US3146102A - Photographic multicolor diffusion transfer process using dye developers - Google Patents

Photographic multicolor diffusion transfer process using dye developers Download PDF

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US3146102A
US3146102A US50963A US5096360A US3146102A US 3146102 A US3146102 A US 3146102A US 50963 A US50963 A US 50963A US 5096360 A US5096360 A US 5096360A US 3146102 A US3146102 A US 3146102A
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dye
silver halide
dye developers
layer
layers
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Walter J Weyerts
Wilho M Salminen
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US50963A priority Critical patent/US3146102A/en
Priority to FR870939A priority patent/FR1313767A/fr
Priority to DEE21550A priority patent/DE1157484B/de
Priority to DEE21543A priority patent/DE1157479B/de
Priority to DEE21548A priority patent/DE1168768B/de
Priority to DE19611422851D priority patent/DE1422851B1/de
Priority to GB30324/61A priority patent/GB1003672A/en
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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
    • 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 the art of photography and more particularly to a multicolor diffusion transfer process in photography and materials adapted to use in the process.
  • a diffusion transfer color process has been described in a number of patents, including British Patent 804,971, published November 26, 1958, wherein photographic elements containing silver halide emulsion layers and layers containing diffusible dye developers (dyes having a silver halide developing function) are exposed to record the latent image in the silver halide and then treated with an alkaline processing composition which permeates the emulsion layers and layers containing the dye developers which then develop the latent images to silver images. At the same time oxidation products of the dye developers are formed in situ with the silver images and which are relatively nondiifusing in the colloid vehicle of the layers.
  • the non-diffusing character of the oxidized dye developers is apparently due at least in part to a decrease in solubility in the alkaline processing liquid, and may also be due to a hardening eifect of the oxidized developer upon the colloid vehicles of the layers which retards the diffusion of the oxidized dye developers.
  • the residual unoxidized dye developers remaining in the layers in imagewise distribution are transferred by difiusion to a superposed reception element substantially to the exclusion of the silver image and oxidized dye developer to provide a positive dye image.
  • the success of the process depends in part upon the extent to which the dye developers in the exposed (negative) regions of the emulsion layers have been rendered substantially non-diffusing in the development reaction.
  • a quantity of unoxidized dye developer remains in a fully exposed negative region corresponding to the highlights of the subject, it will be transferred to the reception layer along with the unreacted dye developer in the positive regions and appears as high minimum density on the resultant color print.
  • Typical dye developers such as 1,4-bis[fi-(2,5-dihydroxyphenyl)- ethyl amino] -anthraquinone are relatively weak silver halide developing agents even when used at the comparatively high pH of the order of 13 required in the process and do not so rapidly develop silver halide emulsion as to take full advantage of known sensitometric properties of the emulsions and to obtain dye images having a full scale of density and contrast expected with other developing agents.
  • color prints obtained in the processes may exhibit an undesirable high minimum density in the highlight regions, low color saturation, contrast and density and the color separation is poor.
  • auxiliary colorless silver halide developing agent such as 1-phenyl-3-pyrazolidone
  • the alkaline processing composition containing the auxiliary developing agents still does not cause the development to proceed so that the different dye developers of a multicolor system are each immobilized at the required rate, to the necessary extent and in the proper layer.
  • the development products of one emulsion tend to effect the development of the other emulsions
  • the diffusion of a dye developer from a lower layer can be aitected, i.e., be hindered, by a dye developer or other substance in an upper layer
  • the exhaustion of the processing solution by an outer layer may affect development of a lower layer and one layer may not develop to the extent of another layer, and particularly one dye developer may not be immobilized sufficiently to prevent it from transferring and causing color contamination of a dye image of another color.
  • a given dye developer may develop some grains of silver halide in the wrong emulsion layer with the result that an insufficient amount of that dye developer is available for transfer and the corresponding colors are unsaturated, thus a magenta dye developer may develop some grains of red sensitive silver halide and become immobilized thus decreasing the magenta available to produce red colors which then appear unsaturated.
  • the present invention embodies sensitive multilayer elements and procedures which tend to overcome or compensate for such interaction or interdependence of the various layers, dye developers and other ingredients of a multilayer system, with the result that multicolor reproductions are obtained having a quality higher than previously believed to be possible.
  • the multicolor transfer processes using dye developers are carried out in contiguity with certain substantially colorless onium compounds diifusible in alkaline solution through the organic colloid layers of the sensitive elements.
  • the onium compounds of the invention are heterocyclic quaternary am- Patented Aug. 25, 1964 monium compounds capable of forming methylene bases soluble in alkaline solution and which quaternary ammonium compounds are diffusible in alkaline solution through organic layers of the sensitive elements.
  • the compounds may be present in the alkaline processing composition, in the reception element or in the lightsensitive element containing the dye developers.
  • a preferred embodiment of the invention includes the use of pyridinium compounds which form diffusible methylene bases in alkaline solution, in combination with hydroquinone derivatives which are substantially colorless, substantially water-insoluble, and soluble and ditfusible in alkaline solution through the organic colloid layers of the sensitive element.
  • quaternary ammonium compounds and indeed onium compounds, in general, are effective in improving the color quality of the prints in some, but not necessarily the same, respects.
  • heterocyclic quaternary ammonium compounds of the invention which form the methylene bases in alkaline solution, are distinct in their behavior from other quaternary ammonium compounds which do not form methylene bases.
  • the quaternary ammonium compounds reduce color contamination of the dye developer prints
  • the heterocyclic quaternary ammonium compounds of the invention not only reduce color contamination, but also greatly reduce color dropoff and other undesirable characteristics of the process such as minimum density.
  • Color contamination usually appears in the prints as a degradation of one or more colors by one or more other colors and may be due to the failure of one or more dye developers to be immobilized sufficiently to prevent them from transferring from regions where they should have been immobilized.
  • Drop-off appears as a degradation in color quality of the prints apparently caused by one dye developer developing silver halide grains in the wrong emulsion layer, e.g.
  • magenta dye developer developing some red sensitive silver halide grains with the result that more magenta dye developer is immobilized than should be and the red colors are thus deficient in magenta.
