US3301772A - Electrolytic color development - Google Patents

Electrolytic color development Download PDF

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Publication number
US3301772A
US3301772A US454240A US45424065A US3301772A US 3301772 A US3301772 A US 3301772A US 454240 A US454240 A US 454240A US 45424065 A US45424065 A US 45424065A US 3301772 A US3301772 A US 3301772A
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United States
Prior art keywords
color
image
positive
developing agent
silver halide
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Expired - Lifetime
Application number
US454240A
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English (en)
Inventor
Viro Felix
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GAF Chemicals Corp
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General Aniline and Film Corp
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Publication date
Priority to BE614376D priority Critical patent/BE614376A/xx
Priority to DEG34346A priority patent/DE1182064B/de
Priority to FR889208A priority patent/FR1318893A/fr
Priority to GB4503/62A priority patent/GB1002858A/en
Priority to CH238362A priority patent/CH426479A/de
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US454240A priority patent/US3301772A/en
Application granted granted Critical
Publication of US3301772A publication Critical patent/US3301772A/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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • 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
    • G03C5/263—Processes using silver-salt-containing photosensitive materials or agents therefor with an exterior influence, e.g. ultrasonics, electrical or thermal means
    • 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
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to color photography and the production of colored photographic images. More particularly, the invention relates to certain improvements in the development of color reproductions, especially positive color prints, of the type formed by the imagewise transfer of colorants from an exposed original photographic element to a receiving layer.
  • the formation of positive colored photographic images can be effected in numerous ways and the prior art has been cognizant of these techniques for a long time.
  • a method much practiced today is based on the silver halide system of photography, wherein the production of a black and white image is utilized in such a manner as to regulate or control a concomitant colored image.
  • the source of the colored image may be a color forming component, commonly incorporated in the photographic element.
  • Such a color process is referred to as color development and depends on the reaction of the oxidation product of a primary aromatic amino developing agent with a color coupler to yield a subtractively colored dye image in situ with a black and white image.
  • the resulting negative dye image is utilized as a pattern to form a second positive color image which corresponds to the original color aspects of the subject being photographed.
  • it is, of course, necessary to carry out two exposures in order to obtain a positive colored reproduction.
  • a more direct method for achieving a positive color reproduction makes use of a reversal development technique.
  • a reversal development technique In this system of forming :a positive colored image, a multilayer color photographic film is exposed and developed with a black and white silver halide developer, such as hydroquinone. The so-obtained negative silver image is then dissolved or otherwise removed in the usual manner, thereby leaving a silver halide image.
  • This is next subjected to a high intensity n'on-imagewise exposure followed by development using a primary aromatic amino type developing agent, whereby color development takes place, the density of which is proportional to the residual silver halide and inversely proportional to the original exposure.
  • a primary aromatic amino type developing agent whereby color development takes place, the density of which is proportional to the residual silver halide and inversely proportional to the original exposure.
  • After removal of the second silver image there remains on the original photographic element a colored positive reproduction corresponding to the color aspects of the initial or first exposure.
  • the receiving layer is provided with an oxidizing agent, the purpose of which is to catalyze or bring about the color forming reaction. If this same process is utilized for producing multicolor positive images, a plurality of receiving sheets must be used, since a color separation dye image is formed in each receiving sheet, with the result that such sheets must be superimposed in order to produce the final colored reproduction. Although of academic interest, such a system is too complex for the commercial market, primarily because of the plurality of receiving sheets which make for a rather unwieldy and uneconomical operation. A later and improved color ditfusion process dispenses with the plurality of receiving sheets and substitutes a single light sensitive photographic element capable of recording all of the color aspects of the subject.
  • the basis of the improved diffusion system is the utilization of color forming components, which are non-difi'usible during coating and negative development, but are rendered diff-usible under conditions of positive development.
  • the colorless migrating coupler image is then converted into a visible dye image at the receiving sheet.
  • the receiving sheet is conveniently provided with an oxidizing agent which oxidizes the paraphenylenediamine developer to the active coupling form for producing the aforedescribed positive dye image.
