EP0047449A2 - Procédé pour la production d'images photographiques en couleurs - Google Patents

Procédé pour la production d'images photographiques en couleurs Download PDF

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Publication number
EP0047449A2
EP0047449A2 EP81106722A EP81106722A EP0047449A2 EP 0047449 A2 EP0047449 A2 EP 0047449A2 EP 81106722 A EP81106722 A EP 81106722A EP 81106722 A EP81106722 A EP 81106722A EP 0047449 A2 EP0047449 A2 EP 0047449A2
Authority
EP
European Patent Office
Prior art keywords
color
color developer
group
developer compound
azomethine
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.)
Withdrawn
Application number
EP81106722A
Other languages
German (de)
English (en)
Other versions
EP0047449A3 (en
Inventor
Peter Dr. Bergthaller
Friedrich-Wilhelm Dr. Kunitz
Karl-Wilhelm Dr. Schranz
Erich Dr. Wolff
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.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert 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 Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0047449A2 publication Critical patent/EP0047449A2/fr
Publication of EP0047449A3 publication Critical patent/EP0047449A3/de
Withdrawn legal-status Critical Current

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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • the invention relates to a method for producing color photographic images, in which azomethine dyes produced by chromogenic development are stabilized by complexation with metal salts.
  • color developer compounds which contain a group capable of chelating adjacent to a primary amino group, and the azomethine dyes produced in the chromogenic development are converted into corresponding azomethine dye-metal complexes.
  • Chromogenic development is usually used to produce color images, in which silver halide emulsion layers exposed to image are developed in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers.
  • color developers oxidation product of the developer substances which arises in accordance with the silver image reacts with the color coupler to form a dye image.
  • Aromatic compounds containing at least one primary amino group in particular those of the p-phenylenediamine type, which give azomethine dyes with the color couplers are usually used as color developers.
  • the object of the invention is to improve the stability of image dyes obtained by chromogenic development.
  • the stability, in particular the lightfastness, of azomethine dyes can be improved by complexing with metals if an additional coordination point and thus the prerequisite for an increased tendency to form complexes is created in the azomethine dye, in particular in the vicinity of the azomethine group formed by chromogenic development, by means of suitable substituents .
  • This can be achieved by using color developers which contain a group capable of chelating adjacent to the primary amino group. When treated with metal salts, the azomethine dyes obtained with such color developers are converted into the corresponding azomethine dye-metal complexes.
  • An important characteristic of the invention is therefore the use of special color developer compounds.
  • these have, next to a primary amino group, a group capable of chelating, e.g. in the form of a nitrogen atom or a carbon atom to which a substituent capable of chelating is bound.
  • this group capable of chelating comes into the vicinity of the azomething group formed from the primary amino group, which apparently results in a favorable prerequisite for subsequent complex formation with metal ions.
  • the observed intensive color shift speaks for the participation of the chromophoric azomething group in the complex formation.
  • the primary amino group is therefore bound to a carbon atom of a 5- or 6-membered carbocyclic or heterocyclic aromatic ring, as in the previously known color developer compounds.
  • the carbocyclic or heterocyclic ring completed by X in formula I is otherwise so procured and substituted by Y and optionally further substituents in a suitable manner, so that a color developer compound results.
  • the best known examples of such color developer compounds are those of the p-phenylenediamine type, which result from formula I when the ring completed by X is a benzene ring and the substituent Y is a disubstituted amino group in the p-position to the primary amino group.
  • color developer compounds already contain, in the form of a group capable of chelating, adjacent to the primary amino group (enolic) hydroxyl group and are therefore directly usable for the process of the present invention.
  • color developer compounds of the present invention having an X completed heterocyclic ring include color developer bonds derived from 1,3-diazine.
  • color developers which can be used according to the invention are given below:
  • the color developer compounds used according to the invention have a primary amino group.
  • this does not rule out the fact that the primary amino group is initially only latent is there. This means that the primary amino group is in a capped form. from which it is released during the actual chromogenic development, possibly under the influence of alkali, and which is available for the oxidative coupling with the color coupler.
  • Color developer precursor compounds with a latent primary amino group are known, for example, from GB 783 887, US 3,342,599 or DE-AS 1 007 171. Such compounds are particularly suitable for incorporation into color photographic recording materials.
  • the color developer compounds can be equipped with diffusion-proofing radicals which are either in the actual color developer radical (for example in the form of a longer alkyl radical having up to 18 carbon atoms for R 1 in formula II) or in the radical capping the primary amino group can.
  • color couplers which can be chromogenically developed with known color developer substances can be used as color couplers in the process according to the invention.
  • Color couplers of various types come into question here (4-equivalent coupler, 2-equivalent coupler, DIR coupler, Mask coupler). The prerequisite is that a chromophore azomething group is formed in the chromogenic development.
  • yellow couplers examples are given below:
  • Yellow couplers give yellow to yellow-orange dyes in the oxidative coupling with the color developers according to the invention having the structure D-1 to D-8.
  • Suitable purple couplers for example, have the structure:
  • Purple couplers generally give red to purple hues with the developers of structure D-1 to D-9; M-11 gives gray and M-12 gives yellow dyes.
