US3567448A - Image-forming process utilizing a colored complex of titanium dioxide - Google Patents

Image-forming process utilizing a colored complex of titanium dioxide Download PDF

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Publication number
US3567448A
US3567448A US773355A US3567448DA US3567448A US 3567448 A US3567448 A US 3567448A US 773355 A US773355 A US 773355A US 3567448D A US3567448D A US 3567448DA US 3567448 A US3567448 A US 3567448A
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silver
titanium dioxide
image
photographic
colored
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US773355A
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Paul B Gilman
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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
    • G03C1/00—Photosensitive materials
    • G03C1/705—Compositions containing chalcogenides, metals or alloys thereof, as photosensitive substances, e.g. photodope systems
    • 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
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to photography and more particularly to the production of positive, colored dye images utilizing the silver-dye-bleach process.
  • the reductive dye bleaching is accomplished by one of two known processes, namely as a stoichiometric reaction in an acid solution, wherein the photographic silver functions as the reducing agent, or as a silver catalyzed reaction wherein the reducing agent is a highly alkaline substance such as sodium stannite (alkaline stannous chloride).
  • silver halide is the conventional photosensitive species.
  • spectral sensitizing dyes separate from and additional to the bleachable dyes are required to sensitize the photosensitive silver halide to record red, green and yellow light, since the bleachable dyes used to form the final colored dye image, although of a similar hue and having an adsorption spectra comparable to that of conventional sensitizers, have not functioned adequately as sensitizing dyes. It would be desirable to provide photosensitive species for dye-bleaching systems additional to silver halide.
  • the spectral sensitizing dyes now required in known dye-bleach elements could be advantageously replaced with bleachable dyes having an adsorption to the photosensitive species such that they operate as well to spectrally sensitize the photosensitive component to a selected spectral image.
  • Yet an additional object of the instant invention is to provide a new photographic process for producing positive, colored dye images by dye-bleach means.
  • the objects of this invention are accomplished with a dye-bleaching process for producing positive, colored photographic dye images on an imagewise exposed photographic element including a support having coated thereon at least one light-sensitive layer comprising a colored compleX of titanium dioxide and an unsaturated organic ligand compound having at least one nitrogen-containing linkage and a polydentate-chelating group comprising electrondonating atoms which are separated from each other on said organic ligand compound by 2 to 3 intervening atoms, which process includes:
  • Transition metals such as titanium form metal chelates. Titanium typically has a valence number of four, but possesses the capability of receiving two additional bonds from compounds bearing a chelating group or moiety, a functional grouping containing at least two atoms having unshared electrons and also intervening atoms that join the atoms having unshared electrons.
  • Compounds which possess one or more chelating groups and are amenable to the formation of such chelate complexes are conventionally designated ligands or ligand compounds. Chelating groups having two atoms with unshared electrons are termed bidentate, with three such atoms the designation is tridentate etc., and the like for other polydentate chelating groups.
  • the ligand compounds are designated in like fashion as bidentate, tridentate or other polydentate ligands.
  • the active component of a bidentate chelating group is a pair of electron-donating atoms that are conventionally those atoms, such as oxygen and nitrogen, which after being chemically bonded to another atom or atoms in a compound such as the ligands described herein, possess the capability of donating remaining unshared electrons to coordinate covalent bonds and thereby forming chelate rings with, for example, a titanium atom or ion.
  • the electron donating atoms can be part of the nucleus or backbone of a ligand compound such as the nitrogen atom of a quinoline nucleus, or they can be attached thereto as substitueuts.
  • each can be either the entire substituent as a keto group oxygen atom, or directly attached to the nucleus as part of a larger grouping like the oxygen atom of a hydroxyl radical or the nitrogen atom of an amino group or an azo linkage.
  • the electron-donating atoms can be attached to the nucleus or backbrone via an intervening atom, as in the case of an oxygen atom joined to a ligand nucleus through the carbon atom of a carbonyl group.
