EP0131970A1 - 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
EP0131970A1
EP0131970A1 EP84108556A EP84108556A EP0131970A1 EP 0131970 A1 EP0131970 A1 EP 0131970A1 EP 84108556 A EP84108556 A EP 84108556A EP 84108556 A EP84108556 A EP 84108556A EP 0131970 A1 EP0131970 A1 EP 0131970A1
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EP
European Patent Office
Prior art keywords
urea
silver
acid
bleaching
sulfuric acid
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.)
Granted
Application number
EP84108556A
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German (de)
English (en)
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EP0131970B1 (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
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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
Expired legal-status Critical Current

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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 process for the preparation of sulfuric acid adducts of urea and the use of these adducts in the processing of exposed silver color bleaching materials.
  • German Offenlegungsschrift No. 2,448,433 describes, for example, a process in which steps (B) color bleaching and (C) silver bleaching are combined to form a single step.
  • a processing sequence in which steps (C) silver bleaching and (D) fixation are carried out simultaneously in a single bleach-fixing bath has been described in US Pat. No. 3,866 & 253.
  • German Patent 735 672 a processing method for silver color bleaching materials has become known, in which process steps (B), (C) and (D) in one Bath can be done at the same time.
  • 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 sulfamic 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 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. it to provide strong mineral acids as required in the processing of photographic silver color bleaching materials in a suitable form so as to overcome the aforementioned disadvantages.
  • the present invention 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 introduced in the specified ratio into concentrated sulfuric acid, the rate of entry and external cooling being so be coordinated with one another such that the temperature during the mixing time is between 70 and 100 ° C. and that the neutral or acidic urea sulfate obtained in this way is converted into solid form by cooling and optionally comminuted.
  • the acid amides used to prepare the adducts with the strong mineral acids are those of low molecular weight aliphatic acids, for example with 1 to 4, in particular 1 or 2, carbon atoms, and also of monocyclic aromatic acids, in particular, if appropriate 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 ⁇ , ⁇ and t-amino acids (4 to 6 carbon atoms) which may be substituted on the nitrogen atom with lower alkyl (C 1 -C 4 ), in particular with methyl.
  • Examples of the lactams mentioned are Piperidone ( ⁇ valerolactam, and in particular 2-pyrrolidone (y-butyrolactam), N-methyl-2-pyrrolidone and caprolactam.
  • Strong mineral acids include 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, 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 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 produced 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 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.
  • 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. A suspension of the crystallizing urea sulfate is thus obtained, 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 flow completely when exposed to an atmosphere with 76% relative humidity.
  • the adducts of these acids with e.g. However, urea, pyrrolidone or thiourea remain in crystalline form under the conditions mentioned.
  • 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. known 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.
  • a suitable silver complexing agent can e.g. Be thiourea.
  • a water-soluble iodide alkali metal iodide, preferably sodium or potassium iodide, furthermore ammonium iodide
  • an anti-oxidation agent 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 reductones with a 3-carbonylenediol (1,2) grouping, such as reductin, triose reductone or preferably ascorbic acid.
  • mercapto compounds are thioglycerin, but especially the compounds of the 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 that can be used as oxidative protection agents are described in DE-OS 2 258 076 and DE-OS 2 423 814.
  • oxidizing agents are suitable 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 formaldebydisulfite 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 also serves 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 22673/69.
  • the compounds of component (e) serve to flatten the gradation.
  • Suitable bleach accelerators (f) are e.g. quaternary ammonium salts as are known from German Offenlegungsschriften 2 139 401 and 2 716 135. These are preferably quaternary, optionally substituted piperidine, piperazine, pyrazine,
  • 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 1 -CH 2 CH 2 CN or - (CH 2 ) 2 OCH 3 , Y 1 - (CN 2 ) 2 SO 3 ⁇ M ⁇ - (CH 2 ) 3 -S O3 M ⁇ , - (CH 1 ) 4 -SO 3 ⁇ M ⁇ , - (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, eg the sodium or potassium cation.
  • a cation in particular an alkali metal cation, eg the sodium or potassium cation.
  • Baths of conventional composition can be used for silver development, e.g. those which contain 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.
  • the fixative used is e.g. 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, of course, being shorter at a higher temperature than at a lower temperature.
  • the bleaching baths are stable within the specified temperature range. In general, those for the. Processing required aqueous bleaching preparations in the form of dilute aqueous solutions containing the components mentioned. However, other methods are also conceivable, e.g. application in paste form.
  • the aqueous bleaching preparation according to the present invention can be produced, for example, from solid or liquid, in particular aqueous concentrates of individual or all components ((a) to (f)). It is advantageous to use, for example, a solid and a liquid or two liquid concentrates, one of which contains the acid adduct (a) and the oxidizing agent (e) and the other of which contains the other components (b), (c) and, if appropriate, (d) and (f) , in the latter concentrate to improve the solubility, in particular component (c), an additional solvent such as ethyl or propyl alcohol, ethylene glycol methyl or ethyl ether can be added.
  • These concentrates (partial concentrates), which are also the subject of the present invention, have excellent stability and are therefore storable for a long time. These concentrates can optionally be used after dilution with water or with a mixture of water and an organic solvent.
  • a transparent, metallic-reflecting, or preferably white-opaque material which is not able to absorb 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 photosensitive layers are located on at least one side of this support, preferably in the known arrangement, i.e. 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 ⁇ .
  • 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:
  • Adduct A. - E. (see table below)
  • 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 development 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
  • 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.
  • the finished treated and dried test strips give identical sensitometric values, with a D max of each
  • Example 3 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, except that 14 ml of 96X sulfuric acid are used in the color bleaching solution and 20 ml of 96% sulfuric acid per liter of solution in the silver bleaching solution.
  • the two positive gray wedges obtained in this way corresponded in all sensitometric values.
  • the measured maximum and minimum densities (reflectance densities) are:
  • Example 4 In this example, using the same dyes as in Example 1, a six-layer material is used, which in the first layer contains the cyan dye and the associated red-sensitized silver halide emulsion, and the second layer contains a thin, pure gelatin-containing intermediate layer the third layer contains the purple dye with the associated green-sensitized silver halide emulsion, the fourth layer contains 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 made of pure gelatin.
  • a so-called two-bath process consisting of a developer bath and a subsequent combined bath, in which the dye and silver bleaching and the fixing take place practically simultaneously.
  • An identical bath as in Example 3 is used as the silver developing bath; the combined bleaching and fixing bath has the following composition:
  • 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 seasitometric values.
  • the measured densities (remission values) are:
  • Example 5 Concentrate for the preparation of a combined color and silver bleach bath.
  • a preparation consisting of a solid and a liquid partial concentrate is prepared as follows:
  • a combined color and silver bleach bath is prepared by dissolving part III 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)
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)

