US3676136A - Photographic stabilizer compositions - Google Patents

Photographic stabilizer compositions Download PDF

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US3676136A
US3676136A US48547A US3676136DA US3676136A US 3676136 A US3676136 A US 3676136A US 48547 A US48547 A US 48547A US 3676136D A US3676136D A US 3676136DA US 3676136 A US3676136 A US 3676136A
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acid
group
color
bisulfite
stabilizer
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Rowland G Mowrey
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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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

  • Aqueous stabilizer compositions comprising 1) a Water-soluble addition complex of an alkali metal bisulfite and an aldehyde that preferably contains from one to six carbon atoms and from one to three carbonyl groups with at least one of the carbonyl groups being part of an aldehyde group in the concentration range of from about 0.5 g./l. to about 100 g./l.
  • a buffer comprising (a) an acid, such as, sulfuric, nitric, phosphoric, boric, hydrochloric acids and organic carboxylic acids in the concentration range of from about 0.5 g./l. to about 2'5 g./l.
  • This invention is related to color photography, color photographic processing, photographic processing compositions and more particularly to photographic stabilization compositions and to the stabilization of color photographic images.
  • Multicolor, multilayer photographic elements are well known in the art of color photography. Usually, these photographic elements have three different selectively sensitized silver halide emulsion layers coated on one side of a single support.
  • One emulsion layer is blue-sensitive, another green-sensitive and another red-sensitive.
  • these layers can be arranged on a support in any order, they are most commonly arranged with the support coated in succession with the red-sensitized layer, the green-sensitized layer and the blue-sensitive layer (advantageously with a bleachable blue light-absorbing filter layer between the blue-sensitive layer and the greensen'sitized layer) or with the opposite arrangement and no filter layer.
  • Colored photographic images are formed from latent images in the silver halide emulsion layers during color development by the coupling of oxidized aromatic primary amine color developing agent with couplers present either in the color developer solution or incorporated in the appropriate light-sensitive layers.
  • Photographic elements containing incorporated couplers usually have a nondiifusible phenolic or naphthalic coupler that forms a nondilfusible cyan dye in the red-sensitized emulsion layer, a nondiifusible S-pyrazolone or 2-(a-cyanoacetyl)coumarone coupler that forms a nondiifusible magenta dye in the green-sensitized emulsion layer and a non-diffusible open-chain ketomethylene coupler that forms a nondiifusible yellow dye in the bluesensitive emulsion layer.
  • Couplers and dyes used in color photographic systems are subject to degradation by heat, humidity and actinic radiation. Residual incorporated couplers in processed photographic elements generice ally turn yellow with such treatment, while dyes generally fade or change hue and fade. In medium-to-low density regions of color photographs, where excess coupler is present with the dye (in incorporated coupler systems), it is known that coupler and dye can react slowly with one another and thus degrade a color image.
  • Stabilizing baths are desired that not only reduce fading and staining from exposure to high humidities and high temperatures, but also reduce the dye image fading and hue shift produced by prolonged exposure to light. Stabilizing baths are also desired that will give this additional protection with shorter treatment times than is required by the prior art. Stabilizer baths are desired whose efiee tiveness does not change with concentration changes within the operating limits.
  • an object of my invention to provide a novel stabilizer composition which is valuable as a final treatment bath in a color process to reduce dye image fading and hue shift caused in the finished color photograph by prolonged exposure to light, as well as to reduce the dye image fading and stains produced in the finished color photograph by exposure to high humidities and high temperatures.
  • compositions for use in stabilizing a processed color photographic element said composition com prising:
  • At least one water-soluble addition complex of an alkali metal bisulfite and an aldehyde is advantageously used in aqueous solution having a pH in the range of from 3 to 7 and containing a total concentration of addition complex in the range of from about 0.5 g./l. to about g./l. with a particularly useful range being from about 1 g./l. to about 50 g./l.
  • a more preferred composition comprises:
  • An even more preferred composition comprises:
  • a dye image either in the presence or absence of excess reactants used to form the dye is stabilized by contacting the dye image with my aqueous stabilizer solution having a pH in the range of from 3 to 7 and containing an addition complex of an alkali metal bisulfite and an aldehyde, and then drying the treated dye image in the presence of the stabilizer solution.
