EP0034793B1 - Procédé pour le traitement de matériaux pour la décoloration des colorants à l'argent, compositions appropriées à la décoloration et leur préparation à partir de concentrés et concentrés partiels, les concentrés et concentrés partiels - Google Patents

Procédé pour le traitement de matériaux pour la décoloration des colorants à l'argent, compositions appropriées à la décoloration et leur préparation à partir de concentrés et concentrés partiels, les concentrés et concentrés partiels Download PDF

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Publication number
EP0034793B1
EP0034793B1 EP81101124A EP81101124A EP0034793B1 EP 0034793 B1 EP0034793 B1 EP 0034793B1 EP 81101124 A EP81101124 A EP 81101124A EP 81101124 A EP81101124 A EP 81101124A EP 0034793 B1 EP0034793 B1 EP 0034793B1
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Prior art keywords
acid
component
bleaching
silver
optionally
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Expired
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EP81101124A
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German (de)
English (en)
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EP0034793A2 (fr
EP0034793A3 (en
Inventor
Hansjörg Dr. Buser
Adolf Morand
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Novartis AG
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Ciba Geigy AG
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Priority to DE8484108556T priority Critical patent/DE3175718D1/de
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Publication of EP0034793A3 publication Critical patent/EP0034793A3/de
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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
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/44—Bleaching; Bleach-fixing

