US3232756A - Colloid transfer process - Google Patents

Colloid transfer process Download PDF

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Publication number
US3232756A
US3232756A US217831A US21783162A US3232756A US 3232756 A US3232756 A US 3232756A US 217831 A US217831 A US 217831A US 21783162 A US21783162 A US 21783162A US 3232756 A US3232756 A US 3232756A
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US
United States
Prior art keywords
layer
colloid
sheet
emulsion
unhardened
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
US217831A
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English (en)
Inventor
Edward C Yackel
Herbert B Cowden
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE636329D priority Critical patent/BE636329A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US217831A priority patent/US3232756A/en
Priority to DEE25334A priority patent/DE1283676B/de
Priority to FR944743A priority patent/FR1367154A/fr
Priority to GB39544/66A priority patent/GB1060806A/en
Priority to GB32446/63A priority patent/GB1060805A/en
Application granted granted Critical
Publication of US3232756A publication Critical patent/US3232756A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D9/00—Diffusion development apparatus
    • 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
    • Y10S430/151—Matting or other surface reflectivity altering material

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,
  • the alkaline solution which has been used for activation of the exposed emulsion layer has contained a gelatin softening agent to facilitate tran'sferof the less exposed portioris ofthe emulsion to the receiving sheet.
  • a gelatin softening agent to facilitate tran'sferof the less exposed portioris ofthe emulsion to the receiving sheet.
  • Urea and certain other gelatin softening agents have been used-for this purpose;
  • sodium carbonate' has been used as an alkaline component of the alkaline solution used for initiating development of the exposed emulsion.
  • such a transparent receiver sheet could be used in making copies for use with a projector which will project positive transparencies of an original onto a screen.
  • transparencies had to be prepared by inking or drawing the desired replica upon a matte surface and then projecting it.
  • a transparent receiving sheet' involves the use of colloidal silica dispersed in a binder such as cellulose acetate on a transparent support which might be cellulose triacetate or the like.
  • a binder such as cellulose acetate on a transparent support which might be cellulose triacetate or the like.
  • the resulting image is not of satisfactory density, since the transferred gelatin does not adhere as well as to normally used paper receiving sheets.
  • One object of this invention is to provide a simple photographic colloid transfer process for obtaining an image on a transparent support.
  • Another object is to provide a transparent support which can be used in com- 3,232,756 Patented Feb. 1, 1966 provide a coating for a transparent support which will be receptive to the adhesion of the transferrable colloid portion when used with the colloid transfer process.
  • a still further object is to provide a coating for a transparent receiving sheet which results in an improved density of the image so that it can be used for projection purposes.
  • FIGURE 1 shows, in cross-sectional view, the appearance of a silver halide emulsion bearing support after exposure to a subject and development in the presence of a tanning developer.
  • FIGURE 2 shows, in enlarged cross-sectional view, theappearance of the transferred untanned emulsion image stratum in printing relation to the element of FIGURE 1.
  • FIGURE 3 shows, in enlarged cross-sectional view, a transparent receiving sheet which is identified as the transparent support shown in FIG. 2.
  • FIGURE 4 is a diagrammatic sectional view of typical apparatus, materials and methods used in our invention.
  • substantially unhardened light-sensitive, preferably pig merited, gelatino-silver-halide emulsion layer is exposed to an object and developed in the presence of a tanning developing agent incorporated into the emulsion layer. After exposure and development, the processed photographic element appears as shown in FIGURE 1 where,
  • FIGURE 4 illustrates a method of making prints by this process wherein the transparent sheet 13 is contacted with the tanned negative image in layer 11 and passed around hot roller 26 in order to increase the density of the image.
  • the exposing light24 at point 25 also improves the density of the image.
  • various transparent supports may be used, such as glass or any of a number of transparent polymeric materials, including cellulose esters, polystyrene, polyethylene terephthalate, or the like.
