US3510302A - Transfer method for silver salt diffusion and liquid agent for use in this method - Google Patents

Transfer method for silver salt diffusion and liquid agent for use in this method Download PDF

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Publication number
US3510302A
US3510302A US613452A US3510302DA US3510302A US 3510302 A US3510302 A US 3510302A US 613452 A US613452 A US 613452A US 3510302D A US3510302D A US 3510302DA US 3510302 A US3510302 A US 3510302A
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Prior art keywords
liquid
substances
solution
silver salt
nuclei
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US613452A
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English (en)
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Walter Limberger
Rudolf Wendt
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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

Definitions

  • the invention relates to a silver salt diffusion transfer method making use of a negative material, having a silver halide emulsion layer on which an image is formed by exposure, and a receiving material, to which the image is transferred, wherein the exposed negative material is moistened with a liquid effecting the development and is subjected to compression together with the moistened receiving material, which is made of paper, felt or textile material, the receiving material being wetted with another liquid.
  • the invention also relates to the composition of said other liquid.
  • the German Pat. No. 764,572 describes the so-called silver salt diffusion method and states that widely varying substances may be used as receiving materials, such as, for example, uncoated papers, textile sheets, wood, celluloid and other plastics and the like materials.
  • material relates to foliate materials.
  • the transfer may be aided by the presence of substances supportingthe diffusion process.
  • the diffusing or diffused silver halide can be developed image-wise without exposure, the development being supported by added nuclei or substances forming reducing nuclei.
  • the developed picture may be produced, for example, on a baryta paper or on a textile base which has been wetted in the same bath as the silver halide material.
  • a separate positive or receiving-layer which contains the reducing nuclei or the said substances.
  • This layer is usually arranged on a special carrier so that the layer and the carrier form together the receiving material.
  • this receiving layer independently of a carrier and to apply it, for example, as covering layer to the negative layer.
  • An arrangement of this kind has been described in German Pat. No. 1,171,740 where it has been designated as a colloidal covering and receiving layer.
  • This layer need not contain any reducing nuclei, but, according to the mentioned specification, reducing nuclei are added to the colloidal receiving layer 3,510,302 Patented May 5, 1970 by way of the liquid treatment agent.
  • suitable nuclei-formers are sulphides, selenides, polysulphides, polyselenides, thiourea, mercaptans, stannous halides, heavy metals or their salts, fogged silver halide, sulphides of heavy metals such as antimony, bismuth, cadmium, cobalt, lead, nickel and silver.
  • the heavy metals for example, silver, gold, platinum, palladium, and mercury, preferably in colloidal form, and the noble metals, are regarded as the most efficient.
  • the image-receiving layer is thus provided as a cover layer on the negative, and a sheet of material is provided for receiving the image developed in the cover layer. Since according to patent specification 764,572 the difficulty soluble silver compound or colloidal silver, which is produced in the receiving layer, is non-diffusable, the colloidal cover or image-receiving layer containing the developed image is also transferred during the transfer to the receiving sheet, paper or the like.
  • German Pat. Nos. 764,572 and 1,171,740 are based on the use of reducing nuclei, such as used, for example, in the silver salt diffusion method generally known as the Copyrapid method.
  • the reduction nuclei according to patent specification 1,171,740 are provided in the processing liquid, which not only serves for carrying out the developing, but also for the complex salt formation of the unexposed and undeveloped silver halide, then the same limitations exist, in respect to the stability of such solutions, as are known to exist in developers used in the silver salt diffusion method. These limitations are due to the simultaneous presence of air oxidation products, used and unused developing substances, the rising content of silver halide solvents caused by the increased number of copies and silver halide complex compounds which diffuse into the solution and may be active as reduction nuclei.
  • the term uncoated means that the carrier does not contain any filmforming colloids, but does not exclude the wetting with a liquid of the kind referred to hereinbefore as the other deliquid.
  • the receiving material is processed in the moist state produced by the wetting.
  • the said other liquid should containing reducing nuclei or substances forming reducing nucleifi as well as a silver salt solvent, or that these substances should be present in a aqueous solution.
  • the liquid for the development of the exposed negative in the method is an activator known per se in the development of commercially used negative materials.
  • the proposed prior art method has the advantage of using simple and cheap materials, while eliminating the problem of coating, particularly the application of a coating of the receiving material on a carrier. Additional advantages are that the materials can be stored for prolonged periods and are not influenced by fluctuations in the air moisture and temperature. Generally, the durability and usefulness of the used liquids are significantly improved because mutually reacting substances may be provided in different baths. For example, in the proposed method, alkali is supplied from the liquid developer for the exposed negative solely by contact between the wetted negative and the receiving material wetted with the other liquid, so that there is a low proportion of alkali. Alkali 3 residues which remain in the copy are known to cause yellowing of the produced picture.