  • My stabilizing process is advantageously used to stabilize the dye image, usually an indoaniline dye or an azomethine dye, regardless of the method used to form the dye image and regardless of the binder or carrier in which the dye image is formed.
  • alkali metal bisulfite and aldehyde are advantageously made from any of the alkali metal bisulfites (e.g., sodium, potassium, lithium, etc.) and aldehydes that preferably contain from one to six carbon atoms and from one to three carbonyl groups with at least one of the carbonyl groups being part of an aldehyde group.
  • alkali metal bisulfites e.g., sodium, potassium, lithium, etc.
  • aldehydes that preferably contain from one to six carbon atoms and from one to three carbonyl groups with at least one of the carbonyl groups being part of an aldehyde group.
  • Aldehydes used to advantage are included in those having the formulas:
  • R is a member, such as, hydrogen, a lower alkyl group having from 1 to carbon atoms, e.g., lower alkyl (e.g., methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-am'yl, isoamyl, isopropyl, n-butyl, iso-butyl, tbutyl, n-amyl, isoamyl, t-amyl, etc.), hydroxy lower alkyl (e.g., hydroxyethyl, hydroxybutyl, hydroxyamyl, etc.), halogenated lower alkyl (e.g., chloroethyl, chlorobutyl, bromoethyl, fluoroethyl, etc.), lower alkoxy lower alkyl (e.g., methyl, ethyl, propyl, iso
  • Acids used advantageously in my compositions include inorganic acids (such as, sulfuric acid, nitric acid, boric acid, hydrochloric acid, etc.) and organic carboxylic acid including those having the formula:
  • R represents a member such as hydrogen, a lower alkyl group having from 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, amyl, cyclohexyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, methoxyethyl, aminoethyl, N-methylaminoethyl, Z-methoxycarbonylethyl, 2-ethoxycarbonylethyl, sulfoethyl, sulfopropyl, sulfobutyl, carbamylethyl, carbamylpropyl, u-amino carbamylethyl, ahydroxybenzyl, benzyl, phenethyl, a-aminophenethyl, uamino-4-hydroxyphenethyl, etc.), a carbonyl group [e.g., an alkoxycarbonyl group
  • L represents a member, such as, a bond, an alkylene group having from 1 to 6 carbon atoms (e.g., methylene, ethylene, propylene, isopropylene, hexylene, hydroxyethylene, hydroxypropylene, dihydroxyethylene, dihydroxypropylene, methoxyethylene, ethoxyethylene, carboxylmethylene, carboxyethylene, carboxyh'ydroxymethyl, carboxymethoxyethyl, carboxyethoxyethyl, carboxybutoxypropyl, etc); a vinylene group (e.g. vinylene); a phenylene group (e.g., phenylene, chlorophenylene, methylphenylene, etc.); all organic carboxylic acid having the formula:
  • R6 Ra Rio N -group I I I l R5 R1 L Rn u CEL -C0011 R2, R3, R4, R5, R5, R7, R3, R9, R10 and R11 CaCh represent the same or ditferent member, such as, hydrogen, hydroxyl, an amino group, nitro halogen a lower alkyl group having from 1 to 6 carbon atoms (e.g.
  • V R12SO3H wherein R represents a group, such as, a lower alkyl group having from 1 to 7 carbon atoms (e.g., methyl, ethyl, propyl, etc.) and a phenyl group (e.g., phenyl, tolyl, etc.).
  • My preferred stabilizer compositions are non-polluting and use acids (when needed) other than phosphoric or boric.
  • My alkali metal aldehyde bisulfite addition complexes are advantageously made by reacting an alkali metal bisulfite (e.g., sodium, potassium, lithium, etc. salt of the bisulfite ion) with an aldehyde having from 1 to 5 carbon atoms, including the carbon atoms in from 1 to 3 carbonyl groups, at least one of which is part of a formyl group.
  • aldehydes include, formaldehyde, acetaldehyde, propionaldehyde, malonaldehyde, succinaldehyde, glutaraldehyde, glyoxylic acid, propane 3-al carboxylic acid, etc.
