US3287133A - Photographic dye developer dispersions utilizing water-soluble sulfites - Google Patents

Photographic dye developer dispersions utilizing water-soluble sulfites Download PDF

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US3287133A
US3287133A US262167A US26216763A US3287133A US 3287133 A US3287133 A US 3287133A US 262167 A US262167 A US 262167A US 26216763 A US26216763 A US 26216763A US 3287133 A US3287133 A US 3287133A
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dye
water
dye developer
photographic
dispersion
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Jr Carl J Williams
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE644383A priority patent/BE644383A/xx
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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
    • G03C8/18—Dye developers
    • 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

  • the present invention concerns photographic materials, and more particularly, photographic dye developers.
  • Photographic elements containing such dye developers generally comprise a plurality of photosensitive silver halide emulsions Wherein each of theemulsions is selectively sensitized to a different region of the spectrum.
  • a dye developer is positioned contiguous to the silver halide in each of such emulsions.
  • Such a photoelement is processed with an alkaline solution and the latent image is developed in the negative image areas with the dye developers, this development immobilizing the dye developers in such negative image areas, and the dye developers in the unexposed areas diffuse to the surface imagewise and are mordanted in a receiving sheet to form a positive color image.
  • Such color diffusion transfer processes are disclosed in US. Patents 2,559,643, 2,647,- 049, 2,698,798, 2,774,668 and 2,983,606, as well as elsewhere in the literature.
  • a particularly useful method for incorporating dye developers into compositions used for coating layers on photographic elements is to dissolve the dye developer in a high-boiling water-immiscible organic solvent and to disperse the organic solvent in finely-divided droplets in a hydrophilic organic photographic vehicle or substrate such as gelatin.
  • Such dispersions of dye developer in highboiling solvents are known in the art and can be used to prepare particularly uniform distributions of the dye developer in the photographic element.
  • the use of such dispersions of dye developers in photographic elements is disclosed in Belgian Patent 607,420 granted August 15, 1961, copending Weyerts application, U.S. Serial No. 50,932 filed August 22, 1960, now abandoned and US. Patent 2,983,606.
  • the present invention concerns photographic hydrophilic organic colloids containing substantially uniformly dispersed therein finely-divided droplets of water-immiscible organic solvents containing dissolved therein dye developers that have been treated with water-soluble sulfites.
  • Dispersions of dye developers can be prepared by dissolving the dye developers in a high-boiling solvent and thereafter dispersing the resulting solution in a hydrophilic organic colloid.
  • a high-boiling solvent Generally, water-soluble or low boiling solvents are used with the high-boiling solvent as auxiliary solvents.
  • the present sulfite treatment for dye developer dispersions can be efiected by the addition of a water-soluble sulfite to any stage in the preparation of the subject dye developer dispersions and intimately associating or contacting the dye developer and the water-soluble sulfite.
  • the water-soluble sulfite can be added with the dye developer in the hydrophilic organic colloid during the preparation of such dispersions, after the preparation of the dispersions as a final aqueous washing or treating bath, to the dye developer dispersions after their preparation, or at more than one of such stages.
  • the amount of water-soluble sulfite used in preparing the dye developer dispersions can be widely varied, although concentrations of water-soluble sulfite utilized generally range from about .001 to .65 mole of water-soluble sulfite for each mole of dye developer.
  • Suitable water-soluble sulfites include such inorganic sulfite salts as ammonium sulfite and alkali metal sulfites such as sodium and potassium sulfite.
  • Such emulsions or photographic coating materials can be stored for substantial periods prior to coating without deleterious eifect on the properties of the properties of the emulsion.
  • Dye developers are well known in the photographic art. Such compounds function both as a silver halide developing agent and as a dye in photographic diffusion transfer systems.
  • Dye developers are characterized as being relatively nondiffusible in colloid layers such as the hydrophilic organic colloids used in photographic emulsions at neutral pH, but difiusible in the photographic elements in the presence of alkaline processing solutions.
