US3512972A - Photographic developer systems - Google Patents

Photographic developer systems Download PDF

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Publication number
US3512972A
US3512972A US445743A US3512972DA US3512972A US 3512972 A US3512972 A US 3512972A US 445743 A US445743 A US 445743A US 3512972D A US3512972D A US 3512972DA US 3512972 A US3512972 A US 3512972A
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United States
Prior art keywords
image
copper
latent
ion
silver
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Expired - Lifetime
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US445743A
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English (en)
Inventor
Laura K Case
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Northrop Grumman Guidance and Electronics Co Inc
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Itek Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development

Definitions

  • the present invention relates to data storage systems and methods, and relates in particular to systems and methods for image reproduction.
  • the phenomenon can be used for image reproduction.
  • the light-sensitive materials, incorporated in a copy medium are exposed to an image pattern of radiation and then developed by contact of the medium with a reducible metal ion, a latent image comprising free metal is formed in the copy medium.
  • latent metal images of this type can be amplified or intensified by bringing the latent images into contact with silver ion and a redox system, usually an organic redox system, such as hydroquinone, metol, or phenidone, for example.
  • a redox system usually an organic redox system, such as hydroquinone, metol, or phenidone, for example.
  • additional metal is precipitated by reaction of silver ion with the reducing components of the redox system.
  • Analogous amplification or intensification systems have heretofore been used in the art for the development of images in silver halide photography, for example.
  • a disadvantage of this prior art image intensification process is its dependence on the use of silver, a material which is bottoming increasingly more rare and more expensive.
  • cupric ion has been employed according to the present invention to amplify latent images comprising ice free metals, particularly images of copper and silver.
  • compositions suitable for the non-electrolytic deposition of copper are known in the prior art, for example mixtures of Rochelle salts, copper ion, and formaldehyde.
  • such compositions give a uniform deposition of copper and if employed in an attempt to develop an image according to the present invention, they deposit copper indiscriminately over both image areas and background areas, without preferential deposition.
  • the developing compositions of the present invention comprise cupric ion in combination with ascorbic acid and, suitably, an acid acceptor. It is known in the prior art that ascorbic acid reduces cupric ion to copper, and the reaction has been used in analytic chemistry. However, the autocatalytic nature of the reaction, critically resulting in selective deposition of copper where metal is already present, has heretofore not been recognized in the art. This selective autocatalytic feature brings about the preferential deposition of copper metal in those areas of an exposed and developed data processing medium in which a latent image of deposited metal already exists, resulting in amplification of the latent image without a corresponding intensification of the background.
  • Cupric ion and asconbic acid react with the formation of dehydro-ascorbic acid and free copper according to the equation:
  • the equilibrium of this reaction can be displaced by the presence of an acid acceptor neutralizing hydrogen ions formed in the reaction. Accordingly, in the preferred compositions of the present invention, an acid acceptor is present.
  • any basic material not precipitating copper hydroxides can be employed.
  • inorganic hydroxides are not suitable, but ammonium hydroxide can be employed, apparently because formation of copper ammonia complexes discourages the precipitation of copper hydroxides.
  • Amine acceptor materials are, however, the preferred reagents. Amines of the widest variety can be employed, including primary, secondary, and tertiary aliphatic, cycloaliphatic, and aromatic amines, including isocyclic and heterocyclic compounds. The amines need not be hydrocarbon materials, but include such substituted amines as triethanol amine, and urea.
  • Cycloaliphatic amines such as N-methyl cyclohexyl amine can be employed, as can heterocyclic amines such as pyrrole, imidazole, quinoline, morpholine, and hexamethylenetetramine. Since the principal function of the amine or NH OH acid acceptor is to neutralize hydrogen ions, the chemical structure of the acid acceptor is immaterial providing only, as mentioned earlier, that the material is not one precipitating copper hydroxides. What is critical to the present invention is the well-known property of amines to accept or neutralize hydrogen ions.
  • nitrogenous acid acceptor is used to define amine materials of the type discribed and ammonium hydroxide as the sole inorganic acid acceptor.
