US3615508A - Photographic blixes and blixing - Google Patents

Photographic blixes and blixing Download PDF

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US3615508A
US3615508A US873497A US3615508DA US3615508A US 3615508 A US3615508 A US 3615508A US 873497 A US873497 A US 873497A US 3615508D A US3615508D A US 3615508DA US 3615508 A US3615508 A US 3615508A
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per liter
ammonium
water
blix
amine
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Keith H Stephen
John J Surash
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • Photographic blix compositions containing (a) an ammonium or amine salt of the Fe'**, Co***, or Cu complex with a polyfunctional ligand as the silver bleaching agent, (b) an amine or an ammonium thiosulfate and (c) a salt having as a cation an ammonium ion or a water-soluble amine with an ionizable proton attached to a nitrogen atom in the amine and as an anion a sulfite ion, bisulfite ion or a metabisulfite ion either with or without (d) an amine or ammonium salt of unchelated polyfunctional ligand are advantageously prepared in concentrated stock solutions or as dry mixtures to make working blix solutions that clear silver
  • PHOTOGRAPHIC BLIXES AND BLIXING This invention is related to chemical compositions for photographic processing and to blix compositions for use in photographic blixing of silver in developed photographic elements, and to blixing photographic elements.
  • both silver and dye images are produced in the image layers by the photographic developing step or steps.
  • the silver image and any residual silver halide in the developed photographic element are usually removed by converting the silver to a silver salt by a silver bleach solution followed by the conversion of the silver salt into a diffusible, water-soluble complex with a fixing bath and then subsequently washing the bleached and fixed photographic element to remove the silver salt complex, leaving the unobscured dye images.
  • Blix (bleach-fix) baths are known which combine the bleaching and fixing steps into a single-process step.
  • Known blix solutions used complexed iron III as the oxidant, usually as ethylenedinitrilotetraacetato ferrate (Ill) salts and various simple silver ligands, such as, thiosulfate or thiocyanate, alone or in combination.
  • ethylenedinitrilotetraacetato ferrate (Ill) salts and various simple silver ligands, such as, thiosulfate or thiocyanate, alone or in combination.
  • German Pat. No. 866,605 describes a blix containing from 25 to 60 g./l. of sodium ethylenedinitrilotetraacetato ferrate (Ill), from to g./l. of an alkali metal or ammonium thiocyanate and from 75 to 200 g./l. of an alkali metal or ammonium thiocyanate.
  • This blix solution and other known blix solutions do not have the desired blixing rates for the rapid processing of photographic elements now desired or, in some instances, required. Furthermore, known blix solutions are not practical for blixing photographic elements containing high concentrations of silver.
  • Farmer's reducer produced by mixing an alkali metal ferricyanide and an alkali metal thiosulfate is another known blix; however, because of its short life, it is not practical for the usual commercial processing applications.
  • Blix compositions are desired which are stable, are rapid acting and will be useful for removing silver from photographic elements containing high cohcentrations of silver.
  • Another object is to provide a novel blix composition for removing silver from photographic elements that contain a high concentration of silver.
  • Another object is to provide a novel blix composition which has good keeping stability both at working concentrations, as well as at concentrated stock solution concentrations.
  • Another object is to provide novel concentrated stock solutions that are advantageously used for preparing blix solutions for photographic processing.
  • the blix compositions ofour invention contain a. a bleaching agent for silver that is a salt of an unchelated cation such as ammonium ion or a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and has an anion that is a complex of a transition metal, such as, Fe***, Co***, Cu, etc., chelated by a polyfunctional ligand;
  • a bleaching agent for silver that is a salt of an unchelated cation such as ammonium ion or a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and has an anion that is a complex of a transition metal, such as, Fe***, Co***, Cu, etc., chelated by a polyfunctional ligand;
  • a thiosulfate fixing agent having as a cation an ammonium ion or a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine;
  • our blix compositions advantageously also contain d. a salt with an ammonium ion or a water-soluble organic amine with an ionizable proton attached to a nitrogen atom in said amine as the cation and an uncomplexed polyfunctional ligand as the anion.
  • Our blix compositions are characterized by containing essentially no alkali metal ions. No alkali metal salts are used in our blix compositions.
  • hydrogen an alkyl group, especially an alkyl group having from one to six carbon atoms (e.g., methyl, ethyl, hydroxyethyl, propyl, hydroxypropyl, methoxyethyl, chloroethyl, fluoroethyl, butyl, amyl, hexyl, cyclohexyl, etc.), an aryl group, such as a phenyl group e.g.
