US3706561A - Compositions for making blixes - Google Patents

Compositions for making blixes Download PDF

Info

Publication number
US3706561A
US3706561A US23022A US3706561DA US3706561A US 3706561 A US3706561 A US 3706561A US 23022 A US23022 A US 23022A US 3706561D A US3706561D A US 3706561DA US 3706561 A US3706561 A US 3706561A
Authority
US
United States
Prior art keywords
blix
water
group
silver
soluble
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US23022A
Other languages
English (en)
Inventor
Rowland G Mowrey
Keith H Stephen
Eugene F Wolfarth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3706561A publication Critical patent/US3706561A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • compositions containing a sufiicient amount of (a) a water-soluble complex of a ferric ion with a pentadentate or a hexadentate primary ligand to produce, when dissolved in water, a solution containing from about 0.4 mole/liter to about 2.0 moles/liter and (b) a sufficient amount of a water-soluble monodentate secondary ligand, such as, a thiocyanate, a borate, boric acid, a fluoride or a thiourea so that the mole ratio of the thiocyante to (a) is at least 5:1, the mole ratio of the borate, boric acid or fluoride to (a) is at least 1:1 and the mole ratio of the thiourea to (a) is at least 3:1 are advantageously used to prepare blix solutions for removing silver and silver halide in color-developed photographic processing.
  • This invention is related to photography, compositions for making photographic blixes, blix compositions and the use of these blix compositions for photographic processing.
  • 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 dilfusible, 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.
  • the usual blix solutions for removing silver and silver halide from processed color photographic elements consist of from 20 to 60 g./l. of ferric ion complexed by a multidentate ligand and a simple silver halide solvent such as hypo in the range of from 50 to 150 g./l.
  • the pH range is usually between pH 4.0 and 8.0. At the acid end of the pH scale, the oxidant powers of the blix are highest, but
  • the oxidant attacks the silver halide solvent; also, the ferric ion complex is least soluble, being limited to about .25 mole/l. or about 90 g./l. At the most alkaline pH value, a blix is least reactive, is more stable, and the solubility of the complex is about .45 mole/l. or about 150 g./l. These blixes having a pH of about 8 are so slow that prohibitive time is required by these blixes to remove developed silver and residual silver halide even at the maximum concentration disclosed in the prior art.
  • blixes often require complicated mixing, due to the limited solubility of the ferric ion complex.
  • the complexes are sometimes prepared during mixing of the solution, requiring several parts to be stored for each blix solution.
  • the making of a practical concentrate of the ferric ion complex has been impossible using the prior art.
  • Another object of the invention is to provide a novel blix composition for removing silver from photographic elements that contain a high concentration of silver by using a ferric ion complex concentrate without dilution.
  • Another object is to provide a novel blix composition having a uniformly high level of blix activity as the pH of the working solution is made more alkaline.
  • compositions for the blix step in a color process said composition containing:
  • a multidentate i.e., pentadentate or hexadentate
  • a water-soluble monodentate secondary ligand e.g., a thiocyanate, a borate, boric acid, a flouride or a thiourea to produce, when dissolved in water with (a) and (c), a mole ratio of the thiocyanate to (a) of at least 5:1, a mole ratio of the borate, boric acid or of the fluoride to (a) of at least 1:1 and a mole ratio of the thiourea to (a) of at least 3 :1 in order to displace the pentaor hexa-coordinate water from (a);
  • a water-soluble monodentate secondary ligand e.g., a thiocyanate, a borate, boric acid, a flouride or a thiourea
  • a sufficient amount of a water-soluble silver halide fixing agent e.g., a thiosulfate, a thiocyanate, a thiourea, a thioether, etc., to produce, when dissolved in water with (a) and (b), a concentration in the range of from 0 to about 1.5 moles/l. (in the concentrate or in solutions made by diluting the concentrate);
  • a water-soluble silver halide fixing agent e.g., a thiosulfate, a thiocyanate, a thiourea, a thioether, etc.
  • compositions are used to prepare blix compositions.
  • Our invention includes blix compositions in which (a) is in the concentration range from .05 mole/ l. to 0.4 mole/ 1. when (b) is a water-soluble fluoride or borate, and (c), (d) and (e) are as already described.
