US3257205A - Method for heat development - Google Patents

Method for heat development Download PDF

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Publication number
US3257205A
US3257205A US147388A US14738861A US3257205A US 3257205 A US3257205 A US 3257205A US 147388 A US147388 A US 147388A US 14738861 A US14738861 A US 14738861A US 3257205 A US3257205 A US 3257205A
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US
United States
Prior art keywords
layer
silver halide
silver
pyrazolidone
phenyl
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
US147388A
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English (en)
Inventor
Cassiers Paul Maria
Haes Louis Maria De
Vanreusel Gerard Laurens
Willems Josef Frans
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 US3257205A publication Critical patent/US3257205A/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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • G03C11/00—Auxiliary processes in photography
    • G03C11/08—Varnishing, e.g. application of protective layers on finished photographic prints
    • 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
    • G03C8/40—Development by heat ; Photo-thermographic processes

Definitions

  • Suitable reducing compounds for heat development processes are aromatic amino-, hydroxy-, and aminohydroxy-compounds and their derivatives, many examples of which are described in German patent specification 895,101 and Belgian patent specifications 544,850,
  • the image obtained is of an inferior quality because of the too low density and the too soft gradation of the light-sensitive material.
  • a process has been found for the production of photographic images by heatdevelopment, wherein a photographic material comprising a silver halide emulsion layer and incorporated in this silver halide emulsion layer and/or in a layer adjacent thereto, a S-pyrazolidone compound of the formula wherein:
  • the pH of the silver halide emulsion during the heat-development being 7 or less.
  • the developing substances according to this invention may be incorporated, either into the silver halide emulsion or into a separate adjacent layer.
  • the developability of the above described silver halide emulsions can still be improved by incorporating into these emulsions compounds which on heating liberate water.
  • hydrophilic plasticizers e.g., glycerol, caprolactam, polyethylene glycol and the like
  • hydrophilic plasticizers e.g., glycerol, caprolactam, polyethylene glycol and the like
  • the image quality can be improved by incorporating into the emulsions compounds which favorably influence the image tone, e.g., l-phenyl-S-mercaptotet-razole or similar products, which are described in British patent specification 561,875 and Belgian patent specification 502,525.
  • An advantage of the new process is the excellent quality of the produced images with regard to the density as well V as in respect of the gradation. After rinsing and fixing, the obtained density is also much better kept than it is in the case with the most known developing substances.
  • a second advantage is the short developing time: in some cases the development has to last for only 1 to 10 sec. at a temperature between and 200 C. Furthermore, the material according to the invention has very good keeping properties'before its exposure, as derivatives of 1-phenyl-3-pyrazolidone in a non-alkaline medium and a normal temperature show but a poor reactivity.
  • a further advantage is the broad thermal margin of working up or the silver halide emulsions which are prepared with these new compounds. It has been experienced that the temperature fluctuations during the heatdevelopment may amount to 30 to 40 C. without incurring the risk that less good images are obtained.
  • the amount of warmth which is necessary for the development may be applied onto the material in various waves possess a wave-length of to 10" cm.
  • the silver halide emulsion can be developed by conduction, by contacting it with heated plates or rollers, by placing it between two capacitor plates which are subjected to a high frequency field, or by subjecting it to the Joule effect.
  • the silver halide emulsion can also be developed by convection, e.g., by contacting it with directed warm gas stream. For this purpose, e.g., warm air or steam may be used.
  • the silver halide emulsion can also be developed by warmth radiation.
  • the use of infrared radiation sources is especially suited therefor, not only because they have an intensive developing power, but also because they enable simultaneously to expose and to develop in a fraction of a second.
  • infrared radiation sources those radiation sources are understood of which the major part of the radiated energy In this way it is possible to contact a light-sensitive material, prepared according to this invention, with a film negative and to move it along a light-source which is rich in infrared radiations so as to obtain immediately a very strong positive image.
  • An especially interesting embodiment of this invention is the manufacture of prints of the heat-developed images according to the transfer process, which is described in the German patent specification 895,101.