  • the mentioned effects of the heterocyclic quaternary ammonium compounds forming the methylene bases, when used alone or in combination with the hydroquinone derivatives, is particularly evident when the organic colloid vehicle of the sensitive element containing the dye developers, is composed principally of gelatin.
  • Many of the common optical sensitizing dyes are quaternary ammonium salts but they are ordinarily not useful in place of the colorless quaternary ammonium compounds particularly because they are not sufficiently soluble and diffusible and they impart stain to the prints.
  • One object of the invention is to provide photographic elements comprising several superposed differentially sensitized silver halide emulsion layers having contiguous dye developers and preferably also the contiguous hydroquinone derivatives, and to provide means for processing the elements in contiguity with the heterocyclic quaternary compounds.
  • Sensitive elements, processing compositions and reception elements particularly adapted to the taking of pictures in a camera and the processing thereof in a camera will be provided.
  • the objects of the invention are accomplished in part by description hereinafter of representative sensitive elements comprising a plurality of silver halide emulsion layers differentially light-sensitive (sensitive to different regions of the spectrum), having contiguous dye developers which may be subtractively colored with respect to the sensitivity of the corresponding emulsion layer and preferably contiguous hydroquinone derivatives, and by processing the exposed element by wetting with alkaline processing solution in contact with the reception layer in contiguity with the quaternary ammonium compounds, to develop the exposed silver halide in the emulsion layers and thereby render the dye developers thereof non-diffusing in the regions of development, and allowing the dye developers in the undeveloped regions to transfer imagewise by diffusion and in register to the reception layer to yield a multicolor dye developer image thereon.
  • FIG. 1 of the drawings is shown in flow-sheet form a typical process embodying our invention according to which in Stage 1 the sensitive element comprises a support 10, layers 11, 12 and 13 containing subtractively colored alkali-soluble cyan, magenta and yellow dye developers, the light-sensitive halide emulsion layers 14, 15 and 16 sensitive to red, green and blue light respectively, the interlayers 17 and 18 separating the green-sensitive emulsion and its contiguous subtractively colored magenta dye developer layer from the other layers and the overcoating layer 19 containing a developing agent such as one of the hydroquinone compounds of the invention.
  • the sensitive element comprises a support 10, layers 11, 12 and 13 containing subtractively colored alkali-soluble cyan, magenta and yellow dye developers, the light-sensitive halide emulsion layers 14, 15 and 16 sensitive to red, green and blue light respectively, the interlayers 17 and 18 separating the green-sensitive emulsion and its contiguous subtractively colored magenta dye developer layer from the other layers and the overcoating layer 19
  • the reception element containing support 20 and reception layer 21 (which may contain the pyridinium salt) is positioned so as to receive dye images transferring by diffusion from the sensitive element, with a rupturable container of alkaline, pyridinium salt processing solution 22 therebetween.
  • the solution Upon rupture of the container 22 as by means of passing the assembly between rollers in a camera so as to distribute the contents uniformly across a predetermined area of the sensitive element, the solution penetrates layer 19 dissolving the substantially water-insoluble, alkali-soluble and diffusible hydroquinone derivative and transporting it to the under lying layers
  • the latent images in the silver halide of areas 23, 24 and 25 are developed to silver and the dye developers in the areas contiguous to areas 23, 24 and 25 each become immobilized and rendered non-diffusing.
  • the unreacted dye developers of layers 11, 12 and 13 diffuse imagewise in register to the reception layer 21 and form the dye images thereon.
  • FIG. 2 of the drawings is shown an element in which the dye developers are incorporated into the differentially sensitized emulsion layers 31, 32 and 33, and the hydroquinone derivative is present in the layer 34 outermost from the support.
  • FIG. 3 of the drawings is shown in schematic form, a light-impervious enclosure useful for processing an exposed roll of film containing silver halide emulsions and dye developers so as to wet the film with alkaline activator solution and bring it into contact with a mordanted reception sheet for transfer of several multicolor dye developer images to the sheet.
  • the quaternary compounds interact with the dye developers to form salts thereof and that the improvements particularly in density and highlights are at least due in part to the effect of such salt formation on the solubility and diffusibility of the dye developers.
  • the quaternary compounds actually temporarily delay the migration of the dye developers so that the initial diffusion rates of the dye developers are reduced, yet more of the dye developers transfer from less exposed areas to increase the density.
  • Onium compounds have'been used in the photographic art for quite some time.
  • U.S. Patent No. 2,648,604 discloses the use of non-surface-active quaternary ammonium compounds as development accelerators
  • U.S. Patents Nos. 2,271,623, 2,271,622 and 2,275,727 disclose the use of quaternary ammonium, quaternary phosphonium and tertiary sulfonium compounds as sensitizers for silver halide emulsions.
  • the mentioned results obtained by using the quaternary compounds in conjunction with the dye developers in the diffusion-transfer process of this invention are worthy of note.
  • the improvements in the present processes are not necessarily the result of improved surface activity due to the onium compounds because the onium compounds which usually bring about the greatest improvement in density would not be generally classified as surface active. It is believed that the increase in density is at least due in part to the ability of the onium compounds to increase the solubility of the dye developers.
  • onium compounds including ternary sulfonium, quaternary phosphonium and quaternary ammonium compounds, are in general effective in improving the color quality of the dye developer prints in some, but not necessarily the same, respects.
  • the present quaternary compounds which form the methylene bases are distinct in their activity from the other onium, and even other quaternary ammonium compounds.
  • the onium compounds all appear to at least reduce the mentioned color contamination whereas the present quaternary compounds not only reduce color contamination but also reduces drop-01f and have other beneficial effects. These differences are especially noticeable when auxiliary developing agents such as the colorless hydroquinone derivatives (below) are present.
  • the particularly efiicacious heterocyclic quaternary ammonium compounds which form the methylene bases diifusible in alkaline solution have the general formula 1 RI TZ OHCH)n OOH R' wherein D represents the non-metallic atoms necessary to complete the heterocyclic nucleus of the quaternary ammonium compound containing 1 or more of the reactive methyl groups -CH R' in one or more of the nuclear positions, the other nuclear positions being substituted or not, such as quaternary salts of the pyridine, quinoline, benzoquinoline, benzoxazole, benzoselenazole, thiazole, benzothiazole, naphthothiazole, benzimidazole, isoquinoline series, etc., n is 0 or 1, R is an alkyl group, an aryl or aralkyl group of the benzene series, or substituted alkyl, aryl or aralkyl groups of the benzene series, the alky
  • One or more of these compounds can be used alone or in combination with the other onium compounds which do not form the methylene bases and are advantageously employed in either the processing solution, the reception element, or both, and less desirably in the light-sensitive element per se, to improve the print quality by a mechanism not fully understood.