  • the last two aldehydes listed also contain a carboxy group.
  • antioxidants e.g., glucose, galactose, sorbitol, mannitol, etc.
  • any water-soluble optical brighteners that are commercially available, any commercial wetting agents that are used to prevent the formation of drying spots, etc.
  • My stabilizer compositions will stabilizer a color photographic image regardless of the method which is used to form the dyes. Any dye image formed by reaction of an oxidized p-phenylenediamine developing agent with a coupler is advantageously stabilized. It is believed that dyes are stabilized by virtue of the mild reducing properties of the aldehyde bisulfite addition complex, while the residual unreacted coupler, if present, is prevented from yellowing by having reacted at the active site with the aldehyde.
  • any color photographic elements are advantageously used in my invention, including those described in patent references, such as, Mannes et al., U.S. Pat. 2,252,718; Froehlich et al., U.S. Pat. 2,376,679; Vittum et al., (US. Pat. 2,322,027; Fierke et al., US. Pat. 2,801,171; Godowsky, US. Pat. 2,698,794; Barr et al., US. Pat. 3,227,554; Graham, US. Pat. 3,046,129; Martinez, US. Pat. 2,284,- 877 and Wolf et al., US. patent application Ser. No. 634,- 104, now Pat. No. 3,516,831, filed Apr. 27, 1967.
  • any of the photographic silver halide emulsions e.g., silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver bromochloroiodide, etc.
  • silver halide emulsions including coarse grain or fine grain prepared by well-known procedures are used.
  • 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 dextrose, gum arabic, etc. and synthetic polymeric substances, such as, soluble polyvinyl compounds like poly (vinylpyrrolidone) acrylamide polymers, etc.
  • Any of the known Z-equivalent and 4-equivalent nondififusible colorforming couplers known in the art are advantageously used in emulsions that contain incorporated couplers.
  • the phenolic and naphtholic couplers are advantageously used as cyan-dye-formers; the S-pyrazolone couplers are advantageously used as magenta-dye formers and the openchain ketomethylene couplers are advantageously used as yellow-dye-formers.
  • the nondiffusible couplers used to advantage are those described in column 4 through 10 of Wolf et al., US. patent application Ser. No. 634,104, now Pat. No. 3,516,831, filed Apr. 27, 1967.
  • the light-sensitive layers of photographic elements are advantageously coated on a wide variety of photographic supports including cellulose nitrate film, cellulose acetate film, polyacetal film, polystyrene film, polyterephthalate film, polyethylene film and related films of resinous materials as well as paper, glass and others.
  • color photographic elements such as those described above, are usually color processed according to one or" the following process cycles:
  • a rapid jet rinse or dip rinse of the emulsion surface of the photographic element is possible, provided that it is not sufficient to Wash the stabilizing compound out of the dye-containing layers.
  • the drying step is usually carried out at elevated temperatures that drive off free aldehyde, such as, formaldehyde that is used as a stabilizing agent in some prior art stabilizers. Loss of the free aldehyde from the element during the drying step following stabilization with a prior art formaldehyde stabilizer represents a substantial loss in the active stabilizing agent from the photographic element with the accompanying loss in stabilization of the color image.
  • My invention gives improved light stability at very low treatment times in addition to the advantages of the stabilizer of the prior art.
  • the maximum treatment times for my stabilizer treatments are 4 minutes at 24 C., 3 minutes at 29 C. and 1 minute at 38 C. while the pre ferred treatment times are 2 minutes at 24 C., 1 minute at 29 C. and 30 seconds at 38 C.
  • the time required to optimize stabilization is independent of stabilizer concentration but the maximum degree of stabilization is dependent upon concentration.
  • the use of formaldehyde and formaldehyde-bisulfite as a hardening agent in prehardener solutions used in color processing is not to be confused with my invention.
  • the prehardening step where used is the first step of a color process and essentially all of the formaldehyde and formaldehyde-bisulfite complex is removed from the photographic element before the developer step, so obviously there would be no formaldehyde or its bisulfite addition complex left in the photographic element following the 4 to 7 additional process steps (including washes) preceding the stabilization step.