  • the liquid agent for the receiving material is an aqueous solution of nuclei-forming substances and sodium thiosulphate, as well as wetting agent (Mirasol).
  • a preferred nuclei-former is a platinum solution, and conveniently a solution containing a concentration of about 0.02% of a hexachloroplatinum(IV)acid and/ a gold(III)chloride-hydrochloric acid is used in the liquid for the receiving material.
  • the already proposed method provides a new solution for carrying out the silver salt diffusion method on an uncoated carrier. Hitherto this has not been possible in a comparable manner from a practical point of view so that always a separate positive and receiving layer was provided which in most cases contained the reducing nuclei.
  • the receiving layer may be arranged on a special carrier or as covering layer on the negative.
  • a liquid chemical agent serving not only for carrying out the developing, but also for the complex salt formation of the unexposed and undeveloped silver halide.
  • solutions of this type are not very durable, because air oxidation products, used and unused developer substances and a content of silver halide solvent caused by a higher number of copies, have an adverse effect.
  • reducing nuclei means hereinafter noble metal in colloidal form; while substances forming reducing nuclei are metals which are not amongst the noble metals, such as, for example, zinc, copper and cobalt.
  • substances acting as reducing agents are substances which reduce silver halide to metallic silver, that is to say, chemically active substances which are not present in the form of nuclei or capable of forming nuclei, but which contribute to the production of a black picture by chemical action.
  • the present invention has the object of improving the method already proposed, both by improving the quality of the copies with regard to the blackening and to their durability, and with regard to the durability and usability of the said other liquid for the receiving material, in the case a larger number of copies is to :be produced.
  • the said other liquid contains, in addition to nucleiforming substances and a silver salt solvent, also substances which are known as reducing agents in photographic developers or photographic layers and/ or organic acids which can act as reducing agents and/or improve the durability and which stabilize the produced picture.
  • The' efiect produced according to the invention can be explained in that the addition of organic acids improves 4 be transferred during contact with the negative material, is neutralized after the production of the copy.
  • the reducing nuclei-containing liquid that is to say, in conventional methods also the ordinary liquid developer, could be prematurely reduced, upon the occurrence of certain phenomenon, or where such liquid had been stored for prolonged periods.
  • the organic acids have a stabilizing effect.
  • the reducing agents assist in the production of the picture with regard to the blackening and also with regard to the speed of operation. Both these eflects represent a substantial improvement of the already proposed method.
  • the reducing agent and the organic acids may be used together or separately.
  • a generally uniform effect is achieved in that there is added to the liquid for the receiving material a substance which acts both as an acid in the sense hereinbefore outlined,
  • Such a substance is, for example, ascorbic acid.
  • organic acids used are, for example, acetic acid, citric acid, salicylic acid, phthalic acid and acids of corresponding effect.
  • Suitable reducing agents are, in addition to the ascorbic acid already mentioned, substances used in photography as developers, such as, for example, hydroquinone, methyl-p-amino-phenolsulphate, aminophenol and derivatives of aminophenol, pyrocate'chol, l-phenyl-3-pyrazolidon, and derivatives of 3-pyrazolidon, hydroxylamin hydrochloride and substances with similar action.
  • the said additives neutralize residual alkali in the receiving material and achieve a particularly good picture stability even under adverse conditions.
  • This also results from the fact that the pictureformingsubstances in the receiving material, namely the complex undeveloped silver halide, are concentrated in a state which is largely insenstive to moisture, while the substances in the liquid for the receiving material ensure, by virtue of the complete surface wetting, that subsequently reacting substances are transformed on the surface into a stable compound.
  • the negative material may be commercially available Copyrapid-Dry- Negative paper, and the developer may be an activator designed therefor.
  • the developer may be an activator designed therefor.
  • ordinary negative diifusion papers are used, a known, commercial developer for these papers can be used.
  • the former solution is designated as a 0.02% platinum solution as and the latter solution a gold solution with a 1% concentration.
  • Example 7 H O1000 ml. Mirsasol15 ml. Gold solutionml. N2S2O31 ml. Ascorbic acid--O.1 g.
  • the additions to the starting solution are of the order of up to 0.6 gram. More particularly, in the case of the organic acids, the addition is preferably of the order of magnitude up to 0.5 gram, calculated on a starting charge of 1000 ml. H 0.
  • a silver salt difiusion transfer method wherein an image is formed by exposure on the silver halide emulsion layer of a negative sheet and the thus exposed negative sheet is developed by a developer liquid, whereupon the developed image is transferred by pressure contact to a receiving sheet
  • the improvement which c0m prises that the receiving sheet is uncoated sheet material which, immediately prior to the pressure contact with the negative material is moistened with a liquid of dif ferent composition than said developer liquid, said liquid comprising an aqueous solution containing (a) a silver salt solvent,
  • a liquid for use in silver salt diffusion transfer methods for wetting the uncoated receiving sheets to which the exposed and developed picture is transferred comprising an aqueous solution of (a) hexachloroplatinum (VI) acid or gold (III) chloride hydrochloric acid.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US613452A 1966-02-10 1967-02-02 Transfer method for silver salt diffusion and liquid agent for use in this method Expired - Lifetime US3510302A (en)

