US3148060A - Colloid transfer process and activator solution therefor - Google Patents

Colloid transfer process and activator solution therefor Download PDF

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Publication number
US3148060A
US3148060A US242526A US24252662A US3148060A US 3148060 A US3148060 A US 3148060A US 242526 A US242526 A US 242526A US 24252662 A US24252662 A US 24252662A US 3148060 A US3148060 A US 3148060A
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United States
Prior art keywords
emulsion layer
gelatin
emulsion
silver halide
grams per
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Expired - Lifetime
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US242526A
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English (en)
Inventor
Fruchard Alain
Richard Andre Jean
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/315—Tanning development
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers

Definitions

  • the developed emulsion is pressed into contact with an absorbent receiving sheet such as paper to cause the less exposed regions, and thus the less developed regions, of the emulsion to adhere to a receiving sheet. Subsequentially, when the emulsion and receiving sheet are separated, a stratum of the less exposed regions of the emulsion remains on the sheet and appears as a positive image of the original subject.
  • the alkaline solution which has been used for activation of the exposed emulsion layer has contained a gelatin softening agent to facilitate transfer of the less exposed portions of the emulsion to the receiving sheet.
  • a gelatin softening agent to facilitate transfer of the less exposed portions of the emulsion to the receiving sheet.
  • Urea and certain other gelatin softening agents have been suggested for this purpose.
  • sodium carbonate has been suggested as an alkaline component of the alkaline solution used for initiating development of the exposed emulsion.
  • the colloid transfer system is used extensively for making copies in business ofiices, it has been desirable to have an activator solution which would have a long life and which would be active satisfactorily near the depletion point. Moreover, the activator should have a relatively long temperature range during which several copies can be made from a single matrix or emulsion and the activator should be free from crystallization in the tray used for immersing the matrix to initiate development. It has also been desirable to have an activator solution which would result in a large number of copies being formed than have previously been obtainable.
  • the very first masters treated in a new bath are not quite sufiiciently hardened after seconds of activation and, accordingly, show an excessive tendency to adhere to the copying paper, particularly if 3,148,060 Patented Sept. 8, 1964 the surface of the latter is not perfectly smooth. This usually decreases after treatment of three or four masters and disappears after about fifteen masters.
  • One object of this invention is to provide an improved activator solution for use with the colloid transfer process.
  • An additional object is to provide an activator solution which will enable several copies to be made from a colloid transfer emulsion at temperatures as high as 88 F., as well as at room temperature.
  • Another object is to provide an activator which can be prepared in powder form which is easy to dissolve and forms a solution which has no tendency to crystallization.
  • a further object is to provide an activator which has a moderate pH and which promotes a desirable hardening-softening equilibrium.
  • a still further object is to provide an activator which has the desirable tanning softening equilibrium which does not tend to crystallize in the trays and which gives optimum results when first used.
  • the activator according to our invention is an aqueous solution of sodium sesquicarbonate, potassium carbonate, and urea.
  • a sequestering agent such as the tetrasodium salt of ethylenediamine tetraacetic acid, trisodium aminotriacetaate, or the like, and also a small quantity of alkaline or alkaline earth chloride.
  • the diagram has been divided into 4 areas according to the working characteristics of the activator.
  • Area 1 shows that a pH higher than 10.20 is too favorable to hardening.
  • Area 2 shows that a pH lower than 10.10 (for a fresh activator) reduces the development too much and prolongs the activating time when the bath is half exhausted.
  • Area 3 shows that for a pH between 10.10 and 10.20 a total alkalinity lower than 0.7500 N renders insufficient the number of emulsion coated matrix sheets that can be treated with a given volume of solution.
  • Area 4 is the preferred working area. The hatched area shows the relatively narrow concentration which corresponds to the concentration of the activator of this invention.
  • the above objects are attained by mixing sodium ses quicarbonate, potassium carbonate, urea and a sequestering agent such as the sodium salt of ethylenediamine tetraacetic acid or trisodium aminotriacetate.
  • a sequestering agent such as the sodium salt of ethylenediamine tetraacetic acid or trisodium aminotriacetate.
  • This activator solution has a pH of about 10.10 to 10.20.
  • the proportions may be varied from 30-40 g./l. sodium sesquicarbonate, 22-28 g./l. potassium carbonate, 20-30 g./l. urea, and 1.0-5.0 g./l. sequestering agent.
  • sodium sesquicarbonate an equivalent molar mixture of sodium carbonate and sodium bicarbonate with 2 mols of water may be used 3 (Na CO -NaI-ICO -2H O), and is intended to be within the scope of the term sodium sesquicarbonate as used herein.
  • a small quantity of alkaline or alkaline earth chloride added to the above activator solution improves the development, the tanning and the reproduction of the emulsion.
  • the activator is used according to the invention, with the addition of the chloride, a perfect balance of tanning and of softening is obtained for the normal activation of 20 seconds. This avoids the tendency for the first matrices treated in a fresh activator to be tanned insufficiently after 20 seconds of activation causing excessive adhesion to the receiver sheet, especially when the surface is not perfectly smooth.
  • Example 1 A substantially unhardened gelatino silver halide emulsion (having a hardness as defined in the above patents) is prepared as described in U.S. Patent 2,716,059, above, containing a mixture of tanning and substantially nontanning silver halide developing agents such as 4-phenol catechol and 4-methoxy-a-naphthol. The emulsion is coated on a paper support and dried. The resultant sensitive element is then exposed to a two-tone subject (a line or half-tone subject) if desired by reflex methods and placed in the following alkaline solution of the invention to initiate development.
  • a two-tone subject a line or half-tone subject
  • gelatin tanning silver halide development occurs principally in the highly exposed areas of the emulsion and little or no tanning development in the other areas.
  • the sensitive element is pressed into contact with an absorbent sheet such as paper by means of a squeegee blade or rollers.
  • the sensitive element and receiving sheet are separated leaving a stratum of the less exposed and thus less hardened regions of the emulsion adhered to the receiving sheet.
  • the result is a positive line or half-tone silver containing image afiixed to the sheet.
  • the transfer operation may be repeated at number of times by merely rewetting the sensitive element with the alkaline solution and squeegeeing to a fresh reception sheet.