  • T and T supply the atoms required with the nitrogen atom (to which they are attached) to complete a heterocyclic ring having from five to six atoms in the ring, such as, a pyridine (e.g., pyridine, methyl pyridine, chloropyridine, etc. a morpholine (e.g., morpholine, methyl morpholine, chloromorpholine, etc.), a piperidine (e.g., piperidine, methylpiperidine, chloropiperidine, etc.), etc.
  • a pyridine e.g., pyridine, methyl pyridine, chloropyridine, etc.
  • a morpholine e.g., morpholine, methyl morpholine, chloromorpholine, etc.
  • piperidine e.g., piperidine, methylpiperidine, chloropiperidine, etc.
  • Typical amines used to form a cation for our salts include methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, hydroxyethyl amine, di(hydroxyethyl)amine, tri(hydroxyethyl)amine, propyl amine, butyl amine, amyl amine, hexyl amine, cyclohexyl, amine, aniline, m-toluidine, pyridine, methyl pyridine, chloropyridine, morpholine, methylmorpholine, chloromorpholine, piperidine, etc.
  • our blix compositions are advantageously used over wide ranges of concentrations.
  • our bleaching agent (a) is advantageously used in the concentration range from about X 0.0] mole/liter to about l mole/liter with a preferred range of from about 0.1 mole/liter to about 0.6 mole/liter;
  • our fixing agent (b) is advantageously used in the range of from about 0.01 mole/liter to about 5. moles/liter and preferably in the range of from about 0.1 mole/liter to about 2.
  • our salt (c) used as a source of sulfite ions is advantageously used in the concentration range of from about 0.001 mole/liter to about 2. mole/liter, and preferably in the range of from 0.01 mole/liter to about 0.2 mole/liter.
  • an ammonium or amine salt of unchelated polyfunctional ligand (salt d) is used in our blix, it is usually used at up to about 0.1 the concentration of the chelated salt (a).
  • Our working blix solutions are advantageously used over the pH range of from about 4 to about 9 and preferably in the range of from 6 to about 7.
  • polyfunctional ligands used include those having the formulas:
  • an alkyl group e.g., methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, etc., including an aralkyl group, e.g., benzyl, B-phenethyl, o-acetamidobenzyl, etc., and including a heterocyclylalkyl group (e.g., pyrrolidylmethyl, pyrrolidylbutyl, benzothiazolylmethyl, tetrahydroquinolylmethyl, me), an aryl group, such as, a phenyl group (e.g., phenyl, tolyl, 0-, p-carboxyphenyl, etc.), a napthyl group (e.g., a-naph
  • R R represents a member, such as, hydrogen, hydroxyl, an amino group, nitro, halogen, a lower alkyl group (e.g., methyl, ethyl, butyl, etc.) and a lower alkoxy group (e.g., methoxy, ethoxy, butoxy, etc.) such that no single carbon atoms in the structure containing said groups R through R contains more than one hydroxyl group, more than one amino group and more than one nitro group;
  • A- represents an integer of from 2 to 4; 11 represents an integer of from 1 to 4; and L represents a carboxy group or a phosphono group as described previously for L, L, L and L.
  • R represents a lower alkyl group (e.g., methyl, ethyl, butyl, etc), an aryl group, such as a phenyl group (e.g., phenyl, tolyl, etc.), a naphthyl group (e.g., anaphthyl, B-naphthyl, etc);
  • R and R each represent a member, such as, hydrogen, a lower alkyl group (e.g., methyl, ethyl, butyl, etc.) and a (OH L group; It represents an integer of from l to 2;
  • L represents a carboxy group or a phosphono group (e.g., a P 0- (Q group);
  • O and Q" each represent a member, such as, hydrogen, an ammonium group, a water-soluble amine having an ionizable proton attached to a nitrogen atom
  • L and L are as defined previously for formula I, and L is as defined previously for formula III;
  • L represents a car- PO- (Q group);
  • O and 0 each represent a member, such as, hydrogen, an ammonium ion, a water-soluble amine having an ionizable proton attached to a nitrogen atom (such that not more than one of Q and Q represent an ammonium ion or a water-soluble amine with an ionizable proton), an alkyl group, an aryl group and a heterocyclic group, said alkyl, aryl and heterocyclic groups being as described previously for Q and Q;
  • i, j, m and n each represent integers of from 2 to 4;
  • Z is as defined previously for formula ll, excepting that L is further defined as a carboxy group or a phosphono group P 0-- group);
  • Q and Q" each represent a member, such as, hydrogen, an ammonium ion, a water-soluble amine with an ionizable proton (such that not more than one of Q or Q represents an ammonium ion or a water-soluble amine with an ionizable proton), an alkyl group, an aryl group and a heterocyclic group, said alkyl, aryl and heterocyclic groups being as described previously for Q and Q.
