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
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
• • 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
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
• • 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
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
  • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
  • G03C8/14—Oxidation of the chromogenic substances
  • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment

Definitions

• This invention relates to photography and, more particularly, to novel photographic products and processes for preparing color images utilizing dye developers.
• Another object is to provide novel products and processes for improving the color separation of color transfer images.
• US. Patent No. 2,983,606 issued to Howard G. Rogers relates to diffusion transfer processes wherein dye developers are utilized to develop an exposed photosensitive element and to form a color transfer image on a superposed image-receiving layer.
• Dye developers are dyes which contain, in the same molecule, a silver halide developing function and a chromophoric system of a dye.
• a particularly useful class of dye developers are those con taining a hydroquinonyl developing function.
• an exposed photosensitive element containing at least one silver halide emulsion is wetted by a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the exposed photosensitive element may be superposed prior to, during, or after wetting, on a sheet-like image-receiving element containing a dyeable stratum for receiving a dye transfer image.
• the photosensitive element contains a layer of dye developer associated with each of one or more silver halide emulsions (depending upon whether monochromatic or multicolor images are contemplated) and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed relationship with the image receiving element.
• the processing composition may be confined in a rupturable container which is capable, upon rupturing, of spreading its contents in a substantially uniform layer between the superposed elements.
• the dye developer may also be present initially in the liquid processing composition.
• the processing composition permeates the emulsion to initiate development and as a function thereof, the dye developer is oxidized and rendered less mobile and less diffusible, at least in the processing composition which is alkaline.
• the dye developer is unreacted land diffusible, thus providing, as a function of the point-to-point degree of development of the silver halide emulsion, an imagewise distribution of unoxidized dye developer diffusible in the liquid processing composition. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to the superposed imagereceiving element to form thereon a positive dye image.
• a dye developer having a free amino group as a part of its developing function, e.g., an aminophenol or diaminobenzene developing function
• a dye or coupler capable of coupling with the oxidized developer to provide a less mobile reaction product may also be employed.
• the present invention relates to an alternate method of precluding transfer of oxidized dye developer, which provides cerain advantages over the use of onium compounds or onium compounds alone.
• unwanted transfer of the oxidation product of a dye developer containing a dihydroxyphenyl developing function formed as a function of development of an exposed photosensitive silver halide emulsion with the said dye developer, and/or reduction of the oxidation product and subsequent transfer thereof may be obviated by utilizing in conjunction therewith a compound capable of coupling with the oxidation product to form a more bulky molecule which is substantially less mobile and preferably is effectively insoluble and immobile in the processing composition.
• the dihydroxyphenyl developing functions to which this invention is directed are those containing at least one free or unsubstituted position ortho to one of the said hydroxy radicals, e.g., hydroquinonyl and substituted hydroquinonyl radicals containing at least one free position.
• These coupling compounds may be defined as compounds containing a methine H or methylene (CH group substituted by at least one activating group having no formal charge, preferably a strongly activating group such as a cyano or carbonyl group, and most preferably substituted by (bonded to) two activating groups.
• the third substituent bonded thereto may be an activating group, an insolubilizing group or a group which inhibits or minimizes color in the reaction product.
• These compounds may also be described as having an activated hydrogen atom on a carbon atom alpha to at least one activating group having no formal charge, preferably a strongly activating group, and most preferably alpha to two activating groups.
• the designated carbon atom may be part of an open chain structure or it may be a member of a ring system.
• the compound containing the same may be a monomer or a polymer and is preferably colorless or substantially colorless.
• the coupling reaction contemplated by the Present invention is also distinguishable chemically from the aforementioned known coupling with amine-containing developers. In the latter case coupling occurs on the nitrogen atom whereas in the present case, coupling is believed to occur on a ring carbon atom ortho to a quinone linkage formed as a function of oxidation of the dihydroxyphenyl developing moiety.
• photosensitive elements containing a single emulsion layer i.e., a monochrome photosensitive element
• a multilayer photosensitive element i.e., one employed in the preparation of multicolor images.
• a photosensitive element may for example contain a blue-sensitive emulsion and associated yellow dye developer; a green-sensitive emulsion and associated magenta dye developer; and a red-sensitive emulsion and associated cyan dye developer.
• the dye developers may be present in the respective associated emulsion layers or they may be present in a layer therebeneath.
• Suitable spacer layers may be provided, if desired, in which event the coupler may be incorporated into one or more spacer layers, or, as mentioned above, it may be incorporated in a single layer or overcoat over the outermost emulsion layer.
• a coupler compound may be associated with any or all of the emulsion layers, e.g., in a layer between the emulsion layer and dye developer-containing layer associated therewith. It will also be appreciated that the coupler may be used in conjunction with the onium compounds heretofore mentioned or other compounds for increasing dye density and/or color separation.
• the ability to employ the compounds of this invention in the photosensitive element affords a distinct advantage over the use of onium compounds for the same purpose, since it has been found that many onium compounds cannot be employed in the photosensitive emulsion in large amounts without causing desensitization of the emulsion and other such problems.