  • 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 photoelements.
  • the dye developers are particularly characterized as containing both a chromophoric or dye moiety and at least one moiety having a silver halide developing agent function.
  • the invention is particularly useful in preparing dispersions of dye developers wherein the chromophoric moiety is an azo or anthraquinone dye moiety and the silver halide developing moiety is a benzenoid moiety such as a hydroquinonyl moiety.
  • M is an aromatic or heterocyclic ring or ring system such as a benzene, naphthalene, tetralin, anthracene, anthraquinone, pyrazole, quinoline, etc., ring which can be substituted with such groups as hydroxyl amino, keto, nitro, alkoxy,
  • D represents a silver halide developing agent moiety imparting the developing agent function to the dye developer such as a hydroquinolyl group which can be substituted with amino, alkylarnino, alkyl, hydroxyl, alkoxyl or halogen groups.
  • German Patent 1,036,640, August 14, 1958, and have the general formulas YRArN N Q i: )m P and wherein R is an alkylene group preferably of from 1 to carbon atoms; Ar is an aryl group of the benzene or naphthalene series; each Z is a lower alkyl group having 1 to 5 carbon atoms and preferably methyl or ethyl, or halogen, e.g., chlorine; Z is a lower alkoxyl group having 1 to 5 carbon atoms and preferably methoxy or eth- 'oxy, halogen or a lower alkyl group having 1 to5 carbon atoms; In is an integer of 0, 1 or 2; A is an integer of l or 2; Y is a 2,5- or 2,3- or 3,4-dihydroxypheny1 group which can be substituted by alkyl or halogen groups; Q is the residue of a photographic color coupling component such as a phenol, naphthol, S
  • Q represents a hydrogen atom or an alkyl group or, when the substituents on the aryl nucleus of D are hydroxyl groups, Q can also be an acyl group, which can be aliphatic, (e.g., acetyl) or aromatic (e.g., benzoyl), Z is a bivalent organic radical containing at least one methylene (CH group, m is an integer of 1 to 4 and each Ycan 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 difierent atoms.
  • alkylene radicals such as CH CH CH 5 --CHz-CH- as Well as bivalent radicals such as It is also intended that Z can be saturated, unsaturated, such as CH --CH:CH-CH or substituted, such as chloroalkylene or hydroxyalkylene.
  • Z is an alkylene group, best results are obtained by the use of a lower alkylene group, e.g., an alkylene group, containing 1 to 5 carbon atoms, and preferably an ethylene group.
  • Acylation of amino-nitrogen atoms which are part of the chromophoric system of dye developers 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- 6 [,8-(2',5'-dihydroxyphenyl)-ethylamino] anthraquinone changes its color to a magenta
  • acylating both the amino-nitrogen atoms changes its color to an orangeyellow.
  • the acylation of hydroxyl groups of the above-described types of dye developers can be expected to shift the color of the dye developers.
  • the dye developers can 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 Z-hydroquinoneamino-4-(p-phenylazo)anilino-6-hydroxy-4 triazine described in Canadian Patent 579,038.
  • Anthraquinone dye developers such as 1,4-bis(2',5'-dihydroxyanilino)-anthraquinone and 1,4-diamino-N-(B-2,5'-dihydroxyphenyl-amethyl-ethyl)2,3 anthraquinonedicarboximide.
  • Amino substituted anthraquinone dye developers such as prepared by reaction of 1-amino-4-(p-aminoanilino)-anthraquinone-Z-sodiurn sulfonate with chloroacetamido hydroquinone monobenzoate.
  • Dye developers obtained by reaction of 1-phenyl-3-amino-4-phenylazo-5-pyrazolone or 1,4-bis(fi-aminoethylamino)-anthraquinone with homogentisic acid lactone or acid chloride, or gentisic acid chloride, e.g., 1-phenyl-3-(2',5'-dihydroxyphenylacetamido)-4-phenylazo-S-pyrazolone described in Canadian Patent 577,021 dated June 2, 1959.