  • electron-donating atoms are, for optimum chelate ring stability, typically separated from each other on the ligand compound by either two or three intervening atoms. All of the interposed ligand atoms, including such atoms as the carbon atom of a carbonyl or carboxyl radical also containing an electron-donating oxygen atom, are deemed intervening atoms since they alfect the size and therefore the stability of the ultimate chelate ring.
  • the subject invention is concerned with the spectral sensitization of titanium dioxide to visible light radiation by complexing it with various unsaturated ligand compounds bearing chelating moieties to form visible-light-sensitive, colored complexes.
  • the mechanism whereby the colored complexes of this invention are formed is not completely understood, but it is speculated that titanium atoms at the outer surface of an octahedral titanium dioxide crystalline structure lack the coordinate saturation which is present for such atoms within the crystal, and the occurrence of coordinate unsaturation at the outer surface operates to render the titanium dioxide receptive to forming a new, complex photosensitive species with suitable ligands via the coordinate covalent bonding of chelate ring formation.
  • Titanium dioxide sensitive to blue-ultraviolet radiation
  • polydentate ligand compounds as are described herein to provide a colored photosensitive species which exhibits sensitivity to visible light radiation. It is unnecessary that a ligand exhibit color prior to complexing.
  • certain colorless or slightly colored ligand compounds such as catechols, tannic acid and other polyhydroxylic gallate esters produce strongly colored titanium dioxide complexes of a hue different from that of the ligand.
  • ligands useful in the present invention are limited only by their potential to form a colored complex with titanium dioxide.
  • the formation of such a complex renders titanium dioxide visible-light-sensitive to a degree which, at the spectra of maximum absorption, is substantially equivalent to the ultraviolet photoresponse of unsensitized titanium dioxide.
  • the cyclic nucleus containing both the metal component and the electron-donating and intervening atoms of the ligands chelating group is for advantageous stability of fiveor six-membered ring.
  • a suitable ligand structure includes compounds wherein only two or three interposed atoms can separate the electron-donating atoms of the chelating groups noted herein.
  • advantageous bidentate and other polydentate ligands contain such electron-donating atoms as an oxygen atom and a nitrogen atom in a variety of structural relationships such as those mentioned hereinabove.
  • Particularly suitable ligands are aromatic vicinal polyols including aryl vicinal polyols, S-hydroxyquinolines,
  • the remaining portion of the ligand can be a typical chromophore or another conjugated or other potential chromophoric configuration which becomes colored in the ultimate visible light absorbing complex.
  • the chromophoric portion of the ligand compound have included therein at least one nitrogen containing linkage that is susceptible of reduction when treated with a reducing agent (such as those included in dyebleaching solutions) in the presence of a silver image according to conventional dye-bleach procedures.
  • a reducing agent such as those included in dyebleaching solutions
  • nitrogen-containing linkages are such configurations as a diazo radical (N N), a hydrazone-type linkage a bivalent amino linkage tioned herein, form visible-light-sensitive, colored complexes with both microcrystalline, vacuum-deposited titanium dioxide and particulate titanium dioxide such as colloidal titanium dioxide having, for example, rutile or anatase crystalline structure.
  • N N diazo radical
  • a hydrazone-type linkage a bivalent amino linkage tioned herein
  • the titanium dioxide and a ligand compound having a polydentate chelating moiety as described herein are complexed, generally by conventional means such as admixing with stirring or dipping, the two reagents are typically present with a molar excess of ligand compound since it is desirable to ensure that
  • the production of a composite, light-sensitive photographic element is accomplished either by coating the visible-light-sensitive, colored titanium dioxide complex on a support material or, subsequent to coating, by treating the titanium dioxide with a ligand compound to form the desired colored complex in situ on the support.
