EP0095650B1 - Elément récepteur d'image pour le procédé par diffusion-transfert de colorants - Google Patents

Elément récepteur d'image pour le procédé par diffusion-transfert de colorants Download PDF

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EP0095650B1
EP0095650B1 EP83104831A EP83104831A EP0095650B1 EP 0095650 B1 EP0095650 B1 EP 0095650B1 EP 83104831 A EP83104831 A EP 83104831A EP 83104831 A EP83104831 A EP 83104831A EP 0095650 B1 EP0095650 B1 EP 0095650B1
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Prior art keywords
image
denotes
layer
alkyl
atoms
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EP0095650A2 (fr
EP0095650A3 (en
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Jürgen Dr. Strauss
Günter Dr. Helling
Peter Dr. Bergthaller
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • G03C8/56—Mordant layers

Definitions

  • the invention relates to an image receiving element for the production of 'color photographic images according to the color diffusion transfer process, wherein predominantly post-metallizable diffusible dyes are used for the production of the color image.
  • the image-receiving element has a layer combination arranged on a layer support, consisting of a layer which can be colored by diffusible organic dyes and an adjacent hydrophilic binder layer which contains a metallizing agent in the form of a dispersion of a water-insoluble organic copper (II) or nickel complex.
  • dye developers are suitable as coloring compounds, which are compounds which are originally diffusible and have a chromophoric residue and a developer function by means of which the compounds are immobilized during development, or non-diffusing coloring compounds with a chromophoric residue, which is released during development as a diffusible dye or dye precursor (color releaser).
  • the chromophoric rest of the dye developer or the dye releaser contains special substituents that are suitable as ligands for complex formation with polyvalent metal cations, it is possible to use the complex formation to improve the light stability, to influence the color tone and to fix the image dyes transferred into the image-receiving layer.
  • the complexation is expediently carried out only after the color transfer has taken place, for which purpose either the image-receiving material with a solution of the complex-forming polyvalent metal cations, for. B.
  • the polyvalent metal cations are embedded in one or more layers of the image-receiving material so that they can react immediately during the development process with the diffusing dyes to form a complex.
  • US-A4282305 describes an image-receiving element with a double-layer structure, consisting of a metal donor layer containing a metallizing agent in a hydrophilic binder and a dyeable layer arranged above it.
  • Aqueous solutions of metal salts e.g. B. mentioned nickel sulfate.
  • the dyeable layer contains a polymeric mordant with heterocyclic tertiary amino groups, e.g. B. polyvinylimidazole.
  • casting problems arise during the production due to the reaction of copper (II) or nickel ions with polyvinylimidazole.
  • such an image-receiving element is unusable if copper salts are used as the metallizing agent, since even proportions of 5 mmol / m 2 or less then cause an undesirable prohibitive coloring of the image whites.
  • the object of the invention is to design an image receiving element for color photographic images according to the color diffusion transfer process, in which the metallizing agent and polymeric mordant are contained in separate but adjacent layers, in such a way that the nickel or copper (II) ions serving as the metallizing agent are bound diffusion-resistant, do not agglomerate with cationic pickling agents and have no disadvantages for the resulting image, in particular no disruptive intrinsic coloration.
  • the metallizing agent and polymeric mordant are contained in separate but adjacent layers, in such a way that the nickel or copper (II) ions serving as the metallizing agent are bound diffusion-resistant, do not agglomerate with cationic pickling agents and have no disadvantages for the resulting image, in particular no disruptive intrinsic coloration.
  • the invention relates to an image-receiving element for the color diffusion transfer process, with a layer arranged on a layer support which can be colored by diffusible organic dyes and an adjacent hydrophilic binder layer containing a metallizing agent for post-metallizable dyes, characterized in that the adjacent hydrophilic binder layer forms the metallizing agent in the form an optionally oil-containing dispersion of a water-insoluble organic copper (II) or nickel complex of a compound of one of the following formulas I to VI.