  • Naphthamide dye developer such as 1-(2,5-dimethoxyphenylazo)-2- hydroxy-N-(2',5'-dihydroxyphenyl)-3 naphthamide described in French Patent 1,168,292 dated August 25, 1958.
  • Diazo dye developers such as 2-[p-(1-hydroxy-3, 6-disulfo-8-amino-2 naphthylazo) 3,3 dimethoxybisphenyleneazo]-hydroquinone and 2-(2',5'-dimethoxy-4- [p (2,5" dihydroxyphenethyl)phenylazo] phenylazo)-1,8-naphthalene diol-3,6-disulfonic acid.
  • Arylazonaphthol dye developers e.g., 1-amino-4-phenylazo- Z-naphthol.
  • Anthrapyridone dye developers e.g., 1- acetyl 3 ,3 (2,5 dihydroxyphenyl) ethyl 6 )3- (2,5' dihydroxyphenyl) ethylaminoanthrapyridone.
  • Thiohydroquinoly dye developers e.g., 1-phenyl-3- methyl 4 [p (2',5' dihydroxyphenylthioethyl)- phenylazo1-5-pyrazolone described in Belgian Patent 5 68,- 344.
  • Ortho coupled dye developers exhibiting limited sensitivity to changes of pH, e.g., 2-[p-(2,5"-dihydroxyphenoxy)phenylazo] 4 methoxy 1 naphthol and 1 phenyl 3 methyl 4 [p hydroquinolylsulfonyl)- phenylazo]-5-pyrazolone.
  • Oxalyl ester dye developers e.g., 1 phenyl 3 amino 4 [p (2',5' bisethoxalyloxyphenethyl)-phenylazo]-5-pyrazolone.
  • Leuco compounds can also be used similarly, e.g., 1-phenyl-3- methyl 4 (2' methyl 4 diethylamino)anilino 5- pyrazolone, which do not exert a filtering action on underlying emulsion'layers and which are immobilized in the developed regions, difiuse imagewise from undeveloped areas to the reception layer and are oxidized to colored images therein.
  • Suitable high-boiling and water-immiscible organic liquids have a boiling point above about C.
  • the high-boiling solvent can be used alone in dissolving the dye developer and in forming the dispersion or can be mixed with a low-boiling organic solvent (e.g., boiling at least 25 C. below the boiling point of the higher boiling solvent), or a water-soluble organic solvent, as an auxiliary solvent to facilitate solution of the dye developer.
  • a preferred range of proportions of high-boiling solvent to auxiliary are 1/0 to 1/10 on a weight basis.
  • Such auxiliary solvents can be readily removed from the high-boiling solvent, for example, by
  • Typical high-boiling, water-insoluble solvents that can be used to dissolve dye developers in preparing the dis-- persions of the invention are described on page 2, col. 2 and page 3, col. 1 of US. Patent 2,322,027 can be used.
  • Such classes of solvents as organic carboxylic acid esters, organic phosphate esters, N-lower alkyl acetanilides, N,N-
  • di-(lower. alkyl)alkylamides and the like are typically employed.
  • guaiacol acetate o-methoxyphenyl acetate
  • tetrahydrofurfuryl propionate ethyl benzyl malonate
  • triethyl citrate acetyl
  • triethyl citrate tetrahydrofurfuryl succinate
  • tricresyl phosphate tri-p-tert, butylphenyl phosphate, triphenylphosphate, ditetrahydrofurfuryl succinate, ditetrahydrofurfuryl adipate, tetrahydrofurfuryl benzoate, N-namylphthalimide, ethyl N,N-di-n-butylcarbamate, diethyl lauramide, dibutyl lauramide, lauroyl piperidine, N-nbutyl acetanilide, tetraethyl phthalamide, N-n-amyl sucketone, ,B-ethoxy ethyl acetate, ,8ebutoxy-p-ethoxy ethyl acetate, tetrahydrofurfuryl adipate, diethylene glycol monoacetate, fl-methoxymethyl acetate, acetonyl acetone, cyclohexanone, tri
  • hydrophilic organic colloid used in preparing the present emulsions or dispersions of dye developers as protective colloids include gelatin and its water-soluble derivatives, polyvinyl alcohol and its water-soluble derivatives and copolymers, water-soluble copolymers such as polyacrylamide, imidized polyacrylamide, etc., and other water-soluble film-forming materials that form water-permeable coatings such as colloidal albumin,
  • water-soluble cellulose derivatives such as ethanolamine Compatible mixtures of two or more such colloids can be utilized.
