US2196036A - Subtractive process for color photography - Google Patents

Subtractive process for color photography Download PDF

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Publication number
US2196036A
US2196036A US199093A US19909338A US2196036A US 2196036 A US2196036 A US 2196036A US 199093 A US199093 A US 199093A US 19909338 A US19909338 A US 19909338A US 2196036 A US2196036 A US 2196036A
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United States
Prior art keywords
silver
ferrocyanide
layer
color
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
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US199093A
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English (en)
Inventor
Eugene G Seary
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.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
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Filing date
Publication date
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US199093A priority Critical patent/US2196036A/en
Priority to BE433563D priority patent/BE433563A/xx
Priority to FR852360D priority patent/FR852360A/fr
Application granted granted Critical
Publication of US2196036A publication Critical patent/US2196036A/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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/26—Silver halide emulsions for subtractive colour processes

Definitions

  • ducing multi-color partpictures involves the exposure of a multi-pack in an ordinary camera to simultaneously produce vblack and white colorseparation latent images. The separation images are then converted into proper dye images by a controlled diusion development. In this controlled diffusion method, chemical agents are permitted to diffuse to a limited extent into the tripack to effect the changes desired. As is evident,
  • silver halides i. e. the chloride, iodide and bromideLdiier considerably as regards their solubility in ammoniacal solutions.
  • silver chloride is the most soluble of the three,
  • the light-sensitive vmaterial may be a tri-pack with a layer of vsilver chloride, a.
  • a further object of my invention involves a light-sensitive material in the form -of a multipack in which at least two of the layers contain different silver halides.
  • a multi-pack which may have a base of paper, cellulose nitrate, cellulose acetate or the like, in which at least'two layers carry a different silver halide gelatin emulsion.
  • 'Ihe particular manner of compounding the light-sensitive material from the standpoint of arranging the layers on the base and of arranging the order of the different halide layers may be I varied to a considerable extent. For instance all three layers may be positioned on one side of the The vyellow and blue color is imparted to the proper layers by means of inorganic pigments.
  • Ierric ferrocyanide may be used for producing the blue color and vanadium ferrocyanide for producing the yellow color. It is also possible to produce the red color by means of a ferrocyanide pigment such as uranium ferrocyanide. Similarly nickel di-methyl glyoxime may be used for this purpose. However, due to the lack of brilliance of the red pigments, it is advisable for best results to produce the red color by the process known as color development. -A discussion of color development may be found on pages 404-407 of History of Three-Color Photography by Wall.
  • the facility with which my process may be vaccomplished may be perceived by considering its application in its general aspects to, for example, a light-sensitive material having a gelatino-silver chloride 1ayer,.sensitized to red, positioned ⁇ on a base, a gelatino silver iodide emulsion layer sensitized to green positioned on said first layer, land a gelatino-silver bromide emulsion layer not specially sensitized, positioned on said second layer.
  • Said light-sensitive material is exposed and developed in the ordinary way after which it is subjected to the action of white light.
  • the developer employed may be any developer.
  • Silver ferrocyanide is produced in the silver chloride layer by this treatment as a result of the dissolution of the silver chloride by the ammonia and its reaction with said iferrocyanide. ⁇ The silver ferrocyanideis then converted to ferrie ferrocyanide by an acid treatment with ferrie chloride.v 'I'he silver bromide layer is now colored by means of vanadium ferrocyanide by dissolving the silver bromide with a stronger ammoniacal solution than that used in the ilrst treatment, said solution also containing an alkali metal ferrocyanide, the silver ferrocyanide thus obtained being converted to vanadium ferrocyanide by an acid treatment with vanadium chloride.
  • a silver and dye image is next formed in the silver iodide layer by development in a paraphenylene diamine developer containing a color component which is capable of reacting with the oxidation product of the'developer to produce a dye imparting a reddish color.
  • Fig. 2 the processing of a film.
  • Example 1 The tri-pack of Fig. 1 comprises a paper support I upon which is superimposed a red sensitized silver chloride gelatin emulsion 2, a green sensitive silver iodide gelatin emulsion 3 and a non-sensitized silver bromide gelatin emulsion 4.
  • the latter emulsion contains an agent for imparting a yellow. color to the emulsion for the purpose of preventing blue light from passing to the green and red sensitive emulsion layers. It desired, the same result may be obtained by interposing a yellow dye layer between layers 3 and 4.
  • tartrazine which is discharged during development has been employed although it is to be borne in mind thatother dyestuil's usually employed in the art for this purpose may be utilized.
  • 'Ihe paper is exposed either directly or through iilters to the action of light, whereupon there is produced in the lowermost layer a latent image of the red sensations of the object,
  • the paper is next developed in a bromideless developer such as amidol, rinsed, and subjected to the action of white light.
  • a bromideless developer such as amidol, rinsed, and subjected to the action of white light.
