SU416970A3 - BLEACHING AND FIXING COMPOSITION - Google Patents

Description

- one

The invention relates to bleaching-fixing compositions used for processing cinema photographs.

A bleaching-fixing composition is known that contains a water-soluble silver-bleaching substance consisting of an alkali metal cation, ammonium or amine and an anion — a complex of ferric iron with a polyfunctional ligand, an ammonium thiosulfate and sodium sulfite soluble in water fixing material. The molar ratio of bleaching agent and fixing agent is 1: 1-1: 5.

However, such bleaching-fixing solutions do not provide fast processing, and they are also not suitable for processing materials with a high concentration of silver, for example, photosensitive color photographic materials, especially photosensitive bromine or iodide-silver emulsions.

The purpose of the invention is to obtain concentrated compositions that are stable during storage. To achieve this goal, it is proposed that the bleaching-fixing composition introduce a water-soluble secondary ligand - thiocyanate, borate, boric acid, fluoride or thiourea, and the ratio of thiocyanate and bleaching agent is less than 1: 5, borate, boric acid or fluoride and bleed2

pouring substance - at least 1: 1 and thiourea n bleaching agent - at least 3: 1.

The white-fixing composition is applied in the form of an aqueous solution containing 0.4-2.0 mol / l bleaching agent and up to 1.5 mol / l fixing agent. These solutions have pH values in the range of 5-9.

The proposed bleaching-fixing compositions allow to obtain concentrated solutions that are stable during storage and are used to process materials that have a high silver content. They have a high activity that cannot be significantly affected by an increase in the pH value. The complexes have a large molecular size and limited solubility at a pH of 4-5, usually equal to 150 g / l or 0.45 mol / l. As the pH of the solution changes towards an increase in alkalinity, the water molecule rearranges to form a bridge between the two ferric ions — the primary ligand molecules — thus increasing the size and weight of the molecule by a factor of two. The oxidative and diffusion abilities of this molecule are significantly reduced. It was found that carefully selected secondary ligands, used in a certain proportion, cv 3

Zainy with a complex of primary ligapts (ferric ion) will replace the water molecule in these complexes and prevent dimerization at pH values 4-9. The proposed formulations may also include free (not located in a complex compound) nnfunctional Lingand or its salt, the content of quatone n.1ocellular metal, ammonium or amine.

Any water soluble primary, secondary or tertiary amnn, a non-ionizable proton, can be used as a cation in salts used in the proposed composition. These amines are able to diffuse into photographic emulsion layers.

Listed below are five- and six-membered ligands.

Ethylenediaminetetraacetic acid. Diammonium salt of ethylenediaminetetraacetic acid.

Tetra (trimethylammonium) salt of ethylenediaminetetraacetic acid.

Tetra (hydroxyethylammonium) salt of ethylenediaminetetraacetic acid. Diethylenetriaminepentaacetic acid. Tetramorpholine salt of ethylenediaminetetraacetic acid.

Sodium salt of ethylenediaminetetraacetic acid.

Tetrakalnev salt of ethylenediaminetetraacetic acid.

Tetralithium salt of ethylenediaminetetraacetic acid.

Diethylenetriamine-sodium salt of peitaacetic acid.

Diethylene triamine pentaammonium salt of penta acetic acid.

Ethylenediamine-M- (p-hydroxyethyl) - N, N, N-TpH acetic acid.

The sodium salt of ethylenediamine-L- (p-hydroxyethyl-M, H, M-triacetic acid.

Triammoiievy salt of ethylenediamine-N- (p-hydroxyethyl) -Y, N, N-triacetic acid.

1,3-Diaminopropanol-S, H, M, S-tetramethlenlenphosphinic acid.

Ethylenediamine-M, 1M, S, M - tetramethlenlenphosphinic acid.

l, 2-Cyclohexylenediamin-N, N, N, N - tetramethylenephosphinic acid.

1,3-Diamnopropanol-N, M, M, M - tetramethylene phosphinic acid.