  • Nickel complexes of 2,2'-thiobisphenols, 2,2'-sulfinylbisphenols or 2,2'-sulfonylbisphenols (formulas III and IV)
  • Nickel complexes and copper (II) complexes of enolizable 1,3-dicarbonyl compounds e.g. B. 1,3-diketones (formula V) or ⁇ -ketocarboxylic acid esters (formula VI)
  • the radicals R 1 to R 8 shown in the formulas I to VI have, inter alia, the function of ballast radicals, ie the size of all the radicals present in a compound is such that diffusion-resistant incorporation of the nickel or Copper (II) complexes in photographic layers is guaranteed.
  • hydrocarbon radicals represented by R 1 and R 4 are: alkyl, aralkyl, cycloalkyl or aryl. Particular examples are ethyl, n-butyl, 2-ethylhexyl, n-dodecyl, n-octadecyl, benzyl, phenylethyl, phenyl, 4-dodecylphenyl, cyclohexyl.
  • a hydrocarbon radical interrupted by -0- is, for example, an alkoxyalkyl radical or an aroxyalkyl radical; an example of this would be a 4- (2,4-bis-tert-amylphenoxy) butyl group.
  • An alkyl group represented by R 2 , R 3 , R 5 , R 7 , R 9 , R 11 or R 12 is, for example, methyl, ethyl, n-propyl, n-butyl, isobutyl or n-heptadecyl.
  • aryl groups represented by R 2 , R 7 , R 11 or R 12 are phenyl and naphthyl, which may optionally be further substituted, e.g. B. by hydroxy, methoxy, t-butyl or a group with ballast character, such as an n-dodecylthio or n-hexadecyloxy group.
  • iminobismethylenephosphonic or phosphinic acids used to produce suitable nickel or copper (II) chelates are known in principle. Their production is described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume XII / 1, pages 486-488 and in the articles by Petrov Makljaev and Bliznjuk in Chem. Abstr. 54, 260 (1960) and G.M. Kosolapoff in J. Amer. Chem. Soc. 67.1 180 (1945); further in US Pat. No. 2,470,190.
  • N-substituted iminobismethylenephosphonic diester or iminobismethylenephosphinic acid ester formed can be easily saponified with mineral acids, in particular with hydrobromic or hydroiodic acid.
  • the starting materials for the iminobismethylenephosphonic acids and phosphinic acids according to the invention are all known and technically easily accessible compounds.
  • So z. B the alkanephosphonous monoalkyl from the easily accessible dialkyl esters by acidic saponification in a simple manner and in high yields.
  • Detailed information on individual syntheses can be found in M. Sander, Chem. Ber. 93, 1220 (1960) and K.A. Petrov, Zhnr. obszh. Khim. 31, 179 (1961).
  • iminodicarboxylic acids used to produce suitable nickel or copper (II) chelates are also known in principle. Their manufacture is described for example in Houben-Weyl, volume XI / 2 pages 404-416 and in the article by Stein, Gregor and Spoerri in J. Amer. Chem. Soc. 77, 191 (1955).
  • 2,2'-thiobisphenols (formula 111) is known in principle and z. B. in GB-A 858 890 and described in DE-A 29 37 294. All of the 2,2'-thiobisphenols listed were prepared by reacting the corresponding phenol with the 0.5 molar amount of sulfur dichloride in the presence of a little ZnCl 2 by the process indicated there. If the phenol used has two unsubstituted o-positions to the phenolic hydroxyl group and sulfur dichloride is used in excess, reaction products are obtained which, in addition to the thiobisphenols, contain higher molecular weight compounds with 2, 3 or more radicals.
  • the sulfoxides and sulfones can be prepared from the thiobisphenols by mild oxidation with H 2 0 2 in glacial acetic acid or in dimethylformamide in the presence of tungstic acid. They are more soluble in methanol than the thiobisphenols.
