EP0565152B1 - Procédé de diffusion-transfert de sel d'argent - Google Patents

Procédé de diffusion-transfert de sel d'argent Download PDF

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Publication number
EP0565152B1
EP0565152B1 EP19930200656 EP93200656A EP0565152B1 EP 0565152 B1 EP0565152 B1 EP 0565152B1 EP 19930200656 EP19930200656 EP 19930200656 EP 93200656 A EP93200656 A EP 93200656A EP 0565152 B1 EP0565152 B1 EP 0565152B1
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Prior art keywords
silver halide
silver
process according
halide emulsion
image
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German (de)
English (en)
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EP0565152A1 (fr
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Jules c/o Agfa-Gevaert N.V. Berendsen
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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • 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
    • G03C8/32—Development processes or agents therefor
    • G03C8/36—Developers
    • G03C8/365—Developers containing silver-halide solvents

Definitions

  • the present invention relates to a silver complex diffusion transfer reversal (DTR) process.
  • the developing agent or a mixture of developing agents can be present in an alkaline processing solution and or in the photographic silver halide emulsion layer material.
  • the processing solution can be merely an aqueous alkaline solution that initiates and activates the development.
  • the silver solvent mostly sodium thiosulphate, may be supplied from the non-light-sensitive image-receiving element as mentioned above, but it is normally at least partly already present in the alkaline processing solution.
  • the alkaline processing solution usually contains sufficient alkaline substances to bring the pH above 10. e.g. sodium hydroxide, sodium carbonate and a great many other compounds which can raise the pH, for example borax, tertiary sodium phosphate, lithium hydroxide and amines, particularly alkanolamines.
  • alkaline substances e.g. sodium hydroxide, sodium carbonate and a great many other compounds which can raise the pH, for example borax, tertiary sodium phosphate, lithium hydroxide and amines, particularly alkanolamines.
  • the DTR-process initially intended for office copying purposes has found now wide application in the graphic art field, more particularly in the production of screened prints from continuous tone originals.
  • the processing characteristics remain steady for a large set of prints and that the gradation, optical density (transmission density in the case of film material and reflection density in the case of opaque material e.g. paper material) and the neutrality of the colour tone (black) of the screen dots in the screened prints satisfy graphic art standards which are particularly high compared with normal copying.
  • the man skilled in the art would have directed his attention to the composition of the alkaline solution in order to achieve this objective.
  • this objective can be achieved by a modification of the composition of the silver halide emulsion.
  • a silver complex diffusion transfer reversal process in which an information-wise exposed photographic silver halide emulsion layer material is transformed by a silver solvent into soluble silver complex compounds which are allowed to diffuse into an image receiving element and are reduced therein with a developing agent in the presence of an alkaline solution to form a silver image, characterised in that the silver halide emulsion layer includes a polyoxyethylene thioether and the alkaline solution contains a tertiary alkanolamine and is substantially free of primary and secondary alkanolamines.
  • the invention lies in the combination of two features, namely an alkaline solution containing a tertiary alkanolamine and which is substantially free of primary and secondary alkanolamines and a silver halide emulsion which comprises a polyoxyethylene thioether compound.
  • the image receiving layer is the image receiving layer
  • the DTR-image can be formed in the image-receiving layer of a sheet or web material being a separate element with respect to the photographic silver halide emulsion material or in a so-called single-support-element, also called mono-sheet element or unitary DTR-material, which contains at least one photographic silver halide emulsion layer and the image-receiving layer in waterpermeable relationship therewith, e.g. on top of each other or separated by a thin waterpermeable stripping layer or alkali-degradable interlayer as described e.g. in US-P 3,684,508 or wherein the photographic silver halide emulsion layer is optically masked from the image-receiving layer, e.g. with a white waterpermeable pigment layer as described e.g. in US-P 3,607,270 and 3,740,220.