  • Support materials upon which to coat the photosensitive titanium dioxide are subject to wide variation and are limited only by the use to which the completed photograph will be applied. Additionally, where vacuum deposited titanium dioxide is utilized, the support material must necessarily be resistant to degradation by those temperatures incurred during the actual vacuum deposition. Glass is suitably employed as are metals such as aluminum, copper, zinc and tin.
  • Conventional photographic film bases such as cellulose acetate, cellulose nitrate, cellulose acetate butyrate, poly(ethylene terephthalate), poly-styrene and paper including polyethylenecoated paper and poly-propylene-coated paper are all susceptible of advantageous use.
  • Coating thickness can be typically varied between about .02 micron and about .5 micron, with thicknesses of between about .05 micron and about .4 micron preferred. At substantially less than .02 micron, there is in.-
  • the titanium dioxide is rendered visible-light-sensitive by forming the subject colored complexes.
  • Complexing is typically obtained by contacting the layer of vacuum-deposited titanium dioxide with an organic solvent or aqueous solution of one or more of the subject ligands. Alternatively, mixtures of solvents can be used.
  • the method of contacting can be immersion, spraying, dipping, swabbing or any other means whereby the ligand compound contacts the titanium dioxide for a period of time sufficient to promote the colored complexes of the present invention.
  • excess solution is permitted to drain off the coated support and the coating is dried to produce a composite, vacuum-deposited titanium dioxide photographic element which is spectrally sensitized to visible light.
  • binder material is largely dependent upon the use to which the completed photographic element will be applied.
  • the ultimate photographic image is a silver or other metallic image produced by conventional photographic techniques such as the physical development described herein
  • hydrophilic binders such as gelatin, polyvinyl alcohol and other water permeable polymers are particularly compatible with processing media which are typically aqueous solutions.
  • the amount of binder material which is coated with the titanium dioxide can be widely varied in accordance with conventional practice.
  • hydrophilic binder materials are employed in the production of conventional photoimages, from about .05 to about 1 part by Weight of polymeric binder per 1 part by weight of titanium dioxide is employed, but more extensive variations can be used if desired.
  • the subject elements and especially those incorporating crystalline titanium dioxide, such as the varieties of colloidal titanium dioxide, dispersed in a hydrophilic binder material, can be coated in layered fashion to provide a composite, multicolor photographic element having individual cyan, magenta and yellow hued layers sensitized by the subject complexes to record light of the red, green and blue portions of the spectrum respectively.
  • a full color, positive image is obtained, 'with the image colors being provided by the unbleached colored complexes that originally served to spectrally sensitize the titanium dioxide to record red, green and blue light.
  • a photographic element coated and produced as described hereinabove can be stored under lighted conditions. If it it so stored, then immediately prior to exposure it must be dark adapted.
  • Dark adaptation constitutes storing the titanium dioxide coated support under dark conditions for a time sufiicient to raise the resistivity of the titanium dioxide to a point where the ratio of dark resistivity to light resistivity is sufficiently great to permit the development of a suitable dense photographic image.
  • the length of this period of dark conditioning depends in part upon the intensity with which the element has been previously exposed and the intensity with which it will receive its intended imagewise exposure. Typically, however, dark adaptation of from about 10 to about 24 hours will insure adequate photographic response.
  • storing the photographic element under conditions of elevated temperature may enhance photosensitivity.
  • a latent image in such of the present photographic elements is preferably a twostep physical development sequence.
  • the image- Wise exposed element is treated with a solution typically containing silver ions.
  • a solution typically containing silver ions.
  • a solution can be, for example, an aqueous solution of a silver salt such as silver nitrate, silver perchlorate, silver p-toluene sulfonate, etc., and treatment therewith produces microscopic deposits or development centers of metallic silver in the exposed areas.
  • the treating technique can be by immersion, swabbing, spraying or any other means whereby suflicient solution contacts the exposed element.