  • a transparent sheet of sheet the image can be increased in density by exposing the receiving sheet to a photoflood lamp or to some other suitable source of radiation.
  • transparent polymeric materials may require an additional surface treatment in order to obtain adherence of a subbing or coating composition.
  • the colloid layer coated on the transparent support for reception of the image has been found to be critical, since many coatings will not result in a satisfactory image transfer, particularly if the material is not sufficiently absorbent. Moreover, if the colloid is too soluble in the activator solution, it tends to dissolve during contact with the exposed matrix with the resultant transfer of the colloid to the matrix. For instance, gelatin layers which are hardened with formaldehyde are usually not absorbent enough, while most .gelatins are too soluble when coated unhardened. Moreover, bone and calf skin gelatins are too soft when coated unhardened and not absorbent when hardened by the usual methods. In addition, the sodium salts of ethyl cellulose phthalate or the sodium salt of the lactone of an interpolymer of vinyl acetate and maleic anhydride have not been found to he useful since they are too soluble.
  • pig gelatin can be used and also the ammonium salts of ethyl cellulose phthalate and the ammonium salts of the lactone of the interpolymer of vinyl acetate and maleic anhydride can be used.
  • a further treatment may be used to prevent loss of ammonia from the ammonium ethyl cellulose 1phthalate salts and from the ammonia salt of the carboxy ester-lactones of an interpolymer of vinyl acetate and maleic anhydride which might cause these layers to become too insoluble so that insufiicient water is absonbed and the materials lose their ability to accept a transfer.
  • the coating can be heated such as by drying the coating at a high temperature. For instance, a temperature range of 220-240 F.
  • the surface may be treated with acid solutions, which convert the surface stratum of the coating to the impervious acid form of the colloid which seals the ammonia of the lower strata in the layer.
  • the acid is not critical and dilute hydrochloric or acetic acid solutions as low as 2.5% concentration may be applied in an amount of about 3-4 nil/sq. ft.
  • the concentration is not critical since the acid is volatilized when the coating is dried.
  • the carboxy ester-lactone is a water-soluble salt of a carboxy ester-lactone of an interpolymer of maleic anhydride and vinyl acetate as described in US. Patent 3,007,901 of Louis M.
  • Minsk reacted with an aliphatic alcohol in such a ratio as to provide a polymer containing a carboxyl content between about 3.5 and 6 milliequivalents per gram of polymer and preferably between 4.5 and 5.5 milliequivalents per gram.
  • the salt is then 2598% neutralized with ammonia.
  • a typical coating is disclosed in Sterman and Minsk US. patent application Serial No. 201,808.
  • the sodium or ammonium salt of a copolymer of ethyl acrylate and acrylic acid may also be used.
  • a 75% ethyl acrylate-25% acrylic acid proportion is used, but other proportions may be used.
  • Conventional polymerization processes such as emulsion polymerization and the like may be used to prepare the copolymer.
  • matting agent such as silica of colloidal size or larger is not necessary to make these receiving materials work effectively, but it can be added to improve the latitude of the copying process with regard to exposure, activator temperature, and activator exhaustion.
  • Another advantage obtained from the incorporation of matting agents is the ability to write with pencil or ballpoint .pen on the matted surfaces.
  • Silica having a particle size ranging from about 3-30 microns in diameter are operative, but the preferred range is about -15 microns.
  • the thickness of the coated layers on these transparent receiving sheets may be from about 100 mg. of colloid per sq. ft. to one gram per sq. ft.
  • Our preferred thickness range is 250400 mg. per sq.
  • Example 2 A solution like that used in Example 1 except that the thiourea was omitted and coated at the same coverage and set to a firm jelly by warming to about 60 C. In this condition, the coated layer was passed once through a 5% solution of acetic acid, and then dried as before. This material gave an excellent quality transfer when freshly made, and also after having been incubated for 14 days at 120 F., 35% RH.
  • Example 3 A 4% solution of ammonium salt of a carboxy esterlactone of an interpolymer of vinyl acetate and maleic anhydride in 1:1 acetone-water and containing 0.25% thiourea and 0.2% Syloid 404 (a silica dispersion) was coated at 10 g. per sq. ft. on the subbed side of a transparent cellulose ester film support and dried to give a layer having 400 mg. colloid per sq. ft. When dry, this sample was overcoated with 5% acetic acid applied at 3.5 g. per sq. ft., and again dried.
