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
  • 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 layer for the color diffusion transfer process which contains a polymer containing cationic groups and a further polymer which contains no cationic groups and is derived from N-vinyl-imidazole or 2-methyl-1-vinyl-imidazole.
• 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 in Development is released imagewise as a diffusible dye or dye precursor (color releaser).
• Polymeric ammonium or phosphonium compounds are mostly used for this.
• Polymers with a wide variety of cationic structural units e.g. those which contain the cationic groups in the form of side chains on a polymer backbone, such as those described in US Pat. No. 3,709,690, or else those which contain the cationic groups in a polymer chain itself, for example polymers which pass through Quaternization of basic polyurethanes, polyureas or polyurea polyurethanes are derived (DE-A-26 31 521).
• the known cationic mordant polymers are not yet satisfactory in terms of the lightfastness of the anionic image dyes stained on them.
• the lightfastness of the image dyes stained with cationic polymers can be considerably improved if the cationic polymer used is one which has been obtained by homopolymerization or copolymerization of ethylenically unsaturated monomeric compounds, and if this cationic polymer has no cationic groups containing homo- or copolymer of N-vinylimidazole or 2-methyl-1-vinylimidazole.
• the invention relates to an image-receiving layer for the color diffusion transfer process with a cationic group-containing polymer obtained by homo- or copolymerization of ethylenically unsaturated monomers as a mordant for diffusible anionic dyes, characterized in that it contains a mixture of 5 to 70% by weight of the mordant polymer containing cationic groups and 30 to 95 wt .-% of a second polymer which contains no cationic groups and has been obtained by homopolymerization or random copolymerization of N-vinylimidazole or 2-methyl-1-vinylimidazole and optionally other copolymerizable monomers .
• Examples of the comonomers represented by M are approximately (meth) acrylamides such as acrylamide, N, N-dimethylacrylamide; (Meth) acrylates such as ethyl acrylate, methyl methacrylate, chloroethyl methacrylate, hydroxyethyl acrylate, butyl acrylate; vinyl aromatic compounds such as styrene, vinyl toluene; N-vinyl pyrrolidone, vinyl acetate, N-methyl-N-vinyl-acetamide.
• the copolymer can also contain two or more such comonomers copolymerizable with vinylimidazole in polymerized form, all of which are represented by M in this case.
• M can also comprise polymerized units of comonomers which do not exist in the form of ethylenically unsaturated compounds but which can be obtained by polymer-analogous reactions, e.g. Ethanol or vinylamine.
• the polyvinylimidazoles used according to the invention can be prepared by customary polymerization processes, for example by emulsion polymerization, solution polymerization or precipitation polymerization of N-vinyl imidazole or 2-methyl-1-vinylimidazole, optionally with one or more mono-ethylenically unsaturated comonomers M copolymerizable with vinylimidazole, in the case of emulsion polymerization expediently in the presence of an anionic surface-active compound, for example sodium lauryl sulfate or in the presence of the sodium salt of a sulfonated condensate of an alkylphenol-ethylene oxide condensate ( eg Alipal, manufacturer General Dyestuff Corp., USA) and expediently in the presence of a radical generator or radical initiator, for example in the presence of a free radical initiator of the redox type, for example in the presence of potassium persulfate-sodium bisulfite; Potassium per
• polyvinylimidazole in image-receiving elements is already known, e.g. from US-A-4,282,305, but only in connection with a layer containing a metal ion-providing compound.
• image-receiving elements are suitable for use in connection with light-sensitive elements which release diffusible chelatable dyes as image dyes.
• the image dyes are fixed in the image receiving element in the form of light-stable dye-metal complexes.
• the polyvinylimidazole is mainly used to prevent the diffusion of metal ions into the light-sensitive element, but in the absence of the metal ions provides only slightly light-stable dye images.
• Alkyl radicals as rg e in formula II by R 2, R 3 and R 4 - are assumed are straight or branched and typically have from 1 to to 12 carbon atoms. Examples include methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, dodecyl.
• R 2 , R 3 and / or R 4 in formula II have the meaning of carbocyclic radicals, these are optionally substituted cycloalkyl, aralkyl or aryl residues with preferably 5 to 12 carbon atoms, for example cyclopentyl, cyclohexyl, benzyl, p-methylbenzyl, chlorobenzyl, nitrobenzyl, cyanobenzyl, methoxybenzyl, methoxycarbonylbenzyl, ethylthiobenzyl, phenyl, tolyl.
• Examples of 5- or 6-membered heterocyclic rings completed by two of the radicals R 2 , R 3 and R 4 are, for example, the pyrrolidine, the piperidine and the morpholine ring.
• the cationic group-containing polymer can be prepared by one of the usual addition polymerization techniques, e.g. by emulsion polymerization, from addition-polymerizable monomers which already contain a quaternary ammonium group or are easily quaternizable, optionally in a mixture with further addition-polymerizable monomers.
• the quaternization or introduction of quaternary groups can also be carried out after the polymerization, e.g. by treating tertiary amino groups contained in the polymer with an alkylating quaternizing agent or, for example, by reacting groups contained in the polymer with active halogen atoms with tertiary amines or phosphines.
• Suitable cationic polymers are described, for example, in US Pat. No. 3,709,690.
