US3360368A - Silver complex diffusion transfer process - Google Patents

Silver complex diffusion transfer process Download PDF

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Publication number
US3360368A
US3360368A US207816A US20781662A US3360368A US 3360368 A US3360368 A US 3360368A US 207816 A US207816 A US 207816A US 20781662 A US20781662 A US 20781662A US 3360368 A US3360368 A US 3360368A
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US
United States
Prior art keywords
image
silver
silver halide
layer
diffusion transfer
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.)
Expired - Lifetime
Application number
US207816A
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English (en)
Inventor
George Frans Van Veelen
Brinckman Eric Maria
Willems Jozef Frans
Sevens Gerard Michiel
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.)
Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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Publication of US3360368A publication Critical patent/US3360368A/en
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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
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/243—Toners for the silver image
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/166—Toner containing

Definitions

  • a light-sensitive silver halide emulsion layer is exposed to an image and then pressed into contact with a specially prepared receiving material in the presence of a developer and a silver halide complexing agent.
  • the exposed image areas are developed and dornot undergo any further change.
  • the undeveloped silver halide in the unexposed areas is complexed by the silver halide complexing agent which is present either in the developer or in the receiving layer, transferred by diffusion to the receiving layer of said image-receiving material and converted therein to metallic silver.
  • the conversion is promoted by the action of reducing nuclei. In this way, a positive image of the original is formed in the receiving layer and is apparent after separation of the latter from the silver halide emulsion layer.
  • finely divided metal such as colloidal silver or metal sulfides such as cobalt sulfide can initiate and catalyze the development in the receiving layer of the transferred silver complex to a metallic silver image.
  • a disadvantage of the silver complex diifusion transfer process specially when using metal sulfide nuclei is the brownish image tone of the obtained silver image.
  • black-toning agent generally an organic heterocycl'ic compound containing mercapto groups.
  • Many of the hitherto known compounds show simultaneously with the desired improvement of the image tone the disadvantage of delaying the formation of the image in the image-receiving material. In this way a longer contact time is needed for obtaining sufiiciently strong copies.
  • the used amounts of these compounds have to be kept between determined and rather narrow limits since too high a concentration of blacktoning agent even can completely prevent the development.
  • Compound 5 can be prepared as follows:
  • the black-toning agents according to the invention may be present in the developing bath and/ or in the imagereceiving material and/or in the light-sensitive material.
  • the black-toning agent When the black-toning agent is incorporated into the treating bath solution, it is preferably added in a concentration of between 20 mg. of about 250 mg. per litre.
  • the black-toning agent When the black-toning agent is present in the lightsensitive material, preferably from 5 to 20 mg. of blacktoning agent are present per sq. m.
  • the blacktoning agent according to the invention can be present in any water-permeable layer, which is coated at the same side of the support as the light-sensitive silver halide emulsion layer and from which the black-toning agent can diffuse to the image-receiving layer of the imagereceiving material, e.g. in the light-sensitive silver halide emulsion lay-er itself, in a covering layer etc.
  • the black-toning agent can be present in the image-receiving matreial namely in the image-receiving layer and/or in a water-permeable layer which is in effective contact with the image-receiving layer so that the black-toning agent can diffuse in due time to the imagereceiving layer-
  • the black-toning agent is preferably added in an amount of about 10 to about 300 mg. per sq. m. of image-receiving material.
  • the image-receiving material which can be used in this invention, mostly consists of a support, for instance of paper, onto which one or more layers are coated.
  • a support for instance of paper
  • One of said layers is an image-receiving layer or a nuclei containing layer, wherein the diffusion transfer image is formed in the presence of physical and/ or chemical developing nuclei or substances which are able to form such developing nuclei with the diffusing silver complex.
  • the image-receiving material can also consist of a paper support alone wherein substances such as developing nuclei are incorporated.
  • a material which is suited for obtaining many positive copies of an original by means of one single imagewise exposed light-sensitive material can also be used as an image-receiving material.
  • This kind of image-receiv- 4 ing material is described egg. in the Belgian patent specifications 595,323 and 595,324.
  • the image-receiving layer can also be coated on the same support as the silver halide emulsion layer.
  • the image-receiving layer is mostly applied onto a support e.g. of paper and then coated with a slightly or not hardened light-sensitive silver halide emulsion layer.
  • This kind of image-receiving material is described in the British patent specification 654,631.
  • the exposed and developed unhardened emulsion layer can be removed e.g. by washing with warm water, or by stripping off after having been in contact with a sheet of common paper.
  • the light-sensitive material which is suited for being applied in a diffusion transfer process wherein blacktoning agents may be used as described above, may be any light-sensitive silver halide material, of which the exposed silver halide is developed and the unexposed silver halide is complexed in a sufficiently rapid way to allow the forming of a diffusion transfer image.
  • Silver chloride emulsions which may also contain silver bromide or silver iodide or to which certain ingredients may be added for obtaining the desired emulsion characteristics, are preferably used.
  • the developing substance(s) can be incorporated into the light-sensitive material and/ or into the bath and/or into the image-receiving material.
  • Suited developing substances are among others: hydroquinone, monomethyl-paminophenyl sulfate, aminophenol, 3-pyrazolidone compounds and mixtures of these developing substances such as the mixture of hydroquinone and a 3-pyrazolidone derivative which can be incorporated in the image-receiving material as described in the Belgian patent specification 6llj637.
  • the complexing agent which forms a soluble complex with the silver halide is preferably an alkali thiosulfate and can be incorporated either into the image-receiving material or into the processing bath.