Definitions

  • the present invention relates to a new process for processing exposed and developed silver color bleaching materials and to preparations suitable for this process in the form of ready-to-use aqueous solutions or of water-dilutable concentrates in liquid or solid form.
  • the preparations (baths) used for the color and / or silver bleaching or the combined bleach-fixation are strongly acidic, i.e. H. have a pH of less than 2, especially less than 1.
  • This pH is generally set using strong acids, primarily mineral acids, such as hydrochloric acid, sulfuric acid, nitric or phosphoric acid, and also sulfamic acid. Good results are also obtained with certain strong organic acids, such as p-toluenesulfonic acid.
  • the mineral acids most commonly used for bleaching baths so far have some important disadvantages that can have an adverse effect on general use. So z. B. hydrochloric acid highly volatile and therefore has a particularly corrosive effect on z. B.
  • the sulfamic acid which is suitable per se and can easily be prepared in free-flowing powder form, can in many cases be used as a substitute for liquid mineral acids.
  • One disadvantage is their relatively poor solubility in water. It has also been shown that it reacts with tertiary phosphines, which are used as bleach accelerators, and leads to unstable bleach baths.
  • p-Toluenesulfonic acid which can also be used in free-flowing powder form, has a high water solubility and provides stable bleaching baths.
  • the object of the present invention is to provide strong mineral acids, as are required in the processing of photographic silver color bleaching materials, in a suitable form in order to overcome the disadvantages mentioned above.
  • the invention further relates to the preparations for carrying out the process, furthermore the concentrates and partial concentrates for the production of the ready-to-use aqueous preparations, and also a process for the production of the aqueous preparations.
  • the acid amides used to prepare the adducts with the strong mineral acids are those of low molecular weight aliphatic acids, ie with 1 to 4, in particular 1 or 2, carbon atoms, and also of monocyclic aromatic acids, such as, in particular, optionally with alkyl (C 1 -C 4 ) , Halogen, nitro or cyano substituted benzoic acids as well as the diamides (ureas) of carbonic and thiocarbonic acids.
  • the nitrogen atoms of the amides can be mono- or in particular disubstituted with alkyl having 1 to 4 carbon atoms, in particular with methyl.
  • suitable amides are thiourea, benzamide and preferably urea, formamide, dimethylformamide, acetamide and dimethylacetamide.
  • Suitable lactams are those of y-, ⁇ - and e-amino acids (4 to 6 carbon atoms), which may be substituted on the nitrogen atom with lower alkyl (C 1 -C Q ), in particular with methyl.
  • lactams mentioned are piperidone (ö-valerolactam), and in particular 2-pyrrolidone (y-butyrolactam), N-methyl-2-pyrrolidone and caprolactam.
  • Possible strong mineral acids are phosphoric acid and perchloric acid, and in particular sulfuric acid, hydrochloric acid or other hydrohalic acids (HBr, HJ) and nitric acid.
  • Table 1 shows the composition of the properties of various mineral acid adducts of amides and lactams.
  • the generally colorless and stable addition compounds are partly liquid and partly occur in crystallized form. As far as possible, the melting points of crystalline products are given.
  • the connections are partly hygroscopic.
  • the mineral acid adducts of urea are particularly well known, in particular the adducts of one mole of urea with 0.5 or 1 mole of sulfuric acid.
  • Information about the properties of these adducts, about their stability, the reaction kinetics in the melt and in aqueous solutions can be found u. a. with L. H. Dalman, J. Am. Chem. Soc. 56, 549 (1934), P. Baumgarten, Chem. Ber. 69, 1929 (1936), E. Cherbuliez & F. Landolt, Helv. 29, 1438 (1946) and G. M. Schwab & E. Schwab-Agallidis, Angew. Chemie, 65, 418 (1953).
  • the mineral acid adducts of urea are produced either directly from the components or their solutions or also by the action of mineral acids on cyanamide, the latter decomposing to urea, which then forms the addition compound with the acid.
  • the adducts used according to the invention are stable in solid form and can easily be prepared in the form of free-flowing water-soluble powders or granules.
  • the adducts of urea with sulfuric or nitric acid are preferred, furthermore thiourea with sulfuric acid and acetamide with hydrochloric acid.
  • the melt can by suitable methods, such as. B. be used in the production of alkali metal hydroxides (see. Ullmanns Encyklopadie der industrial chemistry, 4th edition, Verlag Chemie, Weinheim, Vol. 17 (1979), pp. 204 f), converted into a solid form suitable for the application .
  • it can be crystallized in the form of freely flowing pearls, pills, flakes or flakes that are immediately soluble in water.
  • the sulfuric acid adducts can be brought into the form of pearls if they are z. B. sprayed in a cooling tower.
  • the sulfuric acid adducts of urea can also be prepared in an aqueous medium. Thereafter, urea is introduced into an aqueous sulfuric acid solution at about 50 ° C. with stirring. This gives a suspension of the crystallizing urea sulfate, which is filtered off and optionally dried (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, Verlag Chemie, Weinheim, 2, 154, 672, 698 (1972)).
  • solid, hygroscopic acids can also be brought into a less hygroscopic form.
  • trichloroacetic acid and p-toluenesulfonic acid completely melt when exposed to an atmosphere with 76% relative humidity.
  • the adducts of these acids with z. B. urea, pyrrolidone or thiourea remain under the conditions mentioned in crystalline form.
  • the most important constituents of the baths used for color bleaching are a strong acid in the form of the acid adduct (a), a complexing agent for the silver (b) and a color bleaching catalyst (c).
  • Diazine compounds such as pyrazine, quinoxaline or phenazine and their derivatives are primarily used as color bleaching catalysts.
  • Suitable bleaching catalysts are e.g. B. from German patents and patent publications Nos. 735 672, 1 547 720, 2 144 297, 2 144 298, 2 722 776 or 2 722 777 known.
  • a suitable silver complexing agent can e.g. B. be thiourea.
  • a water-soluble iodide alkali metal iodide, preferably sodium or potassium iodide, furthermore ammonium iodide
  • an antioxidant must be used to prevent the iodide from oxidizing to iodine.
  • Reductones or water-soluble mercapto compounds are advantageously used as antioxidants (d).
  • Suitable reductones are in particular aci reductions with a 3-carbonylenediol (1,2) grouping, such as reductin, triose reductone or preferably ascorbic acid.
  • mercapto compounds come e.g. B. thioglycerin, but especially the compounds of formula or preferably into consideration, in which q is an integer from 2 to 12, B is a sulfonic acid or carboxylic acid group and m is one of the numbers 3 and 4.
  • Mercapto compounds which can be used as antioxidants are described in DE-OS 2 258 076 and DE-OS 2 423 814.
  • Suitable further antioxidants are alkali metal, alkaline earth metal or ammonium bisulfite adducts of organic carbonyl compounds, preferably alkali metal or ammonium bisulfite adducts of monoaldehydes with 1 to 4 or dialdehydes with 2 to 5 carbon atoms (DE-OS 2 737 142).
  • Examples include the particularly preferred formaldehyde bisulfite adduct, and also the corresponding adducts of acetaldehyde, propionaldehyde, butyraldehyde or isobutyraldehyde, of glyoxal, malondialdehyde or glutardialdehyde.
  • the tertiary water-soluble phosphines mentioned below as bleach accelerators can also be used simultaneously as antioxidants.