  • Sulfite or bisulfite ions are not generally used in a final bath in color photographic processing because these ions have been known to destroy cyan dyes made from conventional cyan-dye-for ming couplers.
  • sulfite and bisulfite ions are used in a stabilization bath to preserve retained hypo and color developing agent.
  • a stabilizer composition is prepared by dissolving sodium formaldehyde bisulfite addition complex in water with sulfuric acid or sodium hydroxide to produce a solution of 5 g./l. of sodium formaldehyde bisulfite complex having a pH of 7.
  • Strip No. Process steps 1 Wash 3 minutes and dry. 2 Wash 2 minutes, stabilize 1 minute in a bath containing 5 g./1. of sodium formaldehyde bisulfite addition complex and enough sulfuric acid and/or sodium hydroxide to adjust the pH to 7, and dry.
  • the samples are equally white at the end of the process. They are then subjected to 14 days treatment in an oven held at C./% relative humidity and the stain increase is measured at 420 nm.
  • the stain increases are as follows:
  • My stabilizer composition is seen to be an effective agent in retarding stain growth due to decomposition of couplers and other components in a color processed color photographic element.
  • Example 1 is repeated three times, but the samples are image exposed respectively to red, green and blue light, and the dye loss is measured after the test is complete. There are no deleterious effects due to the stabilizer. This shows that the sulfite and bisulfite ions are so constituted in the addition compound that they do not harm the dyes.
  • Example 1 is repeated, but using as the stabilizer a solution comprising 5 g./l. of sodium formaldehyde bisulfite, 1 g./l. of concentrated sulfuric acid and enough of a 40% solution of sodium hydroxide to adjust the solution to a pH of 4.5.
  • the results are substantially the same as obtained in Example 1, with effective retardation of stain growth being provided by my stabilizer composition.
  • Example 2 is repeated, using the stabilizer solution described in Example 3. The results are substantially the same as described in Example 2, i.e., no detrimental elfect from sulfite and bisulfite upon image dye.
  • magenta dye loss at peak wavelength is now measured after two week treatment in the oven as described in 10 stabilizer solution used in Example 1, the stabilizer described hereinabove.
  • EXAMPLE 9 2a, 2b, 2c Green light exposure, Stabilizer compositions B, C and D of my invention and 3a, 3b, 3c Blue light exposure, stabilizer composition Y outside my invention are made containing the following ingredients. These are processed as described in Example 1 through the blix step, then given two minutes water washing, one Stabilize Acid minute stabilizing in the indicated stabilizer and dried. Stabilizer Amn, mt, composition Name g. Name g.
  • Example 1 Four unexposed samples of a as follows multilayer color photographic material on a paper support as described in Example 1 are processed as described in Example 1 through the blix step, then are washed for g sgagag gg ggg ggg 40 two minutes and then each strip is treated for one minute 3 M ma Yellow in a diiferent stabilizer Solution Y, B, C or D described Stabilizer i g dye above. Each strip is arbitrarily identified according to the 1 identification of the stabilizer solution used to treat it. :111:11: g After drying the strips, the stain in the D of each strip 3 5 is measured. The strips are then treated for six days in an oven at 49 C./90% RH.
  • the A Stabilizer Composition A of my invention is made samples treated with the sodium formaldehyde bisulfite y dissolving 40 of Sodium succinaldehyde bisulfite addition product are equal or superior for dye stability to addition complex and hydrochloric acid in water to make h coating treated i f ld h d l one liter of stabilizer Solution A, there being enough hy- EXAMPLE 12 drochloric acid to give a pH of 3.0.
  • a stabilizer Solution X outside my invention, is made by dissolving 40 g. of Example 1 is repeated, using a stabilizer solution consuccinaldehyde in one liter of Water and adjusting the pH taining 5 g./l.
  • Example 7 is repeated, but using in place of the concentrated sulfuric acid and enough of a 40% solution 1 1 of sodium hydroxide to adjust the solution to a pH of 4.8.
  • my stabilizer is shown to be an effective agent in retarding stain growth due to decomposition of couplers and other components in a color processed color photographic element.