• the image-receiving layer preferably contains a mixture of 50 to 90% by weight of polyvinylimidazole and 10 to 50% by weight of cationic polymer.
• the mixture of non-cationic polymeric vinylimidazole and cationic polymer can be cast as such or optionally with a binder additive to the image-receiving layer.
• a wide variety of customary known additives can also be incorporated into the image-receiving layer, for example UV absorbers, for example substituted 2-hydroxyphenylbenzotriazoles (Tinuvin) and hydroxybenzophenones, and antioxidants, for example tert. Butylated hydroxyanisole, butylated hydroxytoluene, substituted chromanols. So to the extent that such additives are substances which are soluble in organic solvents, they are expediently used in the form of an emulsifier in an aqueous medium. Furthermore, in the sense of an improvement in dye determination, it can be beneficial if the image-receiving layer contains certain heavy metal ions, in particular Zn 2 + ions.
• mordants used according to the invention can be used to produce a wide variety of photographic materials which have a mordant layer with the aid of which acidic dyes are to be stained.
• the said polymers are mainly used as mordants for diffusible image dyes, i.e. they represent an essential component of image-receiving layers for the color diffusion transfer process.
• image-receiving layers are usually arranged on a transparent or non-transparent layer support and together with it form the image-receiving element. This is either not photosensitive as a separate image-receiving sheet or it can form an integral part of a light-sensitive material when the image-receiving layer is in firm contact with the photosensitive silver halide emulsion layer (s).
• Suitable supports are, for example, paper, optionally coated with a plastic, glass, metal foils or films made from organic film formers such as Cellulose esters, polyethylene terephthalate, polycarbonate or other polymers.
• organic film formers such as Cellulose esters, polyethylene terephthalate, polycarbonate or other polymers.
• the image-receiving layer according to the invention is arranged on a layer support and, together with it, forms the image-receiving element in the form of an image-receiving sheet.
• the latter can be provided with a conventional adhesive layer.
• an image-receiving sheet is suitable for any type of photographic color diffusion transfer process in which acidic diffusible image dyes or also acidic diffusible color formers (image dye precursors) are used or released imagewise and can be transferred to an image-receiving layer. After the transfer has taken place, such a material in the image-receiving layer has an image-wise distribution of one or more acid dyes.
• a photographic material in addition to an image-receiving layer with the polymer mixture according to the invention, has at least one layer with an acidic dye or a precursor compound for an acidic dye, and at least one light-sensitive layer, in particular a light-sensitive silver halide emulsion layer.
• the acid dyes mentioned or precursor compounds for acidic dyes are collectively referred to below as coloring compounds.
• a photographic recording material can advantageously 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 for the color diffusion transfer process.
• the photographic materials according to the invention ie an image-receiving sheet with the image-receiving layer according to the invention and in particular color photographic recording materials which contain an image-receiving layer according to the invention as an integral part, can also contain acidic layers and so-called braking or deceleration layers, which together form a so-called 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 point in the layer structure, for example above the light-sensitive layers, ie viewed beyond the light-sensitive layers from the image-receiving layer.
• the neutralization system is usually oriented so that the braking or deceleration layer is between the acid layer and the site Det, on which the alkaline development liquid or paste is brought into action.
• the color-imparting compounds assigned to the light-sensitive layers can be colored compounds which are themselves diffusible and which begin to diffuse when the layers are treated with an alkaline processing 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 releasing agent).
• the diffusible dyes released from the dye releasers can belong to the most diverse classes of dyes, for example azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes and triphenylmethane dyes.
• those dyes are preferably used which do not form stable dye-metal complexes with metal ions in the image-receiving layer.
• Pickling layers of the compositions given below were applied to a paper base coated with polyethylene.
• the application per m 2 was 4 g of gelatin and a total of 2 g of pickling polymer (sum of polymer containing cationic groups and polyvinylimidazole).
• the pickling layers were hardened with 2% 1,3,5-trisacryloylhexahydro-1,3,5-triazine.
• the dyes GB 1, PP 1 and BG 1 were bathed in the resulting pickling layers at pH 13.5 until a density of approximately 1.5 was reached. After washing for 2 minutes, the layers were dried, half covered and irradiated with UV light (4.8.10 6 lx.h).
• the percentage decrease in color density in the irradiated areas was then determined by measuring the color density in the irradiated and non-irradiated areas.
• the lightfastness of the pickled dyes is increased by adding polyvinylimidazole.
• Polymer III poly-N, N, N-trimethyl-N-methacryloyloxy-ethyl-ammonium-methyl sulfate according to DE-A-1 000 688.
• a photographic recording material A (not according to the invention) was produced in that the following layers were applied in succession to a transparent layer support made from polyethylene terephthalate. The quantities given relate to 1 m 2 .

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• Engineering & Computer Science (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Thermal Transfer Or Thermal Recording In General (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1983
  • 1983-11-25 DE DE19833342629 patent/DE3342629A1/de not_active Withdrawn
• 1984
  • 1984-11-13 DE DE8484113662T patent/DE3467429D1/de not_active Expired
  • 1984-11-13 EP EP84113662A patent/EP0143389B1/fr not_active Expired
  • 1984-11-22 JP JP59246390A patent/JPS60138547A/ja active Pending

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