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

Definitions

• Color diffusion transfer processes generally involve the use of a photographic element comprising a support, at least one silver halide emulsion, and an image dye-providing material which is contained in or contiguous said layer. After exposure, such a photographic element is treated with an alkaline processing solution to effect imagewise discrimination in the element.
• the dye-providing material can be initially immobile or initially mobile in the processing solution.
• a mobile dye or dye precursor can be released imagewise or the material can be imagewise rendered mobile. If the material is initially mobile, the processing solution typically renders the material insoluble (and thus immobile) in an imagewise fashion.
• the dye-providing material upon treatment with a processing solution the dye-providing material typically is oxidized under alkaline conditions, thereby producing imagewise discrimination in the element.
• Exemplary color diffusion transfer processes are those using developing agents as disclosed in US. Pat. Nos. 2,698,798 and 2,559,643 wherein a latent silver halide image is developed with a color-developing agent.
• the color-developing agent reduces the exposed silver halide to metallic silver and the color-developing agent which is oxidized as a function of development forms an immobile species while the unoxidized color-developing agent is free to migrate to a receiving element.
• the color-developing agent in the receiver is oxidized.
• the oxidized developing agent then self-couples or couples with a color coupler to form a positive dye image.
• Useful materials of that type are oxichromic compounds which contain a developing moiety and an oxichromic moiety and have the general formula D(OC), wherein D- is a group which is a silver halide developer such as a hydroquinone moiety and (C) is a moiety which undergoes chromogenic oxidation to form an image dye.
• D- is a group which is a silver halide developer such as a hydroquinone moiety
• C is a moiety which undergoes chromogenic oxidation to form an image dye.
• These oxichromic compounds are particularly useful in an image-transfer unit format in which the respective initially diffusible oxichromic compounds or the initially nondiffusible compounds are used in combination with the appropriate silver halide emulsions.
• oxichromic compounds In order to achieve optimum results when using such oxichromic compounds, it is desirable to have an oxidant which has no substantial absorption in the visible spectrum (i.e., colorless) and which can be easily incorporated in a photographic element with good stability.
• the oxidative conversion of oxichromic compounds or of other color-providing materials is neces- LII sary in order to achieve color image formation. Accordingly, there is a continuing need in the artfor materials which exhibit suitableoxidation capability.
• the photographic elements of this'invention comprise a support and at least one layer thereon containing an iodoso compound or an iodoxy compound of the formula RQ wherein Q is an'iodoso group which contains an iodine atom and an oxygen atom or Q is an iodoxy group including iodoxy derivatives, i.e., such as iodoxy diacetates, and R is a carbocyclic or heterocyclic group containing from 5-7 carbon atoms in the cyclic moiety and wherein the iodine atom of Q is covalently bonded to a carbon atom in said cyclic group.
• Q is an'iodoso group which contains an iodine atom and an oxygen atom
• Q is an iodoxy group including iodoxy derivatives, i.e., such as iodoxy diacetates
• R is a carbocyclic or heterocyclic group containing from
• R comprises an aromatic group covalently bonded through a carbon atom to the iodine atom in Q.
• iodoso and iodoxy compounds can be incorporated in photographic elements as oxidants with reduced danger of explosion whichvis associated with closely related compounds such as periodates, and with better control of where oxidation occurs during processing.”
• the photographic elements of this invention contain iodoso compounds of the formula:
• X is a carboxylic acid group, a sulfonic acid group and the like, and Z represents a group containing the atoms necessary to form a 5- to 7-membered ring with the remainder of said atoms of said formula.
• the photographic elements of this invention contain iodoxy compounds having the formula:
• 0 represents an iodoxy group which can be the group --lO or is preferably an iodoxy derivative, for example, an iodoxy diacetate such as an iodoxy ethyl diacetate, an iodoxy propyl diacetate, an iodoxy methyl diacetate, an iodoxy maleate and the like, and Z represents a group containingthe atoms necessary to form a 5- to 7-membered carbocyclic or heterocyclic ring with the carbon atom as shown in the formula.
• the iodoso compound or iodoxy compound contain a group thereon which is sufficiently large to render the compound substantially nondiffusible in the photographic element.
• ballast groups which are useful are aliphatic groups containingat least 8 carbon atoms.
• the iodoso compounds and iodoxy compounds which give particularly good results in the practice of this invention can be characterized in terms of their polarographic halfwave potentials, i.e., their oxidation or reduction potentials as determined by polarography.
• Cathodic measurements of the reduction potential can be made with a solution of the iodoso compound or iodoxy compound, typically in a basic solvent such as potassium hydroxide, using a dropping mercury electrode with the polarographic halfwave potential for the most positive wave being designated E.
• the reference electrode is a standard calomel electrode.
• Electrochemical measurements of this type are known in the art and are described in New Instrumental Methods in Electrochemistry, by Delahay, Interscience Publishers, New York, New York, 1954; Polarography, by Kolthoff and Lingane, 2nd Ed., Interscience Publishers, New York, New York, 1952; Analytical Chemistry, 36, 2426 (1964) by Elving; and Analytical Chemistry, 30, 1576 (1958) by Adams. Plus and minus signs are according to IUPAC (International Union of Pure and Applied Chemistry), Sweden Convention, I953.
• Useful compounds should have a polarographic reduction potential which is more positive than the polarographic oxidation potential of the ingredients to be oxidized. In general, useful compounds include those having a polarographic reduction potential more positive than about 0.5 v.
• Typical iodoso compounds or iodoxy compounds for use in oxichromic processes are those having a reduction potential, E between about 0.1 and --0.5 v.
• Typical useful iodoso compounds are as follows:
• the iodoso and iodoxy compounds can generally be prepared by methods known in the art.
• the iodoxyarylene diester compounds can be prepared by taking the respective iodoxyarylene dichlorides prepared according to Organic Synthesis, Vol. 22, John Wiley and Sons, 1942, pp. 69-72, and reacting them with the appropriate acid to yield the diester as described in J. Chem. Society, 1970, pp. 862-864.
• the iodoxy compounds containing the iodine atom in a heterocyclic ring can also be prepared as described in the latter publication.
• oxidants described herein can be used in a wide variety of photographic elements or in photographic film units.
• the oxidants can be used in photographic elements or film units to provide an oxidant for the synthesis of image dyes.
• the oxidants can be used to generate oxidized color-developing agent which then reacts with a color coupler to form the image dye.
• these compounds can be used to oxidize a compound directly to an image dye as in the case of leuco indoanilines, leuco indophenols, leuco triarylmethanes and other dye precursors.
• the present oxidants are useful in color diffusion transfer processes such as those in which unreacted color formers in undeveloped or partially developed areas of a photographic element diffuse imagewise, after color development of the exposed layers, to a receiving layer in which the color formers react with oxidized color developer to produce an imagewise distribution of dye.
• a useful oxidant in the receiving layer or having it in association therewith, dyes are formed imagewise in that element as a result of the interreaction of the oxidant, color developer and diffused color former. Processes of this type are described further in British Pat. No. 926,462 dated May 15, 1963, incorporated herein by reference.
• the oxidants can be used to oxidize the developer portion of a dye developer (i.e., a compound which contains a silver halide developing moiety and a separate moiety which contains the chromophore of an image dye).
• a dye developer i.e., a compound which contains a silver halide developing moiety and a separate moiety which contains the chromophore of an image dye.
• the oxidants selected must have an oxidation potential sufficient to oxidize the developer portion of the molecule, such as the hydroquinone portion.