  • the image receiving layer comprises for best imaging results physical development nuclei normally in the presence of a protective hydrophilic colloid, e.g. gelatin and or colloidal silica.
  • a protective hydrophilic colloid e.g. gelatin and or colloidal silica.
  • Preferred development nuclei are sulphides of heavy metals e.g. sulphides of antimony, bismuth cadmium, cobalt, lead, nickel, palladium, platinum, silver and zinc.
  • suitable development nuclei are NiS.Ag 2 S nuclei as described in US-A 4,563,410.
  • Other suitable development nuclei are salts such as e.g. selenides, polyselenides, polysulphides, mercaptans and tin (ll) halides.
  • Heavy metals or salts thereof and fogged silver halide are suitable as well.
  • the complex salts of lead and zinc sulphides are active both alone and when mixed with thioacetamide, dithiobiuret and dithiooxamide.
  • Heavy metals preferably silver, gold, platinum, palladium and mercury can be used in colloidal form.
  • the transfer behaviour of the complexed silver largely depends on the thickness of the image-receiving layer and the kind of binding agent or the mixture of binding agents used in the nuclei containing layer. In order to obtain a sharp image with high spectral density the reduction of the silver salts diffusing into the image receiving layer must take place rapidly before lateral diffusion becomes substantial.
  • An image-receiving material satisfying said purpose is described in published European Patent Specification EP 306561 and is particularly suitable for being processed with an aqueous alkaline processing liquid according to the process of the present invention.
  • the image-receiving layer and/or other hydrophilic colloid layer of an image-receiving layer and/or other hydrophillic colloid layer of an image-receiving material used in a DTR-process according to the present invention may have been hardened to some extent to achieve enhanced mechanical strength.
  • Appropriate hardening agents for hardening the natural and/or synthetic hydrophilic colloid binding agents in the image-receiving layer include e.g. formaldehyde, glyoxal, mucochloric acid, and chrome alum.
  • Other suitable hardening agents for hardening the hydrophillic colloid binding agents in the image-receiving layer are vinylsulphonyl hardeners, e.g. as described in Research Disclosure 22 507 of Jan. 1983.
  • the image-receiving material can be used in the form of roll film or sheet film or in the form of a filmpack e.g., for in-camera-processing.
  • the silver halide emulsion material The silver halide emulsion material
  • the image-receiving material can be used in conjunction with any type of photographic silver halide emulsion material suited for use in diffusion transfer reversal processing.
  • the silver halide emulsion material may contain one or more hydrophilic colloid - silver halide emulsion layers.
  • the hydrophilic colloid silver halide emulsion layer can be coated from any photosensitive silver halide emulsion comprising a hydrophilic colloid binder, which usually is gelatin.
  • the weight ratio of hydrophilic colloid binder to silver halide expressed as equivalent amount of silver nitrate to binder is e.g. in the range of 1:1 to 10:1.
  • the photosensitive silver halide used in the present invention may comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide and the like, or mixtures thereof.
  • a silver halide emulsion mainly comprising silver chloride is used preferably.
  • the silver halide which is used is silver chloride, but a proportion of silver bromide may also be present.
  • the present invention is especially beneficial when the silver halide present in the silver halide emulsion comprises silver chloride together with at least 5 mole% silver bromide.
  • the silver halide emulsions may be coarse or fine grain and can be prepared by any of the well known procedures e.g. single jet emulsions such as Lippmann emulsions, ammoniacal emulsions, thiocyanate - or thioether-ripened emulsions such as those described in US A 2 222 264, 3 320 069 and 3 271 157.
  • Surface image emulsions may be used or internal image emulsions may be used such as those described in US A 2 592 250, 3 206 313 and 3 447 927. If desired, mixtures of surface and internal image emulsions may be used as described in US A 2 996 382.
  • the silver halide particles of the photographic emulsions may have a regular crystalline form such as cubic or octahedral form or they may have a transition form. Regular-grain emulsions are described e.g. in J. Photogr. Sci., Vol. 12, No. 5, Sept./Oct. 1964 pp. 242-251.
  • the silver halide grains may also have an almost spherical form or they may have a tabular form (so-called T-grains), or may have composite crystal forms comprising a mixture of regular and irregular crystalline forms.
  • the silver halide grains may have a multilayered structure having a core and a shell the silver halide grains may comprise also different halide compositions and metal dopants in between.
