US3234025A - Prevention of dye-diffusion in photographic image bearing colloid layers - Google Patents

Prevention of dye-diffusion in photographic image bearing colloid layers Download PDF

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Publication number
US3234025A
US3234025A US46879A US4687960A US3234025A US 3234025 A US3234025 A US 3234025A US 46879 A US46879 A US 46879A US 4687960 A US4687960 A US 4687960A US 3234025 A US3234025 A US 3234025A
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United States
Prior art keywords
dye
urea
matrix
diffusion
mordants
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Expired - Lifetime
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US46879A
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English (en)
Inventor
Albert Emiel Van Hoof
Hart Rene Maurice
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/25Dye-imbibition processes; Materials therefor; Preparing or processing such materials
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/142Dye mordant

Definitions

  • the present invention relates to the prevention of diffusion of dyes in colloid layers, in particular to a new process for the preparation of mordants for acid dyes and for their application, especially for the manufacture of colour images according to the hytdrotype process particularly on an improved cinematographic blank film on which colour images are printed according to the hydrotype process.
  • a film support bearing a relief image obtained in a photographic way is used as starting material.
  • Said relief image consists of a colloid, in most cases gelatin.
  • the whole is referred to as a matrix or matrix film.
  • This matrix is immersed in a dye-solution and brought into close contact with another film which is referred to as a blank or blank film.
  • the dye of the image relief of the matrix diffuses to the hydrophilic colloid layer on the blank film on which a monochrome image is formed. In the same way a second monochrome print is obtained, etc.
  • This dye-transfer process can thus be repeated to such an extent that many. monochrome prints can be made with one single matrix. Also multicolour images can be obtained by immersing a second matrix in another appropriate dye-solution and by transferring the dye to a blank on which already a monochrome image has previously been printed. This process can be continued with other matrices and dyes as described in Colour Cinematogra phy, A. Cornwell-Clyve, 3rd ed., 1951, pages 451-474.
  • R represents an alkyl or aralkyl radical
  • the staining, also called matrix poisoning, of the matrix by these mordants has to be mentioned.
  • Said matrix poisoning is caused in case the used mordant is not sufficiently fast to diffusion. In consequence thereof some of these mordants pass from the blank upon the matrix when both the films are in close contact with each other.
  • the matrix When the matrix is reimmersed into the dye solution, the latter will not only adhere on the image relief but also precipitate on those areas where the matrix has been poisoned by the mordant. Consequently, besides the desired colour image a more or less uniform colour-fog is formed on a following colour print. This harmful colour-fog formation will be repeated and evidently increased during the production of further prints.
  • other unspecified products of the blank may cause the staining of the matrix.
  • colour absorption is meant the maximum colour density obtainable in definite circumstances of time and temperature under which the dyeimmersed matrix is brought into close contact with the blank. Said conditions are required by the apparatus ensuring the contact between the matrix and the blank film.
  • reaction products of polyethylene imine and urea are formed by reacting, whilst heating, a mixture which consists of polyethylene imine and urea.
  • polyethylene imine is referred to as a polymer consisting of a series of linearly bound groups
  • polyethylene imine is composed of 307 of .CH CH NH units. 40% of 1 units.
  • the specific viscosity of polyethylene imine meas- I ured in a 1% aqueous solution amounts to 0.22.
  • ratio of the reacting amounts of polyethylene .imine and urea may. vary within defined limits.
  • the most suitable mordants however are obtained by condensing 0.1.to 5 7 mols urea with 1 mol polyethylene imine.
  • An advantage of the mordants according to the present invention resides in the possibility that the color absorption can be brought on a favorable level by modifying the composition of these mordants,
  • a further important advantage of the mordants according to the present invention is the absence .of matrix staining.
  • mordants Another advantage of these mordants is their applicability in colloidlayers at pH-values of about 6 to 7 without involving too high an increase of viscosity as in the case of the application of the mordant polymers previously described in the prior art.
  • the blank film on-which color images are printed according to the hydrotype method consists mainly of. one or more layers of a hydrophilic colloid such as gelatin,
  • the usual supports for the manufacture of the matrix film andthe blank film in most-cases are composed of cellulose'derivatives, especiallycellulose-esters, such as cellulose triacetate, cellulose acetobutyrate, cellulose propionate or even fully synthetic polymerization products or polycondensation products eg polyethylene glycol tere'phthalate, polycarbonates and polysulfonates.
  • cellulose-esters such as cellulose triacetate, cellulose acetobutyrate, cellulose propionate or even fully synthetic polymerization products or polycondensation products eg polyethylene glycol tere'phthalate, polycarbonates and polysulfonates.
  • filter layers layers containing a ,hydrophilic colloid such as gelatin which comprises a mordant according to the present invention and an acid dye.
  • filter layers are among others employed in an antistress layer or an inter-mediate layer e.g. in a multicolor film which iscomposed of diflerent emulsion layers,- or even in an antihalo layer.
  • the new process can. furthermore be applied in the preparation of pigmented layers suchas pigmented paper.
  • the polymers according to the present invention can also be used in the manufacture of photographic color material for rendering colorcouplers fast to .diifusion. Detailed particulars regarding these special applica' polyvinyl alcohol, etc.
  • One ofv said composing colloid layers may be a silver. halide obtained. After decanting, the product is dissolved in: 25 cm. of distilled water, andprecipitated again in anexcess of a mixture consisting of equal parts of acetone.
  • reaction product are obtained. Next 10 g. of this product are dissolved in 80 cm. of distilled water, neutralized with:
  • PREPARATION 4 500 cm. of-a 25% aqueous polyethyleneiminesolu-I tion and 25,0 cm?v of a aqueous ure-a'solution are mixed. This mixture isiboiled for 2 hrs. in an open ivessel whereby ammonia. isvliberated. The amount of evap-- orated water'is regulated by filling up with boiling water. After coolingthe reaction mixtureis purified in the same way as in preparation l by precipitationin acetone.
  • Example 1 Alayer-forming solution is made of the following com-.
  • the resulting solution isi coated onto a support of cellulose triacetate film provided with a subbing layer, solidified and dried; on the blank film thus obtained one or more color images can be printed according to the hydrotype process. .When these images are cinematographically projected they show an enlarged image of good definition.
  • Example 2 A silver halide emulsion layer. used for positive prints is applied to a support of cellulose triacetate film which is provided .witha subbing layer.- Ontothis emulsion layer,
  • PREPARATION 1 In a flask fitted with a stirrer and a condenser 19.8 g. of a 50% aqueous polyethylene-imine solution areadded to 72 cm. ofwater and 21.6 g. of urea. The mixture obtained is refluxed for 15 hrs. whereby ammonia. is liberated. After cooling, 100 crn. of acetone are added. to the reaction mixture for precipitating the product thus a layer of following composition is coatedzl Aftensolidifying and drying, a sound .track' can photographically be applied to thefilm-thus obtained. On the; same film, three gelatin image reliefs cansuccessively be printed, each;of these reliefs having previouslybeen ima mersed intan appropriateaacid; dyestutf solution, accord.-
  • Example 3 A solution A and a solution B respectively composed of:
  • Example 4 tributed therein a substantially neutralized water-soluble condensation product obtained by heating in an aqueous medium a water-soluble polyethylene imine having a specific viscosity of 0.22 measured in a 1% aqueous solution and urea with the liberation of ammonia, said imine and urea being present in amounts providing a molar ratio of about 0.15:1 of urea to said imine.
  • condensation product is attained by heating said aqueous medium containing said imine and urea at the boil for about 215 hours.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US46879A 1959-08-04 1960-08-02 Prevention of dye-diffusion in photographic image bearing colloid layers Expired - Lifetime US3234025A (en)

