softener and purified water.

The builder of the present invention is an additive which adds to a soap or a synthetic surfactant to improve its cleaning property, improves processing and storage properties, and is used as an extender to give an economic effect. Builders are sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sesquicarbonate (industrial) (sesqui-sodium carbonate), polyphosphate, tripolycarbonate A component selected from an inorganic builder group consisting of tripolyphosphate, silicate, sodium sulfate, bentonite, and zeolite and an organic builder group consisting of carboxymethyl cellulose may be used alone or in combination. .
The builder may be used in an amount of 0.5 to 4.5 parts by weight based on the total weight of the composition. When the builder is used at 0.5 parts by weight or less, it exhibits too low efficacy, and when used at 4.5 parts by weight or more, there is a problem in that it is dissolved in water when heat is applied.

In order to remove the fixer, an oxidizing agent such as hydrogen peroxide may be additionally added in an amount of 0.05 to 20 parts by weight.

Preservatives are acidic compounds that prevent sulfur precipitation and weakening of hyposulfite in the fixer. Preservatives include sodium bisulfite, sodium metabisulfite, potassium metabi sulfite, sulfites such as ammonium bisulfite, hydroxylamine and its derivatives, hydroxysamine Acids (hydroxamic acids, hydrazines and hydrazides), phenols, hydroxyketones, aminoketones, saccharides, monoamines, diamines ( diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, concentrated cyclic condensed ring-type amines, aromatic sulfinic acids, polyols, amino acids and its compounds.
The preservative may be used in an amount of 0.04 to 1.3 parts by weight based on the total weight of the composition. When the preservative is used in an amount of 0.04 parts by weight, the effect is too low, and in the case of 1.3 parts by weight or more, the efficacy is good, but the manufacturing cost of the composition is increased.

Hard water softener is used to shorten hard water with relatively high content of calcium ions, magnesium and iron ions into a single water. Water softeners include polyphosphoric acid, trisodium phosphate, tripotassium phosphate, diisodium phosphate, dipotassium phosphate and sodium tripolyphosphate. And phosphoric acid compounds such as sodium polymetaphosphate.
The water softener may be used in an amount of 0.003 to 0.17 parts by weight based on the total weight of the composition. When the water softener is used in an amount of 0.03 parts by weight, the effect is too low, and when it is used in an amount of 0.17 parts or more, the amount is more than that exhibits sufficient efficacy.

If necessary, a humectant may be further added to the flush promotion composition of the present invention. Wetting agents use surfactants to help clean the surface of the film or photo paper. Surfactant is a compound consisting of a hydrophilic part and a hydrophobic part, and is a surface active agent that adsorbs to the surface in an aqueous solution to significantly lower its surface tension. Surfactants usually reduce the surface tension of 72 m N / m to 30 m N / m or less at 1% concentration. Cationic, anionic, nonionic, amphoteric surfactants are commercially available, such as Dupont's Zonyl FSN.RTM, Alkanol XC.RTM and Ciba-Geigy Lodyne S-100. .RTM and Olin 10G.RTM from Olin Mathieson. Wetting agents are used in amounts of 0.1 to 3% by volume based on the total composition.

EXAMPLE

An embodiment of the present invention will be described as follows.

The embodiments of the present invention are merely for illustrating the present invention and are not limited to this content. In addition, modifications, avoidances, or equivalents may be made by those skilled in the art within the technical spirit and scope of the present invention, but it will be clearly understood by those skilled in the art.

The present invention prepared a flush promoting composition according to the following composition and measured the washing effect.

(1) Preparation of Flush Promoting Composition

1 part by weight of sodium sulfate, 0.5 parts by weight of sodium metabisulfite, and 0.005 parts by weight of tripotassium phosphate were dissolved in 100 parts by weight of purified water to prepare a flushing composition.

(2) Visual inspection for stains on sanitary clothing using a cloth (cotton)

After fixing, the film before washing with water was washed with the water-promoting composition of the present invention, and the residual solution remaining on the film was repeatedly applied to a cotton cloth for 1 week, dried and subjected to visual inspection. As a result, no discoloration of the surface was observed.

(3) Visual observation of film clarity of the fixed film and film discoloration stored for 6 months

Pre-cleaning the film using the flushing composition of the present invention reduces the fog of the film, resulting in a shiny film and improved image clarity. In addition, no discoloration was observed in the film stored for 6 months.

(4) Extension of the term of use of the fixer

Normally, the fixer using the dental standard film takes about 2 minutes or more when settling time is used. Using the flushing composition of the present invention, the use period of the fixer is extended by about 3 days, and thus 10 days of use is possible. .

(5) The residual amount of the material discolored or faded (silver thiosulfate double salt) was confirmed by using the potassium permanganate method and the silver nitrate method as a method of measuring the washing effect.

(A) Potassium permanganate method

0.5 g of potassium permanganate and 1.0 g of potassium hydroxide are dissolved in 1 L of water to make a reagent. 10 ml of washed water is placed in one sample bottle, and 10 ml of fresh water (film flush water) is placed in another sample bottle. Then, drop a drop of reagent into each sample bottle and observe pink visually.
In the present Example, the film which passed 1 to 2 minutes after fixation was treated with the water-promoting composition of the present invention, and the reagents were dropped into the solution and final flushing water, respectively, which were collected from the film.