  • This element used as a receiver with a colloid transfer matrix gave an excellent quality image of good density; after 28 days incubation at 120 F., 35% RH, the material would still accept a high quality transfer.
  • Example 4 A 5% solution of high jelly strength pigskin gelatin containing 0.25% thiourea'and 0.20% Syloid 404 was coated at 8 g. per sq. ft. on the subbed side of a transparent cellulose ester film support and dried to give a layer having 400 mg. gelatin per sq. ft. This element used as a receiver for a colloid transfer matrix gave a very high quality image of high density. Samples of this material incubated for 28 days at 120 F, 35% RH. still accepted a high quality image of excellent density.
  • an alcohol-Water solution can be utilized.
  • Example 5 Two coatings were made similar to the one described in Example 4 except Dimedone was added to the pig gelatin coating solution in sufiicient quantities to give 2 and 5 mg. of Dimedone per sq. ft. After 3 months aging, the coatings containing the Dimedone gave a better.quality transfer than the coatings without the Dimedone. Best results are obtained with coatings containing 0.5- 10 mg. Dimedone per sq. ft.
  • Example 6 A sample of the ammonium salt of a copolymer of ethylacrylate and 25% acrylic acid containing 8.29% solids was diluted to 2.0% solids with Water and coated on a transparent cellulose ester film support at a Wet thickness of 0.005 inch. After drying, the coating was cured in an oven for 5 hours at C. This element gave good transfers from colloid transfer matrices.
  • the alkali metal salts of the copolymer are operative and can be used without a stabilizing step.
  • the coating for the transparent support may also contain an agent which increases the density of the transferred image.
  • an agent which increases the density of the transferred image For instance, a silver halide fogging agent (that is, a compound which renders silver halide developable in the absence of light), thiourea, thioacetamide, dithioxamide, and dithiobiuret, thiosemicarbazide, or a soluble sulfide may be used.
  • a compound which retards the tanning of gelatin in the presence of fogged silver halide and the gelatin tanning agent may also be incorporated in the coating, for example, sodium formaldehyde bisulfite, sodium formaldehydesulfoxalate, 2,4-dihydroxybenzoic acid, sodium benzene sulfinate, borophosphate, aminomethanesulfuric acid, or borax.
  • the coatings may be surface applied or that the sheet can be surface coated or coated using any of the known coating methods, such as hopper coating, wick, kiss roll, knife, and the like.
  • a process of photographic reproduction which comprises forming by exposure to a two-tone subject and development in a light-sensitive, substantially unhardened, organic colloid-silver halide emulsion layer, a hardened colloid image and leaving substantially unhardened colloid in the remaining area of said layer, said unhardened layer being not harder than a gelatin layer containing 0.7 gram of formaldehye per pound of gelatin freshly coated, the step of pressing the emulsion layer while said emulsion is moist against a nonfibrous, transparent polymeric sheet having thereon a non-light-sensitive coating selected from the class consisting of pig gelatin, the ammonium salt of ethylcellulosephthalate, the ammonium salt of a carboxy ester-lactone of an interpolymer of maleic anhydride and vinyl acetate and the alkali metal and ammonium salts of a copolymer of ethylacrylate and acrylic acid, to cause only said unhardened colloid portion of said layer to adhere
  • the coating on the transparent support is an alkali metal salt of a copolymer of ethylacrylate and acrylic acid.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US217831A 1962-08-20 1962-08-20 Colloid transfer process Expired - Lifetime US3232756A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE636329D BE636329A (de) 1962-08-20
US217831A US3232756A (en) 1962-08-20 1962-08-20 Colloid transfer process
DEE25334A DE1283676B (de) 1962-08-20 1963-08-13 Bildempfangsmaterial zum Empfang von nicht gehaerteten Bildteilen einer Silberhalogenidemulsionsschicht
FR944743A FR1367154A (fr) 1962-08-20 1963-08-14 Nouveau procédé de reproduction photographique avec report d'un colloïde
GB39544/66A GB1060806A (en) 1962-08-20 1963-08-16 Photographic reproduction materials
GB32446/63A GB1060805A (en) 1962-08-20 1963-08-16 Photographic reproduction processes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US217831A US3232756A (en) 1962-08-20 1962-08-20 Colloid transfer process