  • Example 12 is repeated, using 1 g./l. of concentrated hydrochloric acid in place of sulfuric acid. The results are comparable to those obtained in Examples 1 and 12.
  • Example 2 is repeated, using the stabilizer described in Examples 12 and 13. As in Example 2, the sulfite and bisulfite ions are so constituted in the addition complex of my stabilizer solution that there is no change in dyes.
  • Example 9 is repeated, but instead of using g./l. of citric acid in the stabilizer solution, 18 g./l. of citric and 1 g./l. of benzoic acid, 5 g./l. of acetic acid, 5 g./l. of ethylenediamine tetraacetic acid, 10 g./l. of tartaric acid, 10 g./l. of succinic or g./l. of malic acid, is used.
  • Example 1 is repeated, using 5 g./l. of sodium succinaldehyde bisulfite addition complex instead of sodium formaldehyde bisulfite addition complex. Substantially the same effective retardation of stain growth is obtained in the immediate example as is obtained in Example 1.
  • Example 1 is repeated, using 5 g./l. of sodium propionaldehyde bisulfite addition complex. The results again show the effectiveness of my stabilizers in retarding stain formation.
  • Example 2 is repeated, using 5 g./l. of sodium succinaldehyde bisulfite and then 5 g. l. of sodium propionaldehyde in place of the sodium formaldehyde bisulfite.
  • the results obtained are substantially the same as obtained in Example 2, with no detrimental effect produced by sulfite or bisulfite ions on image dye stability.
  • EXAMPLE 19 Examples 1 and 2 are repeated using 5 g./l. of sodium glutaraldehyde bisulfite addition complex in place of sodium formaldehyde bisulfite addition complex. The results show that the immediate stabilizing composition is effective in reducing stain formation in processed color photographs and that the immediate composition has no deleterious effect on dye images.
  • EXAMPLE 20 Examples 1 and 2 are repeated, using 5 g./l. of sodium malonaldehyde bisulfite addition complex in place of sodium formaldehyde bisulfite addition complex. This example again demonstrates that the immediate element is effectively stabilized against strain growth and that the addition complex is not detrimental to image dyes.
  • Example 9 is repeated, using potassium formaldehyde bisulfite at 3.5 g./l., 10.5 g./l. and 35 g./l. concentrations in place of the sodium formaldehyde bisulfite. Substantially the same results are obtained as are described in Example 9.
  • Example 15 is repeated, but with the solution buffered at pHs of 3.0, 4.0, 5.0, 6.0 and 7.0 by adding the necessary amount of 40% sodium hydroxide solution.
  • the sodium formaldehyde bisulfite is shown to be effective in improving dye stability when comparisons are made with 37% formaldehyde at a pH of 3.0, 4.0, 5.0, 6.0 and 7.0.
  • Examples 1 through 7 are repeated, but using pHs of 3.0, 4.0, 5.0 and 6.0 in place of the pH of 7, used in Examples 1 through 7.
  • Example 8 is repeated, but with the pHs of 4.0, 5.0, 6.0 and 7.0, instead of a pH of 3 used in Example 8. In each instance, "a comparison of the results obtained in an example at a given pH show the superiority of my stabilizer over the stabilizer outside my invention.
  • my stabilizer compositions having the alkali metal aldehyde bisulfite addition complexes illustrated in the preceding examples, as well as the other alkali metal aldehyde bisulfite addition complexes of my invention, are used to advantage at concerntration levels in the range of from about 0.5 g./l. to about g./l. at pHs in the range of from 3 to 7.
  • My stabilizer compositions advantageously contain the acids illustrated in the preceding examples, as well as the other acids of my invention, for adjusting the pHs below 7.
  • my acids are advantageously used in the concentration range of from about 0.5 g./l. to about 25 g./l. with sufiicient alkali metal hydroxide being added to buffer the solution at the desired pH.
  • My stabilizer compositions are advantageously prepackaged without water or with enough water to dissolve one or more of the necessary chemicals in one or more concentrated solutions for dilutioin to the working concentration level for use in a processing machine.
  • My stabilizer compositions are particularly valuable because they are not only very effective in preventing or minimizing the formation of unwanted stain in processed color photographs, but does this without giving ofl? toxic vapors that are characteristic of many of the stabilizers used previously.