  • Gelatin is preferred.
  • the dye developers are dissolved in solvents of the type described above and mixed with aqueous solutions of hydrophilic colloids.
  • the water-soluble sulfite can be incorporated into the composition, or used in an aqueous wash to treat the composition, at this point.
  • the amount of solvent utilized to dissolve the dye developer can be widely varied, proportions of dye developer to high-boiling solvent in the range of about 1/ .25 to /2 on a weight basis
  • the resulting oil-in-water emulsion is then emulsified or homogenized until the solvent containing the dye developer is substantially uniformly dispersed in finely-divided droplets, the droplets suitably being less than about 5 microns in a size, more generally less than about 2 microns in size and often times in the range of .5 to less than 5 microns in size.
  • the Water-soluble sulfite can also be added if desired during this emulsifying or homogenizing step.
  • Small amounts of surfactant compounds can be utilized as dis dium diisopropylnaphthalene sulfonate, a sodium lauryl-I sulfonate, p-tert.-actylphenoxy diethoxy sulfonate sodium salt, p-tert.-octylphenoxydiethoxyethylsulfate tammonium salt, sodium N-methyl-N-oleyl taurate, diisobutylcresoxyethoxyethyl, dimethyl, benzylammonium chloride, diisobutylphenoxyethoxyethyl, dimethyl, benzylammonium chloride and the like.
  • the resulting composition can be treated or washed with a water solution of a water-soluble sulfite at this stage of the preparation of the coating composition.
  • the resulting dispersion can be chill-set, noodled and thereafter washed with water in accordance with usual photographic practice.
  • Such compositions can thereafter'be treated or washed with a solution of a water-soluble sulfiite, or the watersoluble sulfite added directly thereto.
  • a typical method for treating the emulsion composition at this stage is to melt the composition, add an aqueous solution of a water-soluble sulfite and maintain this mixture for a few minutes before removing the aqueous portion thereof.
  • Dye developer compositions thus prepared with the use of a water-solublesulfite treatment during its preparation as described above have substantially improved storage stability against dye developer crystallization and agglomeration as compared to dye developer dispersions prepared in the same manner without the use of the.
  • the drawing illustrates a typical light-sensitive element or color film utilizing the dye developer dispersions of the invention.
  • the drawing also illustrates a typical re:
  • rupturable pod 21 containing processing material 20 such as a viscous alkaline aqueous composition. After exposure of the light-sen sitive element in -a camera to an image, rupturable pod 21 can be ruptured by passing the assembly illustrated in the drawing between rollers in the camera or remote from the camera and the processing composition in the pod uniformly distributed across a predetermined area of the light-sensitive element. The receiving sheet is pressed in contact with the light-sensitive element.
  • the processing composition penetrates through layers 11 to 18, latent images develop in light-sensitive layers 12, 15 and 18 and dye developers in contiguous layers 11, 14 and 17 respectively rendered nondiffusing in areas corresponding to the latent image or negative areas, and' the dye developers in the remaining or positive image areas dilfuse imagewise in register to mordant layer 22, of the receiving sheet.
  • phenylhydro quinone 2-hydroxyphenylhydroquinone
  • phenoxyhydroquinone 4-methylphenylhydroquinone
  • dodecylhydroquinone and the like.