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US3232756A true US3232756A (en) 1966-02-01

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US217831A Expired - Lifetime US3232756A (en) 1962-08-20 1962-08-20 Colloid transfer process

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US (1) US3232756A (de)
BE (1) BE636329A (de)
DE (1) DE1283676B (de)
GB (2) GB1060806A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120724A (en) * 1972-10-02 1978-10-17 Fuji Photo Film Co., Ltd. Subbing material for styrene bases used in photographic elements
US4266010A (en) * 1974-07-01 1981-05-05 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63218942A (ja) * 1987-03-06 1988-09-12 Fuji Photo Film Co Ltd 受像材料および画像形成方法
EP0305599B1 (de) * 1987-09-01 1994-11-23 Agfa-Gevaert N.V. Verfahren zur Herstellung von Halbtonbildern
CN106161844A (zh) * 2014-07-25 2016-11-23 滁州华尊电气科技有限公司 一种改进型可拍照文件架

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2576921A (en) * 1948-11-24 1951-12-04 John H Buscher Process for producing an ink-receptive surface on tracing cloth
US2596756A (en) * 1947-11-04 1952-05-13 Eastman Kodak Co Photomechanical copy method
US2858238A (en) * 1955-04-26 1958-10-28 Jr George E Brown Stable completely oxidized macromolecular composition
US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
US2944899A (en) * 1956-10-04 1960-07-12 Eastman Kodak Co Stabilization of photographic silver halide emulsions
US2992213A (en) * 1957-11-08 1961-07-11 Eastman Kodak Co Acid cooked pigskin gelatins for photographic subbing
US3043688A (en) * 1959-05-20 1962-07-10 Eastman Kodak Co Photographic colloid transfer process
US3060023A (en) * 1959-08-05 1962-10-23 Du Pont Image reproduction processes
US3062674A (en) * 1959-01-12 1962-11-06 Eastman Kodak Co Photographic product having layer containing bisepoxy ether crosslinked ethyl acrylate-acrylic acid copolymer
US3072482A (en) * 1958-01-10 1963-01-08 Keuffel & Esser Co Subbed photographically sensitive film element
US3080230A (en) * 1956-02-18 1963-03-05 Agfa Ag Photographic stratum transfer process and element therefor
US3108995A (en) * 1957-03-01 1963-10-29 Charles B Knox Gelatine Co Inc Method of modifying type a gelatin and product thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE517065A (de) * 1952-01-21

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596756A (en) * 1947-11-04 1952-05-13 Eastman Kodak Co Photomechanical copy method
US2576921A (en) * 1948-11-24 1951-12-04 John H Buscher Process for producing an ink-receptive surface on tracing cloth
US2858238A (en) * 1955-04-26 1958-10-28 Jr George E Brown Stable completely oxidized macromolecular composition
US2865745A (en) * 1955-08-25 1958-12-23 Eastman Kodak Co Photographic reproduction process
US3080230A (en) * 1956-02-18 1963-03-05 Agfa Ag Photographic stratum transfer process and element therefor
US2944899A (en) * 1956-10-04 1960-07-12 Eastman Kodak Co Stabilization of photographic silver halide emulsions
US3108995A (en) * 1957-03-01 1963-10-29 Charles B Knox Gelatine Co Inc Method of modifying type a gelatin and product thereof
US2992213A (en) * 1957-11-08 1961-07-11 Eastman Kodak Co Acid cooked pigskin gelatins for photographic subbing
US3072482A (en) * 1958-01-10 1963-01-08 Keuffel & Esser Co Subbed photographically sensitive film element
US3062674A (en) * 1959-01-12 1962-11-06 Eastman Kodak Co Photographic product having layer containing bisepoxy ether crosslinked ethyl acrylate-acrylic acid copolymer
US3043688A (en) * 1959-05-20 1962-07-10 Eastman Kodak Co Photographic colloid transfer process
US3060023A (en) * 1959-08-05 1962-10-23 Du Pont Image reproduction processes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120724A (en) * 1972-10-02 1978-10-17 Fuji Photo Film Co., Ltd. Subbing material for styrene bases used in photographic elements
US4266010A (en) * 1974-07-01 1981-05-05 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material

Also Published As

Publication number Publication date
DE1283676B (de) 1968-11-21
BE636329A (de)
GB1060806A (en) 1967-03-08
GB1060805A (en) 1967-03-08

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