US3843367A - Photographic color developing process - Google Patents

Photographic color developing process Download PDF

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Publication number
US3843367A
US3843367A US00261367A US26136772A US3843367A US 3843367 A US3843367 A US 3843367A US 00261367 A US00261367 A US 00261367A US 26136772 A US26136772 A US 26136772A US 3843367 A US3843367 A US 3843367A
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US
United States
Prior art keywords
color
bath
bleaching
bleach
developed
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00261367A
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English (en)
Inventor
K Schranz
E Schon
W Hunicke
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of US3843367A publication Critical patent/US3843367A/en
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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
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • This invention relates to a photographic color developing process, which is intended in particular for high-speed processing, in which oximes are used as anti-bleach-fogging agents.
  • colored photographic images can be produced by chromogenic development, i.e. by developing silver halide emulsion layers, which have been exposed image-wise in the presence of suitable color couplers by means of suitable color-forming developer substances, known as color developers, the oxidation product of the developer substances being formed in correspondence with the silver image and reacting with the color coupler to form a dye image.
  • color developers suitable color-forming developer substances
  • Aromatic compounds containing primary amino groups, especially those of the p-phenylene diamine type, are generally used as color developers.
  • the photographic material has to be treated with a bleaching bath and a fixing bath, or with a combined bleach and fixing bath in order to remove image silver and any silver halide still present after development.
  • the bleaching substances used are oxidizing agents which oxidize residues of color developers which are still present in the photographic emulsion from the developing process and which, in the presence of color couplers, lead to the undesirable formation of a fog of an azomethine or indoquinone dye, referred to hereinafter as bleach-induced fogging.
  • the object of the invention is to improve bleaching or bleach-fixing baths for color photographic processes, especially for high-speed processing, by the addition of substances which prevent the formation of bleach-induced fogs and which are sutficiently stable in the baths.
  • a photographic color-developing process for the production of colored images using a. color photographic material with at least one image-wise exposed silver halide emulsion layer by color development, bleaching and fixing or bleach-fixing, has now been found in which the bleaching or bleach-fixing operation is carried out in the presence of a water-soluble, aliphatic, carbocyclic or heterocyclic oxime.
  • Oximes corresponding to the following formula are particularly suitable:
  • R hydrogen or an aliphatic, preferably saturated, radical with up to 12, preferably up to 5 carbon atoms which may be substituted, for example with halogen, such as chlorine, hydroxy, short-chain alkoxy radicals with preferably up to 3 carbon atoms such as methoxy, carboxy, esterified carboxy, preferably carboxy esterified with short-chain aliphatic alcohols, or an oxime p;
  • R an aliphatic, preferably saturated, radical with up to 12, preferably up to 5 carbon atoms, which may be substituted, for example with halogen such as chlorine, hydroxy, short-chain alkoxy radicals with preferably up to 3 carbon atoms such as methoxy, carboxy, esterified carboxy, preferably carboxy esterified with shortchain aliphatic alcohols, or an. oxime group,
  • R and R together may represent the ring members required to complete a preferably saturated, carbocyclic or heterocyclic 5- or 6-membered ring such as, for example, cyclopentane, cyclohexane, hexahydropyridine, hexahydropyrrole or the like.
  • R and/or R represent an aliphatic radical with up to 5 carbon atoms.
  • the aforementioned substances are added to the bleaching or bleach-fixing bath preferably in quantities of from 0.5 to 10 g. per litre. It is also possible to pre-treat the material development briefly with an aqueous solution of the compounds according to the invention before the bleaching or bleach-fixing operation. In this case, it is advisable to use the oximes according to the invention in relatively high concentration. Useful results are obtained for example with aqueous pretreatment baths containing from 5 to 50 g. per litre of the oximes to be used in accordance with the invention.
  • the oximes can of course also be used in conventional methods of processing color-photographic materials, in which case intermediate rinsing is generally carried out between the developer bath, and the bleaching and fixing baths or the bleach-fixing bath. However, they are used with particular advantage in so-called high-speed processing which is preferably carried out at a slightly elevated temperature and in which the need for intermediate rinsing should be eliminated where possible. Although, as a rule, heavy bleach-induced fogging readily occurs in this case, it is effectively suppressed in the presence of the oximes.
  • the oximes are used with particular advantage in processing machines with small bath volumes, for example, table-top machines, so-called one-off developing machines and the like, being less suitable for large processing machines with correspondingly large bath volumes on account of the gradual decomposition governed by the pH- value of the processing bath.
  • the bleaching baths normally used in photography can be used as the bleaching or bleach-fixing bath.
  • the bleaching substances are generally oxidizing agents which are able to oxidize metallic silver present in the photographic material into the silver salt.
  • Preferred bleaches are iron (III) compounds, such as, for example, iron (III) chloride, potassium ferricyanide or the iron (III) salt of ethylenediaminetetraacetic acid.
  • Photographic bleach-fixing baths are photographic treatment baths in which bleaching oxidizing agents are combined with a silver salt solvent such as sodium thiosulfate or ammonium thiosulfate. Other complex-forming agents may also be present. Treatment with a bleach-fixing bath not only oxidizes the metallic silver into the silver salt but also subsequently dissolves out of the layer the silver salt formed. Bleaching and bleach-fixing baths are known in the photographic art. Reference is made for example to H. Berger Agfacolor, 6th Edition, pages 260 and 262, and to E. Mutter, Die nike und angewandte Photographie," Vol. IV (1967), pages 348, 352, 353 and 362.
  • the bleach-fixing baths according to the invention preferably contain 100 to 200 g. of sodium or ammonium thiosulfate per litre.
  • White couplers are substances which are able to react with color developer oxidation products without forming a dye.
  • White couplers as such are known, for example, reference is made to German Pat. No. 1,155,675 wherein the preparation of white or colorless couplers can be effected by the process described as follows.
  • bleachfixing baths which, in addition to the oximes and a thiosulfate content which may be increased, contain from 1 to 5 g.. of a white coupler substance per litre.
  • N-butyl-N-w-sulfobutyl-p-phenylenediamine 4 g. of anhydrous sodium sulfite 2 g. of hydroxylamine hydrochloride 100 g. of potassium carbonate 1 g. of potassium bromide made up with water to 1,000
  • the process for the production of colored photographic images including the steps of imagewise exposing a color photographic material containing at least one silver halide layer, developing the exposed material with color-developer to form the dye-image in the presence of color-couplers and treating the material with a bath that bleaches and fixes the developed material to remove developed silver and residual silver halide, wherein the improvement comprises the bleaching of the developed material is in the presence of a water-soluble oxi-me in the bath, corresponding to the following formula:
  • the amount of oxime being such that it reduces the formation of color fog during bleaching.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00261367A 1971-06-12 1972-06-09 Photographic color developing process Expired - Lifetime US3843367A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712129202 DE2129202A1 (de) 1971-06-12 1971-06-12 Fotografisches Farbentwicklungsverfahren