  • the silver halide layers which are developable by heat contain a developing sub- 4, (1,2)triazolium chloride and 2-phenyl-3-(o-carboxyphenyl) -naphtho 1,2) triazolium chloride.
  • tetrazolium compounds according to the above Formula III which appeared from the experiments to give particularly good results are, e.g., 2,5-diphenyl-3-(o-carboxyphenyl)-2,l,3,4-tetrazoliurn chloride, 2,5-diphenyl-3- (o-methoxyphenyl)-2,l,3,4-tetrazolium chloride and 2,5- diphenyl 3 (p-methoxyphenyU-Z,1,3,4-tetrazolium chloride.
  • the process according to the present invention can be carried out by contacting the negative layer containing the developing substance, before the heatdevelopment, with a positive layer containing a colorless triazolium compound of the general formula wherein:
  • each of R and R represents an aliphatic group, a substituted aliphatic group, a homocyclic group, a substituted homocyclic group, a heterocyclic group, or a substituted heterocyclic group;
  • X represents an acid radical
  • Y represents the necessary atoms for closing an homocyclic group, substituted homocyclic group, a heterocyclic group, or a substituted heterocyclic group.
  • the negative layer is contacted, before the heatdevelopment, with a positive layer which contains a colorless tetrazolium compound of the formula:
  • the color tone, the fastness to light and the fastness to washing of these dyes can markedly be improved by the presence in the positive material of salts of multivalent metals, e.g., zinc, copper,
  • R is an aryl radical, which in its ortho position bears an electronegative group such as a canboxyl group.
  • Another interesting embodiment of this invention is based on the formation of a silver image in the positive material.
  • the exposed negative is contacted during the heat-development with a positive material containing silver salts, e.g., silver nitrate.
  • the developing substances which remain unused during the heatdeveloprnent diffuse into the positive layer and there reduce the silver salts into metallic silver.
  • the silver halide emulsion layers in the dried light-sensitive materials preferably contain per sq. m. 3 g. of gelatin and an amount of silver halide corresponding to 1 g. of silver.
  • Example 1 A photographic paper support of 90 g./ sq. m. is coated with a layer from a suspension of the following composi- This paper is then dried, exposed through an original and heat-developed either by contacting this paper with a plate heated at 200 C. or by treating it with a steam jet of 100 C. A sharp print of the original is obtained. This print may be fixed and stabilized according to known processes.
  • Example 2 A photographic paper support of -g./sq. m. is coated with a layer from a suspension of the following composition:
  • Example 3 A photographic paper support of 90 g./sq. m. is coated with a layer from a suspension of the following composition:
  • Example 4 A negative material is prepared by coating a paper support of 90 g./sq. m. with a layer from a suspension of This layer is applied in such a way that 1 l. of this suspension covers 10 sq. m. of paper. Upon this layer is then applied a layer from the following solution:
  • a positive material is prepared by dip-coating a paper support of 90 g./sq. m. with a 0.1% aqueous silver nitrate solution and drying it.
  • the silver halide emulsion side of the negative material, 'in contact with the original, is reflectographically exposed.
  • the negative material is pressed for about 5 sec. with its emulsion side against the prepared positive material by means of a flat-iron at about 150 C.
  • the part of developing substance which during the heat-development did not serve to reduce the silver halide into silver, diffuses onto the positive layer and reduces the silver nitrate into silver. A clear print of the original is obtained.
  • Example 5 A photographic paper support of 90 g./ sq. m. is coated with a layer from a suspension of the following composition:
  • Silver chloride emulsion cm. 100 Water cm. l Ethanol cm. 1-phenyl-3-pyrazolidone g 1 Potassium metabisulfite g 1 Sodium acetate g 20 99% acetic acid cm. 3 Saponine cm. 0.5 40% aqueous formaldehyde solution cm. 0.5 1% solution of l-phenyl-S-mercapto-l,2,3,4-tetrazole in ethanol cm. 2.5 Titanium dioxide g 6 This layer is applied in such a way, that 1 l. of this suspension covers 10 sq. m. of paper.
  • a positive material is prepared by coating a paper support of 90 g./sq. m. with a layer from a solution of the following composition:
  • the negative material is refiectographically exposed to a printed original and developed by pressing it for 10 sec. against a heated plate at 110 C. Then the developed the following composition:
  • a process for the production of photographic copies by heat development which comprises the steps of:
  • R is a member of the group consisting of hydrogen and an aryl radical
  • R is a member of the group consisting of hydrogen and an acyl radical
  • R R R and R are each a member of the group consisting of hydrogen, an alkyl radical and an aryl radical
  • R and R are each a member of the group consisting of an aliphatic group, a homocyclic group, and a heterocyclic group,
  • X is an acid radical
  • Y represents the atoms necessary for closing a ring of the group consisting of a homocyclic ring and a heterocyclic ring;

