US3457077A - Photographic couplers - Google Patents

Photographic couplers Download PDF

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Publication number
US3457077A
US3457077A US550904A US3457077DA US3457077A US 3457077 A US3457077 A US 3457077A US 550904 A US550904 A US 550904A US 3457077D A US3457077D A US 3457077DA US 3457077 A US3457077 A US 3457077A
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United States
Prior art keywords
solution
photographic
compounds
color
sodium
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Expired - Lifetime
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US550904A
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English (en)
Inventor
Walter Puschel
Karl-Wilhelm Schranz
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Agfa Gevaert AG
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Agfa Gevaert AG
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Priority claimed from DE1965A0049318 external-priority patent/DE1472758A1/de
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39224—Organic compounds with a nitrogen-containing function
    • 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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography

Definitions

  • the invention relates to photographic materials which contain acyl monohydrazone couplers that couple with developer oxidation products of silver halide developers to form colorless compounds.
  • Another direct positive process is the so-called silver dye bleaching process.
  • Layers which are colored with azo dyes are used for this purpose. Because of the absorption of light, the sensitivity of those layers does not match practical requirements.
  • British Patent No. 590,637 also describes cyan acetyl color couplers which are, substituted with a monohydrazone grouping and which react in known manner with oxidized color-forming developers to form a dyestuff.
  • German Patent No. 1,175,072 describes photographic materials which contain usual color couplers that react following formula also couple with the oxidation products of photographic developers to form colorless products.
  • the compounds according to the present invention correspond to the following general formula:
  • X and X represent organic groups capable of mesomerism for example, olefinically unsaturated aliphatic groups such as vinyl, butadienyl, aromatic groups such as phenyl or naphthyl, or heterocyclic systems of aromatic structure, for example, furyl, thienyl, and pyridyl.
  • aryl radicals in particular, may optionally be substituted, for example, by C1, SO H, COOH, alkyl with up to 20 carbon atoms and preferably with 12-18 carbon atoms, aryl such as phenyl or naphthyl, N0 0H, lower alkoxy, phenoxy, NH or substituted amino groups.
  • X can also be an alkyl group having up to 17 carbon atoms.
  • Y represents the grouping in which R represents hydrogen, alkyl, preferably methyl, ethyl or propyl or aryl, preferably phenyl.
  • R represents hydrogen, alkyl preferably alkyl having up to 5 carbon atoms, aryl, preferably phenyl, cycloalkyl, preferably cyclohexyl, aralkyl, preferably phenylalkyl, such as benzyl, phenyl ethyl or styryl, or heterocyclic groups, such as 'furyl, furylidenyl, indolyl, pyridyl, thienyl, thiazolyl benzthiazolyl, imidazolyl, oxazolyl, benzimidazolyl, benzoxazolyl, pyrazolyl or quinoazolyl or the groups in which R and R represent hydrogen, alkyl, preferably with up to 20 carbon atoms, aryl, in particular phenyl,
  • phenylalkyl such as benzyl or phenylethyl
  • 5- or 6-membered cycloaliphatic or heterocyclic rings such as benzthiazolyl or benzimidazolyl or R and R together with the nitrogen atom may represent the ring members required .to complete a 5- or 6-membered heterocyclic ring optionally with further hetero atoms, for example, a morpholine ring.
  • R X and Y may together represent the ring members required to complete a heterocyclic or isocyclic ring such as piperidine or pyrolidine, whilst the index n represents 0 or an integer from 1 to 3.
  • Acylhydrazones are also obtained by directly coupling a diazonium salt with an acetyl or benzoylacetic ester derivative, and by subjecting the resulting dye to cleav age.
  • compound 3 can be prepared as fol lows:
  • acyl formazanes are also known from the literature [e.g., Chem. Ber., 24 (3262)].
  • symmetrical formazanes may be prepared in a manner similar to that described above by reacting one mole of acylacetic acid with 2 mols of a diazotized amine.
  • a corresponding diazonium salt is coupled with a monohydrazone of a diacyl compound, for example, compound 5 can be prepared as follows:
  • phenylglyoxylacid amide aryl hydrazones illustrated by the preceding formulae can be prepared by methods described in the literature, for example:
  • the compounds according to the invention may be divided up into two groups:
  • the compounds according to the invention are interesting in many respects from the photographic point of view.
  • the compounds of group 1 may be used as masks in color-photographic materials, or for the production of colored direct-positive images.
  • the compounds of group 2 which remain colorleess throughout processing, may be used as so-called white or colorless couplers for inhibiting color fogging or for improving color definition. They correspond in their functions to the compounds described in British Patents Nos. 861,138 and 914,145.
  • the compounds according to the invention are distinguished by their particularly smooth and quantitative reaction with the developer oxidation products.
  • Thecommon photographic processing baths are suitable for the direct reversal process according to the invention. Examples of some of the baths are set out below:
  • the 4-aminodiethylaniline of the solution specified in A is replaced by 5 g. of 4-amino-N,N-butyl, w-sulfobutyl aniline.
  • Suitable are also p-aminophenol developers, for example, the developer Agfa 10, which is described in the book of Dr. Eduard Schloemann, Photochemikalien und Struktur für.