  • Our blix compositions are characterized by the presence of a secondary ligand which is used in sufficiently high concentration so that the water molecule is displaced from its usual position in the primary ligand-ferric ion complex.
  • Secondary ligands used to advantage in our blix compositions include water-soluble thiocyanates,
  • water-soluble borates water-soluble fiuorides, watersoluble thioureas, etc.
  • a ferric ion chelated with a pentadentate ligand has a water molecule occupying the sixth coordination site. If the complex is considered to be hexacoordinate, the water molecule occupies the heptacoordinate site. This is true in both the solid state and as a solution in water. The water will finally occupy a hexacoordinate site, displacing one of the arms of the polydentate ligand.
  • These complexes are large organicmetallic acids and have limited solubility in the pH range of from 4-5, generally about 150 g./l. or about .45 mole/ 1.
  • the multidentate ligands used as primary ligands in our compositions include those having the formulas:
  • T and T each represent the same or different member, such as, hydrogen, an alkyl group, especially an alkyl group having from 1 to 6 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., phenyl, tolyl, etc.), and together R and T 1 supply the atoms required with the nitrogen atom (to which they are attached) to complete a heterocyclic ring having from 5 to 6 atoms in the ring, such as, a pyridine (e.g., pyridine, methyl pyridine, chloropyridine,
  • a pyridine e.g., pyridine, methyl pyridine, chloropyridine
  • Q and Q also represent members such as an alkyl group (e.g., methyl, ethyl, propyl, butyl, cyclopentyl, cyclohexyl, etc., including an aralkyl group, e.g., benzyl, fi-phenethyl, o-acetamidobenzyl, etc., and including a heterocyclylalkyl group (e.g., pyrrolidylmethyl, pyrrolidylbutyl, benzothiazolylmethyl, tetrahydroquinolylmethyl, etc.), an aryl group, such as, a phenyl group (e.g., phenyl, tolyl, 0-, p-carboxyphenyl, etc.), a naphthyl group (e.g., a
  • hydroxyl, amino, nitro, halogen, a lower alkyl group, a lower alkoxy group, etc. an arylene group (e.g., a phenylene group, a naphthylene group, etc., each of which is unsubstituted or substituted with groups such as hydroxyl, amino, nitro, halogen, a lower alkyl group, a lower alkoxy group, etc.) and a divalent heterocyclene group (e.g., a pyridylene group, a 4,5-oxazolylene group, a 4,5-thiazolylene group, etc.), and Z represents a group,
  • R, R R R 'R R R and R each represent 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 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 represents an integer of from 1 to 4 and L represents a carboxy group or a phosphono group as described previously for L, U, L and L and wherein L, L L L L and Z are as defined previously for Formula I; and i, j, m and n each represent integers of from 2 to 4.
  • a lower alkyl group e.g., methyl, ethyl, butyl, etc.
  • Pentaacetic acid diethylene triamine penta sodium salt 11. Pentaacetic acid diethylene triamine penta ammonium salt 12. Ethylene diamine N-(fl-hydroxyethyl)- N,N',N'-tri acetic acid 13. Ethylene diamine N-(B-hydroxyethyl)-N,N,N'-triacetic acid sodium salt 14.
  • Ethylene diamine N(fl-hydroxyethyl)-N,N',N'-triacetic acid triammonium salt 1,3-diaminopropanol N,N,N',N', tetramethylene phosphonic acid .
  • Phenylene diamine tetraacetic acid Phenylene diamine N-(B-hydroxyethyl)-N,N',N'-
  • Typical amines used to form a cation for salts used in our invention include methylamine, dimethyl amine, trimethyl amine, ethyl amine, triethyl amine, hydroxyethyl amine, di-(hydroxyethyl) amine, tri-(hydroxyethyl) amine, propyl amine, butyl amine, amyl amine, hexyl amine, cyclohexyl amine, aniline, m-toluedine, pyridine, methyl pyridine, chloropyridiue, morpholine, methylmorpholine, chloromorpholine, piperidine, etc.
  • water-soluble borates having the formula:
  • R represents a member, such as, hydrogen, methyl, hydroxyethyl, etc.
  • R represents a member, such as, hydrogen, methyl, hydroxyethyl, -NH NHCH -N(CH N-HCH CH OH, -N(CH 'CH OH) -N(CH )CH CH OH, etc.
  • R represents a member, such as, hydrogen, methyl, hydroxyethyl, --NH NHCI-I --N(CH NHCH CH OH,
  • R represents a member, such as, hydrogen, methyl, hyd-roxyethyl, etc.; such that compounds of Formula VI contain at least one NH group.
  • Typical secondary ligands used to advantage according to our invention include the following:
  • Water-soluble thiocyanates include the following:
  • Water-soluble borates include the following:
  • Water-soluble fluorides include the following:
  • Sodium fluoride Potassium fluoride Lithium fluoride Ammonium fluoride Hydroxyethylammonium fluoride T rimethylammonium fluoride Morpholini um fluoride, etc., and Water-soluble thioureas include the following:
  • Representative examples of compounds of Formula VIII include 3,6-dithia-1,8-octanediol, 3,6,9-trithia-1, l l-undecanediol, 3,6,9-tetrathia-l ,14-tetradecanediol, etc.