  • Another important object of the invention is a provision of a color diffusion transfer process utilizing color former components, the dilfusibility of which can be controlled by adjustments in pH.
  • my invention is based on the finding that a diffusible colorant positive image remaining after negative development can be transformed by electrolytic oxidation into a visible colored positive image, thereby reproducing the primary colored aspects of the original subject.
  • This new electrolytic process can be substituted or is applicable to any process which utilizes chemical oxidation in order to transform a diifusible positive image into a colored visible image. It can be used in the color transfer process in which a color former image diffuses imagewise to a transfer sheet whereby a visible positive image is produced by color coupling of the diffused coupler image with oxidized color developer.
  • the diffusing positive image can be a leuco dye which on migrating to the transfer receiving material is transformed into a positive image by oxidation.
  • My process is admirably suited for this latter system since the electric current is capable of bringing about coupling between the couplers and the transfer layer and the diffusing image of the developing agent.
  • the diffusing positive image is chemically oxidized to produce a visible positive image
  • the chemical oxidizer can be replaced or substituted by the electrolytic oxidation method as herein described.
  • the process requires a relatively low potential or voltage and is, therefore, adaptable for operating within a camera since the voltage can be provided by small dry cells of the type used in small flashlights.
  • the process as described herein can be operated with either direct current or alternating current at a potential of only a few volts.
  • the electrodes which are placed in direct contact with a layer which is to receive the diffusing image rnust be made of an element, the oxidation potentials of which are below the potential of the developer or leuco dye.
  • direct current the anode or positive terminal is placed in contact with the receiving layer. Since the oxidation of color developer is an irreversible reaction, it is possible to employ a low voltage A.C. current to bring about oxidation of the color developer.
  • a negative colored image is first formed by color forming development.
  • the residual positive image composed of uncoupled color former is then caused to diffuse at elevated pH to a receiving sheet wherein the presence of a color developer the migrating positive color former image is converted to a positive colored dye image.
  • the receiving sheet contains an oxidizing agent which oxidizes the color developer and thus provides the oxidized or reactive species of the developer which couples with the color former image.
  • I employ, in lieu of the chemical oxidizers of the application, a low voltage electric potential applied to the receiving layer.
  • the color developing agent is quickly and easily oxidized to the reactive form which then reacts with the diffused color former image with concomitant production of a positive colored photographic reproduction.
  • the color formers which are used in practicing the color diffusion process as described in the aforementioned application are especially designed for this system, it being particularly important that the couplers diffuse at higher pH, i.e., 12.5-13.0, but remain relatively immobile at lower pH values.
  • the color formers which are used in this diffusion process must possess the following attributes:
  • FIGURE 1 discloses in section an elevational view of a mono-layer containing on a clear film or paper support a coating of a gelatino silver halide emulsion having uniformly dispersed therein oily packets containing dissolved color former according to the invention
  • FIGURE 2 shows in section an elevational view of a transfer sheet consisting of a conducting support having coated on one of its surfaces a receiving layer of gelatin or a similar photographic colloid carrier;
  • FIGURE 3 depicts in section an elevational view of a multilayer coating in which each of the layers contain a differently sensitized silver halide emulsion having uniformly dispersed therein oily packets of dissolved color former;
  • FIGURE 4 is a flow sheet illustrating the steps of: (A) Exposing,
  • FIGURES 5, 6 and 7 are schematic views, partly in cross-section, depicting various forms of electrodes in contact with the receiving sheet undergoing development.
  • FIGURES 1 and 3 of the drawings are believed to be self-explanatory when his understood that reference character ltl'represents the base of the sensitized elements of FIGURES land 3.
  • Reference character 11 represents the light-sensitive emulsion layers having distributed through the colloid carrier 14 oily packets of dissolved color former 12 and silver halide grains 13.
  • FIGURE 2 depicts the receiving sheet 25 comprising the base 10a which carries thereon the receiving layer 15.
  • FIGURE 4 the multilayer coating depicted in FIG- 3 is exposed to a pattern representing the primary colored aspects'of a subject.
  • A depicts the exposure step and the re cording of the latent primary images in the three sensitized layers.
  • 16 represents a blue latent image, 17 the green and 18 the red.
  • the opaque area of the pattern forms no images in the sensitized layer; under the clear area of the pattern, latent images are formed in each layer.
  • the exposed photographic element of A is developed in a low pH primary aromatic amino developer for 1-5 minutes, whereby a negative colored image and a negative silver image is recorded at 20, the green image 21 and the red at 22.