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DEL0052815 1966-02-10

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BE (1) BE693787A (en))
FR (1) FR1510383A (en))
GB (1) GB1178713A (en))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637376A (en) * 1967-02-10 1972-01-25 Lumoprint Zindler Kg Silver salt diffusions copyimg method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352014A (en) * 1941-07-21 1944-06-20 Rott Andre Photomechanical printing process and printing material for carrying out the same
DE764572C (de) * 1939-11-02 1952-03-31 Gevaert Photo Prod Nv Verfahren zur Herstellung von Bildern mit Hilfe von Halogensilber
US2644756A (en) * 1947-02-08 1953-07-07 Polaroid Corp Photographic process for forming a positive transfer image
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US3179517A (en) * 1959-08-24 1965-04-20 Eastman Kodak Co Web processing method and composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE764572C (de) * 1939-11-02 1952-03-31 Gevaert Photo Prod Nv Verfahren zur Herstellung von Bildern mit Hilfe von Halogensilber
US2352014A (en) * 1941-07-21 1944-06-20 Rott Andre Photomechanical printing process and printing material for carrying out the same
US2644756A (en) * 1947-02-08 1953-07-07 Polaroid Corp Photographic process for forming a positive transfer image
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US3179517A (en) * 1959-08-24 1965-04-20 Eastman Kodak Co Web processing method and composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637376A (en) * 1967-02-10 1972-01-25 Lumoprint Zindler Kg Silver salt diffusions copyimg method

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Publication number Publication date
FR1510383A (fr) 1968-01-19
GB1178713A (en) 1970-01-21
BE693787A (en)) 1967-07-17
DE1572112A1 (de) 1970-01-02

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