  • oxidizing agent Water-soluble aromatic mononitro and dinitro compounds and anthraquinone sulfonic acid derivatives are expediently used as the oxidizing agent (s).
  • the use of such oxidizing agents serves not only to oxidize the silver but also to influence the color balance and the contrast of the images produced by the color bleaching process and is known from German patent specification 735 672, British patent specifications 539 190 and 539 509 and Japanese patent publication 22 673/69.
  • the compounds of component (e) serve to flatten the gradation.
  • Further bleaching accelerators are the water-soluble tertiary phosphines known from DE-OS 2 651 969, which preferably contain at least one cyanoethyl group.
  • Preferred tertiary phosphines correspond to the formula wherein X, -CH 2 CH 2 CN or - (CH 2 ) 2 OCH 3 , Y 1 - (CH 2 ) 2 SO 3 M, - (CH 2 ) 3-SO 3 M, - (CH 2 ) 4 -SO3M , - (CH 2 ) 2 OCH 3 or -CH 2 N (C 2 H 5 ) 2 , W 1 -CH 2 CH 2 CN or phenyl and M + a cation, in particular an alkali metal cation, e.g. B. is the sodium or potassium cation.
  • Baths of conventional composition can be used for silver development, e.g. B. those containing hydroquinone as developer and optionally additionally 1-phenyl-3-pyrazolidinone.
  • the silver development bath may already contain a bleaching catalyst.
  • the silver fixing bath can be composed in a known and customary manner.
  • a fixing agent z. B sodium thiosulfate or advantageously ammonium thiosulfate, optionally with additives such as sodium bisulfite and / or sodium metabisulfite.
  • the fixing bath can also be combined with the bleaching bath as a so-called bleach-fixing bath.
  • the temperature of the bleaching baths is generally between 20 and 90 ° C, preferably between 20 and 60 ° C, the processing time required being of course shorter at a higher temperature than at a lower temperature.
  • the bleaching baths are stable within the specified temperature range.
  • the aqueous bleaching preparations required for processing are used in the form of dilute aqueous solutions which contain the components mentioned.
  • other methods are also conceivable, e.g. B. application in paste form.
  • the aqueous bleaching preparation according to the present invention can e.g. B. from solid or liquid, in particular aqueous concentrates of individual or all components ((a) to (f)).
  • aqueous concentrates of individual or all components ((a) to (f)).
  • These concentrates (partial concentrates), which are also the subject of the present invention, have excellent stability and can therefore be stored for a long time.
  • These concentrates can optionally be used after dilution with water or with a mixture of water and an organic
  • the concentrates of the individual or all components (a) to (c) and optionally (d) to (f) or their combinations, e.g. B. from component (a) and (e) and from components (b), (d), (c) and (f) can be 2 to 20 times, preferably 5 to 1 times the amount of the individual components per liter contain concentrated preparation as previously stated for the ready-to-use bleach baths. They are usually available as solid, liquid or pasty concentrates.
  • the inventive method for processing exposed and developed silver color bleaching materials can, for. B. in the production of positive color images in copiers or automatic recorders or in the rapid processing of other silver color bleaching materials such.
  • B. for scientific records and industrial purposes, e.g. B. colored screen photography can also be used for the production of color negatives and diffusion transfer images.
  • a transparent, metallic reflecting, or preferably white-opaque material which is unable to absorb any liquid from the baths, can be used as a support for photographic materials to be processed.
  • the carrier can for example consist of optionally pigmented cellulose triacetate or polyester. If it is made of paper felt, it must be coated on both sides or coated with polyethylene.
  • the light-sensitive layers are located on at least one side of this support, preferably in the known arrangement, i. H. a red-sensitized silver halide emulsion layer containing a blue-green azo dye on the bottom, a green-sensitized silver halide emulsion layer containing a purple azo dye above and a blue-sensitive silver halide emulsion layer containing a yellow azo dye above.
  • the material can also contain sub-layers, intermediate layers, filter layers and protective layers, but the total thickness of the layers should generally not exceed 20 mm.
  • the inventive method is particularly suitable for processing exposed silver color bleaching material, which has a special structure and z. B. is suitable for producing self-masked images (DE-OS 2 547 720).
  • This material is constructed in such a way that, when processed with a developer containing a silver ligand, in particular sodium thiosulfate, and the subsequent process steps of color and silver bleaching necessary for the silver color bleaching process, the latter preferably combined in a single step, and finally the fixation, a masking of the blue secondary color densities the purple and cyan layer is effected.
  • a sample strip is cut from this photographic material and exposed additively behind a gray wedge as follows:
  • Example 2 The photographic material used in Examples 2 and 3 below is identical to that of Example 1, with the exception of filter layer (6), which this time contains only colloidal silver but no additional unsensitized emulsion.
  • the processing sequence is similar to that of Example 1, but the silver developing solution does not contain sodium thiosulfate, which does not produce a self-masking effect.
  • a sample strip of the photographic material was exposed additively, similar to that described in Example 1, using the following exposure times:
  • the processing temperature was 30 ° C throughout the processing.
  • a second test strip is exposed in the same way and treated in the same processing solutions, but using a bleaching bath containing 17 ml / liter of 96% sulfuric acid.
  • Example 2 The 9-layer unmasked material used in Example 2 is additively exposed behind a gray wedge in the same way as there and then subjected to a processing sequence with four baths in which a separate bath is used for the successive color and silver bleaching.
  • a second sample strip is exposed and processed in an identical manner, but using 14 ml of 96% sulfuric acid in the color bleaching solution and 20 ml 96% sulfuric acid in the silver bleaching solution per liter of solution.
  • the two positive gray wedges obtained in this way corresponded in all sensitometric values.
  • the measured maximum and minimum densities (reflectance densities) are:
  • a six-layer material is used which in the first layer contains the cyan dye and the associated red-sensitized silver halide emulsion, and in the second layer a thin, pure gelatin-containing intermediate layer in the third layer contains the purple dye with the associated green-sensitized silver halide emulsion, the fourth layer is an intermediate layer consisting of gelatin, the fifth layer contains a yellow halide silver halide layer and finally the sixth layer contains a protective layer of pure gelatin.
  • a second sample strip is exposed and processed in an identical manner, but using a combined bleaching and fixing bath which contains 9.5 g / l of 96% sulfuric acid.
  • the finished and dried test strips each result in a positive gray wedge with identical sensitometric values.
  • the measured densities are:
  • a preparation consisting of a solid and a liquid partial concentrate is prepared as follows:
  • a further preparation of a combined color and silver bleach bath consists of the following two fixed partial concentrates:
  • a combined color and silver bleach bath is prepared by dissolving part 111 and part IV in 900 g of water.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (13)