1,3-Propylene diamine-1M, 1M, M, M - tetramethylene phosphinic acid.

Claims (5)

1,6-Hexylenediami-M, S, H, S - tetramethylene phosphinic acid. Propylene diamine tetraacetic acid. Tetrasodium salt of nopylenediaminetetraacetic acid. Tetraammonium salt of propylenediaminetetraacetic acid. Propylene diamine-N- (p-hydroxyethyl) - N.N. N triacetic acid. Propylenediamine Trisodium Salt-N- (roxyethyl) -H, N, H-triacetic acid. Trnummonium salt propnlenediamine-K- (roxyethyl) -1,1M, L-triacetic acid. (2-Oxypropylene) diaminetetraacetic acid. Tetraammonium salt of 2-oxnronenendnamlnepayj cyconic acid. 2-Oceinronlenediamine-H - (p-hydroxyethyl) N, lN N-three-cycloxylic acid. Triammonium salt of 2-oxinronylenediamine- (p-hydroxyethne) -M, S, M-triacetic acid. Cyclohexyleidiamine tetraacetic acid. Tetraammonium salt of cyclohexylene diamine tetraacetic acid. Cyclohexylenediamine-N - (P - hydroxyethyl) -Y, LH-triacetic acid. Trisodium salt of cyclohexylene diamine-N (R-OXNETHYL) -M, N, L-triacetic acid. Phenylenediaminetetraacetic acid. Phenylenediamine - N - (p-oxnethyl) - N, N, N triacetic acid. Secondary ligands that can be used in the proposed composition are water-soluble thiocyanates of formula 1 M-CNS where M is an alkali metal, sodium, potassium or lithium nanorimer, or an ammonium cation or water-soluble ampna, water soluble borates of the formula IZVOG where M has the specified value, Bornzyu acid, water-soluble fluorides of formula 2 Mf where M has the specified value, and water-soluble thiourea of formula 3 -N-l-r where RI and KS is a hydrogen atom, methyl or hydroxyethyl; R2 and R4 is a hydrogen atom, methyl, hydroxyethyl, NH2, -NHCHa, -Y (CH3) 2, -NHCHa- -CHNOH, -N (CH2CH2OH) 2 or -Y (CH3) -CHNCHNgON, moreover, thiourea contains at least one group -NH-. The secondary ligands that can be used in the proposed composition include the following compounds. Water soluble thiocyanates: sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, ammonium thiocyanate, trimethylammonium thionianate, oxyethylammonium thiocyanate, morpholine thiocanate. Water soluble borates: sodium borate, potassium borate, lithium borate, ammonium borate, oxyethylammonium borate. Water soluble fluorides; sodium fluoride, potassium fluoride, lithium fluoride, ammonium fluoride, oxyethylammonium fluoride, trimethylammonium fluoride, morpholine fluoride. Water soluble thiourea; thiourea, thiosemicarbazide, N-methylthiourea, K, M-dimethylthiosemicarbazide, N, Ndimethylthiourea, M- (p-hydroxyethyl) thiourea, M, M-di- (3-hydroxyethyl) thiourea, thiocarbohydrazdhis, and thiourea, M-M- -tetrametiltiokapbogidrazid, M, N-dimethylthiourea, N, Ndi- (p-hydroxyethyl) thiourea, N- (p-hydroxyethyl) N-metiltiomochevipa, N- (p-hydroxyethyl) -N-metiltiosemikarbazid, N, K-di- ( p-hydroxyethyl) -thiocapbohydrazide. Fixing agents nrmman gota in bleaching-fixing compositions in cases where water soluble fluoride, water soluble borate or boric acid are used as secondary ligands or when water soluble thiocyanate or water soluble thiourea is not enough as secondary ligands and solvent silver halide. As fixing agents can be used compounds of formulas 1 and 3 or compounds of formula 4 M252Oz where M is as defined, thioesters comprising compounds of formula 5 BUT (CHsCHaZ) pCHN where j) is an integer equal to 2-13; Z is an oxygen or sulfur atom, with a minimum of one third of Z being sulfur and the remaining two thirds not sulfur atoms, and also compounds of the formula 6 НОСНг (SCHsCHo) СНаСОО where q is 1, 2 or 3, as well as alkali metal salts, ammonium or amine salts of these compounds. Recommended compounds of molecule 5 are 3,6-dithio-1,8-octanediol, 3,6.9-tritio-1, 11-undecanediol and 3, b, 9-tetrathio-1,14-tetradecanediol, and recommended compounds of the formula b - ethylene-b "c-thioglycolic acid, 3,6,9-tritiyohendanediocid and disodium salt of ethylene-bgs-thioglycolic