  • Nitrilotriacetic acid Oxalic acid Malonic acid .Chloromalonic acid Ethylmalonic acid .Aminomalonic acid Bromomalonic acid Succinic acid 9. Glutamic acid Adipic acid Diglycolic acid Ethyliminodipropionic acid Ethylene di( thioglycolic) acid Thiodiglycolic acid Malic acid Tartaric acid OOQOMAUN- l7. Citric acid 18. Nitrilo-N,N,N-trimethylenephosphonic acid 19. o-Carboxyanilino-N,N-dimethylenephosphonic acid X 20. Propylamino-N,Ndimethlenephosphonic acid 21. 4-(N-pyrrolidino)butylamine-N,N-
  • Ethylene diamine tetraacetic acid 2. do do do do, tetraammonium salt 3. Pentaacetic acid diethylene triamine 4. do do do do do, pentaammonium salt 5. Ethylene diamine-N,N,N, N'-tetramethylenephosphonic acid 6. l,Z-Cyclohexanediamine-N,N,N, N'-
  • tetramethylenephosphonic acid Included among the bleaching agents of our invention are the following typical compounds:
  • Ammonium ethylenedinitrilotetraacetato ferrate (Ill) 2. Ammonium ethylenedinitrilotetraacetato cobaltate (III) 3. Hydroxyethylammonium ethylenedinitriloacetato ferrate (III) 4. Ammonium hydroxyethylethylenedinitriloacetato ferrate (III) 5. Tris(hydroxyethyl) ethylenedinitrilotetraacetato ferrate (Ill) 6. Ammonium ethylenedinitrilodiacetato dichloro cobaltate (III) 7. Ammonium ethylenedinitrilotetraacetato cuprate (II) 8.
  • the silver bleaching agents of our invention are prepared by l reacting the appropriate metal salt, e.g., a ferric salt, cobaltous salt or cupric salt with an aqueous solution or slurry of a polyfunctional ligand, such as, is described by formulas I, II, III and IV, followed by (2) neutralization of residual acid group(s) with either ammonium hydroxide or an amine.
  • the cobaltous complex is oxidized to the cobaltic complex. It is advantageous to elevate the temperature of the aqueous reaction mixture ofligand and appropriate metal salt to a temperature in the range from room temperature to about 95 C.
  • Typical metal salts used to advantage include the following:
  • ferric sulfate ferric chloride ferric bromide ferric hydroxide cobaltous chloride cobaltous acetate cupric chloride cupric nitrate Bleaching Agent 1 i.e., ammonium ethylenedinitrilotetraacetato ferrate (III), for example, is advantageously prepared by adding fresh hydrated ferric hydroxide to a slurry of ethylenedinitrilotetraacetic acid and heating to a temperature of about to C. to form the ferric complex ofethylenedinitrilotetraacetic acid followed by neutralizing the acid complex with ammonium hydroxide.
  • the acid complex is also advantageously prepared by slurrying fresh ferric hydroxide in hot water and adding powdered ethylenedinitrilotetraacetic acid.
  • the precipitate of hydrated ferric hydroxide used in this reaction is advantageously prepared by reacting ferric nitrate hydrate with 9-H 0 in water with ammonium hydroxide. The precipitate is washed free of ammonium nitrate by decantation and centrifugation with water.
  • Bleaching Agent 2 is advantageously prepared by oxidizing diammonium ethylenedinitrilotetraacetato cobaltate (II) with hydrogen peroxide or other suitable oxidizing agent.
  • the diammonium ethylenedinitrilotetraacetato cobaltate II is advantageously prepared by reacting cobaltous acetate in warm water with ethylenedinitrilotetraacetic acid followed by neutralization with ammonium hydroxide.
  • Bleaching Agents 2, 3, 4, 5, 6, 7, 8, 9, 10, ll, 12, l3, l4 and I5 are advantageously prepared by methods similar to those described for Agents 1 and 2, but using the polyfunctional ligand, transition metal salt, amine or ammonium hydroxide listed in the following Table I:
  • the Co++ is oxidized to (30 after complex salt is prepared.
  • Bleaching agents made from other polyfunctional ligands and other amines according to our invention are advantageously prepared by procedures similar to those illustrated for Bleaching Agents 1 through 15.
  • blix compositions can be prepared ahead of use as concentrated stock solutions which have not been possible with compositions containing alkali metal salts of transition metal complexes of polyfunctional ligands.
  • Sodium ethylenedinitrilotetraacetato ferrata III for example, has a solubility of only about 90 g/liter (or about 0.24 mole/liter). This rather low solubility of sodium ethylenedinitrilotetraacetato ferrate Ill has made blix solutions containing it of very limited use in blixing color photographic elements and other elements having high concentrations of silver to be removed.