1. Procédé pour le traitement de matériaux photographiques, exposés et développés, pour blanchiment des couleurs à l'argent, dans lequel on traite le matériau, exposé et développé, avec des préparations aqueuses de blanchiment, qui contiennent
(a) un composant acide,
(b) un complexant de l'argent,
(c) un ou plusieurs catalyseurs de blanchiment,
(d) éventuellement un antioxydant,
(e) éventuellement un oxydant soluble dans l'eau et
(f) éventuellement un accélérateur de blanchiment,

caractérisé en ce que le constituant (a) est un produit d'addition, soluble dans l'eau, d'un amide d'un acide aliphatique à 1 à 4 atomes de carbone ou d'un acide aromatique monocyclique, ou d'un diamide de l'acide carbonique ou thiocarbonique ou d'un lactame d'acides y-, 6- ou e-aminés, et d'un acide mine' rai fort.
2. Procédé selon la revendication 1, caractérisé en ce que les préparations aqueuses de blanchiment sont des bains de blanchiment de la couleur ou de l'argent, des bains de blanchiment combinés déjà couleur et de l'argent, ou des bains de blanchiment-fixage.
3. Procédé selon la revendication 1, caractérisé en ce que le constituant (a) est un produit d'addition de l'urée et de 0,5 ou 1 mole d'acide sulfurique ou 1 mole d'acide nitrique.
4. Procédé selon la revendication 1, caractérisé en ce que le constituant (b) est la thiourée ou un iodure soluble dans l'eau, le constituant (c) est un composé de pyrazine, de quinoxaline ou de phénazine, le constituant (d) est une réductone ou un composé mercapto soluble dans l'eau ou un produit d'addition de bisulfite de métal alcalin, de métal alcalino-terreux ou d'ammonium et d'un composé carbonyle organique, le constituant (e) est un composé mononitré ou dinitré aromatique ou un acide anthraquinonesul- fonique, et le constituant (f) est un composé quaternaire de pipéridine, pipérazine, pyrazine, quinoléine ou pyridine, éventuellement substitué, ou encore un composé de tétraalkylammonium ou d'alkylène- diammonium.
5. Procédé selon la revendication 1, caractérisé en ce qu'on utilise en tant que constituants (f) et/ou (d) des phosphines tertiaires solubles dans l'eau de formule
Figure imgb0043
dans laquelle W est ―CrH2rCN, -CrH2rNO2 ou un radical aryle éventuellement substitué ou un radical hétérocyclique; r vaut 1 à 25; X est un radical alkyle éventuellement substitué, et Y est un radical hydro- xyalkyle, alcoxyalkyle, sulfoalkyle, aminoalkyle, phényle, sulfophényle ou pyridyle.
6. Préparations aqueuses pour le traitement de matériaux photographiques exposés et développés pour blanchiment des couleurs à l'argent, qui contiennent
(a) un constituant acide,
(b) un complexant de l'argent,
(c) un ou plusieurs catalyseurs de blanchiment,
(d) éventuellement un anti-oxydant,
(e) éventuellement un oxydant soluble dans l'eau et
(f) éventuellement un accélérateur de blanchiment,