  • 1,3-diketones (formula V) and ⁇ -keto esters (formula VI) are known in principle and z.
  • a base eg NaH
  • 4-acylpyrazolones (formula VII) are also known in principle and z. B. in BE-A 817 382, DE-A 24 10 370 and US-A4146540.
  • the preparation of compound 9 is described below as an example of the synthetic methods used.
  • Both the Cu (II) chelate and the Ni chelate are readily soluble in ethyl acetate.
  • Chelate 1 probably corresponds to the formula
  • the water-insoluble Ni chelates of 2,2'-thiobisphenols, 2,2'-sulfinyl bisphenols and 2,2'-sulfonyl bisphenols contain 0.5-1.5 moles of nickel per mole of bisphenol (III, IV); in the case of bisphenols III they correspond, for example, to the general formulas VIII, IX, X or XI, in which the radicals given have the meaning described above and L, L 'are non-colored neutral (L) or anionic (L') foreign ligands which be included in the production of the complexes.
  • the water-insoluble nickel complexes of compounds of the formulas 111 and IV can be prepared in various ways. Those processes are preferred in which the bisphenol and optionally an additional ligand are present in a low-boiling, water-immiscible solvent and the nickel salt is introduced via an aqueous or at least partially aqueous phase. The reaction is generally carried out with vigorous stirring and continued until nickel is no longer taken up from the aqueous phase. To accelerate the reaction, the mixture can be heated or part of the solvent can be distilled off. When the reaction has ended, the aqueous phase, which may contain excess nickel salt, is separated off.
  • the reaction is preferably carried out at pH values above 7, based on the aqueous phase.
  • An alkali hydroxide, an alkali alcoholate, an amine or amidine, an alkali phenolate, a water-soluble carbonate or a water-soluble salt of a carboxylic acid can be used as the base.
  • a foreign ligand L which is optionally incorporated in the nickel chelate, for example: a preferably tertiary mono- or diamine or amidine, e.g. B. ethyldiisopropylamine, bis-2-hydroxyethylcyclohexylamine, pyridine, diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -undecene, 1,5-diazabicyclo [4,3,0] -non-5-en, a di- or triester of phosphorous acid, e.g. B. tributyl phosphite, an aliphatic, cycloaliphatic or araliphatic alcohol, a glycol monohydrate, or the corresponding anion.
  • a preferably tertiary mono- or diamine or amidine e.g. B. ethyldiisopropylamine, bis-2-hydroxye
  • the preparation is carried out by boiling the starting compounds (compound 4 and nickel acetate in a molar ratio of 1: 2) in methanol in the presence of calculated amount of namethylate.
  • the complex is colored pale green and is readily soluble in toluene or ethyl acetate.
  • Chelate 10 is believed to have the structure
  • Chelate 11 probably has the structure
  • the metallizing agents used in accordance with the present invention are more or less water-insoluble compounds which are added to the respective layer in dispersed form, in which they are separated because of their water-insolubility Train phase. Incorporation into a hydrophilic binder layer usually takes place in such a way that the water-insoluble Cu (II) or Ni complexes are dispersed as a solution in a low-boiling solvent such as diethyl carbonate or ethyl acetate in the casting composition for a hydrophilic binder layer, expediently with simultaneous use an oil producer.
  • a low-boiling solvent such as diethyl carbonate or ethyl acetate
  • the oil formers are substances which generally boil above 180 ° C. and have good solubility for the water-insoluble organic copper (II) or nickel complexes to be dispersed.
  • the esters of glutaric acid, adipic acid, phthalic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, isophthalic acid, terephthalic acid and phosphoric acid or the esters of glycerol, as well as paraffin and fluorinated paraffin are preferably used because these compounds are chemically stable and very easily accessible, very much can be handled easily and have no adverse effect on the photosensitive materials when the dispersions are used for photographic purposes.