  • ascorbic acid and cupric ion can be present in widely varied proportions. While it is preferred to have substantially equimolar quantities of the materials present in view of the reaction between the substances, images will be formed if according to the invention either of the components is in a ration of 100:1 to the other. Suitably, the components are present in a :1 or 1:10 ratio to avoid waste. If an acid acceptor is present, substantially equimolar quantities of the acceptor and ascorbic acid are preferred, but the acid acceptor can be used in amounts as slight as mol percent of the acid employed. Large amounts of acid acceptor tend to cause precipitation of copper hydroxides, and are preferably avoided.
  • the optical densities of amplified images produced according to the present invention will vary from about 0.1 to greated than 1, measured by diffuse reflectance.
  • the time required for development of a latent image by amplification is between about seconds and about 5 minutes when an acid acceptor is present in the solutions. If no acceptor is present in the solutions, the time of development may vary from between about 2 minutes to about minutes. Still longer development times can be employed, but there is in general no observable improvement in the image after the period of time indicated.
  • the copper-containing amplifying compositions and the techniques of the present invention can be used to amplify latent metal images, particularly ion and exposed to light, whereupon a latent image of copper metal is formed in the light struck areas.
  • the copy medium, still having residual cupric ion thereon, is then suitably simply contacted with a mixture of ascorbic acid and an acid acceptor, additional copper metal is deposited in the image areas where the latent image of copper metal already exists, and the latent image is made visible.
  • EXAMPLES 1-17 For each of Examples 1-17, a primary silver image was prepared as follows. Titanium dioxide dispersed in a commercial acrylate resin binder (Rhoplex) commonly employed in the photosensitive-paper coating art was used to coat paper stock to form a copy medium. After drying, the coated paper was exposed to an image pattern of radiation from a 6 watt black light Raymaster fluorescent bulb for seconds.
  • Rhoplex commercial acrylate resin binder
  • the irradiated sample was then immersed in a saturated solution of methanolic silver nitrate for 10 seconds, washed in a 50:50 mixture of methanol and water for one minute, fixed in a sodium thiosulfate fixer buffered with sodium sulfite and sodium bisulfite for 15 minutes, washed in tap water for 30 minutes, and then dried.
  • the systems of the present invention can be used to amplify images comprising other metals, particularly of metals at least as noble as copper, such as images of palladium, platinum, gold, etc.
  • Latent silver images are formed, for example, by irradiation of a copy medium comprising a readiation sensitive substance such as titanium dioxide or a metal carbonyl, as disclosed in the aforementioned US. patent applications, with subsequent contact of the exposed medium with a solution of silver ion.
  • Metallic silver is deposited on the medium to form a latent image.
  • Contact of the latent silver image with the copper ion-ascorbic acid compositions of the present invention will cause metallic copper to be deposited on the medium in image areas Where silver is already present.
  • the copper ion-ascorbic acid compositions of the present invention can also advantageously be employed to intensify latent images of copper.
  • cupric ion with irradiated TiO for example, cuprous ion is formed.
  • the cuprous ion disproportionates with formation of metallic copper.
  • Latent images of metallic copper can also be formed if copper ion is present in contact with a photosensitive pigment such as titanium dioxide at the time of exposure to activating radiation.
  • the resultant latent copper images can then subsequently be amplified with the compositions of the present invention.
  • a copy medium having a titanium dioxide coating thereon can be contacted with a solution of cupric
  • the resultant primary latent silver image was amplified by immersion of the copy medium into a variety of aqueous solutions containing copper ion, ascorbic acid, and an acid acceptor.
  • free silver latent images can be formed by exposing a copy medium comprising tungsten carbonyl to an image pattern of ultraviolet light and then contacting the medium with a solution of silver ion, as in copending application (CMS 32527).
  • EXAMPLE 18 A silver halide emulsion-coated film (Kodak 649) was exposed for 30 seconds to a step-wedge and fixed to remove all non-photolyzed silver halide. The invisible latent image was then amplified by immersion in a mixture comprising ml. of 1 M aqueous ascorbic acid, 50 ml. of 1 M aqueous Cu(NO and 50 ml. of 0.75 M triethanol amine in 50:50 H O-methanol. After seconds, 15 steps were visible. The maximum optical density was about 1.33.
  • EXAMPLE 19 The paper copy medium of Examples 1-17, coated with titanium dioxide in an acrylate resin binder, was soaked for 5 minutes in a 5% aqueous solution of cupric nitrate, and then dried. The dry paper was exposed to a 6 watt black light Raymaster fluorescent bulb for 60 seconds, then immersed for 150 seconds in a mixture comprising 10 ml. of 1 M aqueous ascorbic acid, 10 ml. of l M aqueous Cu(NO and 10 ml. of 0.75 M triethanol amine in 50:50 H O--CH OH. A black image having an optical density of 0.92 resulted.