caractérisées en ce que le constituant (a) est un produit d'addition, soluble dans l'eau, d'un amide d'un acide aliphatique à 1 à 4 atomes de carbone ou d'un acide aromatique monocyclique, ou d'un diamide de l'acide carbonique ou thiocarbonique, ou d'un lactame d'acides y-, ô- ou r-aminés, et d'un acide miné ral fort.
7. Préparations aqueuses selon la revendication 6, caractérisées en ce qu'elles sont des bains de blanchiment de la couleur ou de l'argent, des bains combinés de blanchiment et de fixage de la couleur et de l'argent.
8. Préparations aqueuses selon la revendication 6, caractérisées en ce que le constituant (a) est un produit d'addition de l'urée et de 0,5 ou 1 mole d'acide sulfurique ou 1 mole d'acide nitrique.
9. Préparations aqueuses selon la revendication 6, caractérisées en ce que le constituant (b) est l'iodure de sodium, de potassium ou d'ammonium, le constituant (c) est un composé de pyrazine, de quinoxaline ou de phénazine, le constituant (d) est une réductone ou un composé mercapto soluble dans l'eau ou un produit d'addition de bisulfite de métal alcalin, de métal alcalino-terreux ou d'ammonium et d'un composé carbonyle organique, le constituant (e) est un composé mononitré ou dinitré aromatique ou un acide anthraquinone-sulfonique, et le constituant (f) est un composé de pipéridine, pipérazine, pyrazine, quinoléine ou pyridine quaternaire, éventuellement substitué, ou encore un composé de tétraalkylammonium ou d'alkylènediammonium.
10. Compositions aqueuses selon l'une des revendications 6 et 7, caractérisées en ce qu'elles contiennent 10 à 200 g/I du constituant (a), 2 à 50 g/I du constituant (b), 0,05 à 10 g/I du constituant (c), éventuellement 0,5 à 10 g/I du constituant (d), éventuellement 1 à 30 g/I du constituant (e), et éventuellement 1 à 5 g/I du constituant (f).
11. Concentré pour la réalisation des préparations aqueuses selon l'une des revendications 6 à 10, caractérisé en ce qu'il contient les constituants (a) à (c) et éventuellement (d) à (f), selon une concentration, par litre de concenté, deux à vingt fois plus élevée que les préparations aqueuses prêtes à l'emploi.
12. Concentrés partiels pour la réalisation des préparations aqueuses selon l'une des revendications 6 à 10, caractérisés en ce qu'on a un concentré avec les constituants (a) et (e), et un deuxième concentré avec les constituants (b), (c) et éventuellement (d) et (f), la concentration des constituants, par litre de concentré, étant deux à vingt fois plus élevée que dans les préparations aqueses prêtes à l'emploi.
13. Procédé pour la réalisation de préparations aqueuses de blanchiment selon l'une des revendications 6 à 10, caractérisé en ce qu'on dilue à la concentration d'utilisation, avec de l'eau ou un mélange d'eau et d'un solvant organique, les concentrés ou concentrés partiels selon l'une des revendications 11 1 et 12 et qu'on les mélange éventuellement les uns aux autres.
EP81101124A 1980-02-22 1981-02-17 Procédé pour le traitement de matériaux pour la décoloration des colorants à l'argent, compositions appropriées à la décoloration et leur préparation à partir de concentrés et concentrés partiels, les concentrés et concentrés partiels Expired EP0034793B1 (fr)

