US3003872A - Photographic products and processes - Google Patents

Photographic products and processes Download PDF

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Publication number
US3003872A
US3003872A US700281A US70028157A US3003872A US 3003872 A US3003872 A US 3003872A US 700281 A US700281 A US 700281A US 70028157 A US70028157 A US 70028157A US 3003872 A US3003872 A US 3003872A
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US
United States
Prior art keywords
image
vinylpyrrolidone
dye
emulsion
dye developer
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
US700281A
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English (en)
Inventor
Elkan R Blout
Howard C Haas
Howard G Rogers
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.)
Polaroid Corp
Original Assignee
Polaroid Corp
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 BE573503D priority Critical patent/BE573503A/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US700281A priority patent/US3003872A/en
Priority to GB36228/58A priority patent/GB893657A/en
Priority to FR780655A priority patent/FR1217185A/fr
Priority to DEI15697A priority patent/DE1130284B/de
Application granted granted Critical
Publication of US3003872A publication Critical patent/US3003872A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • G03C8/56—Mordant layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142—Dye mordant

Definitions

  • This invention relates to photography and more particularly to novel photographic products and processes.
  • One object of this invention is to provide a novel imagereceiving elements for use in color diffusion transfer processes.
  • Another object of this invention is to provide novel color dilfusion transfer processes utilizing said imagereceiving elements.
  • the invention accordingly comprises the several steps and the relation and order or" one or more of such steps with respect to each of the others, and the product possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • the present invention is particularly related to color diffusion transfer processes.
  • a sheet of photosensitive material is exposed to create therein a latent image.
  • the latent image is developed and, concurrent with and under the control of this development, an imagewise distribution of color-providing materials is formed. At least a portion of these color-providing materials is transferred by means of an alkaline aqueous processing liquid to a superposed imagereceiving element to form a colored positive image thereon.
  • an alkaline aqueous processing liquid to a superposed imagereceiving element to form a colored positive image thereon.
  • dye developers i.e., dyes containing a silver halide developing function and capable of developing a latent silver halide image
  • color developers are the color-providing materials
  • processes disclosed in US. Patent No. 2,774,668 issued December 18, 1956 to Howard G. Rogers wherein complete, preformed dyes are used as the color-providing substances.
  • the image-receiving elements used in such processes generally comprise an opaque or transparent support coated with an image-receiving layer of a dyeable material which is permeable to the alkaline aqueous processing solution.
  • a dyeable material which is permeable to the alkaline aqueous processing solution.
  • film-forming materials such as polyvinyl alcohol and nylons such as Nylon Type F8 (trade name of E. I. du Pont de Nemours & Co., Wilmington, Delaware, for N-methoxymethyl polyhexamethylene adipamide) as the image-receiving layer has been proposed.
  • dye developers which when used with the image-receiving elements of this invention atent O produce improved color images, mention may be made of 2 [p (2,5' dihydroxyphenethyl) phenylazo] 4 methoxy-l-naphthol and 1-phenyl-3-N-n-butylcarboxami do 4 [p (2',5 dihydroxyphenethyl) phenylazoJ- 5-pyrazolone, disclosed in the copending US. application of Elkan R. Blout, Milton Green and Howard G. Rogers, Serial No.
  • the novel image-receiving elements containing an image-receiving layer comprising a mixture of polyvinyl alcohol and poly-N-vinylpyrrolidone may be prepared using a suitable support such as cellulose acetate, cellulose acetate-coated baryta paper, etc., which support has been suitably subcoated for proper adhesion of the imagereceiving layer, e.g., subcoated with a mixture of cellulose nitrate and partially hydrolyzed polyvinyl acetate, and coating with an aqueous solution, preferably a 3 to 10% solution, comprising the polyvinyl alcohol and poly-N-vinylpyrrolidone.