  • Sulfides of heavy metals e.g. of antimony, bismuth, cadmium, cobalt, lead, nickel and silver, heavy metals preferably in colloidal form, such as silver, gold, platina, palladium and mercury, and/or other substances which can be used as developing nuclei for the complexed silver halide are incorporated in the image-receiving layer.
  • heavy metals e.g. of antimony, bismuth, cadmium, cobalt, lead, nickel and silver
  • heavy metals preferably in colloidal form such as silver, gold, platina, palladium and mercury, and/or other substances which can be used as developing nuclei for the complexed silver halide are incorporated in the image-receiving layer.
  • an antifogging compound is used to avoid fogging in the exposed silver halide emulsion layers.
  • This antifogging compound can be worked up in the light-sensitive emulsion and/ or in the processing bath.
  • the substances such as developers, complexing agents for silver halide, alkali, development nuclei and others which are needed in the silver complex diffusion transfer process can all be worked up in the used light-sensitive or image-receiving material so that eventually common water can be used as processing liquid (Belgian patent specification 612,103).
  • Example 1 The light-sensitive material is prepared as follows:
  • a gelatino silver chloride emulsion which is prepared from 45 g. of silver nitrate and which is sensitized to light with a wavelength of 500-570 m r a solution of 250 mg. of 6-methyl-tetrahydro-2H-1,3-thiazine- 2-thione in 25 cm. of ethanol is added.
  • This emulsion is coated onto a usual support in such a way that the coated layer contains per sq. m. an amount of silver chloride corresponding to 1.5 g. of silver.
  • the image-receiving material is prepared by coating a paper support with the following coating composition:
  • This suspension is coated in such a way that 13 sq. m. are covered with 1 litre.
  • the formed receiving layer is coated with an anti-sticking layer, which facilitates the separation of the light-sensitive emulsion layer from the image-receiving layer.
  • This anti-sticking layer is coated from a solution of the following composition:
  • the light-sensitive material in contact with the original to be produced, is exposed and then together with the image-receiving material passed through a developing bath of the following composition:
  • Examples 2-4 The same results are obtained by substituting 6-methyltetrahydro-2H-1,3-0xazine-2-thione, 4,4,6-trimethyl tetrahydro-ZH-1,3-thiazine-2-thione and 4,4,6-trimethy1 tetrahydro-ZH-1,3-oxazine-2-thi0ne for fi-methyl-tetrahydro- 2H-1,3-thiazine-2-thione. If no compounds according to the invention are present, copies with a brown image tone are obtained.
  • Example 5 The light-sensitive material, prepared as described in Example 1 containing, however, no black-toning agent is passed together with the image-receiving material through the following developing composition containing a black-toning agent.
  • Example 6 The same favourable result is obtained when in Example 5 6-rnethyltetrahydro-2H-1,3-thiazine-2-thione is replaced by a same amount of 4,4,6-trimethyltetrahydro- 2H-l,3-thiazinc-2-thione.
  • Example 7 A usual paper support for the silver complex diffusion transfer process is coated with a layer from the following coating composition:
  • a silver chloride emulsion paper containing per sq. m. an amount of silver chloride which corresponds to 1.5 g. of silver, is exposed in contact with an original to be reproduced and then, together with the image-receiving material, passed through a developing bath of the following composition:
  • Example 8 Example 7 is repeated replacing, however, the silver sulfide in the image-receiving material by 8 mg. of colloidal silver.
  • Example 9 Example 7 is repeated replacing, however, the silver sulfide in the image-receiving material by a mixture of 1.2.10 mole of sodium sulfide and 3.1.10* mole of cobalt nitrate 6 aq.
  • the amount of 6-methyltetrahydro- 2H-l,3-thiazine-2-thione is tripled, since heavy metal sulfide nuclei such as cobalt sulfide nuclei are less active black-toning agents than silver sulfide or colloidal silver nuclei which absorb the black-toning agents much better and so make them more effective.
  • Example 10 A usual paper support'is coated with an image-receiving layer from the following suspension:
  • the formed image-receiving layer is coated, with an antisticking layer from the following solution:
  • the solution is coated in such a way that 14 sq. m. are covered with 1 litre.
  • Example 11 An image-receiving material is prepared by coating a usual paper support with the following suspension:
  • the light-sensitive material from Example 10 is imagewise exposed and while being pressed into contact with the above image-receiving material, passed through the following developing composition:
  • Example 12 Example 11 is repeated substituting in the developing composition a same amount of tetrahydro-ZH-1,3-thiazine- Z-thione for 4,4,6-trimethyl-tetrahydro-ZH-1,3-oxazine-2- thione. Again, a copy with a perfectly neutral image tone is obtained.
  • Example 13 Example 10 is repeated substituting, however, in the coating suspension for the image-receiving layer mole of colloidal nickel sulfide for l.64 l0 mole of colloidal silver sulfide and 50 cm. of 1% solution of tetrahydro-ZH-1,3-oxazine-2-thione in ethanol for a same amount of 0.2% solution of 4,4,6-trimethyl-tetrahydro- 2H-1,3-oxazine-2-thione in ethanol. Again, a copy with a perfectly neutral image tone is obtained.
  • a photographic silver complex diffusion transfer process comprising developing with a developing solution an image-wise exposed light-sensitive silver halide emulsion layer and image-wise diffusion of the non-developed and complexed silver halide from said emulsion layer into a non-light-sensitive image-receiving layer of an imagereceiving material where the complexed silver halide is converted into a silver containing image in the presence of development nuclei and of at least one compound provided in at least one of said developing solution and said image-receiving material having the following general formula or tautomeric structure thereof:
  • X is an atom selected from the group consisting of a sulfur atom and an oxygen atom
  • each of R R R R R R and R is hydrogen or lower alkyl.
  • X is an atom selected from the group consisting of a sulfur atom and an oxygen atom
  • each of R R R R R R and R is hydrogen or lower alkyl.
  • a photographic image-receiving material for being used in a silver complex diffusion transfer process comprising at least one compound having the following general formula or tautomeric structure thereof:
  • X is an atom selected from the group consisting of a sulfur atom and an oxygen atom, and each of R R R R R and R is hydrogen or lower alkyl. 5.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Indole Compounds (AREA)
US207816A 1961-07-06 1962-07-05 Silver complex diffusion transfer process Expired - Lifetime US3360368A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE2040787 1961-07-06