  • representative compounds of Formula IX include ethylene-bis-thioglycolic acid, 3,6,9-trithiahendecanedioic acid, ethylene-bis-thioglycolic acid disodium salt, etc.
  • compositions are advantageously prepared and packaged as dry mixtures (with any liquid component, such as, an amine or ammonium hydroxide solution when needed in the blix advantageously packaged separately).
  • compositions are advantageously used for preparing Schwan, US. Pat. 2,950,970. either a blix concentrate for blixing photographic elements
  • Any photographic silver halide emulsions are advancontaining a high concentration of silver, or for a stock tageously used in elements processed with our blixing solution for subsequent dilution to make a less concencompositions.
  • These emulsions comprise silver chloride, trated blix solution, or preparing a less concentrated blix silver bromide, silver bromoiodide, silver chlorobromide solution directly from the dry components. or mixtures thereof.
  • a two-part concentrate is advanprepared by any of the well-known procedures are used.
  • tageous in which one part is a solution of (a) the com-
  • the emulsions advantageously contain any of the 'known plex of ferric ion with primary ligand (b) the secondary chemical sensitizers, spectral sensitizers, antifoggants, ligand and the other part is a solution of components, stabilizers, coating aids and other addenda used in photosuch as (c) fixing agent, (d) sulfite ion source, and (e) graphic elements.
  • the silver halide emulsions advanunchelated primary ligand.
  • Our blix concentrates containing components (a) and such as, naturally-occurring substances, e.g., proteins, for (b); (a), (b) and (e); or, (a), (b), (c), (d), and (e), example, gelatin,- gelatin derivatives, cellulose derivatives, i .e., in which (a) is used in the concentration range from polysaccharides such as dextrose, gum arabic, etc. and about 0.4 mole/l. to about 2.0 moles/l.
  • components (a) and such as, naturally-occurring substances, e.g., proteins, for (b); (a), (b) and (e); or, (a), (b), (c), (d), and (e), example, gelatin,- gelatin derivatives, cellulose derivatives, i .e., in which (a) is used in the concentration range from polysaccharides such as dextrose, gum arabic, etc. and about 0.4 mole/l. to about
  • advansynthetic polymeric substances such as, soluble polyvinyl tageously to blix photographic elements, especially the compounds like poly(vinylpyrrolidone) acrylamide polyelements that contain high levels of silver, such as, above mers, etc.
  • Any of the known nondiffusible color-forming 100 mg./ft. in each layer and levels of gelatin at or above couplers known in the art are advantageously used in 100 mg./ft. which even the best prior art blix solutions emulsions that contain incorporated couplers. The pheare incapable of blixing.
  • Photographic elements containnohc and naphtholic couplers are used as cyan-dyeing lower concentrations of silver are advantageously formers; the 5-pyrazolone couplers are used as magentablixed with less concentrated blix solutions made by didye-f0rmers and the open chain ketomethylene couplers luting our blix compositions to the desired concentration. are used as yellow-dye-formers.
  • Any of the usual sup- Typical bleaching and/ or blixing compositions of our port materials used for photographic films and papers are invention are shown above. Compositions 4, 5, 6, 7, 10, advantageously used. 11, 14, 15 and 21 are bleaching compositions and need The photographic processes using our blix solutions use from about 0.05 mole/1.
  • compositions on these pages are r catechols, aminophenols, 3-pyrazolidones, phenylenediblixes.
  • An aqueous Blix Concentrate X outside of our invention and disclosed in British Pat. 991,412 is made having the following composition: Sodium ethylenedinitrilotetraacetato ferrate III hydrate, 150 g./l., ammonium thiocyanate 150 g./l. adjusted to a pH of 5.0 with NH OH or H 50 as required. A residue remains in the bottom of the container used to prepare the concentrate indicating that total solubility is not achieved. The ferric ion complex is not entirely soluble with the previously disclosed mole ratio of about 4.5 :1 of secondary ligand to primary ligand.
  • An aqueous Blix Concentrate A of our invention is prepared by dissolving, in one liter of water, the following mixture:
  • Blix Concentrate A being of higher concentration than blixes of the prior art, will obviously have higher reactivity (than the prior art blixes) if used without dilution. Since thiocyanate is also a silver halide solvent, part (c) of our blix is not necessary if there is suflicient thiocyanate (usually above 150 g./l.) to give the desired silver halide solvent concentration.
  • Aqueous Blix Concentrate B of our invention is made up as in Blix Concentrate A, but to pH 6.3.