  • Example I -Additin of water-soluble sulfite after washing dye developer dispersion
  • To the resulting solution was added, with agitation, 120 g. of 10% aqueous gelatin and 12 cc. of a aqueous solution of the Surfactant, sodium diisopropylnaphthalene sulfonate.
  • the resulting emulsion was passed through a colloid mill five times to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all the droplets being less than 2 microns in size.
  • Suflicient water was added to bring the total weight of the resulting dispersion to 200 g.
  • the dispersion was chill-set at 5 C., noodled, and washed for six hours with cold water. The drained noodles were then divided into two equal samples.
  • Example IA To one-half of the above dispersion was added water (200 cc.), and this mixture was held at 40 C.
  • Example IB One-half of the above dispersion was melted at 40 C. and 1% sodium sulfite (500.) was added; this solution was held for 15 minutes at 40 C., and then diluted with water (200 cc.), and the resulting mixture was held at 40 C.
  • the dispersion stabilities of the samples of Examples IA andv IB are described in Table I of Example II below.
  • Example II -Addition of water-soluble sulfite during preparation of dye developer dispersion
  • To the resulting solution was added, with agitation, 90 g. of 1% aqueous gelatin, 9 cc. of a 5% aqueous solution of sodium diisopropylnaphthalene sulfonate and 9 g.
  • the resulting emulsion was passed through a colloid mill 5 times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all the droplets being less than 2 microns in size.
  • Suflicient water was added to bring the total weight of the resulting dispersion to 200 g.
  • the prepared dispersion was chill-set at 5 C., noodled, and washed for six hours with cold Water.
  • the drained noodles were diluted with Water (200 cc.) and held at 40 C.
  • the improvement in stability of the dye developer dispersions prepared according to Examples I and II can be seen from the following table. When judging -a sample for stability, the sample was considered to be stable until a substantial amount of particle agglomeration of dye developer had taken place.
  • watersoluble sulfites are effective to stabilize dye-developer dispersions both when added to the dispersion during its preparation or when added following washing of the dispersion.
  • To the resulting solution was added, with agitation, 30 g. of 10% aqueous gelatin and 3 cc. of a 5% aqueous solution of sodium diisopropylnaphthalene sulfonate.
  • Dispersion IIIA A second dispersion, herein referred to as Dispersion IIIB, was prepared by the general method used to prepare dispersion IIIA except that 1 cc. of a 10% aqueous solution of sodium sulfite was added to the dispersion prior to passing through the colloid mill. Dispersions IIIA and IIIB were chill-set, noodled, and washed for six hours with cold water.
  • the washed noodles were then diluted with water (200 cc.) and 5% sodium diisopropylnaphthalene sulfonate (0.2 cc.) were added.
  • dispersion HIA formed crystals in 3 /2 hours and dispersion IIIB displaced crystals only after 6 /2 hours.
  • Example IV A ddition of water-soluble sulfite during preparation of dy developer dispersions and after washing the dispersions
  • To the resulting solution was added, with agitation, 300 g. of 10% aqueous gelatin, 30 cc.
  • Example IIIB dispersion No crystals in the prepared dispersion were observed during 10 hours at 40 C. compared to 6 /2 hours for Example IIIB dispersion. Also, no viscosity increases were noted in Examples III and IV.
  • Example V.-Treatment of dye developer dispersion with water-soluble sulfite A g. portion of the cyan dye developer, 5,8-dihydroxy-1,4-bis[(fl-hydroquinonyl a methyl)ethylamino] anthraquinone, was dissolved in 95 cc. of triethyl phosphate and cc. of N-n-butyl acetanilide. To the resulting solution was added, with agitation, 1110 g. of 10% aqueous gelatin, and 111 cc.
  • a 5% aqueous solution of the surfactant p-tert.-octylphenoxydiethoxy-ethylsulfate ammonium salt.
  • the resulting emulsion was passed through a colloid mill five times at 70 C. to uniformly disperse the suspended droplets of solvent containing the dye developer, substantially all of the droplets being less than 2 microns in size.