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

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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
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

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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

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US (2) US4366232A (fr)
EP (2) EP0131970B1 (fr)
JP (1) JPS56132340A (fr)
DE (1) DE3170675D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0351740A1 (fr) * 1988-07-19 1990-01-24 Konica Corporation Méthode de préparation d'un filtre couleur et filtre couleur préparé par la méthode

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5374608A (en) * 1981-11-05 1994-12-20 Union Oil Company Of California Compositions containing adducts and surfactants
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
US5116401A (en) * 1981-11-05 1992-05-26 Union Oil Company Of California Herbicide and method with the glyphosate-urea adduct of sulfuric acid
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
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

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DE239309C (fr) *
DE1568276B1 (de) * 1965-04-29 1972-11-09 Kenvert Internat Corp Verfahren zur Herstellung von Harnstoffnitrat
DE2322114A1 (de) * 1972-05-04 1973-12-06 Ici Ltd Verfahren zur herstellung von anorganischen saeureadditionssalzen des harnstoffs

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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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DE239309C (fr) *
DE1568276B1 (de) * 1965-04-29 1972-11-09 Kenvert Internat Corp Verfahren zur Herstellung von Harnstoffnitrat
DE2322114A1 (de) * 1972-05-04 1973-12-06 Ici Ltd Verfahren zur herstellung von anorganischen saeureadditionssalzen des harnstoffs

Non-Patent Citations (2)

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Title
BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, 69. Jahrgang, 1936, Band II, Abteilung B, Verlag Chemie, Berlin PAUL BAUMGARTEN "Uber die durch Schwefelsaure bewirkte Spaltung (Sulfolyse) von Harnstoff." Seiten 1929-1937 seiten 1929, 1933 *
THE JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Band 56, 1934 LAWRENCE H. DALMAN "Ternary Systems of Urea and Acids." Seiten 549-553 seiten 550-551 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0351740A1 (fr) * 1988-07-19 1990-01-24 Konica Corporation Méthode de préparation d'un filtre couleur et filtre couleur préparé par la méthode

Also Published As

Publication number Publication date
US4879413A (en) 1989-11-07
EP0034793A3 (en) 1982-10-20
US4366232A (en) 1982-12-28
DE3170675D1 (en) 1985-07-04
EP0131970B1 (fr) 1986-12-17
JPS56132340A (en) 1981-10-16
EP0034793A2 (fr) 1981-09-02
JPH0133820B2 (fr) 1989-07-14
EP0034793B1 (fr) 1985-05-29

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