  • Two strips of a conventional multilayer camera speed color film, containing three differently sensitized gelatino silver bromoiodide emulsion layers containing in each layer more than 100 mg. of silver (in silver halide)/ft. and in each layer more than 100 mg. of gelatin/ft. and in each layer a different incorporated color-forming coupler, are lightimage exposed to a wedge step tablet, then given negative development, reversal flash, color development as described by column 11, line 74 through line 36 in column 12 of Carroll et al., US. Pat.
  • Concentrate D of our invention is prepared by dissolving, in one liter of 'water, a mixture of:
  • pH values above 5.0 our blix concentrates have increased activity, due not only to the greater concentration, but also due to the absence of the oxygen-bridged dimer herein described, the formation of which is prevented by the operation of our invention which uses high ratios of the secondary ligand.
  • this embodiment of our invention is worked at lower concentration levels of the ferric ion primary ligand complex and at lower ratios of the secondary ligands using another group of secondary ligands.
  • the following examples are included:
  • Blix Concentrate F of our invention is prepared by dissolving, in one liter of water, a mixture of and then adjusting the pH to 6.6, preferably by adding NH OH or H 50 as is required.
  • Blix Concentrate Z outside of our invention, is prepared having the following composition: 1
  • Blix Concentrates E and F of our invention have a secondary ligand used at a mole ratio of about 1:1 with respect to the ferric ionprimary ligand complex. Dimerization is thereby suppressed and solubility is increased.
  • Blix Concentrate Z uses a secondary ligand which increases solubility of the ferric ion complex, but decreases the blix rate as is shown by the following comparisons: Three strips of the multilayer camera speed film described in Example 2 are exposed to a wedge step tablet and processed as described in Example 2, except that Blixes E, F and Z are used in place of the blix baths used in Example 2.
  • the blix times required to remove silver with these blixes are 6.25 mins. 7.5 mins. and 15 mins., respectively. These data clearly show the novel reactivity of our blixes and the specific nature of the secondary ligand. While the ratio of secondary ligand to ferric-ion primary ligand complex must be at least 5:1 for the thiocyanate ion, the data in this example show that ratios as low as 1:1 are advantageous for other secondary ligands, such as, boric acid and sodium fluoride, set forth in Blixes E and F, respectively, above.
  • secondary ligands such as, boric acid and sodium fluoride
  • the Blix Concentrates E and F are advantageously diluted to lower strength if the very high blix activity of the concentrates is not required as, e.g., in blixing low silver containing photographic elements, e.g., elements for reflection prints.
  • Blix solutions using as the secondary ligands borate ion, fluoride ion, are not described in the prior art.
  • Blix Concentrate H is prepared like Blix Concentrate G but substituting for the 125 g. of thiourea, an equimolar amount of N(fl-hydroxyethyl)-N'-methy-lthiourea.
  • Blix Concentrate A of our invention, described in Example 1 and immediate Blix Concentrates G and H are each used to blix a different strip of the conventional multilayer camera speed color film described in Example 2 after light-image exposure, negative development, reversal flash, color development, acid stop bath (all as described in Example 2).
  • Our Blix Concentrates A, G and H give results similar to that given by our Blix Concentrate B in Example 2:
  • our Blix Concentrates A, B, C, D, E, F, G and H are used advantageously for blixing camera speed photographic elements at pHs other than shown specifically in the examples, but at pHs in the range of from about 5 to 9. These solutions are also advantageously used as they are, or diluted for blixing color elements which contain less silver and gelatin than the camera speed elements.
  • composition comprising:
  • bleaching agent for silver to produce, when dissolved in water with (b) and (c), a concentration in the range of from about 0.4 mole/ l. to about 2.0 moles/l. of said bleaching agent which is a salt with an unchelated cation selected from the class consisting of an alkali metal, ammonium and a water-soluble organic amine having an ionizable proton on a nitrogen atom in said amine and with an anion that is a complex of ferric ion chelated with a multidentate primary ligand;
  • a blix composition comprising:
  • L, L. L and L each represent a member selected from the class consisting of a carboxy and a phosphono group
  • G, G, G and G each represent a divalent group selected from the class consisting of an alkylene group, an arylene group and a heterocyclene group