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US147388A 1960-10-12 1961-10-10 Method for heat development Expired - Lifetime US3257205A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL256771 1960-10-12

Publications (1)

Publication Number Publication Date
US3257205A true US3257205A (en) 1966-06-21

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ID=19752627

Family Applications (1)

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US147388A Expired - Lifetime US3257205A (en) 1960-10-12 1961-10-10 Method for heat development

Country Status (6)

Country Link
US (1) US3257205A (xx)
BE (1) BE609057A (xx)
CH (1) CH397734A (xx)
DE (1) DE1422887A1 (xx)
GB (1) GB1001702A (xx)
NL (2) NL256771A (xx)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3352682A (en) * 1963-09-13 1967-11-14 Ilford Ltd Photographic silver halide emulsion containing finely divided uinert particles dispersed in a synthetic colloid medium and a silver halide developer
US3503741A (en) * 1966-11-04 1970-03-31 Eastman Kodak Co Silver-dye-bleach process utilizing formazan dyes
US3617289A (en) * 1966-12-10 1971-11-02 Fuji Photo Film Co Ltd Stabilization process for thermally developable light-sensitive elements
US3649158A (en) * 1967-08-08 1972-03-14 Oreal Process for dyeing locks of human hair with tetragolium salts
US3880659A (en) * 1973-08-02 1975-04-29 Eastman Kodak Co Triazolium salt photoreductive imaging
US4187108A (en) * 1977-02-07 1980-02-05 Eastman Kodak Company Heat developable material and process

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1288427B (de) * 1963-11-15 1969-01-30 Eastman Kodak Co Verwendung von in 2-Stellung substituierten 3-Pyrazolidonen als photographische Entwicklerverbindungen
US4891309A (en) * 1987-06-04 1990-01-02 Konica Corporation Process for producing silver halide photographic paper
US5206112A (en) * 1991-06-27 1993-04-27 Minnesota Mining And Manufacturing Company Positive imaging diffusion - transfer dry silver system