  • the stabilizing effect of my compositions persist over a substantially longer period of time than most prior art stabilizers after processing and drying, even at elevated temperatures, because the aldehyde is retained in the photographic element as the addition complex which only very slowly releases aldehyde and bisulfite ion. It is not obvious that the bisulfite ion released would protect the dyes to light fading; however, the data presented in the preceding examples, especially in Examples 2, 4, 14, 18 and 19, show that my stabilizer compositions do protect the image dyes. Use of my stabilizer compositions provide valuable technical advances that are illustrated and discussed herein.
  • composition for use in stabilizing a processed color photographic element that contains dye images comprising:
  • composition for use in stabilizing a processed color photographic element that contains dye images and residual color-forming coupler comprising:
  • composition to a pH in the range of from 3 to 7, said acids being selected from those having the formulas:
  • R represents a member selected from the class consisting of hydrogen, lower alkyl group, a
  • L represents a member selected from the class consisting of a bond, a lower alkylene group vinylene and a phenylene group
  • G represents a group selected from the class consisting of an alkylene group, a phenylene group and a heterocyclene group
  • G represents a group selected from the class consisting of a lower alkylene group, a phenylene group and a heterocyclene group
  • G represents a group selected from the class consisting of a lower alkylene group, a phenylene group and a heterocyclene group
  • Z represents a group selected from the class consisting of a cycloacid, P P Q C id, ydrochloric acid, an organic hexylene group, a phenylene group, a carboxylic acld and an organic sulfonic acid to provide, when dissolved in water with 1) and (3), an R2 group aqueous stabilizer solution having a concentration of
  • 2 3, 4, 5 6, 7 8 9 10 and 11 each represent a member selected from the class consisting of hydrogen, hydroxyl, amino, nitro, a halogen atom, a lower alkyl group and a lower alkoxy group so that no single carbon atom in the structure con- 0 taining said R group contains more than one nitro U and l)n-1 group;
  • p represents an integer of from 2 to 4;
  • R represents an integer of from 1 to 4 and R represents a group selected from the class consisting o a lower alkyl group and a phenyl group.
  • a composition for use in stabilizing a processed color photographic element that contains dye images and residual color-forming coupler comprising- (l) a sufficient amount of at least one water-soluble addition complex of an alkali metal bisulfite and an wherein R is a member selected from the class con- 70 sisting of hydrogen, a lower alkyl group and fury], and n represents an integer of from 1 to 5, to provide, when dissolved in water with (2) and (3 an aqueous stabilizer solution having a concentration of said addition complex in the range of from about 0.5 g./l. to about g./l.;
  • R represents a member selected from the class consisting of hydrogen, a lower alkyl group, a carbonyl group and a phenyl group
  • L represents a member selected from the class consisting of a bond, a lower alkylene group, vinylene and a phenylene group
  • G represents a group selected from the class consisting of an alkylene group, a phenylene group and a hetero cyclone group
  • G represents a group selected from the class consisting of a lower alkylene group, a phenylene group and a heterocyclene group
  • G represents a group selected from the class consisting of a lower alkyleue group, a phenylene group and a heterocyclene group
  • G represents a group selected from the class consisting of a lower alkylene group, a phenylene group and a heterocyclene group
  • Z represents a group selected from the class consistof a cyclohexylene group
  • Ra n represent a member selected from the class consisting of hydrogen, hydroxyl, amino, nitro, a halogen atom, a lower alkyl group and a lower alkoxy group so that no single carbon atom in the structure containing said R group contains more than one hydroxyl group, more than one amino group and more than one nitro group;
  • p represents an integer of from 2 to 4;
  • q represents an integer of from 1 to 4 and R represents a group selected from the class consisting of a lower alkyl group and a phenyl group to provide, when dissolved in water with (1) and (3), an aqueous stabilizer solution having a concentration of said acid in the range of from about 0.5 g./l. to about 25 g./l.; and
  • composition of claim 5 in which said addition complex is a complex of an alkali metal bisulfite and formaldehyde.