  • the reception sheet for the colloid transfer process is advantageously prepared as described in the Chan et al. U.S. Patent 2,865,745, issued December 23, 1958, comprising a paper sheet on the surface of which is a mixture of an intensifying agent such as thiourea and a development suppressing agent such as sodium formaldehyde bisulfite.
  • Example 2 An activator solution was prepared as in above Example 1 with the omission of potassium carbonate. The solution exposed to the air was found to form crystals in the activator container due to evaporation.
  • an activator solution was prepared as in Example 1 with the omission of the sodium sesquicarbonate, it was found that the hardening of the emulsion was more rapid than the softening and that only about half as many copies could be made with the same matrix as using the activator solution of Example 1. It was also found that a pH higher than a 10.20 resulted in faster hardening action than softening and a diminution of the number of copies obtained.
  • Example 3 An identical emulsion to that of Example 1 is exposed to an original and immersed during 20 seconds in an activator of the following composition:
  • Example 4 Replacing the sodium chloride used in Example 3 by an equal part of potassium chloride also provides satisfactory results.
  • Example 5 Replacing the sodium chloride used in Example 3 with an equal part of sodium bromide or potassium bromide results in a necessary increase by 10 to 20% in the duration of exposure of the matrices and three times the duration of development in order to obtain satisfactory copies.
  • Example 6 Replacing the sodium chloride used in Example 3 with potassium iodide in an amount of 0.1-0.4 g./1iter results in no difference than when the activator is used without the halide.
  • Example 7 Addition to the activator of large quantity of alkaline halide, for example more than 5 g./ liter, for the chloride or the bromide or more than 1.0 g./ liter of iodide, impairs the satisfactory operation of the process of reproduction.
  • Example 8 Replacing the sodium chloride in the activator of Example 3 with alkaline earth chloride, such as calcium chloride, requires increase in the amount of sequestering agent. By this means the addition of calcium chloride in the amount of 0.5 g./liter produces the same effects as sodium chloride.
  • the quantity of urea may be varied from that given in the above formula depending upon the requirements of the particular emulsion used in the process and the conditions of operation such as temperature, less urea being required at higher operating temperatures.
  • the emulsion should have a maximum hardness of the order mentioned by the above patents corresponding to a gelatin layer containing about 0.7 gram of dry formaldehyde per pound of gelatin freshly coated, more or less urea is required at different operating temperatures.
  • the gelatin tanning and nontanning developing agents are present in the emulsion.
  • either or both developing agents may be present in the alkaline solution and the other in the emulsion.
  • a very useful combination of developing agents is 4-phenylcatechol with 4-methoxy-anaphthol. Since the latter is self-coupling, it forms a colored compound durin developing which contributes density to the print.
  • Other useful tanning and non tanning silver halide developing agents are disclosed by the above patents.
  • a method of photographic reproduction which comprises developing an exposed, substantially unhardened gelatino-silver halide emulsion layer, said emulsion not being harder than a gelatin layer containing 0.7 gram of formaldehyde per pound of gelatin freshly coated, with an aqueous solution having a pH of 10.10 to 10.20 and an alkalinity of above 0.7500 N, consisting essentially of water, 22-28 grams per liter potassium carbonate, 30-40 grams per liter sodium sesquicarbonate, 20-30 grams per liter urea and 0.2 to 3.0 grams per liter of a chloride selected from the class consisting of ammonium chloride, alkali metal chlorides and alkaline earth chlorides, in the presence of both a gelatin tanning silver halide developing agent and a substantially nontanning silver halide developing agent to obtain a hardened gelatin and silver image in the areas of the emulsion layer corresponding to the highlights of the subject, and subsequently unhardened gelatin, silver and silver halide in
  • a method of photographic reproduction which comprises developing an exposed, substantially unhardened gelatino-silver halide emulsion layer, said emulsion not being harder than a gelatin layer containing 0.7 gram of formaldehyde per pound of gelatin freshly coated, with an aqueous solution having a pH of 10.10 to 10.20 and an alkalinity of above 07500 N, consisting essentially of water, 22-28 grams per liter potassium carbonate, 30-40 grams per liter sodium sesquicarbonate, 1.0-5.0 grams per liter sequestering agent, 20-30 grams per liter urea and 0.2 to 3.0 grams per liter of a chloride selected from the class consisting of ammonium chloride, alkali metal chlorides and alkaline earth chlorides, in the presence of both a gelatin tanning silver halide developing agent and a substantially nontanning silver halide developing agent to obtain a hardened gelatin and silver image in the areas of the emulsion layer corresponding to the highlights of the subject, and subsequently
  • a method of photographic reproduction which comprises developing an exposed, substantially unhardened gelatino-silver halide emulsion layer, said emulsion not being harder than a gelatin layer containing 0.7 gram of formaldehyde per pound of gelatin freshly coated, with an aqueous solution having a pH of 10.10 to 10.20 and an alkalinity of above 0.7500 N, consisting essentially of Water, 22-28 grams per liter potassium carbonate, 30-40 grams per liter sodium sesquicarbonate, 20-30 grams per liter urea and 0.2 to 3.0 grams per liter of a chloride selected from the class consisting of ammonium chloride, alkali metal chlorides and alkaline earth chlorides, in the presence of a gelatin tanning silver halide developing agent to obtain a hardened gelatin and silver image in the areas of the emulsion layer corresponding to the highlights of the subject, and subsequently unhardened gelatin, silver and silver halide in the areas of the emulsion layer corresponding to the shadows
  • a method of photographic reproduction which comprises developing an exposed, substantially unhardened gelatino-silver halide emulsion layer, said emulsion not being harder than a gelatin layer containing 0.7 gram of formaldehyde per pound of gelatin freshly coated, with an aqueous solution having a pH of 10.10 to 10.20 and an alkalinity of above 0.7500 N, consisting essentially of Water, 28-28 grams per liter potassium carbonate, 30- 40 grams per liter sodium sequicarbonate, 1.0-5.0 grams per liter sequestering agent, 20-30 grams per liter urea and 0.2 to 3.0 grams per liter of a chloride selected from the class consisting of ammonium chloride, alkali metal chlorides and alkaline earth chlorides, in the presence of a gelatin tanning silver halide developing agent to obtain a hardened gelatin and silver image in the areas of the emulsion layer corresponding to the highlights of the subject, and subsequently unhardened gelatin, silver and silver halide in the
  • An activator solution for use in the photographic gelatino-silver halide colloid transfer process consisting essentially of an aqueous solution having a pH of 10.10 to 10.20 and an alkalinity of above 0.7500 N, containing 30-40 grams per liter sodium sesquicarbonate, 22-28 grams per liter potassium carbonate, 0.2 to 3.0 grams per liter chloride selected from the class consisting of ammonium chloride, alkali metal chlorides and alkaline earth chlorides and 30-30 grams per liter urea.
  • An activator solution for use in the photographic gelatino-silver halide colloid transfer process consisting essentially of an aqueous solution having a pH of 10.10

