US2113329A - Color photography - Google Patents

Color photography Download PDF

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Publication number
US2113329A
US2113329A US8516A US851635A US2113329A US 2113329 A US2113329 A US 2113329A US 8516 A US8516 A US 8516A US 851635 A US851635 A US 851635A US 2113329 A US2113329 A US 2113329A
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US
United States
Prior art keywords
color
images
image
silver
layers
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
US8516A
Other languages
English (en)
Inventor
Leopold D Mannes
Jr Leopold Godowsky
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 NL44563D priority Critical patent/NL44563C/xx
Priority to BE412165D priority patent/BE412165A/xx
Priority to NL44564D priority patent/NL44564C/xx
Priority to NL44565D priority patent/NL44565C/xx
Priority to BE409946D priority patent/BE409946A/xx
Priority to BE409947D priority patent/BE409947A/xx
Priority to GB17743/34A priority patent/GB440032A/en
Priority to DEK135859D priority patent/DE631324C/de
Priority to GB16012/35A priority patent/GB447092A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US8516A priority patent/US2113329A/en
Priority to FR791319D priority patent/FR791319A/fr
Priority to FR791320D priority patent/FR791320A/fr
Priority to DEK138265D priority patent/DE723388C/de
Priority to DEK138267D priority patent/DE721610C/de
Priority to FR797400D priority patent/FR797400A/fr
Priority to FR802755D priority patent/FR802755A/fr
Application granted granted Critical
Publication of US2113329A publication Critical patent/US2113329A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/24Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials combined with sound-recording
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

