US3431108A - Silver complex diffusion transfer process - Google Patents

Silver complex diffusion transfer process Download PDF

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Publication number
US3431108A
US3431108A US585734A US3431108DA US3431108A US 3431108 A US3431108 A US 3431108A US 585734 A US585734 A US 585734A US 3431108D A US3431108D A US 3431108DA US 3431108 A US3431108 A US 3431108A
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US
United States
Prior art keywords
image
silver
ccs
diffusion transfer
silver halide
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
US585734A
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English (en)
Inventor
Jozef Frans Willems
George Frans Van Veelen
Maria Louis De Haes
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.)
Agfa Gevaert NV
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Agfa Gevaert NV
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Publication date
Priority claimed from GB4297065A external-priority patent/GB1120963A/en
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
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Publication of US3431108A publication Critical patent/US3431108A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
    • C07D253/10—Condensed 1,2,4-triazines; Hydrogenated condensed 1,2,4-triazines
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/49—Print-out and photodevelopable emulsions
    • 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

Definitions

  • finely divided metal particles such as colloidal silver or metal sulphide particles such as cobalt sulphide particles can initiate or catalyse the conversion of the transferred silver complex to a silver containing image in the receiving layer.
  • a disadvantage of the silver complex diffusion transfer process, especially when metal sulphide nuclei are used, is the less agreeable brown image tone of the obtained silver containing diffusion transfer image.
  • black-toning agent usually, this is an organic heterocyclic compound containing thioxo or their tautomeric mercapto groups.
  • a widely used black-toning agent is l-phenyl-2-tetrazoline-S-thione, which improves the image tone indeed, but at the same time strongly delays the formation of the diffusion transfer image in the imagereceiving material, so that a longer contact time is required in order for obtaining sufficiently dense prints.
  • the used amount of this compound has to be kept within specific and rather narrow limits, since too high a concentration of black-toning agent even completely prevents development.
  • R R R R and R each represent a hydrogen atom, an alkyl group including a substituted alkyl group, an aryl group including a substituted aryl group, with the proviso, however, that at least one of the substituents R and R represents a hydrogen atom;
  • R and R may also represent the atoms necessary to complete a carbocyclic ring including a substituted carbocyclic ring.
  • COMPOUND 2 1'1 3-thio-1,2,4-triazaspiro[5,5]undecane-3,5-dione.
  • COMPOUND 3 4,6,6-trimethyl-3-thio-1,6-dihydro-as-triazine-3,5 (2H,4H) dione.
  • This compound can be prepared according to preparation 2, as described further hereinafter.
  • COMPOUND 1 phenyl 4 methyl-3thio-1,6-dihydro-as-triazine-3,5 (2H,4H)-dione.
  • COMPOUND 6 (Balls N 1 phenyl 3 thio-l,6-dihydro-as-triazine-3,5(2H,4H)- dione.
  • COMPOUND 7 CH3 111 1129 NH 1 methyl 4 ethyl-3-thio-l,6-dihydro-as-triazine-3,5 (2H,4H) -dione.
  • This compound can be prepared according to preparation 4 as described further hereinafter.
  • PREPARATION 1 A Preparation of the intermediate product 1-(1'-cyano- '-methyl-ethyl)-4-methyl-thiosemicarbazide 21 g. of 4-methyl-thiosemicarbazide are dissolved in 80 ccs. of a mixture of ethanol and water (1:1). Whilst stirring, the solution, there are successively added at room temperature: 11.5 ccs. of acetic acid, a solution of 13 gof potassium cyanide in 25 ml. of water and 12.6 ccs. of acetone. The reaction mixture is refluxed for 1 hour. After cooling, the formed crystals are filtered by suction (yield: 34.5 g., melting point: 197203 C.) and recrystallized from 1600 cos. of ethanol.
  • PREPARATION 2 A Preparation of the intermediate product 1-(1'-cyanocyclohexyl-4-methyl-thiosemicarbazide g. of 4-methyl-thiosemicarbazide are dissolved in 400 ccs. of a mixture of ethanol and water (1:1). Whilst stirring the solution at 10 C. there are successively added: 57.5 cos. of acetic acid, a solution of 65 g. of potassium cyanide in ccs. of water and 98 g. of cyclohexanone. The reaction mixture is refluxed for 2 hours, whilst stirring. After cooling, the crystals formed are filtered 'by suction and Washed with ethanol and ether.
  • PREPARATION 3 70 g. of l-phenyl-l-ethoxyacetyl-hydrazine hydrochloride are dissolved in 450 ccs. of water. By adding 17.1 g. of ammonium carbonate 1 aq., the base is set free from its hydrochloride whereupon it is extracted with ether. After drying the etheric solution over molecular sieves, a solution of 15.6 g. of methylisothiocyanate in 220 ccs. of ether is added. By evaporation of the ether an oil is left which is dissolved in 75 ccs. of anhydrous ethanol and to which a solution of 11.2 g. of potassium hydroxide in ccs. of ethanol is added whilst cooling at 0 C. A yellow precipitate is formed (39 g.) which is filtered by suction, dissolved in 100 ccs. of water and acidified with acetic acid.