  • the imagewise exposed photographic element is treated with a physical developer solution containing heavy metal ions in salt form and a reducing agent for the metal ions, and when the metal ion salt is substantially insoluble in water, a solvent for the metal ion salt, such as water-soluble thiosulfates, thiocyanates, etc., to produce a visible photographic image corresponding to the exposed areas having development centers.
  • a physical developer solution containing heavy metal ions in salt form and a reducing agent for the metal ions
  • a solvent for the metal ion salt such as water-soluble thiosulfates, thiocyanates, etc.
  • Typical reducing agents used in the physical developer include, for example, polyhydroxy-substituted aryl compounds such as hydroquinones, catechols and pyrogallols; ascorbic acid derivatives; aminophenols; p-phenylenediamines, and the like developing agents used in the photographic art.
  • reducing agents for physical developer solutions are 2-methyl-3-chlorohydroquinone, bromohydroquinone, catechol, S-phenylcatechol, pyrogallol monomethyl ether (1 methoxy 2,3 dihydroxybenzene) and S-methylpyrogallol monomethyl ether, isoascorbic acid, N-methylp-aminophenol, dimethyl-pphenylene diamine, 4-amino N,N-di(n-propyl) aniline and 6-amino-l-ethyl-l,2,3,4- tetrahydroquinoline.
  • the completely developed element carries a visible image, typically metallic silver, corresponding to the exposed areas. As such, it is a negative reproduction of the original pattern, and when a negative serves as the original pattern, positive copies are obtained.
  • a conventional dyebleaching solution to render the colored complexes colorless in exposed areas, thereby preparing a positive, colored photographic image.
  • Bleaching is effected by contacting the photographic element with an acidic or an alkaline bleaching solution for a period of time SLllTlClllt to effect the chemical reduction of the colored complexes to colorless forms.
  • Typical alkaline bleaching solutions are reducing agents such as alkali metal hydroxides which have been activated by the addition of a metal salt, stannous salts for example.
  • a preferred alkaline bleaching agent is sodium stannite, a combination of sodium hydroxide and stannous chloride.
  • Acidic bleaching solutions wherein the developed silver image functions as the reducing agent, conventionally include an acid, a silver ion complex former such as thiourea, mercaptans and benzimidazoles and bleach catalysts like phenazines, oxazines and sulfonated anthraquinones.
  • a generally used acidic bleaching solution includes acidic thiourea and has the formulation: concentrated HCl, 100 ml; thiourea, 125 g.; 2-hydroxy-3-aminophenazine, .15 g.; and water to make 1 liter.
  • any residual silver can be removed by treatment with a ferricyanide bleach or other silver bleaching agent and a conventional fixing agent such as sodium thiosulfate.
  • a ferricyanide bleach or other silver bleaching agent and a conventional fixing agent such as sodium thiosulfate.
  • the separate bleaching of residual silver and fixing of undeveloped silver halide can often be avoided.
  • the action of the thiourea and phenazine bleach catalyst operates to remove both silver halide and residual silver by converting them to soluble complexes.
  • the resultant photographic image is a high quality mono or multicolored image which is a positive reproduction of the original.
  • Such image if present on an opaque support, can be viewed in conventional fashion via refiected light. If the support is a transparent material, cellulose acetate or poly(ethylene terephthalate) for example, the final dye image is amenable to viewing via transmitted light such as by projection.
  • EXAMPLE 1 Colloidal titanium dioxide g. is dispersed in 100 SOaNa and known in the trade as Alizarin Veridine, Colour on o l Index 1084, to form a chelate complex between the dye and the titanium dioxide. To this dispersed complex is also added 8 ml. of a 10% by Weight aqueous gelatin solution, 1.0 ml. of a 7.5% aqueous saponin solution and 0.25 ml. of 10% aqueous formaldehyde. The complete mixture is then coated at a .004 in. Wet thickness on baryta-coatcd paper support to prepare a composite photographic element with spectral sensitivity out to 760 nm.