  • OX-IDIZING BATHS The chemical structure of the oxidizing agent is not especially critical and is selected according to the properties of the monohydrazone compound with which the oxidizing agent is to be reacted. Preferred are those agents and baths which are commonly used in color photographic processes for bleaching silver images. Suitable agents are potassium ferricyanide, potassium bichromate or complex compounds of 3-valent iron or cobalt with amino-polycarboxylic acids such as ethylenediamine tetraacetic acid, nitrilo triacetic acid or the like, which are described, for example, in German Patent No. 866,605. Suitable baths are, for example, a 20% by weight aqueous solution of potassium ferricyanide or a 10% by weight aqueous solution of potassium bichromate.
  • FIXING BATHS Any desired photographic fixing baths can be used.
  • the fixing agent must not have reducing properties.
  • Preferred are aqueous solutions of salts of thiosulfate, e.g., sodium thiosulfate, potassium thiosulfate or ammonium thiosulfate.
  • the fixing agents can be used as about 20% by weight aqueous solutions.
  • drying can be performed by means of conventional dryers for photographic materials at slightly raised temperatures.
  • the monohydrazones of the present invention are added to the light-sensitive silver halide emulsion layer in an amount of between 5 and 50 g. per kg. of emulsion, preferably 10-30 g. They can be incorporated into the emulsion layer in a dissolvable diffusion-resistant form.
  • the monohydrazone couplers are first dissolved in an oily organic material, and this combination is dispersed in a finely divided state throughout the emulsion
  • the monohydrazone compound according to the invention can also be used in those processes in which the so-called successive colorant formation is applied.
  • the monohydrazone is incorporated into the developer composition in an amount of between 5 to 40 g. per liter.
  • the successive reaction with the oxidation product of the developer in each of single layers of the multi-layer material is obtained by controlled penetration of the processing solution. For example, in an integral tripack it is possible by means of such a solution to develop the top layer of the material without affecting the lower emulsion if the time of development is carefully controlled.
  • the silver halide of the light-sensitive layers used in accordance with the present invention consists of a silver chloride or silver bromide or mixtures thereof,
  • gelatin it is also possible to use a mixture of several binding agents.
  • the light-sensitive layer may consist further of additives in accordance with the special requirements of the photographic elements, such as sensitizers or stabilizers.
  • the silver halide emulsion can be optically sensitized with the common methincyanine, rhodacyanine or merocyanine dyes. Furthermore it is possible to apply silver halide emulsions which are chemically sensitized by sulfur compounds, complexes of noble metals, such as gold, palladium or iridium, or by polyethylen glycol or derivatives thereof.
  • Example 1 1.5 g. of compound 1 are made into a paste with cc. of methanol and the resulting paste is dissolved in 50 cc. of a 4% by weight sodium hydroxide solution. The solution is mixed with 100 cc. of a conventional silver halide emulsion. T he emulsion is applied to a suitable support, for example, an acetyl cellulose, polycarbonate or terephthalate film. The resulting layer is yellow in color. It is exposed to light and then developed in developer A. Following bleaching out of the image silver in a potassium ferricyanide bleaching bath with a pH of 5.5 and fixing, a direct-positive yellow image is obtained.
  • a potassium ferricyanide bleaching bath with a pH of 5.5 and fixing
  • Example 2 Photographic silver halide layers are prepared as described in Example 1 with compounds 20, 21, 22, 23, 24, 25 and 26. The resulting layers are developed in developer B. In each instance, yellowish to reddish-orange direct positive images are obained.
  • Example 3 1.5 g. of compound 7 are applied to a support as described in Example 1. Following exposure, the layer is developed in developer B. Bleaching is carried out in a potassium ferricyanide bleaching bath with a pH of 7.1. A yellow direct-positive image is obtained.
  • Example 4 The procedure of Example 1 is repeated with compounds 6, and 11. Development is carried out in developer B and bleaching in a 10% by weight solution of sodium bichromate. Red direct-positive images are obtained.
  • Example 5 The procedure of Example 1 is repeated with compounds 4, 5, 8, 9 and 19. Bleaching is carried out in a 10% by weight solution of potassium ferricyanide adjusted to pH 8.5 with sodium borate. Yellow direct-positive images are obtained.
  • Example 6 The procedure of Example 1 is repeated with compounds 13 and 16. -In this instance, bleaching is carried out in a combined bleaching and fixing bath of the type described in German Patent No. 866,605. A yellow directpositive image is obtained.
  • Example 7 The procedure of Example 1 is repeated with compound 4. In this instance, development is carried out in developer C. A yellow direct-positive image is obtained.
  • Example 8 The following silver halide layers are applied to a film support in the order in which they are listed:
  • Bleaching is then carried out with a 20% by weight solution of potassium ferricyanide, followed by fixing in a bath comprising a 20% aqueous solution of sodium thiosulfate.
  • a negative, purple image is obtained in layer 1 and a positive yellow image in layer 2 which compensates for the extra absorption of the purple-colored negative is obtained.
  • n is zero or an integer from 1 to 3
  • R and R are hydrogen or hydrocarbyl, the improvement according to which the coupler has a group linking the (Y) with the 2.
  • the coupler has a group linking the (Y) with the 2.
  • R is hydrogen or hydrocarbyl, the improvement according to which the coupler has its R II (I) connected to X (Y)u where X is also an organic mesomerizable group or alkyl having up to 17 carbon atoms,
  • n is zero or an integer from 1 to 3
  • R is also hydrogen or hydrocarbyl.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coloring (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US550904A 1965-05-26 1966-05-18 Photographic couplers Expired - Lifetime US3457077A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1965A0049318 DE1472758A1 (de) 1963-04-11 1965-05-26 Lichtempfindliches photographisches Material mit mindestens einer Halogensilberemulsionsschicht