acid. When using thiosulfate as a fixing agent, it is desirable to introduce into the composition a source of sulfite ions, for example, water-soluble sulfite, bisulfite, or metabisulfite. Bleach-fixing compositions MAY be obtained and packaged as dry blends, and when any liquid liquid, such as an amine or ammonium hydroxide solution, is needed, it can be packaged separately. Compose MAY be used to obtain either a bleaching-fixing solution intended to whiten and fix photographic materials having a high concentration of silver, or a basic solution intended for subsequent dilution to reduce the concentration of the solution. Two parts of the concentrate can be used, of which one part is a solution of a complex of ferric ion with a functionalized ligich and secondary ligand, and the other part; is a solution of fixed substance in the source with a source of sulphite ions, if they are used, and polyfunctional ligand that is not in a claw compound, if used. Concentrated bleaching-fixing solutions can be used to bleach and fix photographic materials with a high silver content, e.g. above 100 mg by 30.5 cm in each layer, and gelatin content exceeding 100 mg by 30.5 cm in each layer. Photographic materials with low concentrations of silver can be bleached and fixed with low concentration solutions obtained by diluting the concentrated solutions to the desired concentration. Bleach-fixing compositions can be used in photographic processes wherever silver and silver halide from an emulsion layer are needed, for example, in photographic colored material. The bleaching-fixing composition can also be used to treat chlorine-silver emulsions. These emulsions may contain silver chloride, silver bromide, silver bromide, silver chlorobromide or mixtures thereof. . Coarse-grained or fine-grained emu.thii can be used, obtained by known methods. These EMULSIONS can include any known chemical sensitizers, spectral dispersants, anti-venting agents, stabilizers, excipients and others. Galogenserebr nye emulsnn may include gilrofilts |) 1st colloid, for example gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, gum nanrimer or dextrose, or synthetic polymeric solid matter, such as water soluble polyvinyl compounds, poly (vitsilpippoliloi) and .akrilamida polymers. Example 1. An aqueous bleaching, e-fixing solution A is prepared from the following components: Basic sodium-sodium salt of ethylenedinitrile tetraacetic acid 180 g Hydroxy ammonium, g 200 1 Water, l pH adjusted to 6.3 using ammonium hydroxide or sulfuric acid. Two bands of a conventional photosensitive multilayer color film in which the emulsion layers comprise gelatin and silver bromide, sensitive to blue, green and red, each layer containing more than 100 mg of silver (counting on silver halide) by 30.5 cm or more 100 mg of gelatin, 30.5 cm and each layer contains a dye, exposed to light through a vertical wedge. Exposed bands are processed, pass through stages 2 and 3 (negative appearance, repeated exposure and color development), and then in an aqueous fixing solution of acetic acid. Next, one strip is treated in a known manner in a bleaching-fixing solution, and the other strip is bleached with an e-fixing solution A. It takes 10 minutes to process in a known manner to Back Cast silver, while processing with Solution A takes only 5 minutes. The solution used in the known process has the following composition: Basic iron-sodium Sodium ethylene dinitrile tetraacetic acid, g / l 60.0 Tetrasodium ethylene dinitrile tetraacetate, g / l 6.7 Sodium sulfite, g / l 12.0 Ammonium thiocyanate, g / l 12.0 ammonium thiosulfate, g g200 The pH is adjusted to 6.8. Example 2. DacTBop B bleaching and fixing is prepared by dissolving 300 g of the basic ferrous sodium salt of ethylene linitrile tetraacetic acid and 600 g of ammonium thiopianate in 1 l of water. The pH was adjusted