  • the resultant photographic element is then exposed for 5 seconds through a line transparency to the light of a 500 watt tungsten photoflood lamp held at a distance of one foot from the exposing plane, after which it is immersed for 5 seconds in a 1% aqueous silver nitrate solution and rinsed with water for an additional 5 seconds, thereby producing minute silver nuclei in exposed areas of the element.
  • a positive, single-color cyan image is then produced by immersing the partially processed element for one minute in a dye-bleaching solution having the composition:
  • the above bleaching solution removes the silver image and converts the cyan-colored complex to a colorless form. Previously unexposed areas containing no silver image are unaffected, thereby producing a positive, cyan-colored image of the original line transparency.
  • EXAMPLE 2 A piece of poly(ethylene terephthalate) support is coated with a m thick layer microcrystalline titanium dioxide produced by the vacuum deposition of titanium metal at 10- torr. The titanium dioxide is rendered suitably photoactive by dark adaptation for 18 hours. The photographic element so produced is then treated with the dye solution of Example 1 and dried. Exposure and processing are as in Example 1, and a similar high quality cyan-colored positive image is obtained.
  • EXAMPLE 3 l H H i HO N02 9 which results in a coating having a spectral sensitivity range out to 490 nm. Exposure, development and bleaching are as in Example 1, and subsequent to the processing sequence and drying, a colored, positive photographic image of the line transparency remains on the support.
  • a dye-bleaching process for producing positive, col ored photographic dye images on an imagewise exposed photographic element comprising a support having coated thereon at least one light-sensitive layer comprising a light-sensitive colored complex of titanium dioxide and an unsaturated organic ligand compound having at least one nitrogen-containing linkage and a polydentate chelating group comprising electron-donating atoms which are separated from each other on said organic ligand compound by 23 intervening atoms, which process comprises:
  • a dye-bleaching process as described in claim 1 wherein physically developing a silver metal image on the imagewise exposed areas of said photographic element comprises sequentially treating said element with:
  • said physical developer solution has a formula consisting of equal portions of Parts A and B, wherein:
  • Part A consists essentially of- Water-800 cc. Sodium sulfite--20 g. Sodium isoascorbate26 g. Sodium carbonate (monohydrate)50 g. Octyl phenoxy ethoxy ethyl dimethyl-p-chlorobenzyl ammonium chloride (1% in H O)20 cc.
  • a dye-bleaching process for producing positive, colored photographic dye images on an imagewise exposed photographic element comprising support having coated thereon at least one light-sensitive layer comprising a light-sensitive colored complex of titanium dioxide and an unsaturated organic ligand compound having at least one nitrogen-containing linkage selected from the group consisting of an azo linkage, a hydrazo linkage, and a bivalent amino linkage and a polydentate chelating group comprising electron-donating atoms which are separated from each other on said organic ligand compound by 2-3 intervening atoms, which process comprises:
  • Part B consists essentially of- Water-800 cc.
  • said photographic dye-bleaching solution consists essentially of:
  • a dye-bleaching process as described in claim 7 wherein physically developing a silver metal on the imagewise exposed areas of said photographic element comprises sequentially treating said element with:

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  • General Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Chemical & Material Sciences (AREA)
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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US773355A 1968-11-04 1968-11-04 Image-forming process utilizing a colored complex of titanium dioxide Expired - Lifetime US3567448A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1550683B1 (en) * 2002-10-03 2017-04-26 Toray Industries, Inc. Polyester resin compositions, polyester film, and magnetic recording medium

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1550683B1 (en) * 2002-10-03 2017-04-26 Toray Industries, Inc. Polyester resin compositions, polyester film, and magnetic recording medium

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GB1266394A (enExample) 1972-03-08
FR2022538A1 (enExample) 1970-07-31
BE741200A (enExample) 1970-04-16
DE1955231B2 (de) 1974-01-31
DE1955231C3 (de) 1974-08-29
DE1955231A1 (de) 1970-05-14

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