  • oil formers are particularly preferably used as oil formers according to the invention: tricresyl phosphate, triphenyl phosphate, dibutyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, glycerol tributyrate, glycerol tripropionate, dioctyl sebacate, paraffin and fluorinated paraffin.
  • Monoesters of long-chain alkylated succinic acids have also proven to be suitable oil formers. Such compounds are described in US-A 3,689,271.
  • the content of oil-forming agent is preferably between 10 and 200%, based on the amount by weight of the Cu (II) or Ni chelate used.
  • the water-insoluble Cu (II) or Ni complexes are incorporated as metallizing agents in a hydrophilic binder layer of an image-receiving element, which is adjacent to a hydrophilic binder layer that can be colored by diffusible dyes.
  • the metallization agent is expediently contained in a layer of the image-receiving element which is arranged on the side of the dyeable layer facing away from the photosensitive element, i. H. between the layer support of the image receiving element and the dyeable layer.
  • the dyeable layer of the image-receiving element according to the invention preferably contains, as a mordant for the diffusible image dyes, a polymer having structural units which have a heterocyclic amino function, preferably in quaternized or protonated form.
  • a heterocyclic amino function is understood to mean a nitrogen atom which is a ring member of a heterocyclic ring and (in the form of the tertiary base) is exclusively connected to those carbon or heteroatoms which are also ring members of a heterocyclic ring, in particular the same heterocyclic ring.
  • the nitrogen-containing heterocyclic ring completed by Z can contain at least one further nitrogen atom in addition to the nitrogen atom represented in the formula XII and can accordingly be linked to the polymer chain, optionally with the inclusion of a link L, either via a ring C atom or a ring N atom.
  • the ring can also be further substituted, e.g. B. by alkyl, especially methyl.
  • the polymer used as binder can contain further structural units, in particular structural units which contain the heterocyclic amino function mentioned, but not in quaternized or protonated form, but in the form of the tertiary base, and optionally structural units, which are derived from comonomers without the heterocyclic amino function mentioned and which are copolymerizable with the monomers containing the heterocyclic amino function mentioned.
  • the (mixed) polymers can be prepared by methods of solution or precipitation polymerization known to those skilled in the art.
  • the heterocyclic amino function can be introduced either by using appropriate monomers or by polymer-analogous reactions.
  • Suitable monomers are, for example, 4-vinylpyridine, 2-methyl-5-vinylpyridine, N-vinylimidazole, 2-methyl-N-vinylimidazole, 1-methacrolyloxyethylimidazole and their quaternization products with alkylating agents, such as. B. described in J. Polymer Science, Polymer Letters Ed., 16, 393-399 (1978); Polymer, 14, 639 (1973); J. Polymer Science, Polymer Chemistry Ed .; 13, 161-170 (1975).
  • the polymer-analogous reactions are based on predetermined reactive polymers, which are then reacted with appropriately substituted heterocycles.
  • One example is the reaction of polymeric maleic anhydrides with aminopropylimidazole.
  • ß-unsaturated compounds such as. B. vinyl aromatics (styrenes), vinyl esters, vinyl ethers, vinyl chloride, vinylidene chloride, N-vinyl pyrrolidone, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides and maleic acid derivatives.
  • anionic image dyes can suffer a considerable loss in light fastness when fixed on cationic mordants.
  • the loss of light fastness is strongly dependent on the structure and the form of storage of the cationic mordant and is also connected with the constitution of the specified image dye in a manner which is difficult to predict.
  • the metallization is carried out by means of Cu (II) or Ni ions, which are supplied by the so-called metal donor layer adjacent to the dyeable layer, in which these ions are dispersed in the form of water-insoluble organic complex compounds.
  • the copper or nickel complexes used according to the invention can be used in a wide variety of ways in order to store copper (II) or nickel ions diffusion-resistant in layers without losing their reactivity towards complex-forming dyes.