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DE8484108556T DE3175718D1 (en) 1980-02-22 1981-02-17 Process for the production of sulfuric-acid adducts of urea

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CH1435/80 1980-02-22
CH143580 1980-02-22

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EP0034793A2 EP0034793A2 (fr) 1981-09-02
EP0034793A3 EP0034793A3 (en) 1982-10-20
EP0034793B1 true EP0034793B1 (fr) 1985-05-29

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EP84108556A Expired EP0131970B1 (fr) 1980-02-22 1981-02-17 Procédé de préparation de produits d'addition d'acide sulfurique de l'urée

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5411944A (en) * 1981-11-05 1995-05-02 Union Oil Company Of California Glyphosate-sulfuric acid adduct herbicides and use
US5116401A (en) * 1981-11-05 1992-05-26 Union Oil Company Of California Herbicide and method with the glyphosate-urea adduct of sulfuric acid
US5374608A (en) * 1981-11-05 1994-12-20 Union Oil Company Of California Compositions containing adducts and surfactants
US5149355A (en) * 1981-11-05 1992-09-22 Union Oil Company Of California Adduct compositions
US5288692A (en) * 1982-11-17 1994-02-22 Union Oil Company Of California Systemic herbicides and methods of use
EP0149978A3 (en) * 1984-01-20 1988-08-31 Ciba-Geigy Ag Process for the production of photographic images by the silver dye-bleaching process
JPH07122751B2 (ja) * 1988-04-28 1995-12-25 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料用漂白定着液濃縮組成物及び処理方法
EP0351740A1 (fr) * 1988-07-19 1990-01-24 Konica Corporation Méthode de préparation d'un filtre couleur et filtre couleur préparé par la méthode
US4962283A (en) * 1989-02-28 1990-10-09 Union Oil Company Of California Single pass continuous urea-sulfuric acid process
JPH0432837A (ja) * 1990-05-29 1992-02-04 Fuji Photo Film Co Ltd 真空包装写真処理剤
US5221659A (en) * 1991-10-28 1993-06-22 Union Oil Company Of California Plant control composition and methods of use
US5238905A (en) * 1991-10-28 1993-08-24 Union Oil Company Of California Plant control composition and methods of use with thidiazuron and monocarbamide dihydrogen sulfate
US5262285A (en) * 1992-05-04 1993-11-16 Eastman Kodak Company Methods and compositions for retouching film images
RU2101293C1 (ru) * 1992-12-25 1998-01-10 Товарищество с ограниченной ответственностью "Эфиры целлюлозы" Способ получения сложного эфира целлюлозы
WO1996006672A1 (fr) * 1994-08-26 1996-03-07 Us Sulfamate, Inc. Compositions derivees d'uree fondue deshydratee

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE239309C (fr) *
US3330864A (en) * 1965-04-29 1967-07-11 Conversion Chem Corp Method for making urea nitrate
DE1935705A1 (de) * 1968-07-16 1970-03-19 Fuji Photo Film Co Ltd Verfahren zur Herstellung von photographischen Farbbildern
GB1397945A (en) * 1972-05-04 1975-06-18 Ici Ltd Process for the manufacture of inorganic acid addition salts of urea
CH579292A5 (fr) * 1973-05-18 1976-08-31 Ciba Geigy Ag
US4116664A (en) * 1976-11-04 1978-09-26 Jones Leon R Fertilizer composition and method of making same
CH644459A5 (de) * 1978-09-29 1984-07-31 Ciba Geigy Ag Verfahren zur herstellung farbphotographischer bilder nach dem silberfarbbleichverfahren.
US4310343A (en) * 1979-11-27 1982-01-12 Verdegaal Bros. Fertilizer Process for making liquid fertilizer

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JPS56132340A (en) 1981-10-16
US4879413A (en) 1989-11-07
DE3170675D1 (en) 1985-07-04
EP0131970A1 (fr) 1985-01-23
US4366232A (en) 1982-12-28
EP0034793A2 (fr) 1981-09-02
JPH0133820B2 (fr) 1989-07-14
EP0131970B1 (fr) 1986-12-17
EP0034793A3 (en) 1982-10-20

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