  • the dispersion was then chill-set, noodled and washed 6 hours in cold water.
  • Example VA.-T a 104 g. portion of the above dispersion (equivalent to 6 g. of dye developer) was added sodium sulfite (1%, 8.5 cc.) at 40 C. and the resulting dispersion held at 40 C. for 15 minutes. To 52 g. of this solution was added water (50 cc.) and sodium diisopropylnaphthalene sulfonate 0.5 cc.). A 40 C. holding of this mixture gave agglomeration after 15 hours.
  • Example VI Treatment of dye developer dispersion with water-soluble sulfite A 30 g. portion of the yellow dye developer, 1-[4-hydroquinonylethyl]-phenyl 3-ethyl-carboxamido-4(2",4, 6"-trimethylphenylazo)-5-pyrazolone, was dissolved in 60 cc. of N-n-butyl acetanilide and 30 cc. of cyclohexanone.
  • Both the dispersion portion containing the water-soluble sulfite and the portion free of the water-soluble sulfite were stored at 40 C. and compared with respect to stability.
  • the dispersion containing the water-soluble sulfite did'not have crystals until 5 hours while the dispersion not containing the water-soluble sulfite displayed crystals after 1 /2 hours.
  • Example VII illustrates the utility of the dye developer dispersions of the invention in a multilayer photographic element.
  • Example VII A-multilayer photographic element containing dye developer dispersions of the invention
  • a photographic color film having the structure substantially as shown in the drawing was prepared by coating a subbed cellulose acetate film support successively with the following layers:
  • Cyan dye developer layer e.g., layer No. 11 of drawing.A coating of the cyan dye developer disper- I gelatin layer,
  • Magenta dye developer layer (e.g., layer No. 14 of the drawing).-A coating of the magenta dye developer dispersion prepared as described in Example IB.
  • Yellow dye developer layer (e.g., layer No. 17 of drawing).A coating of the yellow dye developer dispersion prepared with the water-soluble sulfite as described -in Example VI.
  • Blue-sensitive emulsion layer (e.g., layer No.18 of drawing).A coating of a developing-out negative gelatino-silver bromoiodide emulsion that is inherently sensitive to blue light.
  • Protective layer e.g., layer No. 19 of drawing.
  • the described color film is exposed to a subject, and then processed by wetting with an aqueous solution containing 3.5% of high viscosity hydroxyethyl cellulose, 4% sodium hydroxide, 2% benzotriazole and 2% lphenethyl-Z-picolinium bromide with a dye image receiving sheet in contact therewith. After 2 minutes at 72 F., the color film and the receiving sheet. are stripped apart. A positive color image of dye developers is transferred to the receiving sheet.
  • a suitable receiving sheet comprises a paper support carrying a gelatin layer containing a mixture of poly-4-vinyl pyridine mordant and I 1-phenyl-5-mercaptotetrazole.
  • Example VIII Comparison of ascorbic acid and watersolable sulfite as treating agents for dye developer dispersions An 18 g. portion of the dye developer, 4-propoxy- 2-[p-(fl-hydroxyquinonylethyl)-phenylazo]-1 naphthol,
  • Example VIIIA control sample.-An 87 g.portion of the original dispersion was diluted with 200 cc..of
  • Example VIIIB A 1% aqueous solution of sodium sulfite (5 cc.) was added to the original dispersion and the resulting mixture stirred for 10 minutes. A 91 g. portion of the resulting dispersion was diluted with 200 cc. of water and the melt held at 40 C.
  • Example VIIIC A 1% aqueous solution of ascorbic acid (7 cc.) was added to the original dispersion and the resulting dispersion held for 10 minutes. A 97 g. portion of the resulting dispersion was diluted with 200 cc.. of water and the melt held at 40 C.
  • Example VIIIB exhibited agglomeration by microscopic examination only after 4.5 hours, while Example VIIIC exhibited agglomeration to unmagnified visual observation in 1 hour.
