US3533790A - Method for washing and protecting photographic silver images - Google Patents

Method for washing and protecting photographic silver images Download PDF

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Publication number
US3533790A
US3533790A US487596A US3533790DA US3533790A US 3533790 A US3533790 A US 3533790A US 487596 A US487596 A US 487596A US 3533790D A US3533790D A US 3533790DA US 3533790 A US3533790 A US 3533790A
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United States
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composition
acid
silver
image
photographic
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US487596A
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English (en)
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Howard C Haas
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Polaroid Corp
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Polaroid Corp
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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
    • G03C11/00—Auxiliary processes in photography
    • G03C11/08—Varnishing, e.g. application of protective layers on finished photographic prints

Definitions

  • This invention relates to the protecting of photographic images by forming protective coatings therefor, to the washing and protecting of photographic silver images by removing residual processing reagents therefrom and forming protective coatings therefor, and to the photographic products of such processes.
  • Objects of the present invention are: to provide a process for increasing the stability of a photographic silver image with a novel composition comprising water for washing the image when the composition is applied and a dispersion of such materials for forming a coating upon the image when the composition is dried; to provide, as a novel product, a protected photographic image produced by such a process; and to provide for use in a process of the foregoing type, a composition comprising a mixture of an acid polymer, zinc oxide, and ammonia.
  • the invention accordingly comprises the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the composition and product possessing the features, properties and relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the appended claims.
  • the process of the present invention is particularly useful for washing and protecting thin photographic silver images prepared in accordance with well-known diffusion transfer processes, for example, as described in US. Pat. No. 2,719,791, issuedto Edwin H. Land on Oct. 4, 1955.
  • An extremely thin, photographic silver image of the foregoing type ordinarily retains traces of the photographic reagents with which it has been processed, and the continued presence of which may adversely affect its stability.
  • silver may be oxidized by sulphur from the residue of sodium thiosulfate which has been employed as a solvent.
  • the silver may be oxidized by numerous oxidizing agents present in the atmosphere.
  • the image may comprise traces of silver ion in equilibrium with the metallic silver; where the image is subjected to materials which form insoluble silver residues, such as sulfides, they react with the silver ion, causing more metallic silver to shift to the ionic state, ultimately destroying the silver image entirely.
  • traces of unoxidized developer if oxidized by at- 3,533,790 Patented Oct. 13, 1970 mospheric oxygen, may discolor the highlights of the image.
  • a preferred composition for this purpose comprises a mixture of compatible components which together possess properties not possessed by the components themselves. These components includes zinc oxide, a polymeric material having acid functional groups thereon, and ammonia.
  • the composition also comprises water and a watermiscible organic solvent.
  • Such a composition when used as a protective coating for photographic silver images of the type described, has been fround to provide the following unusual combination with respect to the images: substantial impermeability to water, elemental sulphur, and hydrogen sulfide, for example, from sulphur-containing materials with which the composition may come into contact; image stability throughout wide temperature and humidity ranges; resistance to generalized oxidation of silver; resistance to the effects of prolonged solar radiation; optical clarity; and non-tackiness.
  • the acid polymer is a phthalaldehydic acid partial acetal of polyvinyl alcohol
  • the crosslinked product from which ammonia, water, and solvent had evaporated would be composed of the recurring unit having the following structure:
  • the organic solvent acts in conjunction with the water and ammonia to effect dissolution of the polymeric material (which may be insoluble in water alone) and to impart to the composition an overall quickdrying character.
  • the zinc oxide serves not only as a cross-linking agent but also provides a heavy metal salt which forms an insoluble colorless sulfide, in accordance with the teachings of US. Pat. 2,866,705, issued Dec. 30, 1958 to Edwin H. Land and Meroe M. Morse. It should be noted that while zinc oxide is the salt of choice for purposes of the instant invention, cadmium oxide is also fully operative in that cadmium forms insoluble sulfides which are nearly as colorless as those of zinc, it forms complexes with ammonia, it can provide the basis of an equilibrium similar to that discussed above for zinc, and can thus effect crosslinking of the acid polymer.
  • the acid polymers within the scope of this invention are preferably cellulose or vinyl film-forming polymers having acid radicals, preferably carboxylic (COOH') or sulfonic (SO H) radicals attached thereto. It is also within the scope of this invention to employ polymers with carboxylic acid anhydride groups, at least some of which have been converted to free carboxyl groups.
  • acid polymeric materials which are operative in this invention, mention may be made of cellulose acetate hydrogen phthalate; cellulose acetate hydrogen glutarate; cellulose acetate hydrogen succinate; ethyl cellulose hydrogen succinate; ethyl cellulose acetate hydrogen succinate; cellulose acetate hydrogen succinate hydrogen phthalate; ether and ester derivatives of cellulose modified with sulfoanhydrides, e.g., ortho sulfobenzoic acid; polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid; acetals of polyvinyl alcohol with carboxyor sulfo-substituted aldehydes, e.g., o, m, or p-benzaldehyde sulfonic acid or carboxylic acid or formyl alkanoic or alkane sulfonic acid; partial est