  • Concentrated stock solutions containing parts of our blix compositions advantageously contain our ammonium or amine salt of a complex of Fe**", Co or Cu chelated by our polyfunctional ligands at concentrations of from about 0.3 mole/liter to about 2 moles/liter.
  • the concentrated stock solution containing our bleaching agent also advantageously contains the ammonium or amine salt of unchelated ligand at concentrations of from about 0.05 mole/liter to about mole/liter and a sufficient amount of ammonium hydroxide or an amine to adjust the pH of this solution in the range of from about 6.5 to about 10.
  • a second concentrated stock solution is advantageously made to contain other components required in the blix such as the ammonium thiosulfate or amine salt of H S O acid fixing agent and salt providing a source of sulfite ions, e.g., ammonium sulfite, ammonium bisulfite, ammonium metabisulfite, and the corresponding amine salts (of these anions).
  • This concentrated stock solution advantageously contains the fixing agent in the concentration range of from about 3.0 moles/liter to about 8.6 moles/liter and enough of the salt (usually up to about 1 mole per liter) providing a source of sulfite ion to adjust the pH of this solution to a pH in the range offrom about 4 to about 7.
  • the pHs of the two stock solutions are advantageously selected so that when they are combined with the necessary amount of water, a working blix solution is obtained having a pH in the range of from about 4 to 9 and preferably in the range from about 6 to about 7.
  • Our blix compositions also advantageously comprise dry mixtures of sufficient amounts of components, such as, our bleaching agent, our fixing agent and our salt providing a source of sulfite ions so that when the mixture is dissolved in water, the desired concentrated stock solution or working solution is obtained
  • a liquid component, such as, an amine or ammonium hydroxide solution when needed in the blix is advantageously packaged separately for use in preparing either a concentrated stock solution or a working blix.
  • Our blix compositions are used advantageously in photographic processing wherever it is desired to remove silver and silver halide from an emulsion layer or layers as for example in any of the photographic elements designed for color photography, such as those containing color-forming couplers such as those described in Frohlich et al. US. Pat. No. 2,376,679; Vittum et al. U.S. Pat. No. 2,322,027; Fierke et al. U.S. Pat. No. 2,80l,l 71; Godowsky, U.S. Pat No. 2,698,794; Barr et al. U.S. Pat. No. 3,227,554 and Graham, U.S. Pat. No.
  • Any photographic silver halide emulsions are advantageously used in elements processed with our blixing compositions. These emulsions comprise silver chloride, silver bromide, silver bromoiodide silver chlorobromide or mixtures thereof. Coarse grain or fine grain emulsions prepared by any of the well-known procedures are usedv The emulsions advantageously contain any of the known chemical sensitizers, spectral sensitizers, antifoggants, stabilizers, coating aids and other addenda used in photographic elements.
  • the silver halide emulsions advantageously contain any of the various hydrophilic colloids, such as, naturally occurring substances, e.g., proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextron, gum arabic,
  • any of the known nondiffusible color-forming couplers known in the art are advantageously used in emulsions that contain incorporated couplers.
  • the phenolic and naphtholic couplers are used as cyan-dye-formers; the 5- pyrazolone couplers are used as magneta-dye-formers and the open chain ketomethylene couplers are used as yellow-dyeformers.
  • Any of the usual support materials used for photographic films and papers are advantageously used.
  • the photographic processes using our blix solutions use the aqueous alkaline developer solutions containing conventional developing agents, such as, hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, etc., the primary aromatic amino developing agents being used advantageously for color development.
  • conventional developing agents such as, hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, etc.
  • Ammonium :thylenedinitrilotetraacetato Blix X outside our invention, is made having the following composition:
  • Blixes A, B and C of our invention are made.
  • Blix A has the composition of Blix A in example I.
  • Blixes B and C contain 0.29 mole/l. and 0.56 mole/l. of ammonium ethylenedinitrilotetraacetato ferrate (Ill), respectively, and contain the same concentrations of ammonium thiosulfate and ammonium sulfite used in Blix A.
  • emulsion coating is prepared as described in example 1. Separate samples of this coating are contacted with Blixes A, B and C and the clearing times are recorded in the following table:
  • Blix Y (outside our invention)
  • Blix E (of invention)
  • Ammonium ehtylenedinitrilotetraacetato ferrate (lll) 0.4 M
  • Ammonium thiosulfate 1.0 M
  • Ammonium sulfite 0.1 M
  • a conventional multilayer color film containing three differently sensitized gelatino silver halide emulsion layers containing three different incorporated color-forming couplers is light-image exposed, then given negative development, reversal flash, color development as described by Column 1 1, lines 74 through line 36 in Column 12 of Carroll et al. U.S. Pat. No. 2,944,990, then given an aqueous acetic acid stop bath and then one portion of this film is treated with Blix Y, another portion with Blix A and another portion with Blix E.