  • a water-soluble monodentate secondary ligand selected from the class consisting of a thiocyanate, a fluoride and a thiourea to produce, when dissolved in water with (a) and (c), a mole ratio of said thiocyanate to (a) of at least 5 :1, a mole ratio of said fluoride to (a) of at least 1:1 and amole ratio of said thiourea to (e) of at least 3:1;
  • a blix composition comprising:
  • L, L, L and L each represent a member selected from the class consisting of a carboxy and a phosphono group
  • G, G, G and G each represent a divalent group selected from the class consisting of an alkylene group, an arylene group and a heterocyclene group
  • R represents a member selected from the class consisting of hydrogen, methyl and hydroxyethyl
  • R9 represents a member selected from the class consisting of hydrogen, methyl, hydroxyethyl, -NII2, NHCH --N(CH3)z, NHCH CH OH,
  • R represents a member selected from the class consisting of hydrogen, methyl, hydroxyethyl, NH NHCH R represents a member selected from the class consisting of hydrogen, methyl, and hydroxyethyl, said thiourea containing at least one --NH-grup;
  • a water-soluble fixing agent selected from the class consisting of a thiosulfate, a thiocyanate, a thiourea and a thioether to produce, when dissolved in water with (a) and (b), a concontration in the range of from 0 to about 1.5 moles/l.
  • composition of claim 1 in which the primary ligand is ethylenediamine tetraacetic acid.
  • composition of claim 1 in which the primary ligand is N-(B-hydroxyethyl)ethylenediamine triacetic acid.
  • An aqueous blix composition containing 180 g./l. of sodium ethylenedinitrilotetraacetato ferrate III hydrate, 150 g./l. of ammonium thiocyanate at a pH of 5.
  • An aqueous blix composition containing 300 g./l. of sodium ethylenedinitrilotetraacetato ferrate III bydrate, 6O0 g./l. of ammonium thiocyanate at a pH of 6.7.
  • An aqueous blix composition containing 180 g./l. of ethylenedinitrilo (B-hydroxyethyl)triacetato ferrate III and 200 g./l. of ammonium thiocyanate at a pH of 6.0.
  • An aqueous blix composition containing 150 g./l. of sodium ethylenedinitrilotetraacetato ferrate H1 hydrate, 27 g./l. of boric acid, 166 ml./l. of 60% solution of ammonium thiosulfate at a pH of 6.5.
  • An aqueous blix composition containing 180 g./l. of sodium ethylenedinitrilotetraacetato ferrate I'II hydrate, 17 g./l. of sodium fluoride, l0 g./l. of sodium sulfite and 200 ml./l. of 60% solution of ammonium thiosulfate at a pH of 6.6.
  • a process for bleaching and fixing an imagewise, color-developed color element to remove silver from image areas and to remove silver halide from non-image areas comprising the step of contacting said silver and said silver halide with an aqueous blix solution containing:
  • a bleaching agent in the concentration range of from about 0.4 mole/l. to about 2.0 moles/l. of said bleaching agent which is a salt with an unchelated cation selected from the class consisting of an alkali metal, ammonium and a water-soluble amine having an ionizable proton on a nitrogen atom in said amine and with an anion that is a complex of ferric ion chelated with a multidentate primary ligand selected from those having the formula:
  • L, L, L and L each represent a member selected from the class consisting of a carboxy and a phosphono group
  • G, G, G and G each represent a divalent group selected from the class consisting of an alkylene group, an arylene group and a heterocyclene group
  • a water-soluble monodentate secondary ligand selected from the class consisting of a thiocyanate, a fluoride and a thiourea having the formula:
  • R represents a member selected from the class consisting of hydrogen, methyl and hydroxyethyl
  • R represents a member selected from the class consisting of hydrogen, methyl, hydroxyethyl
  • NHCH CH OH, --N(CH CH OH) and N(CH )CH,CH OH R represents a member selected from the class consisting of hydrogen, methyl, hydroxyethyl NH NHCHg, N
  • CH R represents a member selected from the class consisting of hydrogen, methyl and hydroxyethyl, said thiourea containing at least oneNH group; and with a mole ratio of said thiocyanate to (a) of at least 5:1, a mole ratio of said fluoride to (a) of at least 1:1, and a mole ratio of said thiourea to (a) of at least 3:1, and
  • a water-soluble silver halide fixing agent in the concentration range of from 0 to about 1.5 moles/ 1., said blix solution containing said fixing agent when (b) is selected from the class consisting of a borate, boric acid and a fluoride until said silver and said silver halide are removed from said color-developed color element.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US23022A 1970-03-23 1970-03-23 Compositions for making blixes Expired - Lifetime US3706561A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US2302270A 1970-03-23 1970-03-23