• Employing the compound in the photosensitive element, as distinguished from having it contained initially elsewhere, e.g., in the processing composition, makes it possible to obtain more eflicient usage thereof, since the coupler is in immediate proximity with the dye developer so as to react with and thus immobilize oxidized dye developer before it has had opportunity to migrate from the photosensitive element.
• the present invention provides a further significant practical advantage over the use of onium compounds.
• auxiliary or accelerating silver halide developing agents such as 4'-rnethylphenylhydroquinone.
• 4'-rnethylphenylhydroquinone 4'-rnethylphenylhydroquinone.
• the coupling compounds of this invention do not so react with auxiliary developers such as 4-methylphenylhydroquinone to form a colored reaction product which causes discoloration of the highlights, and in fact may provide whiter highlight areas than are obtainable with or without additives such as the onium compounds.
• the present invention also makes it possible to employ a wider range of dye developers since it is possible for the dye developers to contain solubilizing groups, for example on the dye moiety, and still be immobilized in terms of exposed areas by the coupling reaction.
• the reaction product formed by coupling may be of substantially the same color as the dihydroxyphenyl-containing compound or the reaction product may possess materially different spectral absorption characteristics.
• Example 1 was repeated employing similar materials 1 Instances negatlve 15 l h blue and processing conditions, except that the processing sensitive, green-sensltlve and redsensltive s lver iodobrocomposition also contained of ethylacetamido bide emulsion layers have positioned behind them, recyanoacetate (Formula spectively, a. yellow dye developer, a magenta dye developer and a cyan dye developer.
• a gelatin interlayer is EXAMPLE 6 Positioned between the Yellow y developed 631 and Example 1 was repeated employing similar materials the gee-Sensitive emulsion, and between the magenta y 15 and processng conditions, except that the processing comdevelopel' and the Tedfiehsitive emulsioh- Multilayfil' hegaposition also contained 1.33 g. of 3-phenyl-2,4-pentadione, tives of this type are disclosed, for example, in "FIG. 9 tautomel- (F l 6), of the aforementioned US. Patent No. 2,983,606.
• the dye developer layers are prepared by dissolving each dye EXAMPLE 7 developer in a water-imiscible solvent and dispersing the The dye transfer images obtained in Examples 1-6 resulting solution in gelatin.
• the particular yellow, rna were analyzed to determine color isolation, i.e., the genta and cyan dye developers employed were: l-phenylamount of unwanted dye transfer from areas correspond- 3 N-n-hexylcarbamyl-4-[p-(2,5'-dihydroxyphenethyl)- ing to exposed areas of the emulsion layer with which the phenylazo]-5-pyrazolone (yellow); 2-[p-(2',5-dihydroxydye was associated.
• the neutral, phenethyl) phenylazo] 4 isopropoxy-1-napth0l(ma-, the red, the green and the blue columns on the respective genta); and 1,4 bis [a methyl-,B-hydroquinonyl-ethyldye transfer images were read on a MacBeth densitomeamino]-5,S-dihydroxy-anthraquinone(cyan). ter.
• the integral densities of red, green and blue light was one containing a received were then transposed to dye densities by use of layer of a polymeric acid separated from the image-rean analytical computer.
• a p control and the processing composition containing the tablet was used to alternate light in one-stop increments 40 coupler were d t i d to form various densities in the neutral colmn from These lt are set forth in the following table, white to black and in the red, green and blue columns wherein C, M and Y represent cyan, magenta and from color to black.
• Example 2 Example 3
• Example 4 Example 5
• Example 6 o M Y o M Y 0 M Y C M Y c M Y Test (Example No.) .02 .10 .14 .03 .24 .20 .01 .16 .20 .01 .13 .23 0 .14 .21 Control (Example 1)
• Density improvement (Decrease in dye density units) None .18 .13 None .10 .01 None .18 .07 None .21 .04 None .20 .06 Percent improvement None 53 .48 None 32 4 None 53 39 None 62 15 None 59 29 negative was developed by spreading between the thus- EXAMPLE 8 pq negatlve.
• Example 1 transfer of oxldlzed magenta and yellow dye developer, EXAMPLE 2 thereby materially improving color separation and thus Example 1 was repeated employing Similar materials the fidelity of reproduction of the original subject matter. and processing conditions, except that the processing Although number of cyan dye t uhlts composition also contained 1.18 g. of 2,2-dicyanoethylgeneraliy lPcreased, by one or F umts, thls mmute benzene (Formula crease 1s visually nconsequential and the overall effect was a substantial improvement in color separation.
• EXAMPLE 3 It will be noted that in each of the above examples, a Example 1 was repeated employing similar materials Single coup e compound was added to the Processing d processing di i except h t th processing composition. It is within the scope of this invention to composition also contained 1.32 g. of benzyl cyanoacetic employ a mixture of two or more such compounds, and, acid (Formula 2). in fact, such a mixture has been found in some instances to provide a still greater improvement in color separa tion. For example, a processing solution containing a mixture of 0.41 g. of benzyl cyanoacetic acid (Formula 2), and 0.32 g.