  • the 1,, time to clear the portions of film of silver as measured by infra red silver density are listed below:
  • EXAMPLE 4 A gelatino silver halide emulsion is divided into three parts. In one portion (A) of the emulsion is incorporated a phenol cyan-dye-forming coupler, dissolved in a coupler solvent; in another portion (B) of the emulsion is incorporated a 5- pyrazolone magenta-dye-forming coupler, dissolved in a coupler solvent and, in another portion (C) of the emulsion is incorporated an open chain, yellow-dye-forming coupler. These emulsions are made and coated to give 100 mg. of coupler/ft", 200 mg. of silver/ftF, 500 mg. of gel/ft?
  • the coatings are lightexposed and color-developed in an aqueous alkaline color developer solution containing N-ethyl-B-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate as the developing agent, followed by an aqueous acid stop bath.
  • the amount of silver in the coatings of portions A, B and C is measured before blixing, after seconds of blixing and after seconds of blixing.
  • the following table gives the results:
  • Part A An aqueous concentrated stock solution having a total volume ofabout 150 ml. is made containing about l g. of ammonium thiosulfate and about 11 g. of
  • Part B An aqueous concentrated stock solution having a total volume of about 150 ml. is made containing about 60 g. of ammonium ethylenedinitrilotetraacetato ferrate (Ill), about 6 g. of ethylenedinetrilotetraacetic acid tetraammonium salt, and about 23 g. of 28 percent ammonium hydroxide (in water).
  • a working blix solution having a pH in the range from about 6.4 to about 6.8 is prepared by combining Part A, Part B and about 700 ml. of water.
  • This blix working solution is used to blix light-image exposed multilayer, multicolor photographic paper elements (containing cyan-, yellowand magenta-colorforming couplers) after they have been color developed in aqueous alkali primary aromatic amino color developing agent solution, then given water washing.
  • Our blix rapidly and effectively removes the developed silver image and residual silver halide, leaving a good color print reproduction of the light-image used for exposure.
  • a photographic blix composition comprising:
  • a bleaching agent for silver that is a salt with an unchelated cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and with an anion that is a complex of a metal selected from the class consisting of Fe, Co, and Cu, chelated by a polyfunctional ligand;
  • a thiosulfate fixing agent having a cation selected from the class consisting of an ammonium ion and a watersoluble organic amine having an ionizable proton attached to a nitrogen atom in said amine;
  • a photographic blix composition comprising:
  • a bleaching agent for silver that is a salt with an unchelated cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and with an anion that is a complex of a metal selected from the class consisting of Fe**, Co" and Cu, chelated by a polyfunctional ligand selected from those having the formulas:
  • R represents a group selected from the class consisting of an alkyl group and an aryl group
  • R and R represent members selected from the class consisting of hydrogen, a lower alkyl group and a(Cl-l ),,,,---L group
  • h represents an integer of from 1 to 4
  • p represents an integer of from 1 to 2
  • Z represents a group selected from the class consisting ofa i ('3 group, a phenylene group, a cyclohexylene group, and a R k group, a
  • R, RR R, R, R R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, an amino group, nitro, halogen, a lower alkyl group and a lower alkoxy group such that no single carbon atom in the structure containing said groups R through R contains more than one hydroxyl group, more than one amino group and more than one nitro group; k represents an integer of from 2 to 4; h
  • L represents an integer of from 1 to 4; and L represents a member selected from the class consisting of carboxy and a phosphono group;
  • a photographic blix composition comprising:
  • a bleaching agent for silver that is a salt with an unchelated cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and with an anion that is a complex of a metal selected from the class consisting of Fe***, Co and Cu, chelated by a polyfunctional ligand selected from those having the formulas:
  • d, e, fand g each represent integers of from I to 4;
  • p represents an integer of from l to 2;
  • X represents a member selected from the class consisting of oxygen, sulfur, a
  • R represents a group selected from the class consisting of an alkyl group and an aryl group
  • R and R represent members selected from the class consisting of hydrogen, a lower alkyl group, and a(CH ),,,,L group
  • It represents an integer of from i to 4
  • L represents a radical selected from the class consisting of a carboxy group (Q 7 group)
  • O and Q each represent members selected from the class consisting of hydrogen, an ammonium group, a watersoluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, an alkyl group, an aryl group and a heterocyclic group; and formula:
  • Z represents a group selected from the class consisting ofa and a group, a phenylene group, a cyclohexylene group and a R, R, R R, R, R and h are as described previously;
  • k represents an integer of from 2 to 4;