  • the complexes can be mixed with binders such as gelatin, polyvinyl alcohol, cellulose derivatives, polyacrylamides and used in the form of these mixtures to produce transparent layers.
  • the Cu (II) or Ni complexes described are also suitable as metal donors for the insert tion in photographic layers in which a uniform or imagewise staining is to be produced by reaction of the complex-bound metal ions with other organic colorless or colored color-forming complexing agents.
  • the generation of a uniform staining serves, for example, to make an undesired image which arises during the development of an integral recording material invisible after the image-wise exposure, e.g. B. a negative color image retained in the photosensitive member when a positive color image is formed in the image receiving layer.
  • the complexes described according to the present invention are advantageously used in a so-called metal donor layer (“metal source”), which together with a dyeable layer and a layer support constitutes a so-called image-receiving element.
  • metal source metal donor layer
  • Such an image receiving member may be an integral part of a multi-layer color photographic light-sensitive material, in which case it either remains attached to the original photosensitive member or is separated therefrom after development.
  • the image-receiving element can, however, also initially be present as a separate, non-light-sensitive photographic material, which is only brought into contact with the light-sensitive recording material during processing and, if appropriate, subsequently separated again.
  • the image receiving element according to the present invention is distinguished by considerable advantages, especially with regard to the high level of light fastness and the clear color tone of the color transfers, in particular when image dyes with chelatable groups are used.
  • the image-receiving elements can be hardened in a conventional manner to improve their scratch resistance and to limit the absorption of liquid during processing with an alkaline medium.
  • the stability of the dispersed copper (II) or nickel chelates is high enough to prevent Cu (II) or NI ions from escaping into the hydrophilic binder phase during prolonged storage and possibly diffusing there as far as the incorporated color releaser. which would result in a loss of diffusibility and photographic sensitivity.
  • the image-receiving element according to the invention is therefore particularly suitable for producing integral mono-sheet or single-sheet materials in which the image-receiving element is present together with the layers of the letter-sensitive element in a closed layer structure and is optionally separated from those only by an opacifying layer which serves for optical separation.
  • the image-receiving element according to the invention with the hydrophilic binder layer containing the described chelates in the vicinity of the dyeable layer is suitable as an image-receiving material for any type of photographic color diffusion transfer process in which diffusing image dyes or diffusing color formers (image dye precursors) with chelating substituents are used and / or released in an imagewise manner can be transferred to an image receiving layer. After the transfer has taken place, such a photographic material in the image-receiving layer has an image-wise distribution of one or more such dyes in the form of the corresponding dye-metal complexes.
  • an integral photographic recording material in addition to the image-receiving element according to the invention with the (hydrophobic) copper (II) or nickel complexes described, can have a layered photosensitive element which has at least one layer with a preferably acidic dye or a corresponding precursor compound and at least one contains a light-sensitive layer, in particular a light-sensitive silver halide emulsion layer.
  • the dyes or dye precursor compounds mentioned are collectively referred to below as coloring compounds.
  • such a recording material can also contain a plurality of light-sensitive silver halide emulsion layers of different spectral sensitivity, as well as further non-light-sensitive layers such as intermediate layers, cover layers and other layers of the most varied functions, as are customary in multi-layer color photographic recording materials.
  • Photographic materials which have an image receiving element with copper (II) or nickel complexes according to the invention i. H. the image-receiving materials themselves and in particular also color-photographic recording materials which contain such an image-receiving material as an integral part may also contain acidic layers and so-called braking or deceleration layers, which together form a so-called combined neutralization system.
  • a neutralization system can be arranged in a known manner between the layer support and the image receiving layer arranged thereon or at another location in the layer structure, for. B. above the photosensitive layers, d. H. beyond these light-sensitive layers, viewed from the image-receiving layer.
  • the neutralization system is usually oriented so that the braking or retarding layer is between the acid layer and the location where the alkaline developing liquid or paste is exposed.
