US3435761A - Premordanted imbibition dye printing blank - Google Patents

Premordanted imbibition dye printing blank Download PDF

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US3435761A
US3435761A US549060A US3435761DA US3435761A US 3435761 A US3435761 A US 3435761A US 549060 A US549060 A US 549060A US 3435761D A US3435761D A US 3435761DA US 3435761 A US3435761 A US 3435761A
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blank
acid
dye
imbibition
colloid
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Expired - Lifetime
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US549060A
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English (en)
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Walter John Weyerts
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/25—Dye-imbibition processes; Materials therefor; Preparing or processing such materials
    • 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 photographic imbibition dye printing processes and materials. lIn one aspect, it relates to improved imbibition dye printing blanks.
  • the imbibition dye printing process is Well known. According to the common procedures, a tanned colloid relief image is ⁇ formed by exposure of a suitable sensitive layer on a support and differentially hardening the colloid layer, thereafter removing the colloid from the support in the regions not exposed by light. The resultant colloid relief image is then dyed and the dye image transferred to a blank by imbibition. In this manner subtractively colored Idye images may be obtained which faithfully reproduce a colored subject.
  • One object of this invention is to provide improved, novel blanks. Another object of this invention is to provide improved, novel imbibition blanks which are treated to prevent matrix poisoning. Still another object of this invention is to provide imbibiton blanks treated to substantially eliminate mordant diffusion. Another object of this invention is to provide novel imbibition blanks which do not stick or slip when pressed against a matrix film. A further object of this invention is to provide imbibition blanks which give good dye density and transfer definition, even after a number of transfers. Still another object of this invention is to provide -a process for preparing such improved imbibition blanks. Another object of this invention is to provide an improved relief imbibition printing process. Other objects of this invention will be apparent from the following disclosure and the appended claims.
  • FIG. 1 is illustrated the manner in which diffusible mordant molecules or particles migrate from an imbibition blank to a matrix film with the adverse effects mentioned.
  • FIG. 2 is shown a similar view of the improved colloid blank of the invention.
  • FIG. 3 is a view similar to FIG. 1 showing the manner in which the blank of FIG. 2 improves the quality of dye transfers and prevents clogging of the matrix and staining of the support.
  • dye imbibition blanks which include a support having a hydrophilic colloid layer thereon containing a basic mordant which tends to diffuse through the colloid, and an effective quantity of a Water soluble acid salt of an alkyl or aryl substituted polyalkoxy ether in the outer stratum of the hydrophilic colloid layer to inhibit or prevent diffusion of the mordant out of said layer. It has been found that the tendency of the mordant to diffuse to the surface, or out of the blank and into a colloid matrix, is effectively prevented with the novel blanks of the invention. At the same time, good dye transfer definition and density are obtained without problems of sticking or slipping.
  • an improvement is provided in the process -for manufacturing mordanted dye imbibition blanks having a hydrophilic colloid layer coated on a support, which features applying to the surface of the hydrophilic colloid layer an acid salt of an alkyl or aryl substituted polyalkoxy ether.
  • an improvement in a relief imbibition printing process that includes transfer of a soluble acid dyestulf from a colloid relief image to ⁇ a colloid blank containing a diffusible, basic mordant and fixing the dyestuff in the blank.
  • This improvement features treating the surface of the blank with an acid salt of an alkyl or aryl substit-uted polyalkoxy ether prior to reacting the dyestuff with the mordant.
  • a wide variety of compounds which are the acid salts of alkyl or aryl su-bstituted polyalkoxy ethers can be employed, such as the alkali metal and ammonium sulfate, sulfonate and carboxylic acid salts of alkyl substituted polyalkoxy ethers. Good results are obtained with such salts which have from l to 100, and preferably l to 5 alkoxy groups, each alkoxy group containing from 2 to 4 car-bon atoms.
  • An especially useful class of compounds are acid salts of polyalkoxyalkyl substituted aryl ethers. Preferred aryl groups are phenyl and naphthyl.
  • the most useful class of acid salts employed in the invention has the following general formula:
  • R represents hydrogen or a straight or branched chain alkyl substituent (including substituted alkyl and alkoxy) containing from 1 to 30, and preferably from 4 to 16 carbon atoms, such as butyl, butoxy, pentoxy, amyl, hexyl, heptyl, p-tertiary octyl, nonyl, decyl, decyloxy, dodecyl, pentadecyl and triacontanyl; n represents an integer of lfrom 1 lto 100, and preferably 1 to 5; B represents an aryl nucleus, such as phenyl or naphthyl; m represents a positive integer of from l to 2; and, X -represents an acid salt selected from the group consisting of the sulfate, sulfonate and carboxylic acid alkali metal, triethanolamine, and ammonium salts.