  • L represents a group selected from the class consisting of a carboxy group and a group;
  • O and Q each represent members selected from the class consisting of hydrogen, an ammonium ion, a water-soluble organic amine having an ionizable proton on a nitrogen atom, an alkyl group, an aryl group and a heterocyclic group;
  • L and l.. each represent a carboxy group
  • R R R R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, an amino group,
  • d, e,fand g each represent integers of from 1 to 4;
  • p represents an integer of from 1 to 2;
  • R represents a group selected from the class consisting of an alkyl group and an aryl group
  • R and R represent members selected from the class consisting of hydrogen, a lower alkyl group and a--(CH,,,,L group
  • Ii represents an integer of from 1 to 4 L represents a carboxy group
  • L represents a carboxy group
  • i, j, m and n each represent integers of from 2 to 4
  • Z represents a group selected from the class consisting of i a I group, a phenylene group, a cyclohexylene group and a Dir- R, R, R", R R R R, R and h are as described previously; it represents an integer of from 2 to 4
  • L represents represents a carboxy group
  • a thiosulfate salt fixing agent having a cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine;
  • a blix composition of claim 2 containing in addition to (b) and (c) described therein,
  • a photographic blix composition comprising:
  • a blix composition of claim 9 containing, in addition to (a), (b) and (c), sufficient ethylenedinitrilotetraacetate tetraammonium salt to produce, when dissolved in water, a solution containing from about 0.001 mole per liter to about 0.1 mole per liter and sufficient ammonium hydroxide to produce a blix solution having a pH in the range from about 5 to about 7.
  • a photographic blix composition comprising:
  • a photographic blix composition comprising:
  • a photographic blix composition comprising:
  • a photographic blix composition comprising:
  • a composition comprising:
  • a bleaching agent for silver that is a salt with an unchelated cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and with an anion that is a complex of a metal selected from the class consisting of Fe Co and Cu, chelated by a polyfunctional ligand;
  • a base selected from the class consisting of ammonium hydroxide and a water-soluble amine; said composition containing a sufficient amount of (a) and (b) to produce, when dissolved in water, a concentrated stock solution containing from about 0.3 mole per liter to about 2 moles per liter of (a), and from about 0.05 per liter to about 0.5 mole per liter of (b) and a sufficient amount of (c) to adjust the pH of the said concentrated stock solution in the range of from about 6.5 to about 8.5, said concentrated stock solution being added to a solution containing ammonium thiosulfate to form a solution for blixing silver in developed photographic elements.
  • composition comprising:
  • a bleaching agent for silver that is a salt with an unchelated cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and with an anion that is a complex of a metal selected from the class consisting of Fe***, Co and Cu, chelated by a polyfunctional ligand selected from those having the formulas:
  • L and L represent groups selected from the class consisting of a carboxy group and a P group
  • O and Q represent members selected from the class consisting of hydrogen, an ammonium group, a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, an alkyl group, an aryl group and a heterocyclic group
  • R, R R R, R, R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, an amino group, nitro, halogen, a lower alkyl group and a lower alkoxy group, such that no single carbon atom in the chain of formula I contains more than one hydroxyl group, more than one amino group and more than one nitro group
  • d, e,fand g each represent integers of from 1 to 4
  • p represents an integer of from 1 to 2
  • X represents a member selected from the class consisting of oxygen, sulfur, a
  • R represents a group selected from the class consisting of an alkyl group and an aryl group
  • R and R represent members selected from the class consisting of hydrogen, a lower alkyl group and a -(Cl-I ),,,,-L group
  • It represents an integer of from I to 4
  • L represents a radical selected from the class consisting of a carboxy group a nitrogen atom in said amine, an alkyl group, an aryl group and a heterocyclic group; and formula:
  • a base selected from the class consisting of ammonium hydroxide and a water-soluble organic amine; said composition containing a SUfflClCl'l! amount of (a) and (b) to produce, when dissolved in water, a concentrated stock solution containing from about 0.3 mole per liter to about 2 moles per liter of (a) and from about 0.05 to about 0.5 mole per liter of (b), and a sufficient amount of (c) to adjust the pH of said concentrated stock solution in the range of from about 6.5 to about 8.5, said concentrated stock solution being added to a solution containing ammonium thiosulfate to form a solution for blixing silver in developed photographic elements.
  • composition of claim 15 in which said cations in said salts of (a) and (b) are ammonium ions and the base of said (c) is ammonium hydroxide.