• the oxidant can function to immobilize the dye developer, such as when it diffuses to the receiver layer, by forming the quinone, quinonimide, etc., of the developer moiety which is generally quite insoluble m an alkaline processing solution.
• a photographic element containing an oxidant can be treated to form an imagewise distribution of the oxidant.
• the photographic element can then be contacted with a material which will undergo oxidation to produce an image record in the photographic element.
• the photographic element containing the imagewise distribution of oxidant can be treated to effect diffusion of the oxidant to an adjacent layer wherein it can oxidize materials to produce an image record.
• a photographic element containing a silver halide emulsion and an adjacent layer containing a nondiffusible iodoso or iodoxy oxidant can be developed with a silver halide developer. Where silver halide is not developed, the oxidant will be reduced.
• the element can then be contacted with a solution of color coupler and color developer to react with the remaining imagewise distri bution of the described oxidant and produce an image dye.
• oxidants of this invention are particularly wellsuited for use as oxidants in photographic elements or film units which contain an oxichromic compound of the type described in copending Lestina and Bush, U.S. Ser. No. 308,869, mentioned above and incorporated herein by reference.
• Preferred oxichromic compounds are those which undergo chromogenic oxidation to form a photographic image dye.
• the oxidants of this invention are incorporated into photographic elements containing oxichromic compounds of the formula:
• (COUP) is a photographic color coupler linked to the nitrogen atom through a carbon atom at the coupling position, such as a phenolic coupler, a pyrazolone coupler, a pyrazolotriazole coupler, couplers having open-chain ketomethylene groups and the like;
• Ar is an arylene group containing from 6 to carbon atoms, including substituted and unsubstituted arylenegroups, fused-ring arylene groups and the like;
• X can be an amino group, including substituted amines, an hydroxyl group or the group:
• R is a group containing from 1 to 12 carbon atoms, which can be an alkyl group, an aryl group, including a substituted alkyl group, a substituted aryl group and the like; R is a hydrogen atom or the group:
• the resultant compound preferably is initially mobile.
• Q is an oxidizable releasing group
• the resultant compound preferably is initially immobile.
• the oxidants of this invention can be used in photographic elements where leuco compounds are employed which provide anthraquinone dyes upon oxidation.
• the leuco compounds can be of the type mentioned in U.S. Pat. No. 2,892,710 issued June 30, 1959, or they can also be improved compounds such as leuco anthraquinone compounds attached to hydroquinone moieties, for example, the compound:
• the present oxidants are used in either the processing fluid or the image-receiving layer of a diffusion transfer film unit employing other image dye-providing materials mentioned above.
• the image-transfer film units can be any of those described in the following patents, all incorporated herein by reference: U.S. Pat. Nos. 2,543,181, 2,983,606, 3,227,550, 3,227,552, 3,415,644, 3,415,645, 3,415,646 and 3,635,707,Canadian Patent No. 674,082, and Belgian Patent Nos. 757,959 and 757,960, both issued Apr. 23, 1971.
• the iodoso compounds or iodoxy compounds are typically present in solution in a concentration of about 0.01 to about 0.1 molar.
• the present oxidants are coated in at least one layer which typically contains a binder such as gelatin, poly(vinyl alcohol), etc.
• the oxidants described herein can also be one of several ingredients as a given layer.
• the described oxidant can be contained in a mordant layer.
• the iodoso compounds or iodoxy compounds are coated at a coverage of about 40 to 500 mg./ft.
• the iodoso compounds and iodoxy compounds are used in image-transfer film units which are designed to be processed with a single processing solution, and the resulting positive image is viewed through a transparent support against an opaque background, preferably where all of the silver halide recording layers and the image-receiving layer remain laminated between two dimensionally stable supports after processing.
• a suitable image-transfer film unit in which the present oxidants are useful typically comprises:
• a photosensitive element comprising a support having thereon at least one layer containing'a silver halide emulsion having associated therewith an image dye-providing material and preferably at least three of said layers wherein one layer contains a blue-sensitive silver halide emulsiomone layer contains a green-sensitive silver halide emulsion, and one layer contains a red-sensitive silver halide emulsion;
• an image-receiving layer which can be located on a separate support superposed or adapted to be superposed on said photosensitive element or, preferably, which can be positioned in the photosensitive element on the same support adjacent the photosensitive silver halide emulsion layers;
• the support is preferably a transparent support
• an opaque layer is preferably positioned between the imagereceiving layer and the photosensitive silver halide layer
• the alkaline processing composition preferably contains an opacifying substance such as carbon of pH-indicator dye which is discharged into the film unit between a dimensionally stable support or cover sheet and the photosensitive element.
• the cover sheet can be superposed or adapted to be superposed on the photosensitive element.
• the im age-receiving layer can be coated on the cover sheet.
• a neutralizing layer is located on the cover sheet.
• the means for containing the alkaline processing solution can be any means known in the art for this purpose, including rupturable containers positioned at the point of desired discharge of its contents into the film unit and adapted to be passed between a pair of juxtaposed rollers to effect discharge of the contents into the film unit, frangible containers positioned over or within the photosensitive element, hypodermic syringes, and the like.
• the silver halide emulsions useful in my invention are well-known to those skilled in the art and are described in Product Licensing Index, Vol. 92, December, 1971, publication 9232, p. 107, par. 1, Emulsion types; they may be chemically and spectrally sensitized as described on p. 107, par. III, Chemical sensitization, and pp. 108-109, par. XV, Spectral sensitization", of the above article; they can, be protected against the production of fog and can be stabilized against loss of sensitivity during keeping by employing the materials described on p. 107, par.
• V Antifoggants and stabilizers, of the above article; they can contain development modifiers, hardeners and coating aids as described on pp. 107-108, par. IV, Development modifiers, par. V11, I-Iardeners", and par. XII, Coating aids", of the above article; they and other layers in the photographic elements used in this invention can contain plasticizers, vehicles and filter dyes'described on p. 108, par. XI, Plasticizers and lubricants, and par. VIII, Vehicles and p. 109, par. XVI, Absorbing and filter dyes", of the above article; they and other layers in the photographic elements used in this invention may contain addenda which are incorporated by using the procedures described on p.
• the image-receiving layer can contain basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as describedin Minsk, U.S. Pat. No. 2,882,156 issued Apr. 14, 1959, and basic polymeric mordants such as described in Cohen et al, U.S. Pat. No. 3,709,690 issued Jan. 9, 1973.
• basic polymeric mordants such as polymers of amino guanidine derivatives of vinyl methyl ketone such as describedin Minsk, U.S. Pat. No. 2,882,156 issued Apr. 14, 1959, and basic polymeric mordants such as described in Cohen et al, U.S. Pat. No. 3,709,690 issued Jan. 9, 1973.
• Additional mordants include cationic mordants such as polymeric compounds composed of a polymer having quaternary nitrogen groups and at least two aromatic nuclei for each quaternary nitrogen in the polymer cation (i.e., having at least two aromatic nuclei for each positively charged nitrogen atom), such polymeric compounds being substantially free from carboxy groups.
• cationic mordants such as polymeric compounds composed of a polymer having quaternary nitrogen groups and at least two aromatic nuclei for each quaternary nitrogen in the polymer cation (i.e., having at least two aromatic nuclei for each positively charged nitrogen atom), such polymeric compounds being substantially free from carboxy groups.
• Useful mordants of this type are comprised of units of the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
• each of R and R represents a hydrogen atom or a lower alkyl radical (of 1 to about 6 carbon atoms), and R can additionally be a group containing at least one aromatic nucleus (e.g., phenyl, naphthyl, tolyl;
• Q can be a divalent alkylene radical (of l to about 6 carbon atoms), a divalent arylene radical, a divalent aralkylene radical, a divalent alkarylene radical,