  • PREPARATION 4 45 g. of l-methyl-l-ethoxyacetyl hydrazine hydrochloride are suspended in 230 ccs. anhydrous ether and whilst thoroughly stirring at 0 C. ammonia gas is introduced. The formed ammonium chloride is removed by filtration. By evaporation of the ether of the filtrate, an oil is left which is again dissolved in 205 ccs. anhydrous ether and this solution is added to a solution of 21.6 ccs. of ethylisothiocyanate in 205 ccs. of anhydrous ether. After stirring for half an hour at room temperature, the ether is evaporated. The residue is dissolved in 100 ccs.
  • the black-toning agent according to this invention can be present in the processing bath and/or in the imagereceiving material. When present in the processing bath, its uses to be in amounts mostly comprised between about 30 and about 1000 mg. per litre of processing bath.
  • the image-receiving material When incorporated into the image-receiving material, i.e. in the image-receiving layer and/or into a waterpermeable layer from which it can diffuse in due time to the image-receiving layer (i.e. in a water-permeable layer, which is in working contact with the image-receiving layer) its uses to be preferably in amounts ranging from about to about 300 mg. of black-toning agent per sq. m. of image-receiving material.
  • the image-receiving material which can be used in a silver complex diffusion transfer process according to this invention mostly consists of a support e.g. of paper which carries one or more layers, one of which is the image-receiving layer or nuclei-containing layer wherein the diffusion transfer image is formed in the presence of developing nuclei (physical and/or chemical) and/or of substances which are capable of forming developing nuclei with the diffusing complexed silver halide.
  • the image-receiving material can also consist of a mere paper support incorporating constituents such as developing nuclei.
  • an image-receiving material can be used which is composed in such a way that several positive copies of an original can be produced from only one image-wise exposed light-sensitive material.
  • Such an image-receiving material is among others described in our British patent specifications 950,960 and 961,177.
  • the image-receiving layer can also be applied to the same support as the silver halide emulsion layer.
  • the image-receiving layer is mostly coated onto a support, e.g. of paper and covered with a non-hardened or slightly hardened light-sensitive silver halide emulsion layer.
  • a support e.g. of paper
  • a non-hardened or slightly hardened light-sensitive silver halide emulsion layer is described among others in our British patent specification 654,631.
  • the exposed and developed unhardened emulsion layer can be removed e.g. by washing away with warm water or by stripping after having been in contact with a sheet of common paper.
  • a separating layer Between the image-receiving layer and the light-sensitive layer there can also be present a separating layer.
  • a starch ether separating layer which enables the detaching of the light-sensitive layer as a coherent sheet, by simply bringing the multilayer material into an aqueous rinsing bath after the diffusion transfer image formation.
  • the light-sensitive material suitable for a diffusion transfer process wherein black-toning agents as described above can be used may be any light-sensitive silver halide material the exposed silver halide of which is sufficiently rapidly developed and the non-exposed silver halide is sufi'iciently rapidly complexed for allowing the formation of a diffusion transfer image to take place.
  • silver chloride emulsions are used which may contain specific amounts of silver bromide or silver iodide or to which some ingredients may be added in order to obtain the desired emulsion characteristics.
  • the developing substance(s) can be incorporated into the light-sensitive material and/or into the bath and/or into the image-receiving material.
  • Suitable developing substances are among others: hydroquinone, monomethyl-p-aminophenol sulphate, aminopheno-l and 3- pyrazolidinone developing substances. These developing substances can occasionally, at least partly be present in the materials used.
  • hydroquinone together with a bisulphite can be present in the image-receiving material, such as described in our British patent specification Ser. No. 1,000,115.
  • combinations of two or more developing agents can be used successfully, such as the combination of hydroquinone and a 3-pyrazolidinone derivative together in the image-receiving material as described in our British patent specification 1,012,476, and the combination of hydroquinone in the image-receiving material and a 3-pyrazolidinone derivative in the lightsensitive material as described in the Belgian patent specifications 633,674 and 635,813.
  • the complexing agent forming a soluble complex with the silver halides is preferably an alkali thiosulphate and can be incorporated into the image-receiving material as well as into the processing bath.