  • R represents hydrogen or a straight or branched chain alky
  • the following acid salts of substituted polyalkoxy ethers are useful in this invention: Stepanol B-129, nonylphenoxypolyethylene oxide sulfate, sodium salt; Stepanol B-153, ammonium alkylphenoxypolyoxyethylene sulfate; Steol 4N, ethoxylated fatty alcohol sulfate where the fatty alcohol base is lauryl alcohol and the cation is sodium; Steol 4T, same as 4N except cation is triethanolamine; Steol CS-460, same as 4N except fatty alcohol is stripped coconut; Steol CA-460, same as CS-460 except cation is ammonium salt; Triton 770, sodium salt of p-tert octylphenoxy (ethoxy)-3ethyl sulfate; Triton W-30, sodium salt of alkylarylpolyether sulfate; Triton X-202, sodium salt of alkylarylpolyether s
  • the preferred compounds are the soluble salts of p-tert.-octyl-phenoxyethyl sulfonate; nonyl phenoxypolyethoxide sulfate and lauryl-polyethoxy sulfate.
  • FIG. 1 shows an enlarged cross-sectional view of the elements concerned, the manner in which ditfusible, perhaps low molecular weight mordant particles, wander out of the colloid layer 11 of gelatin carried on paper support into the dyed relief image 12 and iilm support 13, when dye is being transferred to the colloid blank to be mordanted onto mordant particles 15.
  • this diffusion may clog the relief image, and adsorbed mordant on the support 13 or in a subbing layer thereon results in staining the highlight :region of the print.
  • the blank is conveniently prepared by mordanting the colloid layer with a suitable basic mordant.
  • the mordant is added to a suitable quantity of colloid, such as gelatin with hardener and coated on a support to yield a blank as shown in FIG. 2 wherein a support 10 of paper or film is shown carrying gelatin layer 11 in which basic mordant particles 14 and 15 are dispersed.
  • the blank is bathed for a short time in an aqueous solution of an acid salt of a polyalkoxyalkyl substituted arylether, adjusted to a pH of about 4.0 to 5.0 (e.g., with sodium hydroxide solution).
  • the acid salt may be coated over the colloid surface from such a solution which may in addition contain a vehicle such as gelatin.
  • This treatment of the blank appears to deposit the salt in high concentration as a coating or in an outer stratum of the blank substantially as shown in FIG. 2 according to which support 10 carries the colloid layer 11 containing diffusible and non-ditfusible particles 14 and 15 and a stratum of acid salt particles 16 and some particles 17 which may result from reaction between mordant and acid salt.
  • the acid salts employed in this invention are applied to mordanted blanks from any convenient solution, such as an aqueous solution. Best results are obtained with aqueous solutions adjusted to a pH of 4.0 to 5.0, and using concentrations of about 0.5 to about 1.5 percent acid salt.
  • This invention is applicable to dye imbibition blanks containing any basic mordant.
  • Typical useful basic mordants are described in Sprague et al., U.S. Patents 2,548,- 564, 2,484,430.
  • Especially useful basic mordants are described in Minsk U.S. Patent 2,882,156 issued Apr. 14, 1959.
  • the mordants described in the Minsk patent are derived from carbonyl-containing polymers and aminoguanidine, such as a vinyl polymer containing from about 30- 90% by weight of the recurring unit having the structure.
  • n 0 or 1
  • R represents a hydrogen atom or an alkyl group of from 1 to 4 carbon atoms
  • X represents the acid radical of an inorganic acid such as hydrochloric acid or an organic acid such as lactic acid, glycolic acid, alkanesulfoni acids containing from 1 to 4 carbon atoms such as methanesulfonic acid, n-butanesulfonic acid, etc.
  • a monobasic saturated aliphatic carboxylic acid containing from 2 to 4 carbon atoms such as acetic, propionic or butyric acids
  • the remaining to 10% of the resin molecule being unreacted vinyl oxocompound, for example, acrolein, ly-methyl acrolein or vinyl alkyl ketone or combinations of these with styrene or an alkyl methacrylate in the proportions of from about 10-15% by weight of the unreacted vinyl oxo-compound to from about -85% by weight of the styrene or alkyl methacrylate, where the starting copolymer contains these components in about a 1:1 molar ratio.
