US3535113A - Production of color masking images using p-phenylenediamine mask-forming compounds - Google Patents

Production of color masking images using p-phenylenediamine mask-forming compounds Download PDF

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US3535113A
US3535113A US610023A US3535113DA US3535113A US 3535113 A US3535113 A US 3535113A US 610023 A US610023 A US 610023A US 3535113D A US3535113D A US 3535113DA US 3535113 A US3535113 A US 3535113A
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colour
solution
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Jan Jaeken
Wilhelmus Janssens
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C7/18—Processes for the correction of the colour image in subtractive colour photography

Definitions

  • the present invention relates to the production of photographic colour images, more particularly to a process of colour correction utilizing an integral masking procedure.
  • the cyan dye which should absorb red light and transmit green and blue light, usually absorbs to a minor degree green and blue light together with a major amount of red light.
  • the magenta dye which should absorb green light and transmit blue and red light, usually absorbs to a minor degree red and blue light together with a major amount of green light.
  • the yellow dye which should absorb blue light and transmit green and red light, is usually satisfactory.
  • the mask be integral with the coloured images.
  • coloured mask images are automatically formed in photographic colour materials by the use of a coloured colour coupler absorbing light in the region of side-absorption of the dye formed with said colour coupler on colur development.
  • the mask image is formed by the coloured colour coupler itself, which is left on the nonexposed areas after colour development.
  • the colour coupler which is left, in the non-exposed areas after image-wise exposure and primary colour development of the silver halide emulsion layer is treated oxidatively in the presence of a so-called masking compound for coupling therewith so as to form a masking dyestuff.
  • the oxidative treatment usually is carried out in a photographic bleaching bath, e.g. a potassium hexacyanoferrateflll) containing alkaline aqueous solution used for removing the silver metal formed by development.
  • a photographic bleaching bath e.g. a potassium hexacyanoferrateflll
  • a colour corrected image is formed in a photographic element comprising a silver halide emulsion layer and a colour coupler, e.g. a colour coupler for magenta of the pyrazolone type, which is reactive with the oxidation product of an aromatic amino developing agent to form by colour development a primary dye image, more particularly a magenta dye image which absorbs a major proportion of light in the green region of the visible spectrum, and undesirably absorbs a minor proportion of light in the blue region of the visible spectrum, by treating the exposed and colour-developed photographic element with an oxidizing solution, such as a photographic bleaching bath, in the presence of a compound which oxidatively couples with the residual colour coupler, whereby a secondary dye image is formed more particularly a yellow dye image, having a gradation opposite to that of said primary dye image, and absorbin glue light but transmitting substantially all the light in the green region of the visible spectrum.
  • a colour coupler e.g. a colour coupler for magenta of the
  • That object has been accomplished by forming a dye stuff substantially absorbing in the red region of the visible spectrum by the oxidative copulation of the colourless magenta-forming colour coupler of the pyrazolone type, which is left after the colour development with a compound corresponding to the following general formula:
  • R represents a hydrogen atom, or a monovalent organic group such as an alkyl group, an aralkyl group or an aryl group, or a bivalent organic group linked to an ortho-atom of the aromatic group represented by A including these groups in substituted form:
  • R represents a monovalent organic radical such as an alkyl group, an aralkyl group or an aryl group, or a bivalent organic group linked to an ortho-atom of the aromatic group represented by A, including these groups in substituted form,
  • R repreesnts a.hydrogen atom, or a substituent which splits 01f by said oxidative copulation
  • A represents an aromatic group, which in p-position to the group is substituted by the NHR group, and in the o-positions in respect of theNHR group is substituted with a substituent by which the NHR group is sterically hindered and A includes such an aromatic group which is still further substituted.
  • Sterical hindrance lowers the reduction power of the aromatic phenylenediamine derivative to such an extent that it practically does no longer possess developing power for exposed silver halide.
  • sterically hindering substituents are particularly mentioned a halogen atom, e.g., a chlorine atom or a bromine atom, an alkyl group, e.g.