  • the coating and drying operations involved may be carried out by methods commonly employed in the art.
  • the ratio of poly-N-pyrrolidone to polyvinyl alcohol is preferably less than 1 to 1 and more preferably about 1 to 3.
  • the concentration of poly-N-vinylpyrrolidone should not be so large as to make the resulting image-receiving layer subject to attack by water or alkali. If the concentration of poly-N- vinylpyrrolidone is too low, the images obtained may have reduced brilliance although the stability will not be aifected.
  • Poly-N-vinylpyrrolidones and polyvinyl alcohols suitable for use in preparing the image-receiving elements of this invention are readily available commercially.
  • a suitable poly-N-vinylpyrrolidone mention may be made of PVP, Type NP K-30 (trade name of General Aniline and Film Corp., New York, New York).
  • the polyvinyl alcohols are preferably selected from the high viscosity, substantially completely hydrolyzedmaterials available.
  • PVA 91-65 trade name of E. I. du Pont de Nemours & Co., Wilmington, Delaware, for acid hydrolyzed, high viscosity polyvinyl alcohol
  • Gelvatol 2-75 trade name of Shawinigan Products Corp., New York, New York.
  • the coating solutions may be readily prepared by dissolving said materials in water. Heat may be used to facilitate solubilization.
  • the polyvinyl alcohol is crosslinked in order to prevent excessive swelling of the resulting film in subsequent diffusion transfer process. This crosslinl-zing may be carried out by adding a crosslinking agent such as dimethylolurea or glyoxal to the above solution and reacting it in the presence of hydrochloric acid. Before applying the solution, a small amount of a wetting agent may be added to aid in the subsequent coating operation.
  • a crosslinking agent such as dimethylolurea or glyoxal
  • novel image-receiving elements containing an image-receiving layer comprising a copolymer of vinyl alcohol and N-vinyl-pyrrolidone may be prepared by coating a suitably subcoated film base such as cellulose acetate, cellulose acetate-coated baryta paper, etc., with an aqueous solution, preferably a 3 to solution, comprising the copolymer.
  • the vinyl alcohol N-vinylpyrrolidone copolymer may be prepared by polymerizing vinyl acetate and N-vinylpyrrolidone in the presence of a suitable catalyst such, for example, as azobisisobutyronitrile and hydrolyzing oif the acetate radicals.
  • a suitable catalyst such, for example, as azobisisobutyronitrile and hydrolyzing oif the acetate radicals.
  • the molar ratio of N-vinyl-pyrrolidone to vinyl alcohol in the polymer is preferably less than 1 to l and more preferably about 1 to 3.
  • the novel image-receiving elements within the scope of this invention are particularly useful in color diffusion transfer processes employing dye developers, and their superiority is especially marked when monoazo, disazo and anthraquinone dye developers are used.
  • a photosensitive element including a silver halide emulsion layer is exposed to create therein a latent image.
  • the latent image is developed in the presence of a dye developer and an imagewise distribution of unreacted dye developer, from which the positive image may be created, is formed. At least a portion of said unreacted dye developer is trans ferred to a superposed image-receiving element to create thereon a positive image.
  • the processes are preferably carried out by disposing the dye developer in the photosensitive element prior to exposure and causing it to be solubilized therefrom by an aqueous alkaline processing liquid which is applied between the superposed photosensitive element and image-receiving element.
  • an aqueous alkaline processing liquid which is applied between the superposed photosensitive element and image-receiving element.
  • the exposed silver halide is reduced to metallic silver and the portions of dye developer which are oxidized as a result of the silver development are substantially immobilized in situ of the silver image.
  • At least a portion of the unreacted dye developer is imbibed on the superposed image-receiving element to create thereon the positive dye image.
  • Example 1 3 gms. of PVA 91-65 and 1 gm. of PVP NP K-30 are added to 90 cc. of water and the resulting composition is heated and stirred until solubilization is complete. The resulting solution is made up to 100 cc. by the addition of 1% hydrochloric acid and then 0.3 gm. of dimethylolurea is added and heating and stirring are continued until the dimethylolurea is completely dissolved. A small amount of a wetting agent is added and the solution, while warm, is coated on a cellulose acetate-coated baryta paper.