  • the paper can first be exposed and then contacted with a cupric ion solution. n heating to about 75 C., the cuprous ion formed by reaction of the cupric ion and activated TiO disproportionates to cupric ion and copper.
  • the latent copper image can be amplified with the solution disclosed herein.
  • EXAMPLE 20 Paper treated with cupric nitrate as in Example 19 was exposed after drying, and was then immersed for amplification in a mixture comprising ml. of 1 M aqueous ascorbic acid and 1-0 ml. of 0.75 M triethanol amine solution for a period of 180 seconds. A bluish-black image having an optical density of 0.95 was produced.
  • the cupric ion reacting was ascorbic acid for image intensification of the latent copper image was supplied by the residual copper ion in the coating.
  • EXAMPLE 21 A primary silver image prepared as in Examples 1-17 was immersed for amplification in a solution comprising 25% water and 75% methanol. The concentration of Cu(N0 in said aqueous-methanol solution was 0.25 M and the concentration of ascorbic acid in said solution was also 0.25 M. After immersion for about 180 seconds, a purple image was obtained which had an optical density of about 1.01.
  • cupric ion and ascorbic acid are preferable first combined and the acid acceptor added subsequently since if the acid acceptor is added directly to the cupric ion, precipitation of copper hydroxides may result.
  • ascorbic acid is added first to the copper ion, complexes may be formed between the acid and copper ion which tend to discourage formation of copper hydroxides.
  • Prints produced by the present process are suitably dried soon after their production to discourage air oxidation of, deposited copper in the presence of moisture.
  • the copper salts used to supply cupric ion are not critical, nor are the solvents employed in preparing the compositions of the invention.
  • the solvents should not cause formation of copper hydroxides, and should be miscible with the acid acceptor desired.
  • aqueous solutions, or solutions in lower alcohols are employed, as are mixtures of water and a lower alcohol such as methanol.
  • the chemical deposition of copper for amplification of images in a copy medium according to the present invention must be distinguished from prior art processes using the electrical deposition or electroplating of copper to render metal latent images visible. No passage of electric current is required or used in the present invention, and the copy media employed are not limited to those having conductive carriers to which electrical contact can be made. Insulating carriers such as of ordinary paper, glass, or cloth or wood are acceptable in the present invention.
  • the method of amplifying a metallic image of a metal at least as noble as copper comprises contacting a physically developable copy medium comprising said metallic image with ascorbic acid and cupric ion to deposit selectively metallic copper in image areas of said copy medium where metal is already present.
  • said metallic image comprises metal selected from the group consisting of copper and silver.
  • the method of amplifying a latent metallic image in a copy medium which comprises contacting a copy medium comprising a latent metallic image with a developer comprising ascorbic acid and cupric ion todeposit selectively metallic copper in areas containing the latent image.
  • a process as in claim 4 wherein the latent metallic image is produced by exposing a photosensitive medium comprising a photoconductor and contacting said medium with image-forming materials comprising a solution of metal ions of a metal at least as noble as copper.
  • a process as in claim 4 wherein the latent metallic image is produced by exposing a copy medium comprising photosensitive silver halide.
  • said latent metallic image comprises a metal at least as noble as copper.
  • said latent metallic image comprises metallic silver.
  • the method of producing a visible image in a copy medium comprising titanium dioxide and cupric ion comprises exposing said medium to form a latent image of metallic copper in said copy medium, and then amplifying and making said latent image visible by contacting said medium with ascorbic acid and cupric 14.
  • a developed .photosenitive copy medium comprising a carrier and a visible image comprising a first latent image of a metal more noble than metallic copper and a second, heavier, visible overlying metallic copper image.
  • a copy medium as in claim 16 wherein the copy medium comprises at least one member selected from the group consisting of silver halide and a photoconductor.
  • composition for the amplification of images formed in a copy medium by the presence therein of a 7 8 metal which composition comprises a solution of cupric OTHER REFERENCES an acid acceptor and ascorbic acid in a common Chemical Abstract 52: 16020 of Netadas et a1.
  • Compt. solvent and wherein the acid acceptor is at least one mem- Rend 246 2543 5 (1958) ber of the group consisting of ammonium hydroxide and Neijgrgan et aL'General Chemistry 1959 an Organic amine. 5