  • These are the subtractively dyed images of negative development and as dye images are non-diffusing under pH conditions of the first development.
  • the exposed and first developed layer is then developed in a second developer containing a primary aromatic amino developing' agent under elevated pH conditions, whereby the couplers not utilized for dye formation in first development are rendered diffusible in the higher alkaline medium of the second development.
  • the receiving sheet of FIGURE 2 is placed in contact with the upper layer of the exposed 3-layer coating whereby the migrating coupler image is imbibed on the image receiving layer of the receiving sheet.
  • the receiving sheet which now contains the diffused color former image in addition to imbibed c-olor developer, is placed between the electrodes of a low voltage potential wherein the anode is connected to the image receiving sheet and the cathode is connected to the support of the receiving sheet. Under the action of the low voltage current, the primary aro matic amino developing agent is oxidized to the reactive coupling form which reacts with the diffused color forming image to form on the receiving layer of visible positive colored reproduction of the original subject matter being photographed.
  • the electrodes may consist of a pair of rollers 26 and 27 as shown in FIGURE 5, having electroconductive surfaces which are pressed against the opposite sides of the receiving sheet 25.
  • the latter passes between the rollers as the latter rotate, the conductive surface of roller 26 being connected to the anode and that of roller 27 to the cathode of a source 28 of low DC. voltage.
  • the sheet 25 has its base 10A in contact with the cathode roller 27, and its receiving layer 15 in contact with the anode roller 26.
  • the cathode roller 27 may be replaced by a cathode-connected plate 29 on which the receiving sheet 25 is supported with its base 10A in contact with plate 29.
  • An anode-connected roller 30, similar to roller 26, is passed over the receiving surface 15 of the receiving sheet 25 to effect development thereof.
  • both rollers can be replaced by electrically conductive plates 31 and 32, connected respectively to anode and cathode of a low voltage D-.C. source, and pressed respectively against the receiving side 15 and the base 10A of the receiving sheet 25.
  • rollers of FIGURES 5 and 6 are of such length, and the plates of FIGURES 6 and 7' of such dimensions, as to contact (progressively in the case of the rollers, and simultaneously in the case of the plates) the entire image-bearing area of the receiving sheet 25 when the latter is passed between or under the rollers or lies in contact with the plates.
  • Example I One coating was prepared in which the average size of the oily packet was less than 1 micron. This coating was prepared by dissolving ten millimoles of a cyan color former of the following formula:
  • the developed strip without washing is pressed into contact for 3 minutes with a transfer sheet of b aryta coated paper which had been previously presoaked for 5 minutes in a 2% solution of sodium hydroxide.
  • Contact between the developed strip and transfer sheet is conveniently effected by means of power driven pressure rollers as is well known in the art.
  • the purpose of presoaking the transfer sheet with alkali is to provide the necessary high pH :to effect diffusion of the coupler image. After aprpoximately 1 minute contact with the receiving layer, transfer of the coupler to the receiving sheet has reached equilibrium and the image receiving sheet is separated and brought in contact with ⁇ the electrodes connected to a low voltage D.C. source in such a manner that the anode is in immediate contact with the gel layer of the image receiving sheet.
  • Electrodes there may be used any of the arrangements shown in FIGURES 5, 6 and 7. Under the action of the low voltage current, electrolytic oxidation of the developer takes place with immediate coupling mm the diffused color former image resulting in the production of a positive cyan colored image.
  • Example II Utilizing the procedure as given in Example I, a positive magenta image was produced by substituting a magenta color former of the following (formula:
  • Example III A yellow image was produced by following the procedure of Example I except the cyan color former of the first example was replaced by yellow color former of the following structure:
  • Example IV This example i lustrates the utilization of a three-layer coating as illustrated in FIGURE 3 which is composed of three diiferently sensitized silver halide coatings on a base each coating sensitized one of the primary color regions of the visible spectrum.
  • a baryta treated paper base is coated with the composition described in Example I in which the silver bromo chloride emulsion containing 6% silver halide, is sensitized with a red sensitizer of the following structure:
  • the exposed negative image was developed for 5 minutes at 25 C. in the solution of the following composition:
  • the developed image was then brought in contact with the receiving sheet in the following high pH developer:
  • Example V Light-sensitive materials are prepared as in Examples I-IV, with the only exception of keeping silver halide and color former ratio in the emulsion to 8:1. In this case, the light-sensitive material, after receiving an imagewise exposure, was developed for 90 seconds in the following high pH developer, after which it was brought in contact with image receiving sheet and then was processed as described in Examples I-IV:
  • a full colored reproduction of the original subject is reproduced on the receiving layer. It will be evident that the process contemplated herein can be brought about in a camera or similar copying device. The only requirements are the ability to expose the sensitized material, develop the same, and to contact the developed material at a high pH with a transfer sheet.
  • a layer, having an oxidation potential as above described can be interpolated between the image receiving layer and the support.
  • the support itself may be made of a material having the required oxidation potential
  • the color formers which are employed are those which are capable of forming nondiffusing quinonimine or azomethine dye images upon color development with a primary aromatic amino developer.
  • These color formers are pyrazolones, phenolic derivatives, or straight chain keto methylene compounds. They must not only possess such structural features but must also meet the attributes previously specified.
  • My electrolytic development process could be utilized to produce an image in light sensitive layers by the use of conventional color formers or leuco dyes if the light sensitive layers are capable of causing imagewise change in conductivity of the colloid layer, upon exposure to light, heat or other source of radiant energy.
  • a process of forming a positive multicolor photographic reproduction which comprises exposing to the color aspects of a subject a photographic material comprising a suitable support carrying at least one light sensitive photographic silver halide emulsion layer, containing a coupler compound capable of forming a dye when reacted with the oxidation products of a primary aromatic amino silver halide developing agent, and said coupler compound being characterized by relatively high diffusibility at elevated pH, developing the exposed emulsion layers in the presence of said developing agent at a pH below 12.5, to form non-dilfusible dye images in those areas corresponding to light-exposure, transferring the diffusible invisible positive image of color coupler by imbibition at an elevated pH above 12.5 to a receiving layer having therein a primary aromatic amino silver halide developing agent, applying a relatively low voltage electrical potential to the total moist surface of said receiving layer, the potential of which is sufiicient to bring about electrolytic oxidation of the developing agent to form oxidized developing agent which reacts with the positive image of diffusing color former
  • a process of forming a positive multicolor photographic reproduction which comprises exposing to the color aspects of a subject, a photographic material comprising a suitable support carrying at least two superhuposed silver halide emulsion layers sensitized to different regions of the electromagnetic visible spectrum, each layer being further provided with a different coupler compound capable of forming a dye when reacted with the oxidation products of a primary aromatic amino silver halide developing agent, and said coupler compound being characterized by relatively high dilf-usibility at elevated pH, developing the exposed emulsion layers in the presence of said developing agent at a pH below 12.5, to form non-difliusible dye images in those areas corresponding to light exposure, transferring the difl usible invisible positive images of the color couplers by imbibition at an elevated pH above 12.5 to a receiving layer having therein a primary aromatic amino silver halide developing agent, applying a relatively low voltage electrical potential to the moist imbibed surface of said receiving layer, the potential of which is sulficient to bring about electrolytic
  • a process of torming a positive multicolor photographic reproduction which comprises exposing imagewise to a col-or object a photographic material comprising a suitable support, three superimposed silver halide emulsion layers sensitized to dilferent regions of the visible spectrum, each layer containing a color ttormer capable of forming when reacted with the oxidation products of a primary aromatic amino silver halide developing agent, a dye image complementary in color to that color to which silver halide emulsion layer is sensitized, and wherein the lowest emulsion layer is sensitized to red light and contains a color former capable of forming a cyan image, a middle layer sensitized to green light and containing a color former capable of forming a magneta image, and a top layer sensitive to blue light and containing a color former capable of forming a yellow image, said color tiormers being characterized by a relatively high diffusibility at a pH above 12.5; developing the exposed emulsion layers in the presence of said
  • the photographic element comprises three superimposed silver halide photographic layers each sensitized to one of the primary colors of the electromagnetic visible spectrum, and each emulsion layer having a color coupler compound capable of forming substractively color dye images on first development.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Color Printing (AREA)
US454240A 1961-02-27 1965-04-21 Electrolytic color development Expired - Lifetime US3301772A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE614376D BE614376A (US20100223739A1-20100909-C00005.png) 1961-02-27
DEG34346A DE1182064B (de) 1961-02-27 1962-02-24 Verfahren zur Herstellung von positiven mehrfarbigen photographischen Bildern nach dem Farbdiffusionsverfahren
FR889208A FR1318893A (fr) 1961-02-27 1962-02-26 Procédé pour l'obtention d'images photographiques en couleurs par développement électrolytique
GB4503/62A GB1002858A (en) 1961-02-27 1962-02-27 Electrolytic color development
CH238362A CH426479A (de) 1961-02-27 1962-02-27 Verfahren zur Herstellung von positiven, ein- oder mehrfarbigen photographischen Bildern nach dem Farbdiffusionsverfahren
US454240A US3301772A (en) 1961-02-27 1965-04-21 Electrolytic color development