to 6.7 by adding ammonium hydroxide or sulfuric acid. This solution is a stable liquid concentrate in which the molar ratio of secondary ligand to primary ligand is 15: 1. It can be stored and used as a concentrate or as a diluted solution. Example 3. Bleaching and fixing sheet B is prepared by measuring 1 liter of water with IRO mg of the baseline of the ethylene salt of ethylenedinate L- (B-occut) -triyccyclic acid and 200 g of Pu-moth thioiianate. Then the pH was adjusted to R.O. by addition of ammonium hydroxide or sulfuric acid. Example 4. A bleaching-fixing solution G is prepared by dissolving 150 g of the basic iron-sodium salt of ethylene nitrile tetraacetic acid, 27 g of boric acid and 166 ml of ammonium thiosulfate (60% solution) in 1 liter of water. The pH is then adjusted to 6.5, as in the indicated examples. The other Bleach-Fixing Solution D is prepared by dissolving 180 g of basic sodium disodium salt of ethylenedinitrile tetraacetic acid, 17 g of sodium fluoride, 10 g of sodium sulfite and 200 ml of ammonium thiosulfate and (60% solution) in 1 water. The pH is then adjusted to 6.6 in a similar manner to the preferred Examples. The strips of the multi-layer photosensitive photoplay, as in Example 1, are exposed and treated analogously to Example I, but instead of the solutions used in Example 1, Vayu1G (e-fixing solutions G and D) are used. The time required for the removal of silver when using the specified p. equal to 6.25 minutes and 7.5 minutes respectively. Bleach-fixing solutions D and D can be diluted to weaker if high activity is not required, for example, when processing photographic materials with low sulfur content Example 5. A bleaching-fixing solution 2 is prepared by dissolving 150 g of the basic iron-sodium salt of ethylenedinitrile-tetraacetic acid in 1 l of water and 125 thiourea. The pH value is adjusted to 6.0. The bleaching-fixing solution is prepared in the same way, but instead of 125 g of tyoltochevint 6epvT an equimolar amount of N (P-hydroxyethyl) -K-methylthiourea.Then, a bleaching-fixing solution is also prepared, containing 1НО g / l of the same bleaching substance and 200 g / l of ammonium thioiianate, the pH value is adjusted to 5.0. Each p-leaf is then used to bleach and fix the different bands of a conventional multi-layer photosensitive color photographic film described in Example 1 after exposure and treatment, as described in the example. In each of the bleaching-fixing solutions, results similar to those given in solution A in Example 1 are obtained. Analogously to this. A solutions, B. CG D, E and F can be used to bleach and fix photosensitive photo materials. at pH value The subject matter of the invention is 1. Bleach-fixing aging, containing water-soluble, bleaching silver, a substance consisting of a c hyaline metal, ammonium or amine and Annon - a complex of trivalent iron with a polyfunctional ligand, characterized in that, in order to obtain concentrated formulations that are stable during storage, a bleaching agent is used in an amount 0.4–2 mol / l and a water soluble secondary ligand — thiocyanate, borate, boric acid, fluoride, or thiourea — is introduced into the composition, and the ratio of thiocyanate and bleach content is at least 1: 5, borate, boric acid, or fluoride and bleaching agent at least I: 1 and thiourea and bleaching agent is at least oil. 2. The composition according to claim 1, characterized in that the pH value of the composition is 5-9. ten 3. Composition but Mon. 1 and 2, characterized in that a silver halide fixing substance is introduced into it. 4. A composition according to claim 3, characterized in that water soluble thiosulfate, thiocyanate, thiourea or thioether are used as fixing agent. 5. The composition according to claim 1, wherein ammonium thionianate, boric acid, sodium fluoride or thiourea are used as a secondary ligand.