  • the average size of the silver halide grains may be of at least 0.1 mm, preferably within the range of 0.2 to 1.2 mm, and the size distribution can be homodisperse or heterodisperse.
  • a homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
  • the present invention is especially beneficial when the average (by weight) silver halide grain size is relatively large, such as more than 0.3 ⁇ m , preferably from 0.5 to 2.0 ⁇ m .
  • the silver halide emulsions may contain pH controlling ingredients, and other ingredients such as stabilizers, antifogging agents, development accelerators, wetting agents, and hardening agents for gelatin.
  • the silver halide emulsion coated side of the photographic material can be provided with a top layer that contains hydrophilic colloids that form a waterpermeable layer.
  • a top layer that contains hydrophilic colloids that form a waterpermeable layer.
  • Such top layer is usually free of gelatin. Its nature is such that it does not inhibit or restrain the diffusion transfer of the complexed silver but acts e.g. as an anti-stress layer.
  • Appropriate hydrophilic binding agents for such top layer are e.g.
  • methyl cellulose the sodium salt of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl starch, hydroxypropyl starch, sodium alginate, gum tragacanth, starch, polyvinyl alcohol, polyacrylic acid, polyacrylamide, poly-N-vinyl pyrrolidone, polyoxyethylene, and copoly(methylvinylether/maleic acid).
  • the thickness of this layer depends on the nature of the colloid used and the required mechanical strength. Such layer if present may be transferred at least partially to the image-receiving layer without deleterious action on the image formation.
  • the development and diffusion transfer can be initiated in different ways e.g. by rubbing with a roller that has been wetted with the alkaline processing liquid e.g. acts as meniscus coater, by wiping with an absorbent means e.g. with a plug of cotton or sponge, or by dipping the material to be treated in the liquid composition.
  • they proceed in an automatically operated apparatus such as the COPYPROOF (registered trade name of AGFA-GEVAERT NV. Belgium) type CP 38, CP 380, CP 42 or CP 530 processors.
  • the DTR-process is normally carried out at a temperature in the range of 10°C to 35°C.
  • the silver halide emulsion layer includes a polyoxyethylene thioether.
  • the polyoxyethylene thioether comprises recurring units of the following formula: wherein R represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group.
  • R in the foregoing formula (a) may be an aliphatic, carbocyclic aromatic or heterocyclic group carrying one or more of the following substituents: alkyl , aralkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, acyloxyalkyl (the alkyl groups of such substituents preferably carrying at most 5 C-atoms), cycloalkyl e.g. cyclohexyl, aryl, e.g. phenyl and phenyl substituted with alkyl, alkoxy and alkyl-thio.
  • n is from 2 to 50.
  • Preferred polyoxyethylene thioethers have a molecular weight of between 300 and 7500, most preferably between 500 and 5000.
  • polyoxyethylene compounds can be derived from polyepihalo-hydrins e.g. polyepichlorohydrin and polyepibromohydrin including ethers and esters thereof by reaction with aliphatic, carbocyclic aromatic, or heterocyclic mercaptides.
  • polyoxyalkylene compounds can be prepared which in addition to the structural units of the above formula (a) comprise recurring units of the following formula (c): wherein X is halogen due to incomplete conversion of the polyepihalohydrin. It has been found that it is advantageous to carry out development in the presence of polyoxyethylene compounds comprising units of formulae (a) and (c) but at least 20 mole % of randomly distributed recurring units of formula (a) should be present.
  • the molecular weight of the polyepihalohydrins, ethers or esters thereof may vary within wide limits.
  • Dimeric compounds may be used as well as commercially available polyepihalohydrins which possess generally a molecular weight of at most 3000.
  • polyepihalohydrins of higher molecular weight as described in Jl. Polymer Sci. 40 (1959) p. 571, may also be employed.
  • the concentration of the polyoxyethylene thioether in the silver halide emulsion layer is from 0.1 to 50g, preferably from 1 to 10g, polyoxyethylene thioether per mole of silver halide present in the emulsion layer.
  • the alkaline solution includes one or more tertiary alkanolamines, optionally together with further alkalis.
  • tertiary alkanolamines are e.g. (I) N-methyl-diethanolamine, (II) N,N-dimethylethanolamine or (III) 3-(N,N-diethylamino)propane-1,2-diol.
  • the total concentration of components (I), (II) and/or (III) in the alkaline solution is ideally from 0.3 mol/l to 1.5 mol/l.