Publications (1)

Publication Number Publication Date
US3843367A true US3843367A (en) 1974-10-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
US00261367A Expired - Lifetime US3843367A (en) 1971-06-12 1972-06-09 Photographic color developing process

Country Status (5)

Country Link
US (1) US3843367A (fr)
BE (1) BE784441A (fr)
DE (1) DE2129202A1 (fr)
FR (1) FR2141847B3 (fr)
GB (1) GB1348360A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997348A (en) * 1973-07-13 1976-12-14 Fuji Photo Film Co., Ltd. Color photographic processing method
US4066459A (en) * 1976-01-26 1978-01-03 Horizons Incorporated, A Division Of Horizons Research Incorporated Free radical photosensitive compositions with improved sensitivity and shelf life stability
US4301223A (en) * 1979-05-17 1981-11-17 Fuji Photo Film Co., Ltd. Method of stabilizing organic substrate materials to light
US5534394A (en) * 1989-12-21 1996-07-09 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4966834A (en) * 1987-09-03 1990-10-30 Fuji Photo Film Co., Ltd. Method for processing a silver halide color photographic material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997348A (en) * 1973-07-13 1976-12-14 Fuji Photo Film Co., Ltd. Color photographic processing method
US4066459A (en) * 1976-01-26 1978-01-03 Horizons Incorporated, A Division Of Horizons Research Incorporated Free radical photosensitive compositions with improved sensitivity and shelf life stability
US4301223A (en) * 1979-05-17 1981-11-17 Fuji Photo Film Co., Ltd. Method of stabilizing organic substrate materials to light
US5534394A (en) * 1989-12-21 1996-07-09 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials

Also Published As

Publication number Publication date
BE784441A (nl) 1972-12-06
GB1348360A (en) 1974-03-13
FR2141847A1 (fr) 1973-01-26
FR2141847B3 (fr) 1975-08-08
DE2129202A1 (de) 1972-12-14

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