  • 'I'his invention relates to color photography and more particularly to a process in which a plurality of light-sensitive layers are treated to form a colored photographic record.
  • An object of the present invention is to produce a satisfactorily colored photograph in two or more colors by simple and practical procedure.
  • a further object is to produce a film adapted for taking pictures in' three colors in which no color- A ing matter or color-forming substances is mixed with the emulsion prior to exposure.
  • the colors are formed by a chemical coupling or dye formation, a dye being formed simultaneously and in situ with the development of the image.
  • Fig. 1 is a sectional view of a film having three separate emulsion layers
  • Fig. 2 is a modified form of lm; Figs. 3, 4, 5 and 6 are sectional views of the film illustrating the condition of the emulsion layers at various stages of the processing.
  • Fig. 'I is a sectional view of a finished lm having a sound track recorded in three layers.
  • I0 is the usual type of transparent base such as cellulose nitrate or cellulose acetate.
  • the sensitized silver halide emulsions are' coated on one side of this base in three layers, the layer II coated next to the base being sensitive to red light, the intermediate layer I2 sensitiveto green light and the top or outermost layer I3 sensitive to blue light.
  • These layers are preferably'separated by layers of inert material such as gelatin illustrated at I4 and I5.
  • the layer I5 may con- 5 tain a yellow dye in order to filter out blue light and prevent it-from reaching the layers II and I2, which, while sensitive to red and green, are also sensitive to blue light. This yellow dye may,
  • the layers II and I2 are the usual silver halide emulsion layers sensitized to red and green light, respectively, with sensitizing dyes which are well known in the art.
  • a suitable red sensitizing dye 15 is naphthocyanol, and a suitable green sensitizing dye is erythrosin.
  • the process may be considered as divided into a series of units, each comprising a number of steps, and we will designate these as units A, B, and C.
  • This film is exposed in the usual way to form an image and since no filter is essential except that which is incorporated in the film itself, a shorter exposure may be made than with colored films heretofore used. However, a lter may be used to overcome errors in the color ratio, or to produce special eects.
  • a reversal development may be used, thus forming a posi- 30 tive picture directly or the film may be developed as a negative and positives printed from it.
  • An essential feature inthe processing is a differential treatmentV of the layers by means of which the outer layer I3 may be treated without aifect- 35 ing layers I I and I2 or the outer layers I2 and I3 may be treated without affecting layer II.
  • the inert gelatine layers I4 and I5 are inserted between the sensitized layers to allow the opero ator some leeway. It has been found, however, that the differential treatment of the layers can be controlled with such a degree of accuracy that these inert layers are not absolutely necessary and in Fig. 2 a modification of the film is illus- 45 trated in which the sensitized emulsion layers are coated-directly one on top of the other.
  • the process will first be described with'reference to a reversal development.
  • the process steps may be divided into three separate units, at the end of each' of which one of the layers is colored with the dye winch it finally retains.
  • the illm after exposure contains latent images in each of the three emulsion layers, I I, I2 and I3. These are illustrated in Fig. 3, I6 being the latentv image corresponding to the red of the object photographed, I1 the latent image corresponding to the green and I8 the latent image corresponding to the blue.
  • the film is developed in an M-Q developer, forming silver images I9, 20 and 2
  • a suitable developer has the formula: ⁇
  • the ilim is next washed and then bleached in a bath which removes the silver but does not attack the silver halide present in each layer.
  • This bleach bath may have the followingcomposition:
  • the developer contains, in addition to the usual developer constituents, including a para-amino aniline as the developing agent, a coupling or dye-forming compound such as any of the hydroiw diphenyls described in my copending application, Serial No. 8,520, led February 27, 1935, inatgred into U. S. Patent No. 2,039,730, of May
  • a suitable developer is the following:
  • the first step of unit B is the de-coloring of the dye in the outer layers I2 and I3, and the re-conversion of the metallic silver in these layers to silver halide. This may be done by the use of a bleach bath consisting of a solution of quinone and concentrated hydrochloric acid containing a retardant such as glycerine and isopropyl alcohol to control the depth of penetration of tlie bleach.
  • a bleach bath consisting of a solution of quinone and concentrated hydrochloric acid containing a retardant such as glycerine and isopropyl alcohol to control the depth of penetration of tlie bleach.
  • Such a bath may have the composition:
  • Glycerine cc 500 Iso-propyl alcohol cc 1000 Water cc 75 Quinone g-- 5 Hydrochloric acid (conc.) g 20 Sodium bicarbonate g-- l5 Iso-propyl alcohol cc 1000 Glycerine cc 1000 Water cc 1000
  • the stop bath which will be used will depend, of course, upon the type of bleach bath used, an alkaline stop bath being used to neutralize the action of the acid bleach bath.
  • the dye contained in the outer layers I2 and I3 has now been de-colorized and the silver converted to silver chloride at the points at which there was a bluegreen silver image at 26 and 21 in these layers.
  • a second color-forming developer which develops the silver chloride in the outer o layers I2 and I3 to metallic silver and forms a magenta dyev at the points at which the silver is formed.
  • a developer may contain as the color-forming component p-nitro phenyl aceto nitrile, which couples with the oxidation product of the developer.
  • the magenta developer may have the following composition:
  • ⁇ As the first step in unit "C" the magenta. dye lcontained in the outer layer I3 is bleached and the silver re-converted to silver halide.
  • the bath used for this purpose is similar to the bleach bath used in unit B although the treatment is for a shorter time, for example two minutes at 72 to 74 F.
  • the action of this bath is terminated by a stop bath as in the case of unit B and the' (a) p-Amino dimethyl aniline sulfate g 1 Sodium sulflte g 2 Sodium carbonate -g-.. 30 Water to cc-.. 1000 (b) 4-nitro acetoacetanilide g 2% Iso-propyl alcohol cc (In use, b is added to a.)
  • the film now contains a blue-green image in the inner layer Il, a magenta image in the intermediate layer I2 and a yellow image in the outer layer I3, together with metallic silver in each of the layers.
  • 'I'he metallic silver is removed in a suitable bath such as potassium ferricyanide solution, leaving the film as illustrated in Fig. 7 (where a sound track is included), the emulsion layers now containing blue-green image 29 in the inner layer. magenta image 30 in the intermediate layer, and yellow image 3l in the outer layer.
  • the film is then washed and dried.
  • the exposed film mayy be treated in various ways.