  • Sulphides of heavy metals such as antimony, bismuth, cadmium, cobalt, lead, nickel and silver; heavy metals such as silver, gold, platinum, palladium and mercury, preferably in their colloidal form, and/ or other substances which can serve as developing nuclei for the complexed silver halide are mostly incorporated into the image-receiving layer. However, they can also be present in the processing bath. In the latter case, use is made of a lightsensitive and image-receiving material with a specific composition. Such diffusion transfer process with developing nuclei and/ or compounds capable of forming such nuclei present in the processing bath has among others been described in our British patent specification Ser. No. 1,001,558 and in the Belgian patent specification 635,811.
  • This fog-inhibiting agent e.g. can be present in the light-sensitive silver halide material and/ or in the processing bath.
  • a diffusion transfer process wherein use is made of black-toning agents as described in this invention, yields diffusion transfer images of a very satisfactory bluishblack to black colour.
  • the black-toning agents to the present invention possess a very important advantage over the known black-toning agents. Indeed, if they are used in the developing bath, they keep this bath clear even after frequent use. It is known that during the diffusion transfer process sometimes finely divided metallic silver is formed inthe developer and that after some time this black silver sludge begins to deposit onto the transport parts of the developing apparatus. This involves the disadvantageous consequence that after some time the diffusion transfer copies show black spots. This disadvantage is completely avoided by adding compounds according to the present invention to the developer, which compounds prevent said silver sludge from being formed. At the same time, an additional amount of black-toning agent, occasionally one different from these according to the present invention, may be present in the image-receiving material as well as in the light-sensitive silver halide material.
  • Example 1 An image-receiving material is prepared by coating a paper support with a layer from the following coating composition:
  • This suspension is coated in such a way that I litre covers 13 sq. m.
  • a silver chloride emulsion paper containing per sq. m. 1.35 g. of silver chloride is exposed while being in contact with an original to be reproduced, whereupon it is led together with the above-mentioned image-receiving material in the usual way through a developing bath of the following composition:
  • Example 2 An image-receiving material is prepared by coating a paper support with a layer from the following coating composition:
  • Example 3 An image-receiving material is prepared by coating a paper support with a layer from the following coating composition:
  • a silver chloride emulsion paper containing per sq. m. 1.35 g. of silver chloride is exposed while being in contact with an original to be reproduced, whereupon it is led together with the above-mentioned image-receiving material in the usual way through a developing bath as described in Example 1 but which, moreover, contains 330 mg. of Compound 1.
  • the same neutral image tone is obtained when the Compound 1, present in the developing bath is replaced by a same amount of one of Compounds 2, 3, 4 or 5.
  • Example 4 An image-receiving material is prepared by coating a g./sq. m. paper support in a ratio of 20 sq. m./l. with a layer from a suspension of the following composition:
  • Photographic silver complex diffusion transfer process according to which a positive image of an original is obtained by development of an image-wise exposed lightsensitive silver halide emulsion layer and diffusion of nondeveloped complex silver halide from the emulsion layer into an image-receiving material where the complexed silver halide is converted in the presence of development nuclei into a silver-containing image, wherein said process is carried out in the presence of at least one compound corresponding to the following general formula or to a tautomeric structure thereof:
  • each of R R R R and R is hydrogen, alkyl or ary], wlth the proviso, however, that at least one of the substituents R and R is hydrogen; R and R may also represent the atoms necessary to complete a carbocyclic ring.
  • Photographic silver complex diffusion transfer process according to claim 1, wherein the compound defined is present in at least one water-permeable layer of the image-receiving material.
  • Photographic silver complex diffusion transfer process according to claim 1, wherein the compound defined is present in the processing bath.
  • Image-receiving material for use in a silver complex diffusion transfer process, comprising an image-receiving layer and containing in at least one water-permeable layer at least one compound corresponding to the following general formula or to a tautomeric structure thereof:
  • each of R R R R and R is hydrogen, alkyl or aryl, with the proviso, however, that at least one of the substituents R and R is hydrogen; R and R may also represent the atoms necessary to complete a carbocyclic ring.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Color Printing (AREA)
US585734A 1965-10-11 1966-10-11 Silver complex diffusion transfer process Expired - Lifetime US3431108A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB42969/65A GB1160955A (en) 1965-10-11 1965-10-11 New Light-Developable Photographic Material and Recording Process
GB4297065A GB1120963A (en) 1965-10-11 1965-10-11 Silver complex diffusion transfer process
NL6615205A NL6615205A (enrdf_load_stackoverflow) 1965-10-11 1966-10-27