  • a methyl group an alkoxy group, e.g., a methoxy group or an ethoxy group, an acyl group, an acyl-substituted amino group, a sulphamyl group, a sulphonylalkyl group, a sulphonylaryl group, a sulpho group, or a carboxyl group.
  • R -substituents which can split off by the said oxidative copulation, are particularly mentioned a sulphonylalkyl, group, a sulphonylaryl group, wherein the alkyl and aryl radical may be further substituted, a sulpho group, a carbamyl group, a halogen atom, a sulphomethyl ene group, a carboxymethylene group and a phosphonic acid-substituted methyl group.
  • the aromatic group represented by A may be further substituted, e.g., with a halogen atom, a cyano group, a sulphamyl group, a carboxyl group, a sulpho group, an alkyl group, an aryl group, an aralkyl group or a cycloaliphatic group, or make part of a ring system comprising condensed rings selected from the group of aromatic, alicyclic, or heterocyclic rings, which may be further substituted.
  • a halogen atom e.g., a cyano group, a sulphamyl group, a carboxyl group, a sulpho group, an alkyl group, an aryl group, an aralkyl group or a cycloaliphatic group, or make part of a ring system comprising condensed rings selected from the group of aromatic, alicyclic, or heterocyclic rings, which may be further substituted.
  • R' represents a hydrogen atom or an organic radical, e.g., an alkyl group, an aralkyl group, or an aryl group, including these groups in substituted form,
  • R represents an organic radical, eg an alkyl group, an aralkyl group, or an aryl group including these groups in substituted form, or R together with R' forms a nitrogen-containing nucleus, e.g., a piperidino, morpholino, piperazine or pyrazole ring, including such nuclei in substituted form,
  • each of R' and R represents a sterically hindering substituent for the NH group, e.g., a halogen atom such as a chlorine atom, an alkyl-, alkoxy-, cyano-, acyl, acyl-substituted amino-, sulphamyl-, sulphonylalkyl-, sulphonylaryl-, sulpho-, or carboxyl groups,
  • a halogen atom such as a chlorine atom, an alkyl-, alkoxy-, cyano-, acyl, acyl-substituted amino-, sulphamyl-, sulphonylalkyl-, sulphonylaryl-, sulpho-, or carboxyl groups
  • each of R and R represents a hydrogen atom, or a substituent e.g., a halogen atom, a cyano radical, a sulfamyl radical, a carbamyl radical, an acyl radical, a sulpho radical, a carboxyl radical, an alkoxyl group, an alkyl group, an alicyclic group, an aralkyl group or an aryl group including these groups in substituted form,
  • a substituent e.g., a halogen atom, a cyano radical, a sulfamyl radical, a carbamyl radical, an acyl radical, a sulpho radical, a carboxyl radical, an alkoxyl group, an alkyl group, an alicyclic group, an aralkyl group or an aryl group including these groups in substituted form,
  • R together with R and/or R together with R forms an aromatic, a partly hydrogenated aromatic or heterocyclic condensed nucleus, including such nucleus in substituted form, or
  • R together with R' form a condensed nitrogen-containr ing heterocyclic nucleus including such nucleus in substituted form, or
  • R together with R form a condensed nitrogen containing hereto-cyclic nucleus including such nucleus in substituted form.
  • said compounds contain a substituent making them fast to diffusion in photographic colloids so that they can be selectively incorporated into one silver halide emulsion layer of a photographic multilayer colour material.
  • N Nll2 CII3-(CH2)J5 i 12.1 g. (0.01 mole) of 3,5-dimethylaniline, prepared according to A. Van Loon, Rec.Tr.Ch.Pays-Bas 79 (1960) 986, and 7 cc. of 98% formic acid are refluxed for minutes.
  • the water formed is distilled under reduced pressure on an oil bath of 100 C.
  • the residue is recrystallized from petroleum naphtha. Yield: 10.8 g. of 3,5-dimethylformanilide. Melting point: 74 C.
  • the p-phenylenediamine derivatives yield a cyan mask dyestuff compensating for the unwanted side-absorption in the red region of the spectrum of the magenta dyestulf formed by colour development.
  • the p-phenylenediamine derivatives described in the present invention when used in photographic colour materials are preferably incorporated into a light-sensitive silver halide emulsion layer containing a magenta-forming colour coupler of the pyrazolone type.
  • the p-phenylenediamine derivatives forming a green mask may be used in combination with compounds forming a yellow mask, which compensates for the unwanted side-absorption in the blue of the primary magenta dyestufi formed on colour development.
  • Colour couplers of the pyrazolone type which are particularly suitable for being used in a masking process according to the present invention are 3-acylaminopyrazolone compounds e.g. thos described in the Belgian patent specification 654,110 and UK. patent specification 1,007,847, the latter specification containing a detailed description of the preparation of such couplers.