Publications (1)

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US3457077A true US3457077A (en) 1969-07-22

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US550904A Expired - Lifetime US3457077A (en) 1965-05-26 1966-05-18 Photographic couplers

Country Status (5)

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US (1) US3457077A (enrdf_load_stackoverflow)
BE (1) BE681611A (enrdf_load_stackoverflow)
CH (1) CH464689A (enrdf_load_stackoverflow)
GB (1) GB1109963A (enrdf_load_stackoverflow)
NL (1) NL6607303A (enrdf_load_stackoverflow)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186840A (en) * 1958-12-11 1965-06-01 Agfa Ag Direct positive colored photographic elements containing dihydrazones and process for forming colored masks therefrom
US3245788A (en) * 1959-11-13 1966-04-12 Gevaert Photo Prod Nv Production of color photographic images
US3293032A (en) * 1961-08-02 1966-12-20 Gevaert Photo Prod Nv Process for the preparation of colour images
US3378554A (en) * 1958-12-11 1968-04-16 Agfa Ag Dicarbonyl-dihydrazones
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186840A (en) * 1958-12-11 1965-06-01 Agfa Ag Direct positive colored photographic elements containing dihydrazones and process for forming colored masks therefrom
US3378554A (en) * 1958-12-11 1968-04-16 Agfa Ag Dicarbonyl-dihydrazones
US3245788A (en) * 1959-11-13 1966-04-12 Gevaert Photo Prod Nv Production of color photographic images
US3245787A (en) * 1959-11-13 1966-04-12 Gevaert Photo Prod Nv Production of color photographic images
US3293032A (en) * 1961-08-02 1966-12-20 Gevaert Photo Prod Nv Process for the preparation of colour images
US3384484A (en) * 1963-04-11 1968-05-21 Agfa Ag Silver halide photographic materials containing organic hydrazone compounds

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Publication number Publication date
NL6607303A (enrdf_load_stackoverflow) 1966-10-25
GB1109963A (en) 1968-04-18
CH464689A (de) 1968-10-31
BE681611A (enrdf_load_stackoverflow) 1966-11-28

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