  • acid layers, brake layers or neutralization layers consisting of both are known, for example, from US Pat. No. 2,584,030, US Pat. No. 2,983,606, US Pat. No. 3,362,819, US Pat. No. 3,362,821, DE-A 2,455,762, DE -A 26 01 653, DE-A 26 52 464, DE-A 27 16 505, DE-A 28 16 878.
  • Such a neutralization system can also contain two or more brake layers in a known manner.
  • the photographic material can furthermore contain one or more pigment-containing opaque layers which are permeable to aqueous liquids. These can perform two functions. On the one hand, this can prevent the undesired access of light to light-sensitive layers, and on the other hand, such a pigment layer can be used in particular if a light or white pigment, e.g. B. Ti0 2 were used to form an aesthetically pleasing background for the color image generated. Integral color photographic recording materials with such a pigment layer are known, e.g. B. from US-A 2543 181 and DE-A 1 924430.
  • such pigment layers can be constructed from two or more partial layers, one of which, for example, is a white pigment and the other is, for example, a dark, light-absorbing pigment, e.g. B. carbon black.
  • This material can be composed in such a way that two different parts are produced separately from one another, namely the light-sensitive part (layer elements 1 to 5) and the cover sheet (layer elements 6 to 8), which are then placed on one another on the layer side and connected to one another, if appropriate using spacer strips so that a space for receiving a precisely measured amount of a developing liquid is formed between the two parts.
  • the layer elements 6 and 7, which together form the neutralization system, can also be arranged, albeit in the opposite order, between the layer support and the image-receiving layer of the light-sensitive part.
  • Means may be provided to introduce a developing liquid between two adjacent layers of the integral recording material, e.g. B. in the form of a laterally arranged, splitable container, which pours its contents under the action of mechanical forces between two adjacent layers of the recording material, in the present case between the photosensitive part and the cover sheet.
  • the photosensitive element contains a photosensitive silver halide emulsion layer and associated with this a coloring compound.
  • the coloring compound can be in a layer adjacent to the silver halide emulsion layer or in the silver halide emulsion layer itself, in the latter case the color of the image dye is preferably selected so that the predominant absorption range of the coloring compound does not match the predominant sensitivity range of the silver halide emulsion layer.
  • the light-sensitive element contains three such assignments of coloring compound and light-sensitive silver halide emulsion layer, the absorption range of the image dye resulting from the coloring compound generally matching the range of spectral sensitivity of the assigned silver halide emulsion layer substantially.
  • the color-providing compound is arranged in a separate binder layer (viewed in the direction of the light incident during the exposure) behind the silver halide emulsion layer or has an absorption which is different from that of the image dye ("Shifted image dyes" - US-A 3 854 945).
  • a shift in the absorption generally results in the image-receiving layer as a result of complex formation with the copper (II) or nickel ions present therein if dyes with substituents capable of chelating are used.
  • the coloring compounds can be colored compounds which are themselves diffusible and which begin to diffuse when the layers are treated with an alkaline working liquid and are only determined by the development at the exposed areas.
  • the coloring compounds can also be diffusion-resistant and release a diffusible dye in the course of development.
  • Color-imparting compounds which are a priori diffusible are known, for example, from German patents 1,036,640, 1,111,936 and 1,196,075.
  • the so-called described there Dye developers contain in the same molecule a dye residue and a group that is able to develop exposed silver halide.
  • color releasers are preferably used which contain substituents capable of complex formation in the dye residue.
  • substituents capable of complex formation in the dye residue include, in particular, azo dyes which, in addition to the azo bond, have chelating substituents such as -OH, -NHR or also ring nitrogen atoms.
  • Coloring compounds with such dye residues are described, for example, in Research Disclosure Publications No. 17 334 (September 1978) and No. 18 022 (April 1979), as well as in US Pat. No. 3,081,167, DE-A 27 40 719, DE- A 31 07 540, DE-A 31 15648 and DE-A 31 17 243.