  • the mask-forming compound is incorporated into the light-sensitive silver halide emulsion layer containing the magenta-forming colour coupler in a form made fast to diifusion by the introduction in the structure of said compound of an aliphatic radical containing from 5 to 20 carbon atoms in straight line.
  • the silver halide emulsion is prepared by means of the usual photographic colloids such as e.g. gelatin, polyvinyl alcohol, casein, zein, collodion or other natural or synthetic colloids.
  • the silver halide emulsion can be coated on a support consisting of paper, glass, nitrocellulose, cellulose esters, such as cellulose triacetate, polyester, polystyrene or other natural or synthetic resins, and may form part of a photographic material with one or more silver halide emulsion layers.
  • a multilayer photographic colour material usually comprises the following elements: a support, a red-sensitive emulsion layer having a cyan-forming colour coupler, a green-sensitive emulsion layer having a magenta-forming colour coupler and a blue-sensitive emulsion layer having a yellow-forming colour coupler.
  • a yellow filter composed in most of the cases of a gelatin layer containing dispersed colloidal silver, located between the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
  • a photographic colour negative masked according to the present invention can be formed as follows: after exposure to a coloured original of a photographic material containing in a silver halide emulsion layer sensitive to green light a magenta-forming colour coupler of the pyrazolone type and a mask-forming compound according to the present invention, silver halide is reduced to silver at the exposed areas in a colourdeveloping bath containing an aromatic primary amino colour developing agent, which at the same time is oxidized. The oxidized developing agent reacts with the colour coupler and forms a dyestuff, the mask-forming compound according to the invention not being aifected.
  • the photographic material is treated with an alkaline oxidizing bath, such as a photographic bleaching bath wherein the oxidative coupling of the mask-forming compound with the residual pyrazolone takes place. Thereupon the colour material is washed with water, fixed and dried.
  • an alkaline oxidizing bath such as a photographic bleaching bath wherein the oxidative coupling of the mask-forming compound with the residual pyrazolone takes place.
  • the colour material is washed with water, fixed and dried.
  • N,N-dialkyl-pphenylenediamines such as N-N-diethyl-p-phenylenediamine and N,N-diethyl-Z-methyl-p-phenylenediamine
  • derivatives thereof such as N,N-dialkyl-N -sulphomethylor N,N-dialkyl-N -carboxymethyl-p-phenylenediamine.
  • EXAMPLE 1 225 g. of a photographic silver bromide iodide emulsion, prepared by means of 50 g. of silver nitrate and 80 gof gelatin pro kg., are melted at 40 C. with 150 cc. of water. To this emulsion are added successively:
  • the material is washed for 5 minutes and fixed again for 5 minutes at 20 C. in a fixing bath of the following composition:
  • EXAMPLE 2 225 g. of a photographic silver bromide iodide emulsion, prepared by means of g. of silver nitrate and g. of gelatin pro kg., are melted at 40 C. with cc. of water. To this emulsion are added successively:
  • R is hydrogen, an alkyl group, an aralkyl group or an aryl
  • R is an alkyl group, an aralkyl group, or an aryl group, or R together with R forms a nitrogen-containing heterocyclic nucleus
  • R is hydrogen or a substituent splitting off by said coueach of R and R is a sterically hindering substituent for the NHR group
  • each of R and R is hydrogen, or an aliphatic, alicyclic,
  • R together with R and/or R together with R forms an aromatic, partly hydrogenated aromatic or heterocyclic condensed nucleus
  • R toegther with R forms a condensed nitrogen-containing heterocyclic nucleus
  • R together with R forms a condensed nitrogen-containing heterocyclic nucleus
  • each of said sterically hindering substituents in the said mask-forming compound is a halogen atom, an alkyl group, an alkoxy group, an acyl group, an acyl-substituted amino group, sulfonyl, a sulfonyl-alkyl group, a sulfonylaryl group, sulpho, or carboxy in acid or salt form, and
  • said substituent which splits off by said oxidative coupling is a sulfonylalkyl group, a sulfonylaryl group, sulpho, carbamyl, a halogen atom, sulfomethylene, carboxymeth ylene or phosphoric acid-substituted methyl.
  • a color photographic element having superposed silver halide emulsion layers sensitive to different regions of the visible spectrum, at least one of said layers containing a color coupler for magenta of the pyrazolone type and in non-migratory state a mask-forming compound corresponding to the following general formula:
  • R' is hydrogen, an alkyl group, or an aryl group
  • R' is an alkyl group or an aryl group, or
  • R is hydogen or a substituent splitting off by said coueach of R' and R is a sterically hindering substituent se ected from a halogen atom, an alkyl group, an alkoxy group, and
  • each of R and R is hydrogen, an alkyl group, an alkoxy group or a halogen atom.