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US242526A 1962-10-16 1962-12-05 Colloid transfer process and activator solution therefor Expired - Lifetime US3148060A (en)

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FR912390A FR1344408A (fr) 1962-10-16 1962-10-16 Nouvel activateur pour la reproduction par report de colloïde

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BE (1) BE638911A (en)van)
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GB (1) GB1071639A (en)van)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379528A (en) * 1964-07-17 1968-04-23 Eastman Kodak Co Activator solution rejuvenation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2843485A (en) * 1952-05-03 1958-07-15 Eastman Kodak Co Transfer process of photographic printing
US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
US3043688A (en) * 1959-05-20 1962-07-10 Eastman Kodak Co Photographic colloid transfer process
US3043687A (en) * 1959-05-04 1962-07-10 Eastman Kodak Co Photographic colloid transfer process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716059A (en) * 1952-01-21 1955-08-23 Eastman Kodak Co Photographic transfer process
US2843485A (en) * 1952-05-03 1958-07-15 Eastman Kodak Co Transfer process of photographic printing
US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
US3043687A (en) * 1959-05-04 1962-07-10 Eastman Kodak Co Photographic colloid transfer process
US3043688A (en) * 1959-05-20 1962-07-10 Eastman Kodak Co Photographic colloid transfer process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379528A (en) * 1964-07-17 1968-04-23 Eastman Kodak Co Activator solution rejuvenation

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GB1071639A (en) 1967-06-07
BE638911A (en)van)

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