  • the film is developed in an ordinary metolhydroquinone type of developer which may -have the same formula as that used for the first development in the reversal processing.
  • the film is ihen fixed to remove undeveloped silver halide and the remaining silver bleached to silver halide, for example, in a hydrochloric acid oxidizing -bleach bath..
  • the film is then color developed in a bluegreen color-developer having the same formula as that referred to in the description of the reversal development process. This results in bluegreen negative images in each of the three layers.
  • 'I'he film is then processed as described above under units B and C.
  • the film then has negative blue-green, magenta, and yellow images in the three layers.
  • the negative images may be developed directly in a color forming developer.
  • (3) 'I'he film containing thelatent images may lbe developed directly in a black and white photographic developer, fixed and bleached in dilute potassium ferricyanide to convert the silver images to silver ferrocyanide.
  • This method is substantially the same as that described under method (l) above, except that the silver images are bleached to silver ferricyanide rather than silver halide. This is sometimes desirable because the silver ferrocyanide produced is very easily reducible back to metallic silver.
  • a suitable bleach for this purpose is:
  • the film is developed, fixed, Washed and bleached in potassium ferricyanide to convert the images in both layers.
  • the film is then exposed and the top layer only redeveloped to silver by controlling the penetration of an energetic developer and arresting the development as soon as the desired depth is reached. This arresting action is attained by loading the developer solution with an arresting agent, such as sodium sulphate.
  • an arresting agent such as sodium sulphate.
  • the-film contains a developable silver ferrocyanide .image in the inner layer and metallic silver images in the outer'layers.
  • the film is immersed in a bluegreen color forming developer and the image in the inner layer developed to silver and bluegreen dye.
  • the silver images in the outer layers are, of course, ⁇ inert to the color forming developer.
  • the silver ⁇ images in the outer layers mayl then be bleached in a potassium ferricyanide bath, the diffusion being controlled in the manner described in our said co-pending application SerialNo. 8,517, matured into U. S. Patent No. 2,059,887 of November 3, 1936, to prevent its action on the dyeimage in theinner layer.
  • outer layers may then be color developed to a single color and the outer layer only bleached and recolored, or the outer layer only may be redeveloped to silver and the intermediate layer then color developed by controlled penetration, and the outer layer nally converted to a silver salt and color developed.
  • Fig. 7 shows a multilayer lm in which the base I l carries the three emulsion layers Il, I2 and Il in which an image is recorded and also having a sound track portion 28 having the sound recorded in three layers.
  • the process is also applicable to the formationof two color component images by treating two diierentially sensitized emulsion layers by the methods described. Where two colors only areused, the emulsion layers are sensitized with suitable color separation dyes, such as blue-green and red-orange.
  • the process of forming two.color component images in registry in twodifferent strata on the same side of a photographic support that comprises forming a color component latent image in each stratum by exposing the strata from the same side of the support, developing each latent image into a silver image by a process which includes also the development of a color image in the lowerstratum, subjecting the element for a controlled time to a bleaching bath containing a retardant for the diffusion thereof whereby the effect of the bath is limited to the upper stratum and the image ,therein is transformed into a developable image, and developing said image into a silver image and a color image of a different color than the image in the lower stratum, and removing the silver images from both layers, leaving differently colored images in the respective strata.
  • the method of making a color photograph comprises forming two images of silver and dye in different strata on the same side of a support by exposing the strata from the ⁇ same side of th'e support, bleaching only the-outer image in a bath that transform the silver into a developable salt and decolorizes the we and then redeveloping in a single step the outer image only into an image of silver and of dye of different color from the first named dye.
  • the method of making a color photograph comprises forming two images of silver and dye in different strata on the same side of a support by exposing the strata from the same side of the support, bleaching only the outer image in a bath that transforms the silver into a developable salt and decolorizes the dye and then redeveloping in a single step the outer image only into an image of silver and of dye of different color from the iirst named dye and then removing the silver from both images, leaving in the dverent strata dye images of diiferent colors.
  • the method of making a color photograph in an element having sensitized material in layer form on one side of a support that comprises forming two images of the same color in two dierent strata of said sensitized material by exposing the strata from the same side of the support, submitting said element to a bath that diffuses into said material and is capable of decolorizing said images, said bath including a re tardant for the diffusion thereof, stopping the action of the bath when the outer image only has been decolorized and then coloring said outer image .a different color than the lower layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Peptides Or Proteins (AREA)
US8516A 1934-06-15 1935-02-27 Color photography Expired - Lifetime US2113329A (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
NL44563D NL44563C (xx) 1934-06-15
BE412165D BE412165A (xx) 1934-06-15
NL44564D NL44564C (xx) 1934-06-15
NL44565D NL44565C (xx) 1934-06-15
BE409946D BE409946A (xx) 1934-06-15
BE409947D BE409947A (xx) 1934-06-15
GB17743/34A GB440032A (en) 1934-06-15 1934-06-15 Improvements in and relating to colour photography
DEK135859D DE631324C (de) 1934-06-15 1934-11-09 Verfahren zur Herstellung von Mehrfarbennegativen mit Hilfe von Mehrschichtenfilmen und Direktfarbenentwicklern
GB16012/35A GB447092A (en) 1934-06-15 1934-11-10 Improvements in and relating to colour photography
US8516A US2113329A (en) 1934-06-15 1935-02-27 Color photography
FR791319D FR791319A (fr) 1934-06-15 1935-06-15 Procédés de photographie en couleurs perfectionnés
FR791320D FR791320A (fr) 1934-06-15 1935-06-15 Perfectionnements à la photographie en couleurs
DEK138265D DE723388C (de) 1934-06-15 1935-06-16 Verfahren zur direkten Erzeugung eines Naturfarbenbildes
DEK138267D DE721610C (de) 1934-06-15 1935-06-16 Verfahren zur Herstellung von Naturfarbenbildern durch Umkehrentwicklung von Mehrschichtenfilmen mit Emulsionsschichten auf beiden Seiten des Schichttraegers
FR797400D FR797400A (fr) 1934-06-15 1935-11-07 Perfectionnements à la photographie en couleurs
FR802755D FR802755A (fr) 1934-06-15 1936-02-27 Photographie en couleurs