  • Said tertiary alkanolamine(s) may be used in combination with a minor amount i.e. not more than 0.2 mol. preferably less than 0.05 mol of an inorganic base per litre, e.g. not more than 2g/l of sodium hydroxide to bring the pH of the processing liquid in the range of 10.5 to 13 without a substantial increase in CO 2 -absorption.
  • a minor amount i.e. not more than 0.2 mol. preferably less than 0.05 mol of an inorganic base per litre, e.g. not more than 2g/l of sodium hydroxide to bring the pH of the processing liquid in the range of 10.5 to 13 without a substantial increase in CO 2 -absorption.
  • the present processing liquid is preferably completely free from phosphate ions.
  • the optimum pH of the processing liquid used according to the present invention depends on the type of silver halide emulsion material to be developed, intended development time and processing temperature.
  • a silver solvent is indispensable. It may be supplied from the non-light-sensitive image-receiving element, but it is normally at least partly present already in the alkaline processing solution.
  • the silver solvent which acts as a complexing agent for silver halide, preferably is a water-soluble thiosulphate or thiocyanate, e.g. sodium, potassium or ammonium thiosulphate or thiocyanate or mixtures thereof.
  • the molar amount of thiosulphate compound is preferably in the range of 0.03 to 0.13 mol/1.
  • the developing agent is preferably present in the alkaline solution, but may alternatively or additionally be present in the silver halide emulsion.
  • the silver halide developing agent used in the process according to the present invention is preferably a p-dihydroybenzene compound, e.g. hydroquinone, methylhydroquinone or chlorohydroquinone, preferably in combination with an auxiliary developing agent being a 1-phenyl-3-pyrazolidinone-type developing agent and/or p-monomethylaminophenol.
  • an auxiliary developing agent being a 1-phenyl-3-pyrazolidinone-type developing agent and/or p-monomethylaminophenol.
  • hydroquinone-type developing agents are present in the processing liquid used according to the present invention in an amount of 0.05 to 0.25 mol per litre.
  • 1- Phenyl-3-pyrazolidinone type developing agents may be present in an amount of 1.8 x 10 -3 to 2.0 x 10 -2 mol per litre.
  • Particularly useful l-phenyl-3-pyrazolidinone developing agents are 1-phenyl-4-4-dimethyl-3-pyrazolidinone, and 1-phenyl-4-monomethyl-3-pyrazolidinone. The latter type of developing agents is advantageously present in the image receiving element.
  • the developing agent(s) can be present in the silver halide emulsion layer or are preferably present in a hydrophilic colloid layer in water-permeable relationship therewith, e.g. in the antihalation layer adjacent to the silver halide emulsion layer of the photosensitive element.
  • the alkaline processing solution preferably also contains (a) silver image toning agent(s) providing a neutral (black) image tone to the DTR-produced silver image in the image-receiving material.
  • the aqueous alkaline processing solution used according to the present invention may comprise toning agent(s) in a concentration in a range e.g. from 30 mg to 200 mg per litre.
  • Other additives are thickening agents, e.g. hydroxyethylcellulose and carboxmethylcellulose, fog inhibiting agents, e.g. potassium bromide, potassium iodide and a benzotriazole, calcium-sequestering compounds, wetting agents, e.g. block copolymers of ethyleneoxide and propylene oxide, anti-sludge agents, and hardeners including latent hardeners.
  • a paper support having a weight of 110 g/m 2 being coated at both sides with a polyethylene layer was coated at one side with an orthochromatically sensitized negative working silver halide emulsion layer containing an amount of silver chlorobromide (7.5 mol % bromide, 1.2 mol % iodide) equivalent to 1.4 g/m 2 of silver nitrate.
  • the average grain size of the emulsion was 0.15 ⁇ m with a variance of 0.46.
  • the emulsion layer further contained hydroquinone, 1-phenyl-4-methyl-pyrazolidin-3-on and pyrocathecol as developing agents.
  • Three additional photosensitive materials were prepared as described above with the difference that Compound 1 was added in different amounts as listed in Table 1.
  • One side of a paper support having a weight of 110 g/m 2 and being coated at both sides with a polyethylene layer was coated at a dry coverage of 2 g/m 2 with an image-receiving layer containing silver-nickel sulphide nuclei and gelatin.
  • This layer was applied by slide hopper coating so that the nuclei were in an undermost coating of 1.3 g gelatin per m 2 and a top layer was provided of 0.7 g of gelatin per m 2 .
  • the photographic materials were exposed through a sensitometric wedge in a contact exposure apparatus operating with a light source having a colour temperature of 3200 K.