  • composition of claim 5 in which said addition complex is a complex of an alkali metal bisulfite and succinaldehyde.
  • composition of claim 5 in which said addition complex is a complex of an alkali metal bisulfite and propionaldehyde.
  • composition of claim 5 in which said addition complex is a complex of an alkali metal bisulfite and glutaraldehyde.
  • composition of claim 5 in which said addition complex is a complex of an alkali metal bisulfite and malonaldehyde.
  • An aqueous solution for use in stabilizing a processed color photographic element comprismg:
  • said solution containing said complex at a concentration in the range of from about 0.5 g./l. to about g./l.
  • An aqueous solution for stabilizing a processed color photographic element comprising:
  • sodium formaldehyde bisulfite at a concentration in the range of from about 0.5 g./l. to about 100 g./l.
  • an acid selected from the class consisting of sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrochloric acid, acetic acid, benzoic acid, tartaric acid, succinic acid, maleic acid, malonic acid, malic acid, citric acid, phthalic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, 1,3- diaminopropanol-N,N,N,N-tetraacetic acid and nitriloacetic acid at a concentration in the range of from about 0.5 g./l. to about 25. g./l.; and
  • An aqueous stabilizer solution for stabilizing a processed color photographic element comprising:
  • sodium formaldehyde bisulfite at a concentration in the range of from about 0.5 g./l. to about 100 g./l.
  • An aqueous stabilizer solution for stabilizing a processed color photographic element comprising:
  • sodium succinaldehyde bisulfite at a concentration in the range of from about 0.5 g./l. to about 100 g./l.
  • an acid selected from the class consisting of sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrochloric acid, acetic acid, benzoic acid, tartaric acid, succinic acid, maleic acid, malonic acid, malic acid, citric acid, phthalic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, 1,3- diaminopropanol-N,N,N',N-tetraacetic acid and nitrilotriacetic acid at a concentration in the range of from about 0.5 g./l. to about 25 g./l.; and
  • An aqueous stabilizer solution for stabilizing a processed color photographic element comprismg:
  • sodium succinaldehyde bisulfite at a concentration in the range of from about 0.5 g./l. to about 100 g./l.
  • aqueous stabilizer solution containing an addition complex of an alkali metal bisulfite and an aldehyde containing from 1 to 6 carbon atoms and from 1 to 3 carbonyl groups, at least one of which is part of a formyl group at a concentration in the range of from about 0.5 g./l. to about 100 g./ 1., said stabilizer solution having a pH in the range of from 3 to 7.
  • R is a member selected from the class consisting of hydrogen, a lower alkyl group and the furyl group; n represents an integer of from 1 to 5 at a concentration in the range of from about 0.5 g./l. to about 100 g./1., said stabilizer solution having a pH in the range of from 3 to 7.
  • R is a member selected from the class consisting of hydrogen, a lower alkyl group and furyl, and n represents an integer of from 1 to said addition complex having a concentration in the range of from about 0.5 g./l. to about 100 g./l. in said solution;
  • an acid selected from those having the formulas:
  • R represents a member selected from the class consisting of hydrogen, a lower alkyl group, a carbonyl group and a phenyl group
  • L represents a member selected from the class consisting of a bond, a lower alkylene group and a phenylene group
  • G represents a group selected from the class consisting of an alkylene group, a phenylene group, a heterocyclene group
  • G represents a group selected from the class consisting of a lower alkylene group, a phenylene group and a heterocyclene group
  • G represents a group selected from the class consisting of a lower alkylene group, a phenylene group and a from the class consisting of a lower alkylene group, a phenylene group and a heterocyclene group
  • Z represents a group selected from the class consisting of the class consisting of a group, a phenylene group and a from the class consisting of a lower alkylene group, a pheny
  • R10 and R11 each represent a member selected from the class consisting of hydrogen, hydroxyl, amino, nitro, a halogen atom, a lower alkyl group and a lower alkoxy group so that no single carbon atom in the structure containing said R group contains more than one hydroxyl group, more than one amino group and more than one nitro group;
  • p represents an integer of from 2 to 4;
  • q represents an integer of from 1 to 4;
  • R represents a group selected from the class consisting of a lower alkyl group and a phenyl group; said acid having a concentration in the range of from about 0.5 g./l. to about 25 g./l. in said solution; and
  • said solution at a pH in the range of from 3 to 7.