Publications (1)

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US3360368A true US3360368A (en) 1967-12-26

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US (1) US3360368A (is")
BE (1) BE605802A (is")
DE (1) DE1153991B (is")
GB (1) GB1027741A (is")

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043245A (en) * 1989-01-31 1991-08-27 Agfa Gevaert, N.V. Process for the production of a laminated article

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10234425A1 (de) * 2002-07-29 2004-02-12 Bayer Ag Substituierte Thiazine als Materialschutzmittel

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE608384A (is") * 1960-09-24
BE571916A (is") *
GB753434A (en) * 1953-09-29 1956-07-25 Gevaert Photo Prod Nv Improvements in or relating to photographic material
US2774667A (en) * 1951-07-02 1956-12-18 Polaroid Corp Photographic silver halide transfer process
GB772027A (en) * 1954-10-06 1957-04-10 Mason & Sons Ltd E N Improvements relating to the production of photographic images by a migratory reversal transfer process
GB783793A (en) * 1955-01-03 1957-10-02 Gevaert Photo Prod Nv Improvements in or relating to the photographic diffusion-transfer process
GB867174A (en) * 1958-12-15 1961-05-03 Gevaert Photo Prod Nv Improvements in or relating to the photographic diffusion transfer process
US2987396A (en) * 1958-12-29 1961-06-06 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
GB900093A (en) * 1958-09-05 1962-07-04 Kodak Ltd Improvements in processes of photographic reproduction
US3160505A (en) * 1960-11-08 1964-12-08 Gevaert Photo Prod Nv Process for obtaining a photographic image with improved image-tone according to thesilver halide diffusion transfer process

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE597026A (is") * 1959-11-14
DE1108564B (de) * 1960-06-13 1961-06-08 Polaroid Corp Photographischer Entwickler fuer das Silbersalzdiffusionsuebertragungs-verfahren

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE571916A (is") *
US2774667A (en) * 1951-07-02 1956-12-18 Polaroid Corp Photographic silver halide transfer process
GB753434A (en) * 1953-09-29 1956-07-25 Gevaert Photo Prod Nv Improvements in or relating to photographic material
GB772027A (en) * 1954-10-06 1957-04-10 Mason & Sons Ltd E N Improvements relating to the production of photographic images by a migratory reversal transfer process
GB783793A (en) * 1955-01-03 1957-10-02 Gevaert Photo Prod Nv Improvements in or relating to the photographic diffusion-transfer process
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
GB900093A (en) * 1958-09-05 1962-07-04 Kodak Ltd Improvements in processes of photographic reproduction
GB867174A (en) * 1958-12-15 1961-05-03 Gevaert Photo Prod Nv Improvements in or relating to the photographic diffusion transfer process
US2987396A (en) * 1958-12-29 1961-06-06 Eastman Kodak Co Photographic silver halide diffusion transfer process
BE608384A (is") * 1960-09-24
US3160505A (en) * 1960-11-08 1964-12-08 Gevaert Photo Prod Nv Process for obtaining a photographic image with improved image-tone according to thesilver halide diffusion transfer process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043245A (en) * 1989-01-31 1991-08-27 Agfa Gevaert, N.V. Process for the production of a laminated article

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GB1027741A (en) 1966-04-27
DE1153991B (de) 1963-09-05
BE605802A (is")

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