Publications (1)

Publication Number Publication Date
US3706561A true US3706561A (en) 1972-12-19

Family

ID=21812678

Family Applications (1)

Application Number Title Priority Date Filing Date
US23022A Expired - Lifetime US3706561A (en) 1970-03-23 1970-03-23 Compositions for making blixes

Country Status (13)

Country Link
US (1) US3706561A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS5414499B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE764664A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA976021A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CH (1) CH527444A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CS (1) CS154321B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2113801C3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES389251A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2083830A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1340131A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
SE (1) SE364785B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
SU (1) SU416970A3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ZA (1) ZA711375B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3893858A (en) * 1973-03-26 1975-07-08 Eastman Kodak Co Photographic bleach accelerators
US3907568A (en) * 1971-10-22 1975-09-23 Fuji Photo Film Co Ltd Process for regenerating blixing solution for color photographic processing
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
US3997348A (en) * 1973-07-13 1976-12-14 Fuji Photo Film Co., Ltd. Color photographic processing method
US4028103A (en) * 1976-04-12 1977-06-07 Eastman Kodak Company Processing compositions for color transfer processes comprising alkali metal fluorides and oxalates
US4033771A (en) * 1973-08-16 1977-07-05 Eastman Kodak Company Stabilized bleach-fixing baths
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
EP0266797A2 (en) 1986-11-07 1988-05-11 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material and photographic color developing composition
US4818673A (en) * 1986-08-05 1989-04-04 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material
EP0313083A2 (en) 1987-10-22 1989-04-26 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0317983A2 (en) 1987-11-27 1989-05-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0320939A2 (en) 1987-12-15 1989-06-21 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0435334A2 (en) 1989-12-29 1991-07-03 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing yellow colored cyan coupler
EP0440195A2 (en) 1990-01-31 1991-08-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0452886A2 (en) 1990-04-17 1991-10-23 Fuji Photo Film Co., Ltd. Method of processing a silver halide color photographic material
EP0456210A2 (en) 1990-05-09 1991-11-13 Fuji Photo Film Co., Ltd. Method for processing a silver halide photographic material and light-sensitive material for photographing
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0563985A1 (en) 1992-04-03 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0631185A1 (en) 1993-06-11 1994-12-28 Fuji Photo Film Co., Ltd. Method for continuously processing silver halide color photosensitive material
EP0654705A2 (en) 1993-11-24 1995-05-24 Fuji Photo Film Co., Ltd. Photographic processing composition and method of photographic processing using the same
EP0686875A1 (en) 1994-06-09 1995-12-13 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic materials
EP0720049A2 (en) 1990-05-09 1996-07-03 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method using the same
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US6022680A (en) * 1996-06-11 2000-02-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530828B1 (en) * 1991-09-05 1998-12-02 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method
JP2889999B2 (ja) * 1991-09-05 1999-05-10 富士写真フイルム株式会社 写真用処理組成物及び処理方法