  • Mordanted blanks treated in accordance with this invention are useful for receiving acid dyes from hydrophilic colloid relief images according to prior art techniques.
  • Any suitable acid dye stuif may be transferred to the treated blanks of the invention, such as Anthracene Yellow GR (400% pure Schultz No. 177), Fast Red S. Conc. (Colour Index 176), Pontacyl Green SN Ex. (Colour Index 737), Acid blue black (Colour Index 246), Acid Magenta 0 (Colour Index 692), Naphthol Green B Conc. (Colour Index 5), Brilliant Paper Yellow Ex. Conc. (Colour Index 364), Tartrazine (Colour Index 640), Metanil Yellow Conc. (Colour Index 138), Pontacyl Carmine 6B Ex. Conc. (Colour Index 57), Pontacyl Scarlet R Conc. (Colour Index 487) and Pontacyl Rubine R Ex. Conc. (Colour Index 179).
  • Anthracene Yellow GR 400% pure Schultz No.
  • Gelatin and other hydrophilic colloids can be employed in the blanks of the invention, such as polyvinyl alcohol and any of the colloids (or dispersing agents) referred to in Beavers U.S. Patent 3,039,873 issued June 19, 1962, column 13.
  • Examples 1 and 2 demonstrate the superior results achieved when dye imbibition blanks containing diffusible basic mordants are treated with the acidic salts in accordance with the invention.
  • Example 1 A dye imbibition blank was prepared by soaking 454 g. of gelatin in 5360 cc. of distilled water until well swollen, and the mixture then heated to 40 C. to dissolve the gelatin. There Were then added some saponin solution as a coating aid, 65 cc. of 50% aqueous glycerine and 100 g. of a solution of the resinous mordant produced according to Example 1 of Minsk U.S. Patent 2,882,156 (issued Apr. 14, 1959), in dilute acetic acid. 'Ihe pH of the mixture was adjusted to approximately 4.2 and 27 cc. of 10% formaldehyde solution was added.
  • the resulting solution was coated onto a cellulose acetate film support at the rate of approximately 1.25 g. of gelatin (dry weight) per square foot.
  • the blank thus obtained was prewet for one minute in distilled water, and the excess Water was blown off by means of an air squeegee.
  • the blank was then dipped for approximately 3 seconds in a solution of 1.0 percent (active agent) Stepanol B-129 (believed to be a 50 percent solution of nonylphenoxypolyethylene oxide sulfonate, sodium salt, manufactured by Stepan Chemical Co.) plus 0.5 percent citric acid, with the pH of the solution adjusted to 4.2 with sodium hydroxide.
  • a series of six trensfers were made to these blanks using a gelatin relief matrix containing an acid yellow dye stuff (e.g., Anthracene Yellow GR, Schultz No. 177).
  • the yellow dye stain in the minimum density areas of the matrix after the six transfers was only 0.03, measured through an appropriate blue filter. There was no loss of dye transfer density and the definition was better than transfers made with a control.
  • the same imbibition blank was employed but the process was altered by omitting treatment with the aqueous acid salt solution.
  • the yellow dye stain in minimum density areas of the matrix of the control was 0.15 measured through the same blue filter.
  • Example 2 fers, the matrix showed a stain 0.18 in minimum density r areas.
  • Example 3 The procedure of Example 1 was followed except that after the blank was prewet with water, it was dipped for approximately 3 seconds in a 1 percent solution of sodium laurylpolyethoxy sulfate (Sipon ES, Alcolac Chemical Corp.) at a pH of 4.2. The matrix stain after Isix transfers was only 0.02.
  • Example 4 The procedure of Example 1 was followed except that after the blank was prewet with water, it was dipped for approximately 3 seconds in a 1 percent solution of sodium polyacrylate at a pH of 4.2. The matrix stain after six transfers was reduced to only 0.09 density. Higher concentrations of sodium polyacrylate were viscous and slippery and caused trouble in transfer operations, such as bad sticking between matrices and blanks.
  • Example 5 The procedure of Example 4 was followed except that the blank was dipped, after being prewet with water, in a 1 percent solution (pH 4.2) of low viscosity carboxymethyl cellulose. Matrix stain after six transfers of yellow dye was 0.04 density. However, the images obtained had a much lower transfer definition than those obtained in accordance with Example 1.
  • Example 6 The procedure of Example 5 was followed except that the blank was dipped, after being prewet with water, in a one percent solution of a sulfonated polystyrene (Lustrex 770). After six transfers, the matrix stain was 0.03, lbut there was an undesirablelowering of transfer density with each successive transfer.