  • At least one acid selected from the class consisting of sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrochloric acid, acetic acid, benzoic acid, tartaric acid, succinic acid, maleic acid, malonic acid, malic acid, citric acid, phthalic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, l,3-diaminopropanol-N,N,N, '-tetraacetic acid and nitrilotriacetic acid so that said solution contains a total concentration of acid in the range of from about 0.5 g./l. to about 25 g./l.; and
  • sodium formaldehyde bisulfite at a concentration in the range of from about 0.5 g./1. to about 100 g./l.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US48547A 1970-06-22 1970-06-22 Photographic stabilizer compositions Expired - Lifetime US3676136A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909267A (en) * 1972-12-13 1975-09-30 Fuji Photo Film Co Ltd Stabilization process for color photographic materials
US3997348A (en) * 1973-07-13 1976-12-14 Fuji Photo Film Co., Ltd. Color photographic processing method
US4021247A (en) * 1973-11-13 1977-05-03 Fuji Photo Film Co., Ltd. Method of dispersing organic compounds useful in photography
US4251624A (en) * 1979-02-23 1981-02-17 England Evelyn F Stabilizing colored photographic print against fading and staining
US4336324A (en) * 1980-06-18 1982-06-22 Konishiroku Photo Industry Co., Ltd. Method for the processing of silver halide color photographic light-sensitive materials
US5037725A (en) * 1989-12-11 1991-08-06 Eastman Kodak Company Process for stabilizing photographic elements
EP0506349A1 (en) * 1991-03-28 1992-09-30 Konica Corporation Stabilising solution for lightsensitive silver halide color photographic material, and processing method making use of the stabilizing solution
US5968716A (en) * 1998-02-04 1999-10-19 Eastman Kodak Company Photographic stabilizing processing solution and method of use
US6022674A (en) * 1998-02-04 2000-02-08 Eastman Kodak Company Method of rapid processing using a stabilizing solution

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3522622A1 (de) * 1985-06-25 1987-01-08 Agfa Gevaert Ag Stabilisierbad und verfahren zur herstellung fotografischer bilder
EP0244177B1 (en) * 1986-04-30 1994-05-04 Konica Corporation Method for processing light-sensitive silver halide color photographic material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3909267A (en) * 1972-12-13 1975-09-30 Fuji Photo Film Co Ltd Stabilization process for color photographic materials
US3997348A (en) * 1973-07-13 1976-12-14 Fuji Photo Film Co., Ltd. Color photographic processing method
US4021247A (en) * 1973-11-13 1977-05-03 Fuji Photo Film Co., Ltd. Method of dispersing organic compounds useful in photography
US4251624A (en) * 1979-02-23 1981-02-17 England Evelyn F Stabilizing colored photographic print against fading and staining
US4336324A (en) * 1980-06-18 1982-06-22 Konishiroku Photo Industry Co., Ltd. Method for the processing of silver halide color photographic light-sensitive materials
US5037725A (en) * 1989-12-11 1991-08-06 Eastman Kodak Company Process for stabilizing photographic elements
EP0506349A1 (en) * 1991-03-28 1992-09-30 Konica Corporation Stabilising solution for lightsensitive silver halide color photographic material, and processing method making use of the stabilizing solution
US5278033A (en) * 1991-03-28 1994-01-11 Konica Corporation Stabilizing solution for light-sensitive silver halide color photographic material, and processing method making use of the stabilizing solution
US5968716A (en) * 1998-02-04 1999-10-19 Eastman Kodak Company Photographic stabilizing processing solution and method of use
US6022674A (en) * 1998-02-04 2000-02-08 Eastman Kodak Company Method of rapid processing using a stabilizing solution
US6130028A (en) * 1998-02-04 2000-10-10 Eastman Kodak Company Photographic stabilizing processing solution and method of use

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CA955788A (en) 1974-10-08
GB1350296A (en) 1974-04-18
FR2099781A5 (enExample) 1972-03-17

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