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907568A (en) * 1971-10-22 1975-09-23 Fuji Photo Film Co Ltd Process for regenerating blixing solution for color photographic processing
US3893858A (en) * 1973-03-26 1975-07-08 Eastman Kodak Co Photographic bleach accelerators
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
US3997348A (en) * 1973-07-13 1976-12-14 Fuji Photo Film Co., Ltd. Color photographic processing method
US4033771A (en) * 1973-08-16 1977-07-05 Eastman Kodak Company Stabilized bleach-fixing baths
US4028103A (en) * 1976-04-12 1977-06-07 Eastman Kodak Company Processing compositions for color transfer processes comprising alkali metal fluorides and oxalates
USRE29942E (en) * 1976-04-12 1979-03-20 Eastman Kodak Company Processing compositions for color transfer processes comprising alkali metal fluorides
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
US4818673A (en) * 1986-08-05 1989-04-04 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material
EP0266797A2 (en) 1986-11-07 1988-05-11 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material and photographic color developing composition
EP0313083A2 (en) 1987-10-22 1989-04-26 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0317983A2 (en) 1987-11-27 1989-05-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0320939A2 (en) 1987-12-15 1989-06-21 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0435334A2 (en) 1989-12-29 1991-07-03 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing yellow colored cyan coupler
EP0440195A2 (en) 1990-01-31 1991-08-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0452886A2 (en) 1990-04-17 1991-10-23 Fuji Photo Film Co., Ltd. Method of processing a silver halide color photographic material
EP0456210A2 (en) 1990-05-09 1991-11-13 Fuji Photo Film Co., Ltd. Method for processing a silver halide photographic material and light-sensitive material for photographing
EP0720049A2 (en) 1990-05-09 1996-07-03 Fuji Photo Film Co., Ltd. Photographic processing composition and processing method using the same
EP0476327A1 (en) 1990-08-20 1992-03-25 Fuji Photo Film Co., Ltd. Data-retainable photographic film product and process for producing color print
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563985A1 (en) 1992-04-03 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0631185A1 (en) 1993-06-11 1994-12-28 Fuji Photo Film Co., Ltd. Method for continuously processing silver halide color photosensitive material
EP0654705A2 (en) 1993-11-24 1995-05-24 Fuji Photo Film Co., Ltd. Photographic processing composition and method of photographic processing using the same
EP0686875A1 (en) 1994-06-09 1995-12-13 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic materials
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US6022680A (en) * 1996-06-11 2000-02-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Also Published As

Publication number Publication date
ZA711375B (en) 1971-11-24
CH527444A (fr) 1972-08-31
DE2113801C3 (de) 1979-07-05
CS154321B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-03-29
DE2113801B2 (de) 1978-11-02
SE364785B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-03-04
GB1340131A (en) 1973-12-12
FR2083830A5 (fr) 1971-12-17
JPS5414499B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1979-06-07
CA976021A (en) 1975-10-14
SU416970A3 (ru) 1974-02-25
BE764664A (fr) 1971-08-16
DE2113801A1 (de) 1971-10-14
ES389251A1 (es) 1973-06-16

Similar Documents

Publication Publication Date Title
US3706561A (en) Compositions for making blixes
US3615508A (en) Photographic blixes and blixing
US4144068A (en) Method for color photographic processing
US3870520A (en) Photographic processing composition
JPS6327706B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
US4242442A (en) Method for processing silver halide color photographic material
US3770437A (en) Photographic bleach compositions
JPS6026210B2 (ja) ハロゲン化銀カラ−写真材料の処理方法
US4038075A (en) Development of photographic silver halide material
JP2622839B2 (ja) 漂白用パーツ組成物
JPS609255B2 (ja) ハロゲン化銀カラ−写真感光材料の処理方法
US4737450A (en) Method for bleach-fixing of photographic elements
JPS5944626B2 (ja) カラ−写真処理法
JPS6119982B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
US3846130A (en) Process for developing photographic elements
JPS6016616B2 (ja) ハロゲン化銀カラ−写真感光材料の処理方法
US4605611A (en) Method for processing silver halide color photographic material
JPS6150140A (ja) ハロゲン化銀カラ−写真感光材料の処理方法
US4717649A (en) Photographic bleach-fixing compositions
US3642478A (en) Processes and compositions for converting zero valent metals photographic images to formazan dye images
US4070188A (en) One bath type silver dye bleaching and silver bleaching
JPS61143755A (ja) カラ−写真感光材料の処理方法
JPH07219173A (ja) 像様露光して現像したハロゲン化銀写真要素の処理方法
US4299913A (en) Photographic reversal process without second exposure
US4229521A (en) Method of processing photographic materials