  • the hydroquinone derivatives are also present a co-action with the quaternary compound takes place such that a greatly improved effect is obtained distinguishable from the effect of either the hydroquinone derivative or the quaternary compound.
  • the dye prints obtained exhibit appreciably less color contamination and improved color saturation, density and contrast.
  • the quaternary compounds can be used in varying amounts depending upon the particular compound. When used in the alkaline processing fluid, useful results are obtained which form about 0.2 to 15% of the compound. In some cases about 0.2 to 3% is best. Similarly, the amount used in the sensitive element and receiving sheet will vary with the compound selected.
  • the quaternary ammonium compounds comprising a preferred embodiment of the invention are pyridinium salts which form the diffusible methylene bases and which have the above formula, the pyridinium nucleus being substituted with from 1 to 3 active methyl groups -CH R' present in at least one of the 2, 4 or 6 positions, e.g., a lower alkyl group such as methyl, ethyl, propyl or substituted lower alkyl groups such as hydroxyalkyl, e.g., hydroxyethyl, which alkyl groups act as methylene base precursors. Positions 3 and 5 may or may not be substituted with e.g. halogen, lower alkyl and haloalkyl groups such as chlorine, methyl, ethyl, propyl or chloroethyl groups.
  • Typical salts have the above formula as are follows: 1-benzyl-2-picolinium bromide CH i a eN pts i CH L g 3 (5411350? I ot-Picoline-fl-naphthoylmethylbromide CH Br- 1-,B-phenylcarbamoyloxyethyl-2-picolinium bromide i CH3 BI (i 2H4OCONHC/6H5 1-methyl-2-picolinium pts l-phenethyl-2,4,6-trimethylpyridinium bromide 1-phenethyl-4-n-propylpyridinium bromide 4-y-hydroxypropyl-l-phenethylpyridinium bromide and l-n-heptyl-Z-picolinium bromide
  • a number of pyridinium salts having the above general formula do not form methylene bases sufiiciently diffusible in alkaline solution to be of practical
  • a number of silver halide developing agents can be used in the process, as auxiliary developing agents, in
  • the processes of the invention are thus carried out with the silver halide emulsions and dye developers in contiguity with the quaternary ammonium compounds, and if desired also the hydroquinone derivatives.
  • the quaternary compounds may be present in either or both the alkaline processing fluid and the reception sheet, less desirably in the sensitive element, and the hydroquinone derivative preferably in any of the layers of sensitive element such as an overcoating layer, emulsion layer, dye developer layer, an interlayer or in the reception sheet.
  • hydroquinone derivatives and other developing agents may be present in the processing fluid; however, in the present invention use in the fluid is less desirable since the hydroquinone derivatives are unstable in such solutions and readily undergo oxidation accompanied by discoloration of the prints.
  • the hydroquinone derivatives are preferably incorporated into emulsion layers, overcoating, interlayers or other layers, as dispersions in the hydrophilic organic colloid vehicle of the layer.
  • the hydroquinone derivatives may be dissolved in alkaline solution and precipitated into aqueous gelatin solutions by raising the acidity of the solution. However, this is a less desirable procedure because of the instability of the compounds in alkaline solution.
  • the hydroquinone derivatives may be dissolved in a solvent, such as a lower alcohol, and precipitated into aqueous gelatin solutions for coating on the sensitive element. They may be added to gelatin solutions which are ball-milled to reduce the crystal size.
  • the hydroquinones are preferably dissolved in a low molecular weight water-insoluble organic crystalloidal solvent permeable to the alkaline processing solutions and having a boiling point above about 175 C.
  • a low molecular weight water-insoluble organic crystalloidal solvent permeable to the alkaline processing solutions and having a boiling point above about 175 C. such as dibutyl phthalate and added to an aqueous gelatin solution which is passed through a colloid mill until the desired degree of subdivision has been attained.
  • An auxiliary organic solvent can also be used such as one having a solubility in water greater than that of the crystalloidal solvent, of the order of at least about 2 parts per parts of water.
  • the auxiliary solvent may be one having a boiling point at least about 25 C.
  • the hydroquinone derivatives are quickly and uniformly dissolved by the alkaline processing composition and transported throughout the sensitive element to produce more uniform development than when the hydroquinone derivatives are incorporated into the element by other means.
  • the hydroquinone derivatives may be used in one or more layers of the sensitive element in quantities of the order of from about 10 to 100 mgs. or more per square foot. However, the quantity used depends in part upon the amount of silver halide, the layer in which it is contained, the amount of dye developer and the amount of pyridinium salt in the sensitive element or processing solution of reception element. In some instances it may be desirable to form a complex of the hydroquinone derivatives by reaction with sulfur dioxide in a well-known manner and to incorporate the complex in the overcoating layer, outer emulsion or other layer of the sensitive element. These hydroquinone-sulfur dioxide complexes tend to be more stable than the hydroquinone derivatives themselves.
  • the dye developers which are used in the emulsion layers or in layers adjacent to the emulsion layers are compounds which are both a silver halide developing agent and a dye. They are characterized by being relatively non-difiusible in the colloid layers at a neutral pH but diffusible in the layers in the presence of the alkaline processing solutions. For the most part the dye developers are insoluble in water per se, which property usually necessitates the use of organic solvents to incorporate the dye developers into the organic colloid layers of the sensitive elements. Otherwise, the solubility of the dye developers is not particularly important and so long as the dye developers are capable of being immobilized in the layers in the presence of the alkaline processing solution and they are transferrable to the reception element, they are useful in the process of the invention.
  • the dye developers are particularly characterized by containing both a chromophore moiety and at least one moiety such as a hydroquinonyl radical having a silver halide developing agent function and which radical imparts silver halide development activity to the dye developer molecule as a whole with the result that during development of a silver halide image, the dye developers are oxidized to less difiusible compounds in the region of exposure and development and the residual dye developers in the undeveloped regions are transported imagewise to mordanted reception layers to provide a dye image thereon.