  • Typical examples of cyan couplers are:
  • Phenolic cyan couplers couple with the color developers D-1 to D-8 according to the invention blue to cyan; naphtholic, on the other hand brown, orange or red.
  • C-5 couples brown-red, C-7 orange and C-8 blue-green.
  • the color couplers described as examples have in common that they have groups which make them diffusion-resistant in hydrophilic binder layers. Such couplers are generally embedded in a layer of a photographic recording material in a diffusion-resistant manner.
  • the incorporation methods used depend on whether the couplers are hydrophilic couplers or hydrophobic couplers. The corresponding methods are known and do not need to be explained here.
  • the incorporation in the photographic layer be it a light-sensitive silver halide emulsion layer or a hydrophilic binder layer adjacent to it, ensures a uniform distribution of the Color coupler is produced, from which an image-like distribution of azomethine dyes is formed during the chromogenic development of the light-sensitive material in the presence of the color developer substances according to the invention.
  • soluble color couplers can be used in the same way, but also according to the so-called development process, which, in contrast to the previously mentioned color couplers, are not incorporated into the layer but are contained in solution in the color developer bath.
  • This method also requires no further explanation at this point. Since the developer bath penetrates uniformly into the imagewise exposed silver halide emulsion layer, a uniform distribution of the color coupler in the layer initially arises here, which results in an imagewise distribution of azomethine dye in the layer during development with oxidative coupling with the color developer substance.
  • the processing is accordingly carried out in the customary manner in that the imagewise exposed recording material is chromogenically developed in the presence of a color coupler.
  • a further essential feature of the method according to the invention consists in treating the generated colored image with a solution of a metal salt following the chromogenic development, the corresponding azomethine dye-metal complex being formed.
  • Suitable metal salts are, in particular, salts of metals from main groups I to IV and groups I and II as well as subgroups IV to VIII of the periodic system of the elements, which are known to be suitable as the central atom of organometallic complexes.
  • Salts of the following metal ions are particularly preferred according to the invention: Ag, Ba 2+ , Ca 2+ , Mg 2+ , Co 2+ , Co 3+ , Cu 2+ , Cr 3+ , Fe 2+ , Fe 3+, Ni 2+ , Zn 2+ , Cd 2+ , Mn 2+ , Sr 2+ .
  • the metal salts come in aqueous Solution for use, wherein the concentration of the metal salts can fluctuate within wide limits, for example between 0.001 and 20% by weight, preferably between 0.1 and 1% by weight.
  • the complexation time can. from 0.1 seconds to 30 minutes and preferably from 3 seconds to 3 minutes, at pH values from 2 to 13.
  • certain buffer solutions contain complex-forming anions (eg citrate, phosphate) which are associated with the azomethine dyes can compete the metal ion, so that sometimes secondary Farbumschlä e g be observed.
  • Layers that contain only extremely low dye concentrations can be "visually enhanced” due to the change in the absorption spectra. Due to the shift in the absorption maximum caused by complexation with metal ions.
  • the method according to the invention provides the possibility of shifting the spectrum of a particular dye which is barely perceptible to the eye into a spectral range, in that the eye has a higher intrinsic sensitivity without the extinction being significantly changed. For example, by using the color change from yellow to black or from yellow to blue, a yellow azomethine dye image that is difficult to perceive by the eye can be converted into a much more clearly visible blue azomethine dye-metal complex image. Except for a postponement of the
  • the possibility of moving from a silver image to a color-intensive dye image on the way via a chromogenic development opens up advantageous applications for the method according to the invention.
  • a monochromatic recording material which provides a metal complex dye image instead of a silver image.
  • the silver used can be completely recovered from the recording material by bleaching and fixing.
  • DIR connections can also be used to improve graininess and sharpness.
  • the method according to the invention is therefore suitable for the production of storable documents and for microphotography.
  • the method of the present invention is particularly interesting for X-ray photography, since the possibility of black metal complex dyes with significantly higher stability (compared with the dyes from the so-called color couplers of the m-aminophenol type according to DE-OS 2 818 363 and DE-OS 2 644 194 ) produce a significant silver saving.
  • Multi-colored images can also be produced by the method according to the invention, e.g. if multi-layer recording materials with different couplers are used, which after complexing with the same metal ion. deliver different complex dyes.
  • FIG. 1 shows the absorption spectra of the uncomplexed yellow dye (curve 1) and some of the dye-metal complexes formed.
  • Example 3 A material produced according to Example 1, but containing different silver deposits (AgNO 3 ), was processed with developer D-1 and then post-complexed in 1% CuS04 solution for 1 minute. The results are summarized in Table 3 below.
  • the material thus produced was then bathed in a 1% CuS04 solution for 5 minutes and then washed. This created a deep black layer.
  • Example 1 A material produced and processed in accordance with Example 1 was uncomplexed (yellow) and, after complexing with 1% CoC1 2 solution or 1% CuS04 solution, was irradiated with 4.8 ⁇ 10 7 lux.h in the Xenotest device, resulting in at density 1.5 the following percentage decrease in density
  • a conventional photographic X-ray recording material which additionally contains 1.8 g / m 2 of the yellow coupler Y-10 was exposed to X-rays in a conventional manner and then in a color developer solution which contained 3.0 g / 1 D-1 at pH 13.2 and 23 ° C for 30 seconds.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP81106722A 1980-09-09 1981-08-28 Process for the production of colour-photographic images Withdrawn EP0047449A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803033861 DE3033861A1 (de) 1980-09-09 1980-09-09 Verfahren zur herstellung farbfotografischer bilder
DE3033861 1980-09-09