• R is an alkylene radical; or R can be taken together with Q to form a group; R R and R can be lower alkyl or aryl, or R and R andthe nitrogen atom to which they are attached can together with 0 represent the atoms and bonds necessary to form a quaternized nitrogen-con- Spra gue'et a1, U.S. Pat. No. 2,484,430 issued Oct. 11,
• image dye-providing material as used herein is understood to refer to those compounds which either (1) do not require a chemical reaction to form the image dye or (2) undergo reactions encoun- 10 transparent film base support having a layer of 125 mg./ft. gelatin and 50 mg./ft. of oxichromic compound dissolved in 75 mg./ft. of diethyl lauramide.
• a receiver element is prepared comprising a transparent tered in photographic imaging systems to produce an 5 film base support having on it a first layer of 200 image dye, such as with color couplers, oxichromic mg./ft. of the mordant copoly[styrene:N,N-dimethylcompounds and the like.
• the first class of compounds N-benzyl-N-3-maleiimidopropyl)ammonium chloride] is generally referred to as preformed image dyes and in 100 mg./ft. of gelatin and a second layer (over the includes shifted dyes, etc., while the second class of first layer)comprising 2000 mg./ft. oftitanium dioxide compounds is generally referred to as dye precursors. in 200 mg./ft. of gelatin.
• the two elements are then The terms initially mobile and initially immobile placed in face-to-fa'ce contact for 60 sec. with an alkaas used herein refer to compounds whichare incorpoline processing composition, comprising 20 g.
• the oxichromic compound migrates from the understanding of the present invention. In these exammatrix through the processing composition and the ples, all temperatures indicated are centigrade. All titanium dioxide layer. into the mordant layer of the oxidants referred to are found in Table 1 below. The receiver.
• the oxichromic compound is oxidized by the structural formulas for other compounds used are iodoso oxidant to the corresponding dye which is visifound in the footnotes to the examples. ble through the transparent support and against the white background of the titanium dioxide layer.
• the EXAMPLE 1 oxichromic compounds and the oxidants used, as well The oxidants listed in Table 1 below are tested as as the color and reflection density of the dye in the follows: A matrix element is prepared "comprising a receiver are shown in Table 1 below.
• a transparent cover sheet for the above element is prepared as follows:
• the photographic element is exposed through a multicolor, graduated-density test object, the transparent cover sheet is superposed on the element, and a pod containing an opaque processing composition is ruptured to discharge between the cover sheet and the photosensitive element by passing the film unit through juxtaposed rollers having a gap of about 8 mils.
• processing composition is as follows:
• hydroxyethyl cellulose 30 g./l.
• R Q or x wherein Q is an iodoxy diacetate, R is a group containing a 5- to 7-membered carbocyclic or heterocyclic group covalently bonded to the iodine atom of Q through a carbon atom of said cyclic group, X is a carboxylic acid group or a sulfonic acid group, and Z represents a group containing the atoms necessary to form a 5- to 7-membered ring with the remainder of the atoms of said formula.
• a photographic element according to claim 1 whereingaid oxidant has the formula: wherein Q is an iodoxy diacetate and R is a group containing a 5- to 7-membered carbocyclic or heterocyclic group covalently bonded to the iodine atom of Q through a carbon atom of said cyclic group.
• a photographic element according to claim 2 wherein said 5- to 7-membered group of R is an aromatic carbocyclic group or aromatic heterocyclic group.
• R is an aromatic carbocyclic group which contains a ballast moiety.
• a photographic element according to claim 1 wherein said oxidant has the formula:
• X is a carboxylic acid group or a sulfonic acid group and Z represents a group containing the atoms necessary to form a to 7-membered ring with the remainder of the atoms of,said formula.
• a photographic element comprising a support having thereon at least one layer containing a silver 7 -14 halide emulsion, at least one layer containing an image dye-providing material and at least one layer containing an oxidant according to the formulae:
• Q is an iodoxy diacetate
• R is a group containing a 5- to 7-membered carbocyclic or heterocyclic group covalently bonded to the iodine atom of Q through a carbon atom of said cyclic group