  • the dye developers of course should not have a desensitizing action toward silver halide emulsions.
  • Representative dye developers of use in the sensitive elements of the invention have the general formula in which M is an aromatic or heterocyclic ring or ring system such as a benzene, naphthalene, tetralin, anthracene, anthraquinone, pyrazole, quinoline, etc., ring and may also be substituted, as by hydroxyl amino, keto, nitro, alkoxy, aryloxy, acyl, alkylamido, arylamido, alkyl, aryl, carboxamido, sulfonamido, carboxyl or sulfo groups.
  • D represents a silver halide developing agent moiety imparting the developing agent function to the dye developer such as a hydroquinolyl group which may be substituted with amino, alkylamino, alkyl, hydroxyl, alkoxyl or halogen groups.
  • Q the residue of a coupling component such as a phenol, naphthol, S-pyrazolone or open chain reaction methylene coupler containing the group COCH -CO, for example:
  • V 4 [p (2,5' dihydroxyphenethyl)-phenylazo]-5-benzamido-l-naphthol.
  • A represents an anthraquinone nucleus
  • D represents an organic radical having a developing function and containing an aryl nucleus such as benzene or naph thalene nuclei, substituted by at least two substituents selected from hydroxyl, amino and substituted amino groups so that the resulting compound is capable of developing exposed silver halide
  • Q represents a hydrogen atom or an alkyl group or, when the substituents on the aryl nucleus of D are hydroxyl groups, Q may also be an acyl group, which may be aliphatic, e.g., acetyl or aromatic, e.g.
  • Z is a bivalent organic radical containing at least one methylene (CH group, In is a positive integer less than 5 and each Y may be a hydrogen or halogen atom or an amino, alkyl, aryl, nitro, alkylamino, arylamino, aryloxy, alkoxy, hydroxyl, sulphonamido, carboxamido, carboxy, sulpho,
  • bivalent organic radical Z refers to organic radicals having the two free valences attached to different atoms.
  • alkylene radicals such as --CH CH --CH (3H3 CH2(I]H as well as bivalent radicals such as It is also intended that Z may be saturated, unsaturated, such as -CH CH:CHCH
  • Z is an alkylene group
  • a lower alkylene group e.g. an alkylene group, containing less than about six carbons, and preferably an ethylene (-CH CH group.
  • Alkylene groups containing more carbon atoms may be used, however, providing that the resulting dye developer is capable of being dissolved in the liquid processing composition described herein, and its oxidation product rendered immobile in the developed emulsion layer.
  • Acylation of amino-nitrogen atoms which are part of the chromophoric system has the effect of shifting the Visible absorption band of the compound toward higher frequencies (shorter wavelengths).
  • acylating one amino-nitrogen of the cyan, 1,4-bis-[fi-(2,5-dihydroxyphenyD-ethylamino]anthraquinone changes its color to a magenta
  • acylating both the amino-nitrogen atoms changes its color to an orange-yellow.
  • the acylation of hydroxyl groups of the above types of dye developers can be expected to shift the color of the dye developers.
  • the dye developers may undergo a change in structure and/or color during the development reaction, for example through hydrolysis, and the dye which is transferred may have a color different than that of the dye developer originally present in the sensitive element.
  • Cyanurated dye developers such as 2-hydroquinoneamino-4- (p-phenylazo) anilino-6-hydroXy-4-triazine (Canadian Patent No. 579,038).
  • Anthraquinone dye developers such as 1,4-bis-(2',5'- dihydroxyanilino -anthraquinone and 1,4-diamino-N-(fl- 2',5' dihydroxyphenyl-or-methyl-ethyl)-2,3-anthraquinone-dicarboximide.
  • Amino substituted anthraquinone dye developers such as prepared by reaction of 1-amino-4-(p-aminoanilino)- anthraquinone-Z-sodium sulfonate with chloroacetamido hydroquinone monobenzoate.
  • Dye developers obtained by reaction of 1-phenyl-3- amino-4-phenylazo-5-pyrazolone or 1,4-bis-(B-aminoethylamino)-anthraquinone with homogentisic acid lactone or acid chloride, or gentisic acid chloride e.g. 1-phenyl-3- (2,5 dihydroxyphenyl-acetamido)-4-phenylazo-5-pyrazolone (Blout et al. Canadian Patent 577,021, dated June 2, 1958).
  • Naphthamide dye developer such as 1-(2,5-dimethoxyphenylazo) 2 hydroxy N-(2,5'-dihydroxyphenyl)-3- naphthamide (French Patent 1,168,292, dated August 25, 1958).
  • Disazo dye developers such as 2-[p-(1-hydroXy-3,6- disulfo 8-amino-2-naphthylazo)-3,3-dimethoxybisphenyleneazoJ-hydroquinone and 2-(2,5-dimethoxy-4'-[p- (2",5" dihydroxyphenethyl)phenylazo]-phenylazo)-1,8- naphthalene dio1-3,6-disulfonic acid.
  • Arylazonaphthol dye developers e.g. 1-amino-4-phenylazo-Z-naphthol.
  • Anthrapyridone dye developers e.g. 1-acetyl-3-fi-(2,5'- dihydroxyphenyl) ethyl 6-p-(2',5'-dihydroxyphenyl)- ethylaminoanthrapyridone.
  • Thiohydroquinone dye developers e.g. 1 phenyl 3 methyl 4 [p-(2',5'-dihydroxyphenylthioethyl)-phenylazo]--pyrazolone (Belgium Patent 568,344).
  • Ortho coupled dye developers exhibiting limited sensitivity to changes of pH e.g. 2-(p-[2",5"-dihydroxyphenoxy]phenylazo)-4-methoxy-l-naphthol and l-phenyl-3- methyl 4-[p-hydroquinolylsulfonyl)-pheny1azo]-5-pyrazolone.
  • Oxalyl ester dye developers e.g. 1-phenyl-3-amino-4- [p (2,5' bis-ethoxalyloxyphenethyl)-phenylazo]-5- pyrazolone.