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  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US610023A 1966-01-18 1967-01-18 Production of color masking images using p-phenylenediamine mask-forming compounds Expired - Lifetime US3535113A (en)

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Application Number Priority Date Filing Date Title
GB2241/66A GB1153561A (en) 1966-01-18 1966-01-18 Improvements relating to the Producion of Colour Images

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US3535113A true US3535113A (en) 1970-10-20

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US (1) US3535113A (ru)
BE (1) BE692636A (ru)
DE (1) DE1644046A1 (ru)
FR (1) FR1508682A (ru)
GB (1) GB1153561A (ru)
NL (1) NL6700716A (ru)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066456A (en) * 1974-12-10 1978-01-03 Gaf Corporation Incorporated carboxy substituted p-phenylenediamine color developer
US4066457A (en) * 1974-12-10 1978-01-03 Gaf Corporation Color developer for diffusion transfer
EP0152274A2 (en) * 1984-02-07 1985-08-21 Kyowa Medex Co. Ltd. Method for the determination of Leucine Aminopeptidase (LAP)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE786710A (fr) * 1971-10-04 1973-01-25 Bristol Myers Co Composition pour la teinture du cheveu avec

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE519872A (ru) * 1952-05-13
US3028237A (en) * 1957-04-26 1962-04-03 Agfa Ag Masking of cyan images in color photography

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE519872A (ru) * 1952-05-13
US3028237A (en) * 1957-04-26 1962-04-03 Agfa Ag Masking of cyan images in color photography

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066456A (en) * 1974-12-10 1978-01-03 Gaf Corporation Incorporated carboxy substituted p-phenylenediamine color developer
US4066457A (en) * 1974-12-10 1978-01-03 Gaf Corporation Color developer for diffusion transfer
EP0152274A2 (en) * 1984-02-07 1985-08-21 Kyowa Medex Co. Ltd. Method for the determination of Leucine Aminopeptidase (LAP)
EP0152274A3 (en) * 1984-02-07 1989-10-11 Kyowa Medex Co. Ltd. Method for the determination of enzyme activity

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GB1153561A (en) 1969-05-29
NL6700716A (ru) 1967-03-28
FR1508682A (fr) 1968-01-05
DE1644046A1 (de) 1971-04-15
BE692636A (ru) 1967-07-17

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