• X is a carboxylic acid group or a sulfonic acid group
• Z represents a group containing the atoms necessary to form a 5- to 7-membered ring with the remainder of the atoms of said formula.
• a photographic element according to claim 9 wherein said image dye-providing material is an imagedye.
• a photographic element according to claim 9 wherein said oxidant has the formula:
• Q is an iodoxy diacetate and R isa group containing a 5- to 7-membered carbocyclic or heterocyclic group covalently bonded to the iodine atom of Q through a carbon atom of said cyclic group.
• a photographic element according to claim 9 wherein said oxidant has the formula:
• X is a carboxylic acid group or a sulfonic acid group and Z represents a group containing the atoms necessary to form a 5- to 7 -membered ring with the remainder of the atoms of said formula.
• a photographic film unit comprising a support having thereon at least one layer containing a silver halide emulsion having associated therewith an image dye-providing material, a layer containing an imagedye mordant, means for discharging an alkaline processing solution within said film unit, and at least one layer containing an oxidant of the formula:
• a photographic film unit according to claim 14 wherein said image dye-providing material is an oxichromic developer having the formula:
• (COUP) is a photographic color coupler linked to the nitrogen atom through a carbon atom at the coupling position;
• Ar is an arylene group;
• X is selected from an amino group, an hydroxyl group or a group having the formula:
• R is an alkyl or aryl group
• R is a hydrogen atom or a group having the formula:
• R is as defined above; and Q is a silver halide developing agent or an oxidizable releasing group.
• a photographic film unit comprising:
• a photosensitive element comprising a support having thereon a layer containing a red-sensitive silver halide emulsion having associated therewith a cyan image dye-providing material, a layer containing' a green-sensitive silver halide emulsion having associated therewith a magenta image dyeproviding material, and a layer containing a bluesensitive silver halide emulsion having associated therewith a yellow image dye-providing material;
• said film unit containing an iodoxyarylene diester.
• a photographic element comprising a support and at least one layer containing a silver halide emulsion having associated therewith an image-dye precursor, the improvement comprising at least one layer containing an iodoso compound having the formula:
• X is a carboxylic acid group or a sulfonic acid group
• Z represents a group containing the atoms necessary to form a 5- to 7-membered ring with the remainder of the atoms of said formula.
• a photographic element comprising a support and at least one layer containing a silver halide emulsion having associated therewith an image-dye precursor, the improvement comprising at least one layer containing an oxidant compound of the formulae:
• Q is an iodoxy diacetate
• R is a group containing a 5- to 7-membered carbocyclic or heterocyclic group covalently bonded to the iodine atom of Q through a carbon atom of said cyclic group
• X is a carboxylic acid group or a sulfonic acid group
• Z represents a group containing the atoms necessary to form a 5- to 7-membered ring with the remainder of the atoms on said formula.
• a photographic element according to claim 21 whereinaid oxidant has the formula: and Q is an iodoxy diacetate and R is a group containing a 5- to-7-membered carbocyclic or heterocyclic group covalently bonded to the iodine atom of Q through a carbon atom of said cyclic group.
• a photographic element according to claim 21 wherein said image-dye precursor is an oxichromic UNITED STATES PATENT AND TRADEMARK OFFICE d CERTIFICATE OF CORRECTION PATENT NO. 3,928,0h3
• CCCHCNH CCCHCNH should read 5 NH NH that part of OXichromic Compound B set forth as:

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Priority Applications (4)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23650402

Family Applications (1)

Country Status (4)

Cited By (7)

Citations (10)

• 1973
  • 1973-11-16 US US416551A patent/US3928043A/en not_active Expired - Lifetime
• 1974
  • 1974-10-16 CA CA211,491A patent/CA1047820A/fr not_active Expired
  • 1974-11-14 FR FR7437514A patent/FR2251841B1/fr not_active Expired
  • 1974-11-15 GB GB49600/74A patent/GB1487083A/en not_active Expired

Patent Citations (10)

Also Published As

Similar Documents