  • aldehydic acid substituted partial acetals of polyvinyl alcohol have been found to be especially well suited to the compositions of this invention.
  • the use of these latter materials are disclosed and claimed in copending application of Howard C. Haas, Ser. No. 487,597, filed concurrently herewith.
  • These latter polymeric materials may be prepared by reacting a low molecular weight polyvinyl alcohol, preferably one which is completely hydrolyzed, with a compound having the formula RCHO, Where R has the same meaning as is given above, in the presence of an acid catalyst.
  • the polymers may be prepared by reacting polyvinyl alcohol with an ester having the formula:
  • m is an integer from 1-4, inclusive, and each R is an alkyl radical, or the corresponding acetals of the above esters, and subsequently hydrolyzing the ester group to the corresponding acid.
  • R is an alkyl radical, or the corresponding acetals of the above esters, and subsequently hydrolyzing the ester group to the corresponding acid.
  • a total of 28% to 42% of the hydroxyl groups on the polyvinyl alcohol chain are substituted with the acid function groups. It has been found that if the substitution is as low as 20%, the resulting composition may be undesirably viscous. The substitution can theoretically be as high as about 90% but there are substantially no advantages to be gained thereby.
  • the quantity of ammonia to be incorporated in the compositions of this invention is not critical, other than that it be suificient to render the final pH of the composition basic.
  • the pH of the composition is about 8 to 14, the quantity of ammonia being regulated to achieve this.
  • the preferred material for this purpose is a hydantoin formaldehyde condensation polymer, such as the dimethyl hydantoin formaldehyde polymer described in US. Pat. No. 2,874,045, issued Feb. 17, 1959 to Edwin H. Land, for Process of Washing and Protecting Photographic Silver Images.
  • compositions within the scope of this invention may be prepared by dissolving the acid polymer in the Water, organic solvent, and ammonia at a temperature ranging from room temperature to 40 C. under a reflux condenser to prevent evaporation of the solvent. Thereafter, the zinc oxide, and optionally, the hydantoin formaldehyde polymer are stirred into the mixture.
  • a preferred composition comprises the foregoing ingredients in the following proportions:
  • Hydantoin formaldehyde condensation polymer-5 to Ammoniasuificient to dissolve the polymer and give a final pH of about 9 to the final composition.
  • a composition for washing and protecting photographic silver images was prepared by combining the following materials to provide a uniform solution:
  • the final pH was about 9.
  • Photographic silver transfer images were prepared-by exposing photosensitive silver halide elements to a step- Wedge, and developing the latent images formed thereby by spreading between the exposed photosensitive elements and superposed image-receiving elements a processing composition containing a viscous aqueous solution of a silver halide developing agent, a silver halide solvent, and an alkali.
  • the respective elements were maintained in superposed relation for a predetermined period, during which time the exposed silver halide was reduced to silver in the photosensitive elements.
  • the unreduced silver halide formed a water-soluble complex silver salt which diffused through the layer of composition to the image-receiving elements where, upon being reduced to silver, it formed a silver print.
  • the photosensitive elements together with the layer of composition, were stripped from the image receptive elements.
  • the photographic silver images so prepared were swabbed by means of an absorbent applicator with the coating solution prepared as described above.
  • the polymer used in the foregoing example was prepared as follows:
  • Phthalaldehydic acid partial acetal of polyvinyl alcohol polymer composed of the recurring unit 88 grams (2 moles) of low viscosity, low molecular weight polyvinyl alcohol having less than 1% acetate were dissolved in 500 cc. of water and cooled. 150 grams (1 mole) of phthalaldehydic acid were added with stirring and the mixture was heated at 50 C. under nitrogen. 1 cc. of concentrated sulfuric acid was added. The polymer separated as a soft, rubbery mass. After four hours, the liquid was decanted and the product washed in hot water. It was further purified by precipitation from ethanol-water (containing 1 gram of potassium acetate) into water, washed in water and dried. The final product was predominantly the phthalaldehydic acid partial acetal of polyvinyl alcohol, 'with a small amount of the corresponding phthalide; the composition was confirmed by infrared analysis.
  • the composition of the present invention is 6 i 1 applied to a photographic silver image to be washed and protected by means of an absorbent applicator composed, for example, of flannel, cotton batting, or cellulose sponge charged with the composition.
  • an absorbent applicator composed, for example, of flannel, cotton batting, or cellulose sponge charged with the composition.
  • composition referred to above after being swabbed by means of such an absorbent applicator onto a thin photographic silver image of the above-described type, rapidly dries under ordinary atmospheric con ditions to form a coating having excellent protective properties for the image.
  • a process for washing and protecting a diffusion transfer photographic silver print containing a residue of the reagents with which it has been processed the step of applying to one face thereof, a thin layer of an alkaline composition comprising zinc oxide, ammonia, and an acid film-forming polymer selected from the group consisting of cellulose and vinyl polymers containing groups selected from carboxylic acid and sulfonic acid groups, said alkaline composition has a pH between 8 and 14; and for-m ing a protective coating on said print by removing ammonia by drying said layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Paints Or Removers (AREA)
US487596A 1965-09-15 1965-09-15 Method for washing and protecting photographic silver images Expired - Lifetime US3533790A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US48759765A 1965-09-15 1965-09-15
US48759665A 1965-09-15 1965-09-15
US48757865A 1965-09-15 1965-09-15