  • Leuco compounds may be used similarly e.g. l-phenyl- 3 methyl 4-(2'-methyl-4'-diethylamino)anilino-i-pyrazolone, which do not exert a filtering action on underlying emulsion layers and which are immobilized in the developed regions, diifuse imagewise from undeveloped areas to the reception layer and are oxidized to colored images therein.
  • the dye developers may be incorporated into the emulsion layers or into the layers thereunder by several methods.
  • the dye developers may be dissolved in organic solvents and precipitated into gelatin solution or the dye developers may be ball-milled in gelatin solutions to reduce their particle size.
  • particularly favorable results are obtained when the hydroquinone derivatives of the invention are present in one or more of the layers of the sensitive element and the dye developers have been incorporated into the gelatin layers under the emulsion layers (as shown in FIG. 1) by dissolving the dye developers in high boiling solvents such as ditetrahydrofurfuryl adipate or 2-(2-butoxyethoxy)ethyl acetate and milling the mixture in gelatin solution in a colloid mill.
  • high boiling solvents such as ditetrahydrofurfuryl adipate or 2-(2-butoxyethoxy)ethyl acetate
  • the dye developers are employed in the sensitive ele ments contiguous to the silver halide of the emulsion layers, that is, they may be present in one or more of the emulsion layers or preferably in a hydrophilic organic colloid layer immediately next to and particularly under the silver halide emulsion layer. Especially good results are obtained when the dye developers are positioned so as to be present in the layer immediately under the emulsion layer, the sensitivity of which is complementary to the color of the dye developer as shown in FIG. 1 of the drawings. It appears less desirable to locate the dye developer in a layer positioned above the corresponding layer of silver halide emulsion.
  • the contiguity of the dye developer with respect to the silver halide can take the form of a mixed packet system wherein the dye developer may be present in a matrix surrounding a particle or globule containing silver halide grains.
  • the order of arrangement of the diiferentially sensitized silver halide emulsion layers on the support can be different, e.g. reversed so as to have the blue-sensitive emulsion layer on the support and the red-sensitive emulsion layer outermost.
  • the sensitivities of the silver halide emulsions should be adjusted so as to prevent recording unwanted blue light images in the emulsions primarily sensitive to the red and green regions of the spectrum e.g. a silver bromide emulsion can be used for the blue sensitive emulsion and silver chloride emulsions for the other layers.
  • the hydrophilic organic colloid vehicle of the emulsion layers, overcoating layers, of the dye developer layers and of interlayers can be varied somewhat, for example, gelatin, gelatin derivatives such as dibasic acid esters of gelatin, polyvinyl alcohol and cellulose acetate hydrogen phthalate, or mixtures of these may be used.
  • gelatin gelatin derivatives such as dibasic acid esters of gelatin, polyvinyl alcohol and cellulose acetate hydrogen phthalate, or mixtures of these may be used.
  • gelatin gelatin derivatives such as dibasic acid esters of gelatin, polyvinyl alcohol and cellulose acetate hydrogen phthalate, or mixtures of these may be used.
  • gelatin gelatin derivatives such as dibasic acid esters of gelatin, polyvinyl alcohol and cellulose acetate hydrogen phthalate, or mixtures of these may be used.
  • gelatin interlayers are used as shown in FIG.
  • the processing solution used to initiate development of the exposed sensitive elements containing the dye developers and hydroquinone derivatives, and which may contain the quaternary ammonium salt, should be strongly alkaline to accelerate the development activity of the dye developer as much as possible.
  • Alkali metal hydroxides such as sodium hydroxide or alkaline salts such as sodium carbonate are advantageously used in the activator composition for this purpose.
  • quanternary ammonium hydroxides or volatile amines such as diethyl amine, which have the advantage of being volatilized from the prints and therefore leave no residue of alkali thereon which might tend to decom ose the dye images, may also be used.
  • the hydroquinone derivatives tend to be unstable in the strongly alkaline activator, they are preferably not incorporated in the processing solution although when the pyridinium salts are present, results are obtained which are satisfactory in other respects. The results most desired are obtained when the hydroquinone derivative is present in the layers of the sensitive elements. Therefore, no silver halide developing agent need be present in the processing solution.
  • the sensitive elements of the invention are of course adapted to use in a camera for taking pictures in the usual manner.
  • the development of the sensitive elements i.e. the treatment with an alkaline activator solution to initiate development, can also be carried out in the camera by use of rupturable containers of processing solution used as illustrated in FIG. 1 of the drawings or other means may be used to spread the processing solution uniformly across the picture area of one or more consecutively exposed images and in contact with the reception layer.
  • Other means can be used such as spraying, dipping, roller coating, etc. to apply the processing solution to the exposed element and to initiate its development.
  • the alkaline processing solution may be replaced with water or a water solution of pH? .5 or less if the contiguous receiving sheet contains an alkali or an alkali releasing material. If the water or water solutions are integumented and incorporated in the light sensitive element or in the mordanted receiving sheet they may be released by suitable means such as by pressure or by heat.
  • One method for obtaining the color prints from a strip of the sensitive element containing a series of, for example, three or four consecutive exposures is to apply a viscous processing solution from a releasably confining or rupturable container in a compartment such as a magazine, integral with a camera in the manner described below, to cause each of the exposed areas to be wetted with the processing composition at approximately the same time in contact with a strip of reception material and the corresponding multicolor images to transfer thereto to provide a series of colored images on a single strip of the reception material.
  • a different means for providing prints from the sensitive element containing a series of image exposures such as three or four consecutive exposures is to expose the element to several subjects in a conventional camera not necessarily adapted to use of rupturable containers of the processing composition, and withdrawing the exposed element from the camera in a convenient manner so as to prevent fogging of the emulsions.
  • the element can be exposed and wound upon itself on a spool in an ordinary roll-film type of camera so as to exclude light, by use of a light-impervious covering such as black paper, a cassette or a magazine. The element can then be withdrawn from the camera and placed in a convenient portable light-impervious enclosure of small dimension such as shown in FIG.
  • the element comprising several image exposures on a single strip of differentially light-sensitive emulsion layers and subtractively colored dye developers contiguous to the silver halide of each emulsion layer, is wetted with the alkaline fluid in the presence of the onium salts, and preferably also in the presence of the hydroquinone derivatives, and brought into contact with the reception layer for a time suificient for adequate development of each image, to cause the silver halide in the several exposed areas of each emulsion layer to develop and thereby render the corresponding dye developers immobile and the dye developers in the unexposed portions of each of the several exposed areas to transfer to the reception layer and provide a series of prints thereon composed of the dye developers.