  • the silver chloride emulsion layer is treated for about 5 minutes in a .1 to .5% solution 'of ammonia containing added potassium ferrocyanide. Dissolution of the silver chloride takes place with the immediate precipitation of silver ferrocyanide through reaction of the dissolved chloride with the added potassium ferrocyanide.
  • a washing in water is interpolated between this step and the succeeding step wherein the paper is subjected for a short time, say, about 3 minutes, to the action of a solution containing about 2% of ferric chloride acid termed with hydrochloric ⁇ acid.
  • a reaction ensues between the silver ferrocyanide and the iron chloride resulting in the formation of ferrie ferrocyanide, silver chloride being regenerated.
  • the silver chloride is removed by a treatment in a dilute ammoniacal solution, a treatment for about 5 minutes in a 1% ammonia solution being eiilcacious in accomplishtime, say about 5 minutes with a stronger ammoniaca] solution than that previously used.
  • a 5% solution is employed at this stage.
  • 'Ihe ammoniaca] solution contains potassium ferrocyanide which reacts with the silver bromide to produce silver ferrocyanide.
  • the ferric hydroxide in the lowermost layer 2 is reconverted' to ferrie ferrocyanide by means of an acid potassium ferrocyanide bath.
  • the paper is next treated for about three minutes in a 2% vanadium chloride solution containing free hydrochloric acid. Vanadium ferrocyanide, a light yellow compound, is thus produced in the outermost layer.
  • the silver chloride produced as a by-product in this reaction is removed by a treatment with 5% ammonia solution, whereby the ferrocyanides of iron and vanadium are converted to their respective hydroxides.
  • the paper After rinsing, the paper is then subjected to the action of a p-phenylenediamine developer containing methyl phenyl pyrazolone.
  • the lm base I has arranged on the entrant side of the( illm a silver bromide emulsion layer 2 containing al yellow dyestufl such as tartrazine.
  • emulsion layers 3 and 4 On the opposite side of said lm base there are llocated two emulsion layers 3 and 4, layer 3 being a silver iodide emulsion sensitized for green, and layer 4 being a silver bromide emulsion sensitized for red.
  • layer 3 being a silver iodide emulsion sensitized for green
  • layer 4 being a silver bromide emulsion sensitized for red.
  • the silver chloride which is produced in forming the ferric and vanadium ferrocyanides respectively, is removed with a, say about 5% ammonia solution subsequent to a washing of the film.
  • the ferrocyanides oi iron and vanadium are converted to ferrie hydroxide and vanadium hydroxide respectively.
  • the silver iodide layer 3 is now developed with a paraphenylene diamine developer containing methyl phenyl pyrazolone whereby the oxidation products 'of the diamine combine with the methyl phenyl pyrazolone to produce in this layer a silver and dye image.
  • the film following a rinsing operation, is subjected to the action of an acidifled potassium ferrocyanide solution to cause regeneration of vanadium and ferrie ferrocyanides from their respective hydroxides.
  • chromio acid a transparency having yellow, magenta and blue dye images is obtained.
  • the same or .similar procedure may be adopted in processing a illm having 2 silver chlorideand one silver iodideor one silver bromide-emulsions.
  • ammoniacal solutions Ihave typified the same as ammoniacal solutions. ⁇ This term is to be construed as covering not only solutions of ammonia but in addition solutions oi' ammonium salts as well as solutions of amines.
  • ammonium saltsI are ammonium sulfate, ammonium acetate, ammonium chloride and the like.
  • the amines vare the alkylol amines such as ethanol amine, di-ethanol amine, tri-ethanol amine, propanol amine and the like, alkyl amines such as methyl amine, ethyl amine,
  • I in lieu of removing the silver chloride by means of ammonium hydroxide at the times indicated, I also contemy plate converting the ferrie and vanadium ferrocyanides to their respective hydroxides by means of a dilute alkali such as sodium hydroxide, potassium hydroxide and the like, after which the silver chloride may be removed by dilute aml monia such as that having a concentration of It should be understood that thisl and other modications apparent to a person skilled in the art are within the scope of my invention. Thus instead of using separate layers 'of different silver halide emulsions, I may em- .ploy a single layer in which the different silver halide emulsions are present in admixture with each other.
  • ammoniacal solution is a solution oi an ammonium salt.
  • ammoniacal solution is a. solution of an amine.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US199093A 1938-03-31 1938-03-31 Subtractive process for color photography Expired - Lifetime US2196036A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US199093A US2196036A (en) 1938-03-31 1938-03-31 Subtractive process for color photography
BE433563D BE433563A (lt) 1938-03-31 1939-03-30
FR852360D FR852360A (fr) 1938-03-31 1939-03-30 Procédé de production d'images en plusieurs couleurs destinées à être regardées à la lumière réfléchie et d'images en plusieurs couleurs destinées à être regardées par transparence

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US199093A US2196036A (en) 1938-03-31 1938-03-31 Subtractive process for color photography

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US2196036A true US2196036A (en) 1940-04-02

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BE (1) BE433563A (lt)
FR (1) FR852360A (lt)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183087A (en) * 1961-03-27 1965-05-11 Agfa Ag Color reversal development process utilizing a preliminary development bath free of bromide ions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183087A (en) * 1961-03-27 1965-05-11 Agfa Ag Color reversal development process utilizing a preliminary development bath free of bromide ions

Also Published As

Publication number Publication date
BE433563A (lt) 1939-04-29
FR852360A (fr) 1940-01-31

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