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US445743A 1965-04-05 1965-04-05 Photographic developer systems Expired - Lifetime US3512972A (en)

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US44574365A 1965-04-05 1965-04-05

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US (1) US3512972A (en:Method)
BE (1) BE678769A (en:Method)
CH (1) CH470004A (en:Method)
DE (1) DE1547989A1 (en:Method)
GB (1) GB1139419A (en:Method)
NL (1) NL6604424A (en:Method)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647450A (en) * 1967-09-14 1972-03-07 Ferrania Spa ELECTROLESS DEPOSITION OF Ni OR Co LIGHT-GENERATED Ag NUCLEI
US3893857A (en) * 1968-07-11 1975-07-08 Itek Corp Photographic tin amplification process
US4121938A (en) * 1976-07-07 1978-10-24 Fuji Photo Film Co., Ltd. Photographic material containing TiO2, soluble Cu(II) salt, and soluble silver salt and the use thereof in physical development
US4129445A (en) * 1975-10-13 1978-12-12 Fuji Photo Film Co., Ltd. Metal image formation process
US4156610A (en) * 1977-09-15 1979-05-29 Eastman Kodak Company Copper physical development using heterocyclic ligand copper(I) complexes
US4178180A (en) * 1977-09-15 1979-12-11 Eastman Kodak Company Copper physical development using heterocyclic ligand copper (I) complexes
US4254214A (en) * 1975-11-27 1981-03-03 Fuji Photo Film Co., Ltd. Photographic materials for non-silver images and process for forming non-silver images

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1281700A (en) * 1968-07-15 1972-07-12 Itek Corp Metallic photographic products and processes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE637058A (en:Method) * 1962-09-07
US2854386A (en) * 1955-02-07 1958-09-30 Aladdin Ind Inc Method of photographically printing conductive metallic patterns
US3152903A (en) * 1959-04-30 1964-10-13 Minnesota Mining & Mfg Reproduction system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2854386A (en) * 1955-02-07 1958-09-30 Aladdin Ind Inc Method of photographically printing conductive metallic patterns
US3152903A (en) * 1959-04-30 1964-10-13 Minnesota Mining & Mfg Reproduction system
BE637058A (en:Method) * 1962-09-07

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647450A (en) * 1967-09-14 1972-03-07 Ferrania Spa ELECTROLESS DEPOSITION OF Ni OR Co LIGHT-GENERATED Ag NUCLEI
US3893857A (en) * 1968-07-11 1975-07-08 Itek Corp Photographic tin amplification process
US4129445A (en) * 1975-10-13 1978-12-12 Fuji Photo Film Co., Ltd. Metal image formation process
US4254214A (en) * 1975-11-27 1981-03-03 Fuji Photo Film Co., Ltd. Photographic materials for non-silver images and process for forming non-silver images
US4121938A (en) * 1976-07-07 1978-10-24 Fuji Photo Film Co., Ltd. Photographic material containing TiO2, soluble Cu(II) salt, and soluble silver salt and the use thereof in physical development
US4156610A (en) * 1977-09-15 1979-05-29 Eastman Kodak Company Copper physical development using heterocyclic ligand copper(I) complexes
US4178180A (en) * 1977-09-15 1979-12-11 Eastman Kodak Company Copper physical development using heterocyclic ligand copper (I) complexes

Also Published As

Publication number Publication date
GB1139419A (en) 1969-01-08
DE1547989A1 (de) 1970-02-12
NL6604424A (en:Method) 1966-10-06
CH470004A (fr) 1969-03-15
BE678769A (en:Method) 1966-09-30

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