(B) silver nitrate

A test solution (2 liters) containing 28% acetic acid (125 ml) and silver nitrate (7.5 g) was prepared for the hypo (silver thiosulfate double salt) residual test. The transparent portion of the film treated with the water-washing composition of the present invention and the white portion of the photo paper were cut a little, soaked in the test solution for 3 minutes, and the water-washing ability associated with hypo residues was determined. As a result of the experiment, the transparent part of the film showed no color change.

(6) pH change at the start of use of developer, fixer, and each wash solution and on day 5

On the 5th day of the development, the pH was 10.9, which was the same as the beginning, and the washing amount after development was 2.6 to 9.7, the fixing liquid was 4.1 to 5.2, the washing liquid after fixing was 2.6 to 5.1, and the washing liquid after fixing and flushing agent treatment ( Tap water) varied from 7.5 to 6.4, respectively. From the above results, it can be seen that the flushing promoting composition is transferred to the final flushing water through the film to change the pH.

(7) Inspection of residual amount of silver salt in washed water after using flushing composition of the present invention (using ICPMS)

Treatment of the film with the flushing composition of the present invention prior to final flushing resulted in a quantitative decrease in silver salt in the final flushing solution.

As described above, the flushing composition of the present invention comprises a builder, a preservative, and a hard water softener.

If the operator briefly checks the film or photo paper, some developer chemicals or fixatives that have not been completely removed from the wet or fixed film or photo paper will fall on clothing or sanitary clothing, leaving a brown stain on the fabric. In the case of washing using the water-promoting composition of the present invention as a preliminary step of washing with water during fixing, it was possible to prevent staining of the cloth by the developing chemicals of the film or photo paper and the fixing solution in advance. In addition, after checking the film, while maintaining the wet state and continuing fixing again for permanent fixation, the normal process of fixing could be completed.

According to the present invention, the silver halide crystal remaining in the film and the paper after the fixing process or the fixing is finished is washed with the water-promoting composition of the present invention to prevent the discoloration and sulfation of the film or the paper during long-term storage. The clarity of the image could be improved by preventing it and removing the fog.

The flushing promoting composition of the present invention prevented a phenomenon in which the concentration of the fixer was reduced by simple washing while repeating the washing after the development of the film or the photo paper and the washing after the fixing. Continued incorporation of the flushing composition into the fixer prolonged the efficacy of the fixer and increased the density of the fixer components to prevent bleach on the film. In addition, the post-development water washing introduced some flushing composition instead of water into the fixer to block the influence of the developer in the fixer.

The present invention was able to prevent the shortening of the washing time and the swelling and softening of the emulsion by precipitating the silver salt in advance of the washing process after the fixing of the film or photo paper. In addition, the final washing with water washing treatment composition of the present invention before washing with water was able to prevent the sewage / wastewater containing water and silver salts by a chemical method.

According to the present invention, a surfactant may be used as a humectant to prevent water stains remaining on a part of the film or photo paper during the drying process if necessary.

Claims (11)

A flushing composition comprising a builder, a preservative, a hard water softener and purified water. The water promoting composition according to claim 1, which comprises 0.5 to 4.5 parts by weight of builder, 0.04 to 1.3 parts by weight of preservative, 0.003 to 0.17 parts by weight of water softener, and 100 parts by weight of purified water. According to claim 1, The builder is sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sesquicarbonate (industrial), sesqui-sodium carbonate, poly Inorganic builder group consisting of phosphate (polyphosphate), tripolyphosphate, silicate (silicate), sodium sulfate, bentonite and zeolite, and an organic builder group consisting of carboxymethyl cellulose alone Washing promotion composition, characterized in that used in or mixed. The composition of claim 1, wherein the builder is sodium sulfate. The washing promoting composition according to claim 1, wherein 0.05 to 20 parts by weight of hydrogen peroxide is added to the builder. The method of claim 1, wherein the preservative is sodium bisulfite, sodium metabisulfite, potassium metabi sulfite, sulfite such as ammonium bisulfite, hydroxylamine, and Derivatives thereof, hydroxamic acids, hydrazines and hydrazides, phenols, hydroxyketones, aminoketones, saccharides, monoamines (monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, alcohols, oximes, diamide compounds, Characterized in that it is selected from condensed ring-type amines, aromatic sulfinic acids, polyols, amino acids and its compounds Flushing promoting composition. The method of claim 1, wherein the water softener is polyphosphoric acid, trisodium phosphate, tripotassium phosphate, sodium diphosphate, dipotassium phosphate, tripoly Washing promoting composition, characterized in that it is selected from the group of phosphate compounds consisting of sodium phosphate (sodium tripolyphosphate) and sodium polymeta phosphate (sodium polymeta phosphate). The water-promoting composition according to claim 1, wherein the humectant is further added in an amount of 0.1 to 3 parts by weight based on the total weight of the composition. delete 9. The flushing composition of claim 8, wherein the humectant is selected from cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof. The water promoting composition according to claim 1, wherein the water promoting composition is treated after the development of the black-and-white film or photo paper, before the final washing is performed during and after the fixing.