  • Image-receiving sheets according to the invention and image-receiving sheets not according to the invention were produced by successively applying the layers indicated below on a polyethylene-coated paper backing (amounts per m 2 ):
  • Image receiving sheet 6 (not according to the invention)
  • a prior art image-receiving sheet (US-A 3,282,305) was prepared by following the same procedure as for sheet 1, but with the difference that layer 1 had the following composition:
  • an image-receiving layer with a smooth surface is always obtained.
  • the image receiving layer is faintly blue in the case of the image receiving sheets 7 and 8 and faintly yellow in the case of the image receiving sheets 9 and 10.
  • the optical density measured behind the red filter or blue filter is in any case less than 0.05.
  • Image receiving sheet 11 (not according to the invention)
  • a blue-colored image-receiving layer with a smooth surface is obtained.
  • the density measured behind the red filter is 0.25. This image receiving sheet is unusable for practical purposes.
  • Image receiving sheets 12 to 15 with a smooth surface were obtained. Leaves 12 and 14 were pale green and leaves 13 and 15 were pale blue. The optical density measured behind the red filter was less than 0.05 in each case.
  • Image receiving sheet 16 (not according to the invention)
  • each of the image-receiving sheets 1 to 15 was immersed in a 4% NaOH solution for 2 minutes.
  • Image-receiving sheets 1-5, 7-10 and 12-15 then appeared pale beige to pale blue when viewed in daylight, image-receiving sheet 6 clearly chamois and image-receiving sheet 11 stained clearly blue.
  • 0.03 molar solutions were prepared from the following post-complexable image dyes and made alkaline with 1% NaOH.
  • Dye F (dye 13 of DE-A 31 07 540)
  • the evaluation shows that the desired color tones in the image-receiving sheets according to the invention are achieved essentially without delay compared to the prior art and that the nuances of the image-receiving sheets 1-5, 12 and 14 correspond to those obtained with image-receiving sheet 16 after treatment with Ni-acetate will. There are no brown discolourations. The complexation takes place immediately, a gradual color change cannot be seen. The nuances of image receiving sheet 6 are somewhat cloudy.

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Claims (5)

1. Elément récepteur d'image pour le procédé de transfert par diffusion de la couleur, avec une couche teintable par des colorants organiques capables de diffuser qui est placée sur un support de couches, et avec une couche de liant hydrophile qui lui est avoisinante et qui contient un agent de métallisation pour colorants post-métallisables, caractérisé en ce que la couche de liant hydrophile avoisinante contient l'agent de métallisation sous la forme d'une dispersion, renfermant éventuellement un formateur d'huile, d'un complexe organique de cuivre-(II) ou de nickel, insoluble dans l'eau, d'un composé répondant à une des formules suivantes I à VI,
Figure imgb0096
Figure imgb0097
Figure imgb0098
Figure imgb0099
dans lesquelles
R' représente un radical hydrocarboné ayant jusqu'à 30 atomes de carbone, éventuellement interrompu par -0-,
R2, R2' de l'hydrogène, alcoyle ayant jusqu'à 5 atomes de carbone, cycloalcoyle, aralcoyle ou aryle ayant 6 à 10 atomes de carbone,
R3, R3' alcoyle ou alcoxy anat 1 à 4 atomes de carbone, aralcoyle ou OH,
x
Figure imgb0100
R4 un radical hydrocarboné ayant jusqu'à 18 atomes de carbone, qui est relié soit directement ou par l'intermédiaire de ―O―, de l'halogène ou un groupe R6,
R5 de l'hydrogène, halogène, alcoyle ou alcoxy ayant jusqu'à 18 atomes de carbone, alcényle, un radical pour compléter un noyau benzénique condensé, ou un gorupe R6 au cas où R4 ne signifie pas un groupe R6, R 6
Figure imgb0101
―NH―CO―R11 ou ―NH―SO2―R12
R7, R7' un alcoyle, aryle ou un groupe hétérocylique,
R8 de l'hydrogène ou un groupe R7, ou bien R7 et R8 signifient ensemble un radical pour compléter un noyau carboxylique ou hétérocyclique,
R9 alcoyle, alcoyle ou cycloalcoyle ayant jusqu'à 8 atomes de carbone,
R10, R101 des radicaux comme R2 et R2', ou bien tous deux forment un radical pour compléter un groupe amino cyclique à 5, 6 ou 7 chaînons,
R11 alcoyle, aralcoyle, aryle-OR9 ou
Figure imgb0102
R12 alcoyle, aryle ou
Figure imgb0103
2. Elément récepteur d'image selon la revendication 1, caractérisé en ce que la couche teintable contient, comme agent de mordançage pour colorants d'image organiques capables de diffuser, un polymère avec des unités structurales qui présentent une fonction amino hétérocyclique.