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9201761A 1961-02-27 1961-02-27
US454240A US3301772A (en) 1961-02-27 1965-04-21 Electrolytic color development

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US3301772A true US3301772A (en) 1967-01-31

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US (1) US3301772A (US20100223739A1-20100909-C00005.png)
BE (1) BE614376A (US20100223739A1-20100909-C00005.png)
CH (1) CH426479A (US20100223739A1-20100909-C00005.png)
DE (1) DE1182064B (US20100223739A1-20100909-C00005.png)
GB (1) GB1002858A (US20100223739A1-20100909-C00005.png)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3362823A (en) * 1966-01-11 1968-01-09 Polaroid Corp Production of hydroxyl ions in situ by an electric current in a diffusion transfer process
US3384488A (en) * 1964-07-23 1968-05-21 Xcrox Corp Polychromatic photoelectrophoretic imaging composition
US3383993A (en) * 1964-07-23 1968-05-21 Xerox Corp Photoelectrophoretic imaging apparatus
US3384566A (en) * 1964-07-23 1968-05-21 Xerox Corp Method of photoelectrophoretic imaging
US3549363A (en) * 1966-01-11 1970-12-22 Polaroid Corp Novel photographic processes to produce precipitating nuclei in situ by electrolysis
US3728116A (en) * 1971-06-15 1973-04-17 Gaf Corp Instant access one-layer color photography
US3837852A (en) * 1972-10-02 1974-09-24 Gaf Corp Color diffusion transfer process utilizing azo coupling to actuate diffusion of color providing species
US3899330A (en) * 1973-03-02 1975-08-12 Gaf Corp Color screens for diffusion transfer processes containing color formers
US4060418A (en) * 1976-02-13 1977-11-29 Gaf Corporation Phenoxy carbonyl derivatives of a paraphenylenediamine color developer and their use in an image-receiving sheet for color diffusion transfer
US5411842A (en) * 1993-04-13 1995-05-02 Eastman Kodak Company Method of making a photographic developer solution

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430254A (en) * 1942-12-23 1947-11-04 Rca Corp Fibrous sheet material for producing dyes thereon by electrolytic oxidation
US2756142A (en) * 1953-01-22 1956-07-24 Eastman Kodak Co Photographic color reproduction process
GB853478A (en) * 1956-02-13 1960-11-09 Polaroid Corp Colour photographic processes and products therefor
US3220836A (en) * 1960-11-04 1965-11-30 Polaroid Corp Photographic process for speeding development using electric current

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430254A (en) * 1942-12-23 1947-11-04 Rca Corp Fibrous sheet material for producing dyes thereon by electrolytic oxidation
US2756142A (en) * 1953-01-22 1956-07-24 Eastman Kodak Co Photographic color reproduction process
GB853478A (en) * 1956-02-13 1960-11-09 Polaroid Corp Colour photographic processes and products therefor
US3220836A (en) * 1960-11-04 1965-11-30 Polaroid Corp Photographic process for speeding development using electric current

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384488A (en) * 1964-07-23 1968-05-21 Xcrox Corp Polychromatic photoelectrophoretic imaging composition
US3383993A (en) * 1964-07-23 1968-05-21 Xerox Corp Photoelectrophoretic imaging apparatus
US3384565A (en) * 1964-07-23 1968-05-21 Xerox Corp Process of photoelectrophoretic color imaging
US3384566A (en) * 1964-07-23 1968-05-21 Xerox Corp Method of photoelectrophoretic imaging
US3362823A (en) * 1966-01-11 1968-01-09 Polaroid Corp Production of hydroxyl ions in situ by an electric current in a diffusion transfer process
US3549363A (en) * 1966-01-11 1970-12-22 Polaroid Corp Novel photographic processes to produce precipitating nuclei in situ by electrolysis
US3728116A (en) * 1971-06-15 1973-04-17 Gaf Corp Instant access one-layer color photography
US3837852A (en) * 1972-10-02 1974-09-24 Gaf Corp Color diffusion transfer process utilizing azo coupling to actuate diffusion of color providing species
US3899330A (en) * 1973-03-02 1975-08-12 Gaf Corp Color screens for diffusion transfer processes containing color formers
US4060418A (en) * 1976-02-13 1977-11-29 Gaf Corporation Phenoxy carbonyl derivatives of a paraphenylenediamine color developer and their use in an image-receiving sheet for color diffusion transfer
US5411842A (en) * 1993-04-13 1995-05-02 Eastman Kodak Company Method of making a photographic developer solution

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GB1002858A (en) 1965-09-02
BE614376A (US20100223739A1-20100909-C00005.png)
DE1182064B (de) 1964-11-19
CH426479A (de) 1966-12-15

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