  • a sulfonated polystyrene Lustrex 770
  • a dye imbibition blank comp-rising a support having coated thereon a hydrophilic colloid layer containing a basic mordant which tends to diffuse through said colloid, at least the outer stratum of said colloid layer containing an effective quantity of an acid salt of an alkyl or aryl ⁇ substituted polyalkoxy ether to prevent diffusion of said Imordant out of said colloid layer.
  • R represents an alkyl substituent containing from 4 to 16 carbon atoms
  • B represents an aryl nucleus
  • m represents an integer of from 1 to 2
  • n represents an integer of from 1 to 5
  • Iand, X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts.
  • R represents a substituent selected for the group consisting of hydrogen and an alkyl substituent containing from 1 to 30 carbon atoms
  • B represents an aryl nucleus
  • m represents an integer of from 1 to 2
  • n represents an integer of from 1 to 5
  • X represents an acid salt Selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts, provided that when mi represents 1, R represents an alkyl substituent.
  • R represents an alkyl substituent containing from 4 to 16 carbon atoms
  • n represents an integer of from 1 to 5
  • X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts
  • B represents an aryl nucleus
  • m represents an integer of from 1 to 2.
  • R represents a substituent selected from the group consisting of hydrogen and an alkyl substituent containing from 1 to 30 carbon atoms
  • B represents an aryl nucleus
  • m represents an integer of from l to 2
  • n represents an integer of from 1 to 5
  • X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts, provided that when m represents 1, R represents an alkyl substituent.
  • a dye imbibition blank comprising a support having coated thereon a hydrophilic colloid layer containing
  • R represents an alkyl substituent containing from 4 to 16 carbon atoms
  • B rep-resents an aryl nucleus
  • m represents an integer of from 1 to 2
  • n represents an integer of from 1 to 5
  • X represents an acid salt selected from the group consisting of the sulfate, sulfonate, and carboxylic acid alkali metal, triethanolamine and ammonium salts
  • said mordant is a vinyl polymer compound cnosisting of from -85% by weight of a recurring structural unit represented by the following general structure:
  • R1 represents an alkyl group containing from 1-4 carbon atoms and X1 represents the radical of an 'acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alkanesulfonic acid containing from 1-4 canbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from 50-15% by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from 1-4 carbon atoms and is the same alkyl radical as the said R1 radical.

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US549060A 1966-05-10 1966-05-10 Premordanted imbibition dye printing blank Expired - Lifetime US3435761A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288522A (en) * 1979-01-24 1981-09-08 Agfa-Gevaert N.V. Non-photosensitive receptor material suited for producing black-and-white silver images and dye images and a process for the production of such images therewith
EP0346072A3 (en) * 1988-06-08 1990-09-12 Eastman Kodak Company (A New Jersey Corporation) Improved inbibition dye printing blank
US5622808A (en) * 1995-06-20 1997-04-22 Eastman Kodak Company Receiver for dye imbibition printing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2548575A (en) * 1948-10-15 1951-04-10 Eastman Kodak Co Mordanted imbibition dye-printing blank
US2868077A (en) * 1954-07-19 1959-01-13 Polaroid Corp Film stock for dichroic dye images
US3271147A (en) * 1962-07-19 1966-09-06 Eastman Kodak Co Coacervate mordant dispersions for acid dyes
US3312549A (en) * 1962-12-12 1967-04-04 Eastman Kodak Co Receiving sheet for photographic dyes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2548575A (en) * 1948-10-15 1951-04-10 Eastman Kodak Co Mordanted imbibition dye-printing blank
US2868077A (en) * 1954-07-19 1959-01-13 Polaroid Corp Film stock for dichroic dye images
US3271147A (en) * 1962-07-19 1966-09-06 Eastman Kodak Co Coacervate mordant dispersions for acid dyes
US3312549A (en) * 1962-12-12 1967-04-04 Eastman Kodak Co Receiving sheet for photographic dyes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4288522A (en) * 1979-01-24 1981-09-08 Agfa-Gevaert N.V. Non-photosensitive receptor material suited for producing black-and-white silver images and dye images and a process for the production of such images therewith
EP0346072A3 (en) * 1988-06-08 1990-09-12 Eastman Kodak Company (A New Jersey Corporation) Improved inbibition dye printing blank
US5622808A (en) * 1995-06-20 1997-04-22 Eastman Kodak Company Receiver for dye imbibition printing

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GB1183607A (en) 1970-03-11
BE696535A (da) 1967-09-18

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