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB17743/34A GB440032A (en) 1934-06-15 1934-06-15 Improvements in and relating to colour photography
DEK0135859 1934-11-08
GB3244134 1934-11-10
US8516A US2113329A (en) 1934-06-15 1935-02-27 Color photography
GB1774335 1935-06-01

Publications (1)

Publication Number Publication Date
US2113329A true US2113329A (en) 1938-04-05

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US8516A Expired - Lifetime US2113329A (en) 1934-06-15 1935-02-27 Color photography

Country Status (6)

Country Link
US (1) US2113329A (xx)
BE (3) BE409946A (xx)
DE (2) DE723388C (xx)
FR (4) FR791320A (xx)
GB (2) GB440032A (xx)
NL (3) NL44565C (xx)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2507183A (en) * 1945-03-23 1950-05-09 Eastman Kodak Co Silver bleach for color materials
US2529981A (en) * 1945-11-28 1950-11-14 Eastman Kodak Co Bleaching silver images
US2551086A (en) * 1945-12-11 1951-05-01 Du Pont Multicolor motion-picture film with sound record
US2567401A (en) * 1947-04-18 1951-09-11 Raibourn Paul Process of producing colored photographs
DE968447C (de) * 1947-11-18 1958-02-20 Gen Aniline & Film Corp Verfahren zur gleichmaessigen Entwicklung von belichteten, mehrschichtigen Farbumkehrfilmen
DE1285312B (de) * 1963-10-26 1968-12-12 Agfa Ag Verfahren zur Entwicklungsbeschleunigung eines mehrschichtigen farbphotographischen Materials
DE2163576A1 (de) * 1970-12-22 1972-07-13 Eastman Kodak Co., Rochester, N.Y. (V.StA.) Photographisches Verfahren zur Herstellung von Szenenbildern und Silbertonspurtyp-Hilfsbildern und photographisches Aufzeichnungsmaterial zur Durchführung des Verfahrens
US3716362A (en) * 1969-07-30 1973-02-13 Ciba Geigy Ag Process for the removal of metallic silver from photographic material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2507183A (en) * 1945-03-23 1950-05-09 Eastman Kodak Co Silver bleach for color materials
US2529981A (en) * 1945-11-28 1950-11-14 Eastman Kodak Co Bleaching silver images
US2551086A (en) * 1945-12-11 1951-05-01 Du Pont Multicolor motion-picture film with sound record
US2567401A (en) * 1947-04-18 1951-09-11 Raibourn Paul Process of producing colored photographs
DE968447C (de) * 1947-11-18 1958-02-20 Gen Aniline & Film Corp Verfahren zur gleichmaessigen Entwicklung von belichteten, mehrschichtigen Farbumkehrfilmen
DE1285312B (de) * 1963-10-26 1968-12-12 Agfa Ag Verfahren zur Entwicklungsbeschleunigung eines mehrschichtigen farbphotographischen Materials
US3716362A (en) * 1969-07-30 1973-02-13 Ciba Geigy Ag Process for the removal of metallic silver from photographic material
DE2163576A1 (de) * 1970-12-22 1972-07-13 Eastman Kodak Co., Rochester, N.Y. (V.StA.) Photographisches Verfahren zur Herstellung von Szenenbildern und Silbertonspurtyp-Hilfsbildern und photographisches Aufzeichnungsmaterial zur Durchführung des Verfahrens

Also Published As

Publication number Publication date
BE409946A (xx)
BE409947A (xx)
FR797400A (fr) 1936-04-25
GB440032A (en) 1935-12-16
NL44564C (xx)
NL44565C (xx)
NL44563C (xx)
FR791320A (fr) 1935-12-07
DE721610C (de) 1942-06-11
FR791319A (fr) 1935-12-07
DE723388C (de) 1942-08-13
GB447092A (en) 1936-05-11
FR802755A (fr) 1936-09-15
BE412165A (xx)

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