  • a photosensitive element for use with the above imagereceiving element is prepared by coating a gelatin-coated cellulose acetate film base with a solution containing 3% of 2-[p-(2,5dihydroxyphenethyl)-phenylazo]-4 methoxy-l-naphthol (prepared as disclosed in the aforementioned US. application Serial No. 612,045) in a 4% solution of cellulose acetate hydrogen phthalate in an 80 to mixture, by volume, of acetone and methanol. After 4 this coating has dried, a silver iodobromide emulsion is applied.
  • aqueous processing composition comprising:
  • the image-receiving element is separated and contains a magenta positive image of the subject.
  • Example 2 A photosensitive element similar to that described in Example 1 is prepared. Processing of the exposed photosensitive element in a manner similar to that employed in Example 1 using as the image-receiving element a layer of polyvinyl alcohol (cast from a 4% aqueous polyvinyl alcohol solution) on a cellulose acetate-coated baryta paper support gives a magenta positive image.
  • Example 3 Use of a photosensitive element prepared and processed similar to that described in Example 1 using as the imagereceiving element a sheet of cellulose acetate-coated baryta coated with a 4% solution of Nylon Type F8 in ethanol gives a magenta image.
  • a comparison of the positive images obtained in the above examples shows the image on the poly-N-vinylpyrrolidone-polyvinyl alcohol image-receiving element to have superior over-all quality as compared with either nylon or polyvinyl alcohol. Thus, it is more brilliant than the image on polyvinyl alcohol and almost as brilliant as the image on nylon.
  • the image on the polyvinyl alcohol poly-N-vinylpyrrolidone element was more stable than the image on the nylon element and almost as stable as the image on the polyvinyl alcohol element.
  • the following nonlimiting example illustrates the preparation of a vinyl alcohol-N-vinylpyrrolidone copolymer for use in preparing the novel image-receiving elements of this invention.
  • Example 4 20 gms. (0.23 mol) of vinyl acetate and 5 gms. (.045 mol) of N-vinylpyrrolidone are dissolved in 20 ml. of benzene and are polymerized in the presence of 0.1 gm. of azobisisobutyronitrile for eighteen hours at 66 C. in the absence of air. The reaction medium is diluted with benzene and the resulting polymer is precipitated in hexane and dried. Upon hydrolysis in ethanol and sodium methoxide, a copolymer containing about 25 mol percent N-vinylpyrrolidone and about mol percent vinyl alcohol is produced.
  • mentoin may be made of dye mordants, oxidizing agents, and acids and alkalies for pH adjustments.
  • image-receiving elements herein set forth are also suitable for use in multicolor transfer processes such as those set forth in the previously mentioned U.S. Patent No. 2,647,049.
  • said dyeable material is a mixture of polyvinyl alcohol and poly-N- vinylpyrrolidone and the ratio of poly-N-vinylpyrrolidone to polyvinyl alcohol in said mixture is less than 1 to 1 by weight.
  • said dyeable material is a mixture of polyvinyl alcohol and poly-N- vinylpyrrolidone and the ratio of poly-N-vinylpyrrolidone to polyvinyl alcohol in said mixture is about 1 to 3 by weight.
  • said dyeable material is a copolymer of vinyl alcohol and N-vinylpyrrolidone and the ratio of N-vinylpyrrolidone segments to vinyl alcohol segments in said copolymer is less than 1 to 1 on a molar basis.
  • said dyeable material is a copolymer of vinyl alcohol and N-vinylpyrrolidone and the ratio of N-vinylpyrrolidone segments to vinyl alcohol segments in said copolymer is about 1 to 3 on a molar basis.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Coloring (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
US700281A 1957-12-03 1957-12-03 Photographic products and processes Expired - Lifetime US3003872A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE573503D BE573503A (en(2012)) 1957-12-03
US700281A US3003872A (en) 1957-12-03 1957-12-03 Photographic products and processes
GB36228/58A GB893657A (en) 1957-12-03 1958-11-11 Improvements in or relating to image-receiving elements
FR780655A FR1217185A (fr) 1957-12-03 1958-12-01 Produits et procédés photographiques
DEI15697A DE1130284B (de) 1957-12-03 1958-12-01 Unter Verwendung eines besonderen Bildempfangsmaterials durchfuehrbare Farbdiffusionsuebertragungsverfahren