Publications (1)

Publication Number Publication Date
US3431108A true US3431108A (en) 1969-03-04

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US585734A Expired - Lifetime US3431108A (en) 1965-10-11 1966-10-11 Silver complex diffusion transfer process
US585731A Expired - Lifetime US3502471A (en) 1965-10-11 1966-10-11 New light-developable photographic material and recording process

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Application Number Title Priority Date Filing Date
US585731A Expired - Lifetime US3502471A (en) 1965-10-11 1966-10-11 New light-developable photographic material and recording process

Country Status (6)

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US (2) US3431108A (enrdf_load_stackoverflow)
BE (2) BE688065A (enrdf_load_stackoverflow)
DE (2) DE1522401A1 (enrdf_load_stackoverflow)
FR (1) FR1496596A (enrdf_load_stackoverflow)
GB (1) GB1160955A (enrdf_load_stackoverflow)
NL (2) NL6614290A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650741A (en) * 1968-03-25 1972-03-21 Agfa Gevaert Nv Silver complex diffusion transfer process
US3854948A (en) * 1971-05-15 1974-12-17 Minnesota Mining & Mfg New development composition for radiographic film
US4436805A (en) 1981-10-26 1984-03-13 Mitsubishi Paper Mills, Ltd. Silver complex diffusion transfer process using two toning agents

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001025A (en) * 1974-10-10 1977-01-04 Minnesota Mining And Manufacturing Company Process of sensitizing silver halide emulsions with heterocyclic sulfur compounds
JPS56115777A (en) 1980-02-19 1981-09-11 Sumitomo Chem Co Ltd 3-thiooxo-5-oxo-hexahydro-1,2,4-triazine, its preparation, herbicide and germicide comprising it as active ingredient
DE69001808T2 (de) * 1990-03-19 1994-01-05 Agfa Gevaert Nv Halogenacceptoren enthaltende photographische Raumlicht-Materialien.
DE69120934T2 (de) * 1991-04-15 1997-02-20 Agfa Gevaert Nv Als Montagehilfsmittel und Postionierprobe geeignetes Silberhalogenid-Auskopiermaterial
US20050096319A1 (en) * 2003-02-21 2005-05-05 Balzarini Jan M.R. Identification of compounds that inhibit replication of human immunodeficiency virus
CA2515679A1 (en) * 2003-02-21 2004-09-02 Tripep Ab Glycinamide derivative for inhibiting hiv replication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1025651A (en) * 1962-01-05 1966-04-14 Kodak Ltd Preparation of photographic silver halide emulsions
GB1059782A (en) * 1962-09-11 1967-02-22 Eastman Kodak Co Photographic silver halide emulsions and sensitive materials prepared therefrom
US3367780A (en) * 1963-08-19 1968-02-06 Eastman Kodak Co Direct-print photographic silver halide emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650741A (en) * 1968-03-25 1972-03-21 Agfa Gevaert Nv Silver complex diffusion transfer process
US3854948A (en) * 1971-05-15 1974-12-17 Minnesota Mining & Mfg New development composition for radiographic film
US4436805A (en) 1981-10-26 1984-03-13 Mitsubishi Paper Mills, Ltd. Silver complex diffusion transfer process using two toning agents

Also Published As

Publication number Publication date
BE688065A (enrdf_load_stackoverflow) 1967-04-11
BE688068A (enrdf_load_stackoverflow) 1967-04-11
GB1160955A (en) 1969-08-13
FR1496596A (fr) 1967-09-29
DE1522403A1 (de) 1969-08-14
US3502471A (en) 1970-03-24
NL6615205A (enrdf_load_stackoverflow) 1967-03-28
DE1522401A1 (de) 1969-07-24
NL6614290A (enrdf_load_stackoverflow) 1967-03-28

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