  • FIG. 3 is shown a schematic representation of an apparatus useful for this purpose and the process for making the series of prints from a sensitive element containing a series of exposures.
  • the film 40 wound emulsion side inwards having the structure shown in FIG. 1, Stage 1, and comprising a support having superposed thereon differently sensitized emulsions and contiguous dye developers, which has been exposed so as to record a series of multicolor subjects, is quickly passed between rollers 41 and 42 so as to pick up the alkaline activator solution 43, such as Activator II, contained in pan 44, which is supplied by roller 42 dipping into the solution. Thence the film continues between rollers 45 and 46 where it is brought into contact with the mordanted receiving sheet 47, such as Receiving Sheet A, to form the sandwich 48.
  • the alkaline activator solution 43 such as Activator II
  • the reception layers to which the dye developers are transferred imagewise to obtain the multicolor images may be composed of various materials such as linear polyamides, proteins such as gelatin, polyvinyl pyrrolidones, poly-4-vinyl pyridine, polyvinyl acetate, polyvinyl alcohol, cellulose acetate, polyvinyl salicylal, partially hydrolyzed polyvinyl acetate, methyl cellulose, regenerated cellulose, carboxymethyl cellulose and hydroxethyl cellulose.
  • These reception layers are coated on a suitable support such as a paper support, a transparent film or white pigmented cellulose ester support.
  • the prints composed of the dye developers undergo decomposition to some extent when exposed to heat, light and moisture. Accordingly, it is advantageous to treat the prints to reduce these eifects as much as possible.
  • solutions of a number of materials can be swabbed on, sprayed on or otherwise applied to the prints to improve the stability of the dye images such as solutions of tannic acid, a condensation product of naphthalene sulfonic acid and formaldehyde, and polyvinyl pyrrolidinone.
  • An exceptionally useful synergistic composition is a solution of polyvinyl alcohol containing a saccharide such as mannitol, levulose, arabinose, maltose, mannose, etc., neither the polyvinyl alcohol nor the saccharide being effective per se to stabilize the dye developer images.
  • an antifoggant in the sensitive element, in the alkaline processing solution or in the reception element or in each, and a development arresting compound in the reception element.
  • development arresting compounds When development arresting compounds are present in the reception element rather than in the sensitive element or solution they do not become effective until dissolved by the processing solution and have migrated to the sensitive element under development. As a result, the latent image is allowed to develop very rapidly and the arrestment is delayed until the development of the exposed areas has essentially reached cornpletion before development is appreciably arrested. This results in the prevention of development in the unexposed areas and increases the amount of dye developer transferring.
  • Suitable development arrestors are heterocyclic mercaptans such as mercaptotetrazoles and mercapto benzothiazoles, e.g. 1-phenyl-5-mercaptotetrazole, Z-mercaptobenzothiazole, etc. Many compounds usually considered to be anti-foggants for silver halide do not arrest development as desired.
  • a small amount of a silver halide solvent such as alkali metal or ammonium thiosulfate or thiocyanate may be incorporated into the alkaline processing composition or the receiving layer, or both, with the result that the effective photographic speed of the process is increased.
  • a silver halide solvent such as alkali metal or ammonium thiosulfate or thiocyanate
  • the efiect of the silver halide solvent becomes most apparent when either or both the mentioned hydroquinones and quaternary salts are present.
  • the amount of silver halide solvent used is not sufficient to cause any appreciable amount of silver halide to be dissolved from the unexposed and undeveloped areas of the sensitive element and to be transferred to the reception layer.
  • the invention contemplates sensitive elements wherein the emulsion layers, contiguous hydroquinone derivatives and dye developer layers are integral with the support e.g. coated on a support capable of receiving the dye developer images, the support being of a nature such that it can be stripped away from the sensitive layers or a stripping layer may be provided between the reception layer and the other layers to facilitate the stripping operation.
  • the alkaline fluid can thus be supplied as described above or in case the alkali is contained in one of the layers the fluid may merely be water supplied to release the alkali.
  • the silver halide emulsions of the sensitive elements of the invention include well-known silver halides and mixtures thereof, for example, silver bromide, silver bromoiodide or silver chlorobromide emulsions.
  • Layer 12 An aqueous gelatin solution containing the magenta dye developer (Compound 11 above) dissolved in a mixture of cyclohexanone, N-n-butylacetanilide and Alkanol B, and the mixture passed through a colloid mill several times, coated and dried to volatilize the cyclohexanone.
  • magenta dye developer Compound 11 above
  • Part A was slowly added to Part B with the aid of mechanical agitation.
  • the solution obtained was then passed through a Manton-Gaulin laboratory colloid mill five times.
  • the colloid mill was then rinsed and the dispersion was adjusted to a weight of 3775 g., chill set and stored in a refrigerator.
  • the coating composition for layer 19 was prepared as follows.
  • Parts I and II were then combined and diluted with water to 22,700 ml. This solution was coated as layer 19 of FIG. 1 to yield a coverage of approximately 120 mg. of gelatin per sq. ft. and 40 mg. per sq. ft. of 4'-methylphenylhydroquinone identified hereinafter as HQ.
  • Tests 1 to 6 of the table below show the improvement in minimum density of the neutral scale of the prints resulting from the use of the quaternary salts. These tests show that when the element containing no HQ was processed with Activators IIQ and IIIQ (Tests 2 and 3) the minimum densities of the neutral scale of Tests 2 and 3 read by red and green light is reduced, compared to Test 1 where Activator 1 contained no quaternary salt. In addition visual examination of the samples of Tests 2 and 3 showed color contamination was decreased and drop off was considerably improved. It will be noted from Tests 4 to 6 that While HQ per se decreases minimum density (Test 4) when the quaternary is present (Tests 5 and 6) an additional decrease in minimum density is obtained.
  • EXAMPLE 2.HYDROQUINONE DERIVATIVE IN EMULSION LAYER A film No. 69 was prepared identical in structure to that of Example 1 except that sufiicient of the Dispersion D-1 was added to emulsion layer 16 (rather than to layer 19) to obtain 45 mg. of 4-methylphenylhydroquinone HQ per sq. ft.