  • the exposed photographic materials were pre-moistened with the hereinafter defined processing liquid 1, the contact time with said liquid being 6 seconds before being pressed together with an image-receiving material as defined above.
  • the transfer processor employed was a COPYPROOF (Registered Trade Name of Agfa-Gevaert N.V.) type CP 380.
  • the transfer contact times were 30, 45 seconds at 16° and 24 o C processing temperature.
  • a film support having a thickness of 100 ⁇ m was coated at one side with an antihalation layer containing carbon black and titanium dioxide dispersed in gelatin.
  • an antihalation layer containing carbon black and titanium dioxide dispersed in gelatin.
  • the average grain size of the emulsion was 0.38 ⁇ m with a variance of 0.20.
  • the emulsion was fogged by ripening with a gold compound and a reductor.
  • the obtained photosensitive material was called E.
  • a photosensitive material (F) similar to E but for the addition of 1g/m 2 of Compound 2 was made.
  • a subbed polyethylene terephthalate film support was coated at both sides at a dry coverage of 1.8 g/m 2 with an image-receiving layer containing silver-nickel sulphide nuclei dispersed in gelatin. This layer was applied by slide hopper coating so that the nuclei were in an undermost coating of 1.4 g gelatin per sq.m. A top layer was provided of 0.4 g gelatin per m 2 .
  • the photosensitive material F according to the invention shows better transfer characteristics than the comparative photosensitive material E.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Procédé d'inversion-transfert de complexes d'argent par diffusion, dans lequel un matériau photographique exposé sous forme d'informations contenant une couche d'émulsion à l'halogénure d'argent est transformé par un solvant de l'argent en composés de complexes d'argent solubles, qu'on laisse diffuser dans un élément récepteur d'image et qui y sont réduits avec un développateur en présence d'une solution alcaline pour produire une image argentique, ladite solution alcaline contenant une alcanolamine tertiaire et étant essentiellement exempte d'alcanolamines primaires et secondaires, caractérisé en ce que la couche d'émulsion à l'halogénure d'argent renferme un thioéther poly(oxyéthylénique).
  2. Procédé selon la revendication 1, caractérisé en ce que la couche d'émulsion à l'halogénure d'argent contient des cristaux d'halogénure d'argent avec une granulométrie moyenne supérieure à 0,3 µm, de préférence entre 0,5 et 2,0 µm.
  3. Procédé selon la revendication 1, caractérisé en ce que l'halogénure d'argent contenu dans l'émulsion à l'halogénure d'argent se compose de chlorure d'argent ainsi que d'au moins 5 moles % de bromure d'argent.
  4. Procédé selon la revendication 1, caractérisé en ce que la concentration du thioéther poly(oxyéthylénique) dans la couche d'émulsion à l'halogénure d'argent varie entre 0,1 et 50 g, de préférence entre 1 et 10 g, de thioéther poly(oxyéthylénique) par mole d'halogénure d'argent contenu dans la couche d'émulsion.
  5. Procédé selon la revendication 1, caractérisé en ce que le thioéther poly(oxyéthylénique) possède un poids moléculaire inférieur à 7500, de préfénce entre 500 et 5000.
  6. Procédé selon la revendication 1, caractérisé en ce que le thioéther poly(oxyéthylénique) contient des motifs structuraux répondant à la formule suivante:
    Figure 00210001
    dans laquelle R représente un groupe aliphatique, aromatique ou hétérocyclique substitué ou non.
  7. Procédé selon la revendication 6, caractérisé en ce que le thioéther poly(oxyéthylénique) contient un composé répondant à la formule ci-après:
    Figure 00210002
    dans laquelle n varie entre 2 et 50.
  8. Procédé selon la revendication 1, caractérisé en ce que ladite alcanolamine tertiaire est (I) la N-méthyldiéthanolamine, (II) le N,N-diméthylaminoéthanol ou (III) le 3-(N,N-diéthylamino)propane-1,2-diol.
EP19930200656 1992-04-10 1993-03-08 Procédé de diffusion-transfert de sel d'argent Expired - Lifetime EP0565152B1 (fr)

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EP92201031 1992-04-10
EP92201031 1992-04-10

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EP0565152B1 true EP0565152B1 (fr) 1998-10-14

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Publication number Priority date Publication date Assignee Title
EP0634688B1 (fr) * 1993-07-12 1999-10-13 Agfa-Gevaert N.V. Matériaux photographiques à grain tabulaire sensibilisés spectralement
GB2345151B (en) * 1998-12-22 2002-11-06 Ilford Imaging Uk Ltd Photographic developing solutions

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GB1455413A (en) * 1972-12-07 1976-11-10 Agfa Gevaert Development of photographic silver halide elements
EP0398435B1 (fr) * 1989-05-18 1994-11-09 Agfa-Gevaert N.V. Liquide pour la photographie DTR

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JP3136224B2 (ja) 2001-02-19
EP0565152A1 (fr) 1993-10-13
DE69321507D1 (de) 1998-11-19

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