EP0131970B1 - Procédé de préparation de produits d'addition d'acide sulfurique de l'urée - Google Patents

Procédé de préparation de produits d'addition d'acide sulfurique de l'urée Download PDF

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Publication number
EP0131970B1
EP0131970B1 EP84108556A EP84108556A EP0131970B1 EP 0131970 B1 EP0131970 B1 EP 0131970B1 EP 84108556 A EP84108556 A EP 84108556A EP 84108556 A EP84108556 A EP 84108556A EP 0131970 B1 EP0131970 B1 EP 0131970B1
Authority
EP
European Patent Office
Prior art keywords
urea
silver
sulfuric acid
acid
bleaching
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
Application number
EP84108556A
Other languages
German (de)
English (en)
Other versions
EP0131970A1 (fr
Inventor
Hansjörg Dr. Buser
Adolf Morand
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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 Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0131970A1 publication Critical patent/EP0131970A1/fr
Application granted granted Critical
Publication of EP0131970B1 publication Critical patent/EP0131970B1/fr
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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 method for producing sulfuric acid adducts of urea.
  • steps (B) and (C) and (B), (C) and (D) can be carried out simultaneously in a single bath.
  • the preparations (baths) used for the color and / or silver bleaching or the combined bleach-fixation are strongly acidic, i.e. 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 sulfanic acid. Good results are also obtained with certain strong organic acids, such as p-toluenesulfonic acid.
  • Hydrochloric acid highly volatile and therefore has a particularly corrosive effect on e.g. Apparatus and devices in which the processing of the photographic material is carried out.
  • the use of solid instead of liquid acids is particularly advantageous because it facilitates the preparation, transport and storage of preparations for color and / or silver bleaching.
  • the sulfamic acid which is suitable per se and can easily be produced 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.
  • sulfuric acid adducts of urea can be used instead of mineral acids. These adducts are solid, of good stability, high solubility in water and they dissociate easily in their original components in aqueous solution.
  • the present invention thus relates to a process for the preparation of sulfuric acid adducts of urea with a urea-sulfuric acid ratio of 2: 1 or 1: 1, characterized in that the solid urea is entered in the stated ratio in 100 percent sulfuric acid, where Entry speed and external cooling are coordinated so that the temperature during the mixing time is between 70 and 100 ° C, and that the neutral or acid urea sulfate obtained in this way is converted into solid form by cooling and, if necessary, comminuted.
  • the adducts of one mole of urea with 0.5 or 1 mole of sulfuric acid are particularly well known.
  • the melting points of these adducts are 80 and 70 ° C, respectively.
  • Information about the properties of these adducts, their stability, the reaction kinetics in the melt and in aqueous solutions can be found, among others. at 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 sulfuric acid adducts of urea are prepared either directly from the components or their solutions or also by the action of mineral acid on cyanamide, the latter decomposing to urea, which then forms the addition compound with the acid.
  • the adducts produced 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.
  • urea sulfate the adduct of two moles of urea with one mole of sulfuric acid
  • urea hydrogen sulfate the adduct of one mole of urea with one mole of sulfuric acid
  • urea is introduced directly into solid form in 100% sulfuric acid (monohydrate) with cooling, the temperature not being allowed to rise above about 100 ° C. (preferably 70 ° C. to 100 ° C.) during the reaction.
  • the compounds are converted into the solid form by cooling and optionally comminuted.
  • the melt can be removed by suitable methods, e.g. used in the production of alkali metal hydroxides (cf. Ullmanns Encyklopadie der Technische Chemie, 4th edition, Verlag Chemie, Weinheim, Vol. 17 (1979), p. 204 f), are converted into a solid form suitable for the application. In particular, it can be crystallized in the form of free-flowing pearls, pills, flakes or flakes that are immediately soluble in water.
  • the sulfuric acid adducts can be brought into the form of beads if they are e.g. sprayed in a cooling tower.
  • 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 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 silver halide layer containing a yellow dye 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.

Landscapes

  • 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 (1)

1. Procédé pour la préparation de produits d'addition d'acide sulfurique et d'urée, avec un rapport urée- acide sulfurique de 2:1 cu 1:1, caractérisé en ce qu'on introduit l'urée solide, selon le rapport indiqué, dans de l'acide sulfurique à 100 %, la vitesse d'introduction et un refroidissement extérieur étant adaptés l'un à l'autre de telle sorte que la température, pendant la durée du mélange, soit comprise entre 70 et 100°C, et en ce que l'urée-sulfate, neutre ou acide, ainsi obtenu, est converti par refroidissement en une forme solide et éventuellement broyé.
EP84108556A 1980-02-22 1981-02-17 Procédé de préparation de produits d'addition d'acide sulfurique de l'urée Expired EP0131970B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH143580 1980-02-22
CH1435/80 1980-02-22

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP81101124.6 Division 1981-02-17

Publications (2)

Publication Number Publication Date
EP0131970A1 EP0131970A1 (fr) 1985-01-23
EP0131970B1 true EP0131970B1 (fr) 1986-12-17

Family

ID=4210396

Family Applications (2)

Application Number Title Priority Date Filing Date
EP81101124A Expired EP0034793B1 (fr) 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
EP84108556A Expired EP0131970B1 (fr) 1980-02-22 1981-02-17 Procédé de préparation de produits d'addition d'acide sulfurique de l'urée

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP81101124A Expired EP0034793B1 (fr) 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

Country Status (4)

Country Link
US (2) US4366232A (fr)
EP (2) EP0034793B1 (fr)
JP (1) JPS56132340A (fr)
DE (1) DE3170675D1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5116401A (en) * 1981-11-05 1992-05-26 Union Oil Company Of California Herbicide and method with the glyphosate-urea adduct of sulfuric acid
US5411944A (en) * 1981-11-05 1995-05-02 Union Oil Company Of California Glyphosate-sulfuric acid adduct herbicides and use
US5149355A (en) * 1981-11-05 1992-09-22 Union Oil Company Of California Adduct compositions
US5374608A (en) * 1981-11-05 1994-12-20 Union Oil Company Of California Compositions containing adducts and surfactants
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
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
US5221659A (en) * 1991-10-28 1993-06-22 Union Oil Company Of California Plant control composition and methods of use
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
AU3495195A (en) * 1994-08-26 1996-03-22 Us Sulfamate, Inc. Molten urea dehydrate derived compositions

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

Also Published As

Publication number Publication date
JPH0133820B2 (fr) 1989-07-14
JPS56132340A (en) 1981-10-16
EP0131970A1 (fr) 1985-01-23
EP0034793A3 (en) 1982-10-20
DE3170675D1 (en) 1985-07-04
US4879413A (en) 1989-11-07
EP0034793A2 (fr) 1981-09-02
EP0034793B1 (fr) 1985-05-29
US4366232A (en) 1982-12-28

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