• EXAMPLE 9 A multilayer photosensitive element similar to that employed in the foregoing examples was overcoated with a 2% solution of cellulose acetate hydrogen phthalate in acetone/methanol (20:80) at a rate of 15 ft./n1inute to provide a control negative.
• a similar photosensitive element was overcoated at the same speed with a solution prepared by dissolving 0.57 g. of ethyl-a-benzyl acetoacetate (Formula 45) in 14.5 cc. of a 2% solution of cellulose acetate hydrogen phthalate in acetone/methanol (20:80). The solution concentration was 3.8%. Each of these negatives was exposed and processed in the manner described in Example 1.
• the present invention is also useful in black-andwhite photographic products and processes, e.g., in those directed to the preparation of positive silver transfer images.
• staining of the highlight areas sometimes occurs due to the presence on the receiving layer of oxidized silver halide developing agent, e.g., 4- methylphenylhydroquinone, or a reaction product thereof.
• oxidized silver halide developing agent e.g., 4- methylphenylhydroquinone
• a process as defined in claim 2 wherein said strongly activating group is selected from the group conslsting of cyano and carbonyl radicals.
• reaction product possesses substantially the same spectral absorption characteristics as said dye developer.
• a photographic process comprising the steps of exposing a photosensitive element containing a plurality of light-sensitive silver halide emulsions, each of said emulsions having associated therewith a dye developer, each of said dye developers containing a dihydroxyphenyl silver halide developing function, whereby to form a developa'ble image; developing said exposed photosensitive element by contacting it with an aqueous processing composition, oxidizing said dye developer as a function of development to form an imagewise distribution of OX1- dized dye developer in developed areas of each of said associated emulsions while forming in undeveloped areas of each of said emulsions an imagewise distribution of said associated dye developer in unoxidized and dilfusible form, and transferring, by diffusion, at least a portion of each said imagewise distribution of unoxidized dye developer' to a superposed image-receiving layer to form a dye transfer image thereon; the step which comprises contacting at least one of said imagewise distributions of x1- d
• a photographic product comprising a support containing on the same side thereof a dye developer, said dye developer being a dye containing a dihydroxyphenyl silver halide developing radical having a free position ortho to at least one of said hydroxy substituents; a light-sensitive silver halide emulsion; and a compound containing a member of the group consisting of methine and methylene radicals substituted by at least one activating group having no formal charge.
• a photographic product comprising a support having thereon a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a bluesensitive silver halide emulsion layer, each of said emulsion layers having associated therewith, respectively, a cyan dye developer, a magenta dye developer, and a yellow dye developer, each of said dye developers being disposed in an alkali-permeable layer behind its associated emulsion layer, each of said dye developers being a dye containing a dihydroxyphenyl silver halide developing radical having a free position ortho to at least one of said hydroxy substituents, said product further including at least one compound containing a member of the group consisting of methine and methylene radicals substituted by at least one activating group having no formal charge, said compound being capable of reacting with oxidized dihydroxyphenyl silver halide developing agent to form a reaction product which is substantially less mobile than said oxidized developing agent.
• a sheet-like element comprising a support having thereon an image-receiving layer including at least one compound containing a member of the group consisting of methine and methylene radicals substituted by at least one activating group having no formal charge.
• a photographic product comprising: (a) a photosensitive element comprising a support having thereon at least one silver halide emulsion, each of said silver halide emulsion having associated therewith a dye developer, each said dye developer being a dye containing a dihydroxyphenyl silver halide developing radical having a free position ortho to at least one of said hydroxy substituents; (b) an image-receiving element comprising a support carrying an image-receiving layer; and (c) a rupturable container releasably holding an aqueous alkaline processing composition, said photosensitive element and said image-receiving element being adapted to be placed in superposition with said rupturable container positioned therebetween, said rupturable container being adapted to release the processing composition confined therein upon rupturing of said container, in a substantially uniform layer between said superposed elements; one of said photosensitive element, image-receiving element and processing composition further including at least one compound containing a member of the group

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• 0
  • NL NL134143D patent/NL134143C/xx active
• 1965
  • 1965-05-12 US US455302A patent/US3502468A/en not_active Expired - Lifetime
• 1966
  • 1966-05-02 GB GB19241/66A patent/GB1145144A/en not_active Expired
  • 1966-05-10 NL NL6606375A patent/NL6606375A/xx unknown
  • 1966-05-12 SE SE06518/66A patent/SE339402B/xx unknown
  • 1966-05-12 CH CH688666A patent/CH505405A/de not_active IP Right Cessation
  • 1966-05-12 AT AT452066A patent/AT288861B/de not_active IP Right Cessation
  • 1966-05-12 BE BE680921D patent/BE680921A/xx not_active IP Right Cessation
  • 1966-05-12 DE DE19661547995 patent/DE1547995A1/de active Pending

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