3. Elément récepteur d'image selon la revendication 2, caractérisé en ce que l'agent de mordançage polymère contient des unités structurales dans lesquelles la fonction amino hétérocyclique se présente sous la forme quaternisée ou protonisée.
4. Elément récepteur d'image selon la revendication 3, caractérisé en ce que le polymère contenu comme agent de mordançage dans la couche teintable contient des unités structurales de formule suivante :
Figure imgb0104
dans laquelle
Z signifie les atomes nécessaires pour compléter un noyau hétérocyclique renfermant de l'azote,
L une simple liaison chimique ou un chaînon de liaison bivalent entre le noyau hétérocyclique et l'atome de carbone qui porte le radical RB,
RA de l'hydrogène, ―COORc ou ―CONHRc,
RB de l'hydrogène ou un alcoyle ayant 1 à 6 atomes de carbone,
RC de l'hydrogène, un alcoyle ou aralcoyle,
Re un anion mono- ou bivalent.
5. Elément récepteur d'image selon l'une des revendications 1 à 4, caractérisé en ce qu'il est un constituant intégral d'un matériel d'enregistrement de photographie en couleur sensible à la lumière et à couches multiples.
EP83104831A 1982-05-29 1983-05-17 Elément récepteur d'image pour le procédé par diffusion-transfert de colorants Expired EP0095650B1 (fr)

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Application Number Priority Date Filing Date Title
DE3220435 1982-05-29
DE3220435A DE3220435A1 (de) 1982-05-29 1982-05-29 Bildempfangselement fuer das farbdiffusionsuebertragungsverfahren

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EP0095650A2 EP0095650A2 (fr) 1983-12-07
EP0095650A3 EP0095650A3 (en) 1984-09-12
EP0095650B1 true EP0095650B1 (fr) 1986-07-30

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JPH0612430B2 (ja) * 1984-11-14 1994-02-16 富士写真フイルム株式会社 色素固定材料

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NL247650A (fr) * 1959-01-26
JPS5482386A (en) * 1977-12-15 1979-06-30 Fuji Photo Film Co Ltd Stabilizing method for organic basic substance to light
JPS5933899B2 (ja) * 1978-08-31 1984-08-18 富士写真フイルム株式会社 写真感光材料
EP0009411B2 (fr) * 1978-09-21 1986-11-26 EASTMAN KODAK COMPANY (a New Jersey corporation) Matériau d'enregistrement photographique contenant des polymères qui forment des complexes avec des ions métalliques
US4382305A (en) * 1980-03-27 1983-05-10 Monterey Manufacturing Company Self-sealing waterbed mattress
DE3132333A1 (de) * 1981-08-17 1983-03-03 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches material mit einer durch organische farbstoffe anfaerbbaren schicht

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DE3220435A1 (de) 1983-12-01
EP0095650A2 (fr) 1983-12-07
EP0095650A3 (en) 1984-09-12
DE3364908D1 (en) 1986-09-04
JPS58216244A (ja) 1983-12-15

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