  • This element was processed as in Example 1 using Activators I, IIQ and IIIQ with the result shown by the data of the table (Tests 7, 8, and 9), where it can be seen that results similar to those of Example 1 were obtained. Also improvements in color contamination and drop off were obtained. It should be noted that the combination of the hydroquinone derivatives in the element and the quaternary salt in the process (Tests 1-9) gave improvements in color quality considerably superior to the use of either one alone.
  • EXAMPLE 3 SILVER HALIDE SOLVENT AND PYRIDINUM SALT IN ACTIVATOR Films were prepared as described in Example 1 except that a film No. contained no HQ, No. 18 contained 40 mg. HQ per sq. ft. in layer 19, film No. 14 had 40 mg. HQ per sq. ft. in layer 18 and film No. 75 had 40 mg. HQ per sq. ft. in layer 17.
  • the films were processed in Activators IVQ and V below each containing the silver halide solvent sodium thiosulfate and IVQ also contained the pyridinium salt.
  • the density data of Tests 18, 19, and 20 show in part that the HQ in layers 16 and 19 and the pyridinium salt in Receiver B, substantial reduction in the minimum densities is effected, as Well as improvement in color contamination and drop off.
  • Activator IIIQ Activator I plus 2.0% l-benzyl-2- picolinium bromide.
  • Activator XIIQ Activator I plus 2% l-ethyl pyridinium bromide.
  • Receiving Sheet B A white pigmented cellulose ester support carrying a gelatin layer containing a mixture of poly-4-vinylpyridine, 1- phenyl 5 mercaptotetrazole and l-phenethyl-Z-picolinium bromide.
  • the other elfective hydroqinones may be used in the films containing the dye developers and the other effective quaternary salts preferably in the alkaline processing solution or the reception layer or both.
  • EXAMPLE 5 In the manner of Example 1 except using Activator IVQ, a series of 5, 10, 20, 40 and mg. of HQ per sq. ft. were incorporated into layer 19 from which it was observed that the mentioned improvements were obtained at the 5 and 10 mg. levels: however, optimum results were obtained in the range of 20 to 100 mg.
  • the sensitometric scales of the prints processed with Activators IX and X showed a high level of color drop-E since the quaternary salts used were structurally incapable of forming methylene bases, whereas the scales of the prints obtained with Activators VII and VIII, containing the quaternary compounds forming methylene bases, showed extremely low color drop-01f and very low color contamination.
  • EXAMPLE 8 Samples of the sensitive element of Example 1 were processed as in Example 1 with Activators I, XIQ to XVQ with the result that all of the Activators XIQ to XVQ all gave prints showing reduced minimum density, but Activator XIQ also greatly reduced drop-off and the colors were much more saturated.
  • an exposed photographic element comprising a support, a plurality of light-sensitive silver halide emulsion layers sensitive to light of diflferent regions of the spectrum, and a dye developer which is both a silver halide developing agent and a dye contiguous to the silver halide of each of said silver halide emulsion layers, said processing being efiected by treating said photographic element with an alkaline liquid, developing latent images in the regions of exposure of said silver halide emulsion layers and thereby immobilizing dye developers in said regions of exposure, dye developers in undeveloped regions diffusing imagewise in register to a dye developer reception layer, the improvement which comprises effecting said processing in the presence of a heterocyclic quaternary ammonium compound capable of forming a diffusible methylene base in said alkaline liquid.
  • heterocyclic quaternary ammonium compound has the formula wherein:
  • n is an integer of 0 to 1
  • R is selected from the group consisting of an alkyl radical, an aryl radical and an aralkyl radical
  • R is selected from the group consisting of a hydrogen atom, an alkyl radical, an aryl radical and an aralkyl radical.
  • an exposed photographic element comprising a support, superposed red, green and blue light-sensitive silver halide emulsion layers, and a dye developer which is both a silver halide developing agent and a dye contiguous to the silver halide of each of said silver halide emulsion layers
  • said processing being effected by treating said photographic element with an alkaline liquid, developing latent images in the regions of exposure of said silver halide emulsion layers and thereby immobilizing dye developers in said regions of exposure, dye developers in undeveloped regions diffusing imagewise to the surface of said photographic element, and transferring the resulting ditfused images from said undeveloped regions in register to a dye developer receiving sheet superposed on said photographic element
  • the improvement which comprises using in said alkaline liquid a heterocyclic quaternary ammonium compound capable of forming a diiiusible methylene base in said alkaline liquid and having the formula 23 wherein:
  • n is an integer of to 1
  • D represents the nonmetallic atoms necessary to complete a pyridinium nucleus
  • X is an acid anion
  • R is an aralkyl radical
  • R is a lower alkyl radical.
  • an exposed photographic element comprising a support, superposed red, green and blue light-sensitive silver halide emulsion layers, and a dye developer which is both a silver halide developing agent and a dye contiguous to the silver halide of each of said silver halide emulsion layers
  • said processing being eifected by treating said photographic element with an alkaline liquid, developing latent images in the regions of exposure of said silver halide emulsion layers and thereby immobilizing dye developers in said regions of exposure, dye developers in undeveloped regions diffusing imagewise to the surface of said photographic element, and transferring the resulting diffused images from said undeveloped regions in register to a dye developer receiving sheet superposed on said photographic element
  • the improvement which comprises using in said alkaline liquid at heterocyclic quaternary ammonium compound capable of forming a difiusible methylene base in said alkaline liquid and having the formula wherein:
  • n is an integer of 0 to 1
  • R and R are each lower alkyl radicals.
  • an exposed photographic element comprising a support, superposed red, green and blue light-sensitive silver halide emulsion layers, and a dye developer which is both a silver halide developing agent and a dye contiguous to the silver halide of each of said silver halide emulsion layers
  • said processing being effected by treating said photographic element with an aqueous alkaline solution, developing latent images in the regions of exposure of said silver halide emulsion layers and thereby immobilizing dye developers in said regions of exposure, dye developers in undeveloped regions diffusing imagewise to the surface of said photographic element, and transferring the resulting diffused images from said undeveloped regions in register to a dye developer receiving sheet superposed on said photographic element
  • the improvement which comprises using in said alkaline solution a heterocyclic quaternary ammonium compound capable of forming a dilfusible methylene base in said alkaline solution selected from the group consisting of 7.