  • composition comprising:
  • a bleaching agent for silver that is a salt with an unchelated cation selected from the class consisting of an ammonium ion and a water-soluble organic amine having an ionizable proton attached to a nitrogen atom in said amine, and with an anion that is a complex of a metal selected from the class consisting of Fe***, Co**", and Cu, chelated by a polyfunctional ligand;
  • a thiosulfate fixing agent having a cation selected from the class consisting of an ammonium ion and a watersoluble organic amine having an ionizable proton attached to a nitrogen atom in said amine;
  • ammonium thiosulfate at a concentration in the range of from about 0.01 mole per liter to about 5.0 moles per liter of said blix solution
  • ammonium sulfite at a concentration in the range of from about 0.001 mole per liter to about 1.0 mole per liter of said blix solution

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Removal Of Specific Substances (AREA)
US873497A 1969-11-03 1969-11-03 Photographic blixes and blixing Expired - Lifetime US3615508A (en)

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US (1) US3615508A (fr)
AU (1) AU2175570A (fr)
BE (1) BE758333A (fr)
CH (1) CH528099A (fr)
CS (1) CS151569B2 (fr)
DE (1) DE2054060A1 (fr)
ES (1) ES385097A1 (fr)
FR (1) FR2071648A5 (fr)
GB (1) GB1322565A (fr)
IE (1) IE34647B1 (fr)
SE (1) SE355086B (fr)
ZA (1) ZA706762B (fr)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4895236A (fr) * 1972-03-15 1973-12-06
JPS49107737A (fr) * 1973-02-19 1974-10-14
US3841873A (en) * 1973-05-21 1974-10-15 Eastman Kodak Co Cobalt (iii) complex amplifier baths in color photographic processes
US3923511A (en) * 1971-10-14 1975-12-02 Eastman Kodak Co Photographic process and composition employing CO(III) complexes and silver halide solvents
US3928040A (en) * 1973-07-07 1975-12-23 Fuji Photo Film Co Ltd The use of a polyvalent cation-organic phosphonic acid complex as a bleaching agent
JPS5156228A (ja) * 1974-11-12 1976-05-17 Mitsubishi Paper Mills Ltd Harogenkaginkaraashashinkankozairyono shorihoho
US3970458A (en) * 1971-10-14 1976-07-20 Eastman Kodak Company Imagewise hardening with inert transition metal complex oxidizing agents
US4057427A (en) * 1976-01-12 1977-11-08 Eastman Kodak Company Peroxide redox amplification imaging using manganese catalyst images
US4062682A (en) * 1974-11-12 1977-12-13 Agfa-Gevaert N.V. Fixer compositions used in planographic printing containing onium compounds
US4294914A (en) * 1978-09-14 1981-10-13 Eastman Kodak Company Photographic bleach compositions and methods of photographic processing
US4404274A (en) * 1971-03-20 1983-09-13 Fuji Photo Film Co., Ltd. Photographic light sensitive element containing yellow color coupler and method for forming yellow photographic images
US4518680A (en) * 1983-02-17 1985-05-21 Konishiroku Photo Industry Co., Ltd. Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof
US4552834A (en) * 1984-08-06 1985-11-12 Eastman Kodak Company Enhanced bleaching of photographic elements containing silver halide and adsorbed dye
US4748097A (en) * 1985-06-25 1988-05-31 Ciba-Geigy Ag Method of preparing a hologram
US4914005A (en) * 1987-06-01 1990-04-03 Eastman Kodak Company Photographic element containing a cyan dye forming coupler
US4954426A (en) * 1987-04-30 1990-09-04 Fuji Photo Film Co., Ltd. Methods for processing silver halide color photographic light-sensitive materials
US5055384A (en) * 1989-05-10 1991-10-08 Agfa Gevaert Aktiengesellschaft Granulated photographic fixative and its preparation
US5188927A (en) * 1990-06-15 1993-02-23 Fuji Photo Film Co., Ltd. Composition and process for the processing of silver halide color photographic material
US5250402A (en) * 1991-06-26 1993-10-05 Fuji Photo Film Co., Ltd. Photographic bleaching composition and a processing method therewith
US5266449A (en) * 1991-11-13 1993-11-30 Agfa Gevaert Ag Bleaching bath
US5508151A (en) * 1994-12-22 1996-04-16 Eastman Kodak Company Processing of photographic elements using copper ligand complexes to catalyze peracid bleaching agents
US6489089B1 (en) * 2000-11-03 2002-12-03 Eastman Kodak Company Bleach/fix solution for single-use silver removal in color negative films
US6824965B2 (en) 2000-08-04 2004-11-30 Agfa-Gevaert Bleach bath

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU590557B2 (en) * 1985-04-25 1989-11-09 Konishiroku Photo Industry Co., Ltd. Processing method of light-sensitive silver halide color photographic material
US4717649A (en) * 1986-04-18 1988-01-05 Eastman Kodak Company Photographic bleach-fixing compositions
EP0491678A3 (en) * 1986-04-18 1992-09-09 Konica Corporation Method for processing a light-sensitive silver halide color photographic material
DE3786895D1 (de) * 1986-10-08 1993-09-09 Konishiroku Photo Ind Bleichfixierloesung mit einer guten behandlungswirkung und verfahren zur behandlung eines lichtempfindlichen materials, das diese verwendet.