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BE581344 1959-08-04

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3345253A (en) * 1963-08-30 1967-10-03 Hoechst Ag Process of forming cellulosic webs containing urea-alkyleneimine condensation products
US3962527A (en) * 1973-03-09 1976-06-08 Eastman Kodak Company Novel polymers and photographic elements containing same
US4664708A (en) * 1985-11-12 1987-05-12 Xerox Corporation Waterfast ink jet compositions
US6232056B1 (en) 1998-12-21 2001-05-15 Eastman Kodak Company Imaging element with fuser layer to aid splicing
US6399741B1 (en) * 2000-03-13 2002-06-04 Cognis Corporation Color-stable polyalkyleneimine derivatives, fiberglass lubricants containing the same and processes for producing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB755478A (en) * 1953-08-14 1956-08-22 Ici Ltd Water-soluble organic nitrogen compounds
CA543893A (en) * 1957-07-23 H. Gray Russell Silver halide emulsion containing a polymeric polyamine as an acid dye mordant
GB782217A (en) * 1954-07-19 1957-09-04 Polaroid Corp Improvements relating to film stock for dichroic dye images
US2912296A (en) * 1953-08-17 1959-11-10 Bayer Ag Process for improving the fastness properties of dyeings with substantive dyestuffs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA543893A (en) * 1957-07-23 H. Gray Russell Silver halide emulsion containing a polymeric polyamine as an acid dye mordant
GB755478A (en) * 1953-08-14 1956-08-22 Ici Ltd Water-soluble organic nitrogen compounds
US2912296A (en) * 1953-08-17 1959-11-10 Bayer Ag Process for improving the fastness properties of dyeings with substantive dyestuffs
GB782217A (en) * 1954-07-19 1957-09-04 Polaroid Corp Improvements relating to film stock for dichroic dye images

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3345253A (en) * 1963-08-30 1967-10-03 Hoechst Ag Process of forming cellulosic webs containing urea-alkyleneimine condensation products
US3962527A (en) * 1973-03-09 1976-06-08 Eastman Kodak Company Novel polymers and photographic elements containing same
US4664708A (en) * 1985-11-12 1987-05-12 Xerox Corporation Waterfast ink jet compositions
US6232056B1 (en) 1998-12-21 2001-05-15 Eastman Kodak Company Imaging element with fuser layer to aid splicing
US6399741B1 (en) * 2000-03-13 2002-06-04 Cognis Corporation Color-stable polyalkyleneimine derivatives, fiberglass lubricants containing the same and processes for producing the same

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Publication number Publication date
BE581344A (pl)

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