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE554934A (xx) * 1956-02-13 1900-01-01
FR998055A (fr) * 1949-09-28 1952-01-14 Gevaert Photo Prod Nv Procédé pour la production d'images photographiques
GB670883A (en) * 1949-06-21 1952-04-30 Gevaert Photo Prod Nv Improvements in or relating to the production of photographic images
US2751297A (en) * 1953-08-03 1956-06-19 Eastman Kodak Co Photographic emulsion layer containing a 3-pyrazolidone
US2751300A (en) * 1954-07-15 1956-06-19 Eastman Kodak Co Photographic solvent transfer reproduction process
DE1003578B (de) * 1952-09-04 1957-02-28 Zindler Lumoprint Kg Verfahren zur Herstellung von photographischen Bildern und Mittel zur Durchfuehrung desselben
US2891862A (en) * 1956-11-06 1959-06-23 Eastman Kodak Co Stabilized photographic silver halide emulsions
GB845928A (en) * 1957-10-25 1960-08-24 Ilford Ltd Improvements in or relating to photographic emulsions
US2971840A (en) * 1955-02-07 1961-02-14 Agfa Ag Process for the production of nonlaterally reversed positive copies by heat development
US3007795A (en) * 1955-02-11 1961-11-07 Agfa Ag Process for the production of laterally non-reversed positive copies by heat development
US3015562A (en) * 1958-05-07 1962-01-02 Gen Aniline & Film Corp Receiving sheet for use in photographic silver transfer process
US3041170A (en) * 1959-10-29 1962-06-26 Eastman Kodak Co New class of development promoter precursors for dry processing self-developing silver halide coatings
US3042514A (en) * 1959-08-06 1962-07-03 Gen Aniline & Film Corp Diffusion-transfer reversal process

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB670883A (en) * 1949-06-21 1952-04-30 Gevaert Photo Prod Nv Improvements in or relating to the production of photographic images
FR998055A (fr) * 1949-09-28 1952-01-14 Gevaert Photo Prod Nv Procédé pour la production d'images photographiques
DE1003578B (de) * 1952-09-04 1957-02-28 Zindler Lumoprint Kg Verfahren zur Herstellung von photographischen Bildern und Mittel zur Durchfuehrung desselben
BE530883A (xx) * 1953-08-03 1957-10-25
US2751297A (en) * 1953-08-03 1956-06-19 Eastman Kodak Co Photographic emulsion layer containing a 3-pyrazolidone
US2751300A (en) * 1954-07-15 1956-06-19 Eastman Kodak Co Photographic solvent transfer reproduction process
US2971840A (en) * 1955-02-07 1961-02-14 Agfa Ag Process for the production of nonlaterally reversed positive copies by heat development
US3007795A (en) * 1955-02-11 1961-11-07 Agfa Ag Process for the production of laterally non-reversed positive copies by heat development
BE554934A (xx) * 1956-02-13 1900-01-01
US2891862A (en) * 1956-11-06 1959-06-23 Eastman Kodak Co Stabilized photographic silver halide emulsions
GB845928A (en) * 1957-10-25 1960-08-24 Ilford Ltd Improvements in or relating to photographic emulsions
US3015562A (en) * 1958-05-07 1962-01-02 Gen Aniline & Film Corp Receiving sheet for use in photographic silver transfer process
US3042514A (en) * 1959-08-06 1962-07-03 Gen Aniline & Film Corp Diffusion-transfer reversal process
US3041170A (en) * 1959-10-29 1962-06-26 Eastman Kodak Co New class of development promoter precursors for dry processing self-developing silver halide coatings

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3352682A (en) * 1963-09-13 1967-11-14 Ilford Ltd Photographic silver halide emulsion containing finely divided uinert particles dispersed in a synthetic colloid medium and a silver halide developer
US3503741A (en) * 1966-11-04 1970-03-31 Eastman Kodak Co Silver-dye-bleach process utilizing formazan dyes
US3617289A (en) * 1966-12-10 1971-11-02 Fuji Photo Film Co Ltd Stabilization process for thermally developable light-sensitive elements
US3649158A (en) * 1967-08-08 1972-03-14 Oreal Process for dyeing locks of human hair with tetragolium salts
US3880659A (en) * 1973-08-02 1975-04-29 Eastman Kodak Co Triazolium salt photoreductive imaging
US4187108A (en) * 1977-02-07 1980-02-05 Eastman Kodak Company Heat developable material and process

Also Published As

Publication number Publication date
NL256771A (xx)
DE1422887A1 (de) 1968-11-28
NL110284C (xx)
CH397734A (fr) 1965-08-31
GB1001702A (en) 1965-08-18
BE609057A (xx)

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