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4404274A (en) * 1971-03-20 1983-09-13 Fuji Photo Film Co., Ltd. Photographic light sensitive element containing yellow color coupler and method for forming yellow photographic images
US3970458A (en) * 1971-10-14 1976-07-20 Eastman Kodak Company Imagewise hardening with inert transition metal complex oxidizing agents
US3923511A (en) * 1971-10-14 1975-12-02 Eastman Kodak Co Photographic process and composition employing CO(III) complexes and silver halide solvents
JPS5310857B2 (fr) * 1972-03-15 1978-04-17
JPS4895236A (fr) * 1972-03-15 1973-12-06
JPS49107737A (fr) * 1973-02-19 1974-10-14
JPS5810741B2 (ja) * 1973-02-19 1983-02-26 コニカ株式会社 ハロゲン化銀写真感光材料用処理液
US3841873A (en) * 1973-05-21 1974-10-15 Eastman Kodak Co Cobalt (iii) complex amplifier baths in color photographic processes
US3928040A (en) * 1973-07-07 1975-12-23 Fuji Photo Film Co Ltd The use of a polyvalent cation-organic phosphonic acid complex as a bleaching agent
JPS5156228A (ja) * 1974-11-12 1976-05-17 Mitsubishi Paper Mills Ltd Harogenkaginkaraashashinkankozairyono shorihoho
US4062682A (en) * 1974-11-12 1977-12-13 Agfa-Gevaert N.V. Fixer compositions used in planographic printing containing onium compounds
US4057427A (en) * 1976-01-12 1977-11-08 Eastman Kodak Company Peroxide redox amplification imaging using manganese catalyst images
US4294914A (en) * 1978-09-14 1981-10-13 Eastman Kodak Company Photographic bleach compositions and methods of photographic processing
US4518680A (en) * 1983-02-17 1985-05-21 Konishiroku Photo Industry Co., Ltd. Bleach-fixing solution and processing of light-sensitive color photographic material by use thereof
US4552834A (en) * 1984-08-06 1985-11-12 Eastman Kodak Company Enhanced bleaching of photographic elements containing silver halide and adsorbed dye
US4748097A (en) * 1985-06-25 1988-05-31 Ciba-Geigy Ag Method of preparing a hologram
US4954426A (en) * 1987-04-30 1990-09-04 Fuji Photo Film Co., Ltd. Methods for processing silver halide color photographic light-sensitive materials
US4914005A (en) * 1987-06-01 1990-04-03 Eastman Kodak Company Photographic element containing a cyan dye forming coupler
US5055384A (en) * 1989-05-10 1991-10-08 Agfa Gevaert Aktiengesellschaft Granulated photographic fixative and its preparation
US5188927A (en) * 1990-06-15 1993-02-23 Fuji Photo Film Co., Ltd. Composition and process for the processing of silver halide color photographic material
US5250402A (en) * 1991-06-26 1993-10-05 Fuji Photo Film Co., Ltd. Photographic bleaching composition and a processing method therewith
US5266449A (en) * 1991-11-13 1993-11-30 Agfa Gevaert Ag Bleaching bath
US5508151A (en) * 1994-12-22 1996-04-16 Eastman Kodak Company Processing of photographic elements using copper ligand complexes to catalyze peracid bleaching agents
US6824965B2 (en) 2000-08-04 2004-11-30 Agfa-Gevaert Bleach bath
US6489089B1 (en) * 2000-11-03 2002-12-03 Eastman Kodak Company Bleach/fix solution for single-use silver removal in color negative films

Also Published As

Publication number Publication date
GB1322565A (en) 1973-07-04
IE34647B1 (en) 1975-07-09
DE2054060A1 (de) 1971-05-19
IE34647L (en) 1971-05-03
FR2071648A5 (fr) 1971-09-17
ES385097A1 (es) 1973-03-16
BE758333A (fr) 1971-04-01
SE355086B (fr) 1973-04-02
CH528099A (fr) 1972-09-15
ZA706762B (en) 1971-07-28
CS151569B2 (fr) 1973-10-19
AU2175570A (en) 1972-05-04

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