  • Glafkides Photographic Chemistry, Fountain Press, London (1958), pp. -57 and 156-157. (Copy in Sci.

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US50963A US3146102A (en) 1960-08-22 1960-08-22 Photographic multicolor diffusion transfer process using dye developers
FR870939A FR1313767A (fr) 1960-08-22 1961-08-17 Procédé d'inversion-transfert en couleurs et produits pour sa mise en oeuvre
DEE21550A DE1157484B (de) 1960-08-22 1961-08-18 Verfahren zum Lichtbestaendigmachen von farbigen, nach einem Farbstoffentwickler verwendenden Diffusionsuebertragungsverfahren hergestellten positiven Bildern
DEE21543A DE1157479B (de) 1960-08-22 1961-08-18 Photographisches, Farbstoffentwickler verwendendes Mehrfarben-Diffusionsuebertragungsverfahren und Material zur Durchfuehrung des Verfahrens
DEE21548A DE1168768B (de) 1960-08-22 1961-08-18 Photographisches Material und Verfahren fuer die Herstellung von mehrfarbigen Bildern nach einem Farbstoffentwicklersubstanzen verwendenden Diffusionsuebertragungsverfahren
DE19611422851D DE1422851B1 (de) 1960-08-22 1961-08-18 Farbstoffentwickler-Diffusionsverfahren zur Herstellung von mehrfarbigen Bildern
GB30324/61A GB1003672A (en) 1960-08-22 1961-08-22 Photographic multicolour diffusion transfer process using dye developers

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US3212893A (en) * 1961-03-27 1965-10-19 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US3230085A (en) * 1961-04-06 1966-01-18 Polaroid Corp Photographic products, processes and compositions
US3240604A (en) * 1963-02-18 1966-03-15 Polaroid Corp Photographic products containing polytetrafluoroethylene layer
US3253915A (en) * 1964-01-10 1966-05-31 Eastman Kodak Co Photographic dye developer image transfer systems
US3266894A (en) * 1964-04-22 1966-08-16 Eastman Kodak Co Photographic image transfer systems utilizing processing compositions containing high viscosity hydroxyethyl cellulose
US3287127A (en) * 1962-12-28 1966-11-22 Polaroid Corp Photographic processes using a stabilizing composition comprising a glucoside of a phenolic hydroxyl compound
US3364025A (en) * 1962-10-04 1968-01-16 Eastman Kodak Co Multiple compartment processing pod
US3404002A (en) * 1963-06-27 1968-10-01 Eastman Kodak Co Interimage characteristics of silver halide dye developer image transfer systems
US3411904A (en) * 1964-05-19 1968-11-19 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers and element
US3431107A (en) * 1967-07-28 1969-03-04 Eastman Kodak Co Dye developer image transfer systems
US3519428A (en) * 1965-05-21 1970-07-07 Keuffel & Esser Co Direct-positive light-sensitive photographic material
US3649266A (en) * 1970-05-18 1972-03-14 Eastman Kodak Co Magenta dye developer and transfer system employing same
DE2219026A1 (de) * 1971-04-19 1972-10-26 Polaroid Corp., Cambridge, Mass. (V.StA.) Lichtempfindliches fotografisches Material
US3930862A (en) * 1973-05-16 1976-01-06 Fuji Photo Film Co., Ltd. Dye developer transfer photosensitive material with substituted catechol auxiliary developer
US4124391A (en) * 1976-02-24 1978-11-07 Fuji Photo Film Co., Ltd. Process for processing color photographic material
US5705312A (en) * 1996-02-09 1998-01-06 Polaroid Corporation Photograph system

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US2886437A (en) * 1955-12-01 1959-05-12 Eastman Kodak Co Photographic emulsions sensitized with alkylene oxide polymers and quaternary ammonium compounds
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US3034894A (en) * 1959-06-24 1962-05-15 Eastman Kodak Co Hardening of gelatin
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Publication number Priority date Publication date Assignee Title
US3212893A (en) * 1961-03-27 1965-10-19 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US3230085A (en) * 1961-04-06 1966-01-18 Polaroid Corp Photographic products, processes and compositions
US3364025A (en) * 1962-10-04 1968-01-16 Eastman Kodak Co Multiple compartment processing pod
US3287127A (en) * 1962-12-28 1966-11-22 Polaroid Corp Photographic processes using a stabilizing composition comprising a glucoside of a phenolic hydroxyl compound
US3240604A (en) * 1963-02-18 1966-03-15 Polaroid Corp Photographic products containing polytetrafluoroethylene layer
US3404002A (en) * 1963-06-27 1968-10-01 Eastman Kodak Co Interimage characteristics of silver halide dye developer image transfer systems
US3253915A (en) * 1964-01-10 1966-05-31 Eastman Kodak Co Photographic dye developer image transfer systems
US3266894A (en) * 1964-04-22 1966-08-16 Eastman Kodak Co Photographic image transfer systems utilizing processing compositions containing high viscosity hydroxyethyl cellulose
US3411904A (en) * 1964-05-19 1968-11-19 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers and element
US3519428A (en) * 1965-05-21 1970-07-07 Keuffel & Esser Co Direct-positive light-sensitive photographic material
US3431107A (en) * 1967-07-28 1969-03-04 Eastman Kodak Co Dye developer image transfer systems
US3649266A (en) * 1970-05-18 1972-03-14 Eastman Kodak Co Magenta dye developer and transfer system employing same
DE2219026A1 (de) * 1971-04-19 1972-10-26 Polaroid Corp., Cambridge, Mass. (V.StA.) Lichtempfindliches fotografisches Material
US3930862A (en) * 1973-05-16 1976-01-06 Fuji Photo Film Co., Ltd. Dye developer transfer photosensitive material with substituted catechol auxiliary developer
US4124391A (en) * 1976-02-24 1978-11-07 Fuji Photo Film Co., Ltd. Process for processing color photographic material
US5705312A (en) * 1996-02-09 1998-01-06 Polaroid Corporation Photograph system

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