Publications (2)

Publication Number Publication Date
EP0047449A2 true EP0047449A2 (fr) 1982-03-17
EP0047449A3 EP0047449A3 (en) 1983-03-16

Family

ID=6111471

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81106722A Withdrawn EP0047449A3 (en) 1980-09-09 1981-08-28 Process for the production of colour-photographic images

Country Status (4)

Country Link
US (1) US4386155A (fr)
EP (1) EP0047449A3 (fr)
JP (1) JPS5782838A (fr)
DE (1) DE3033861A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087446B1 (fr) * 1981-09-02 1986-07-09 Kodak Limited Procede de formation d'une image photographique de coloration

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8630304D0 (en) * 1986-12-18 1987-01-28 Kodak Ltd Photographic acetanilide couplers
JP2717467B2 (ja) * 1991-06-20 1998-02-18 富士写真フイルム株式会社 発色現像主薬、処理組成物およびカラー画像形成方法
JP4808459B2 (ja) * 2005-09-29 2011-11-02 富士フイルム株式会社 染料含有ネガ型硬化性組成物、カラーフィルタおよびその製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE584545A (fr) * 1958-11-12
USB342599I5 (fr) * 1965-06-07
US3762922A (en) * 1971-03-31 1973-10-02 Du Pont Silver halide photographic images
JPS589938B2 (ja) * 1977-04-27 1983-02-23 コニカ株式会社 感光性ハロゲン化銀多層カラ−写真材料
JPS5482234A (en) * 1977-12-14 1979-06-30 Fuji Photo Film Co Ltd Photostabilizing method for organic base material
JPS5916261B2 (ja) * 1978-12-20 1984-04-14 富士写真フイルム株式会社 カラ−画像形成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0087446B1 (fr) * 1981-09-02 1986-07-09 Kodak Limited Procede de formation d'une image photographique de coloration

Also Published As

Publication number Publication date
DE3033861A1 (de) 1982-04-29
US4386155A (en) 1983-05-31
JPS5782838A (en) 1982-05-24
EP0047449A3 (en) 1983-03-16

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Inventor name: SCHRANZ, KARL-WILHELM, DR.

Inventor name: KUNITZ, FRIEDRICH-WILHELM, DR.