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US700281A US3003872A (en) 1957-12-03 1957-12-03 Photographic products and processes

Publications (1)

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US3003872A true US3003872A (en) 1961-10-10

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US700281A Expired - Lifetime US3003872A (en) 1957-12-03 1957-12-03 Photographic products and processes

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US (1) US3003872A (en(2012))
BE (1) BE573503A (en(2012))
DE (1) DE1130284B (en(2012))
FR (1) FR1217185A (en(2012))
GB (1) GB893657A (en(2012))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183090A (en) * 1962-07-11 1965-05-11 Polaroid Corp Photographic products, processes, and compositions employing azo dye developers
US3345165A (en) * 1963-07-31 1967-10-03 Polaroid Corp Photographic product and process of using same
US4038082A (en) * 1973-08-30 1977-07-26 Fuji Photo Film Co., Ltd. Image-receiving material for color diffusion transfer comprising pva and polymethylol compounds

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB687751A (en) * 1950-01-13 1953-02-18 Bayer Ag Process and material for the direct production of positive photographic images
US2719831A (en) * 1951-01-20 1955-10-04 Basf Ag Production of pigmented prints and coatings on fibrous material
US2774668A (en) * 1953-05-28 1956-12-18 Polaroid Corp Process and product for forming color images from complete dyes
DE1003577B (de) * 1955-02-11 1957-02-28 Agfa Ag Verfahren zur Herstellung seitenrichtiger positiver Bilder durch Waermeentwicklung
DE1004043B (de) * 1955-02-07 1957-03-07 Agfa Ag Verfahren zur Herstellung seitenrichtiger, positiver Bilder durch Waermeentwicklung
US2802735A (en) * 1946-10-08 1957-08-13 Polaroid Corp Photographic transfer process utilizing the reducing action of a developer for producing a colored photographic transfer image
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US2853417A (en) * 1955-09-19 1958-09-23 Gen Aniline & Film Corp Method of controlling plant pests with an iodine adduct of a copolymer of nu-vinyl pyrrolidone and a polymerizable vinyl compound containing one aliphatic double bond

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2802735A (en) * 1946-10-08 1957-08-13 Polaroid Corp Photographic transfer process utilizing the reducing action of a developer for producing a colored photographic transfer image
GB687751A (en) * 1950-01-13 1953-02-18 Bayer Ag Process and material for the direct production of positive photographic images
US2719831A (en) * 1951-01-20 1955-10-04 Basf Ag Production of pigmented prints and coatings on fibrous material
US2774668A (en) * 1953-05-28 1956-12-18 Polaroid Corp Process and product for forming color images from complete dyes
DE1004043B (de) * 1955-02-07 1957-03-07 Agfa Ag Verfahren zur Herstellung seitenrichtiger, positiver Bilder durch Waermeentwicklung
DE1003577B (de) * 1955-02-11 1957-02-28 Agfa Ag Verfahren zur Herstellung seitenrichtiger positiver Bilder durch Waermeentwicklung
US2834676A (en) * 1955-07-19 1958-05-13 Sperry Rand Corp Photographic diffusion transfer process for producing multiple direct positive copies
US2853417A (en) * 1955-09-19 1958-09-23 Gen Aniline & Film Corp Method of controlling plant pests with an iodine adduct of a copolymer of nu-vinyl pyrrolidone and a polymerizable vinyl compound containing one aliphatic double bond

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183090A (en) * 1962-07-11 1965-05-11 Polaroid Corp Photographic products, processes, and compositions employing azo dye developers
US3345165A (en) * 1963-07-31 1967-10-03 Polaroid Corp Photographic product and process of using same
US4038082A (en) * 1973-08-30 1977-07-26 Fuji Photo Film Co., Ltd. Image-receiving material for color diffusion transfer comprising pva and polymethylol compounds

Also Published As

Publication number Publication date
GB893657A (en) 1962-04-11
BE573503A (en(2012))
DE1130284B (de) 1962-05-24
FR1217185A (fr) 1960-05-02

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