Publications (1)

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US3533790A true US3533790A (en) 1970-10-13

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US487596A Expired - Lifetime US3533790A (en) 1965-09-15 1965-09-15 Method for washing and protecting photographic silver images
US487597A Expired - Lifetime US3529962A (en) 1965-09-15 1965-09-15 Process of washing and protecting photographic silver images
US487578A Expired - Lifetime US3533789A (en) 1965-09-15 1965-09-15 Process of washing and protecting a diffusion transfer photographic silver print

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US487597A Expired - Lifetime US3529962A (en) 1965-09-15 1965-09-15 Process of washing and protecting photographic silver images
US487578A Expired - Lifetime US3533789A (en) 1965-09-15 1965-09-15 Process of washing and protecting a diffusion transfer photographic silver print

Country Status (5)

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US (3) US3533790A (forum.php)
BE (1) BE686815A (forum.php)
DE (1) DE1572008C3 (forum.php)
GB (2) GB1164642A (forum.php)
NL (1) NL6612967A (forum.php)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE794397A (fr) * 1972-01-24 1973-07-23 Du Pont Bains d'activation photographiques

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2759825A (en) * 1948-02-12 1956-08-21 Polaroid Corp Photographic image transfer process
US2794740A (en) * 1954-02-24 1957-06-04 Polaroid Corp Methods for washing and protecting photographic silver images
US2830900A (en) * 1956-10-04 1958-04-15 Polaroid Corp Process of washing and protecting photographic silver images, and photographic products thereof
US2866705A (en) * 1953-07-01 1958-12-30 Polaroid Corp Process of washing and protecting photographic silver images
US2874045A (en) * 1954-02-26 1959-02-17 Polaroid Corp Process of washing and protecting photographic silver images
US2956877A (en) * 1956-10-04 1960-10-18 Polaroid Corp Process of washing and protecting photographic silver images, and photographic products thereof
US2979477A (en) * 1958-05-08 1961-04-11 Polaroid Corp Composition comprising a vinylpyridine polymer and a hydantoin formaldehyde condensation polymer
US3174858A (en) * 1959-09-24 1965-03-23 Gevaert Photo Prod Nv Process for obtaining multiple photographic positive images by diffusiontransfer
US3325283A (en) * 1964-01-16 1967-06-13 Polaroid Corp Photographic diffusion transfer products and processes employing image receiving elements containing a layer of polyvinyl pyrrolidone and polyvinyl hydrogen phthalate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB496049A (en) * 1937-04-19 1938-11-21 Ig Farbenindustrie Ag Improved manufacture of light-sensitive photographic preparations
US2855298A (en) * 1954-02-24 1958-10-07 Polaroid Corp Methods for washing and protecting photographic silver images

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2759825A (en) * 1948-02-12 1956-08-21 Polaroid Corp Photographic image transfer process
US2866705A (en) * 1953-07-01 1958-12-30 Polaroid Corp Process of washing and protecting photographic silver images
US2794740A (en) * 1954-02-24 1957-06-04 Polaroid Corp Methods for washing and protecting photographic silver images
US2874045A (en) * 1954-02-26 1959-02-17 Polaroid Corp Process of washing and protecting photographic silver images
US2830900A (en) * 1956-10-04 1958-04-15 Polaroid Corp Process of washing and protecting photographic silver images, and photographic products thereof
US2956877A (en) * 1956-10-04 1960-10-18 Polaroid Corp Process of washing and protecting photographic silver images, and photographic products thereof
US2979477A (en) * 1958-05-08 1961-04-11 Polaroid Corp Composition comprising a vinylpyridine polymer and a hydantoin formaldehyde condensation polymer
US3174858A (en) * 1959-09-24 1965-03-23 Gevaert Photo Prod Nv Process for obtaining multiple photographic positive images by diffusiontransfer
US3325283A (en) * 1964-01-16 1967-06-13 Polaroid Corp Photographic diffusion transfer products and processes employing image receiving elements containing a layer of polyvinyl pyrrolidone and polyvinyl hydrogen phthalate

Also Published As

Publication number Publication date
DE1572008B2 (de) 1978-12-14
NL6612967A (forum.php) 1967-03-16
US3533789A (en) 1970-10-13
DE1572008C3 (de) 1979-08-23
DE1572008A1 (de) 1970-02-19
BE686815A (forum.php) 1967-03-13
US3529962A (en) 1970-09-22
GB1164641A (en) 1969-09-17
GB1164642A (en) 1969-09-17

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