  • the process for preparing photographic compositions which comprises dissolving in a water-immiscible organic solvent boiling above about 175 C. a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide, and substantially uniformly dispersing the resulting solution in finely-divided droplets in an organic hydrophilic colloid, said dye developer having been treated with a water-soluble sulfite during said process.
  • the process for preparing photographic compositions which comprises dissolving in a water-immiscible organic solvent boiling above about 175 C. a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide, and substantially uniformly dispersing the resulting solution in finely-divided droplets less than about microns in size in aqueous gelation, said dye developer having been treated with about .001 to .65 mole of a watersoluble sulfite for each mole of said dye developer during said process.
  • watersoluble sulfite treatment is effected by adding water-sebuble sulfiite to the dispersion of droplets of organic solvent solution of dye developer in the 'geletin while a htn solvent solution of dye developer in the gelatin while the dispersion is in molten form.
  • auxiliary solvent is utilized with the water-immiscible organic solvent to dissolve the dye developer, said auxiliary solvent being selected from the group consisting of (1) a water-soluble organic solvent, and
  • organic solvent is selected from the group consisting of (1) N-n-butyl acetanilide and (2) ,N,N-diethyllauramide and the dye developer is selected from the group consisting of (l 4-propoxy-2-( ,B-hydroquinonylethyl) -phenylazol-lnaphthol,
  • a photographic composition comprising an organic hydrophilic colloid containing substantially uniformly dispersed therein finely-divided droplets of a water-immiscible organic solvent boiling above about C., and dissolved in said solvent a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide, said dye developer having been treated with a water-soluble sulfite.
  • a photographic composition comprising aqueous gelatin containing substantially uniformly dispersed therein finely-divided droplets less than about 5 microns in size of a water-immiscible organic solvent boiling above about 175 C., and dissolved in said solvent a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquin-onyl moiety capable of developing photographic silver halide, said dye developer having been treated with about .001 to .65 mole of a water-soluble sulfite dor each mole of said dye developer in said composition.
  • a photographic composition as defined by claim 12 wherein the organic solvent is selected from the group consisting of (1 N-n-butyl acetanilide and (2) N,N-diethyllauramide, and the dye developer is selected from the group consisting of (1) 4 propoxy-2-[p-(B-hydroquinonylethyl) phenylazoJ-l-napthol,
  • a photographic element comprising a support having coated thereon at least one silver halide emulsion layer having contiguous thereto a layer of the photographic composition defined by claim 10.
  • a photographic composition comprising an organic hydrophilic colloid containing substantially uniformly dispersed therein finely-divided droplets of a water-immiscible organic solvent boiling above about 175 C., a photographic dye developer having in the same molecule both the chromophoric system of a dye and a hydroquinonyl moiety capable of developing photographic silver halide being dissolved in said solvent, and a watersoluble sulfite.

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  • General Physics & Mathematics (AREA)
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US262167A US3287133A (en) 1963-03-01 1963-03-01 Photographic dye developer dispersions utilizing water-soluble sulfites
DEE26451A DE1188944B (de) 1963-03-01 1964-02-21 Verfahren zur Herstellung einer Farbstoffentwicklersubstanz-Dispersion fuer farbphotographische Materialien
FR965014A FR1389755A (fr) 1963-03-01 1964-02-25 Nouveaux produits photographiques contenant des colorants développateurs
BE644383A BE644383A (es) 1963-03-01 1964-02-26
GB8808/64A GB1060241A (en) 1963-03-01 1964-03-02 Dispersions of dye developers

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US262167A US3287133A (en) 1963-03-01 1963-03-01 Photographic dye developer dispersions utilizing water-soluble sulfites

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BE (1) BE644383A (es)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3630730A (en) * 1970-06-01 1971-12-28 Eastman Kodak Co Diffusion transfer processes and elements comprising dye developers and bis-sulfonyl alkane speed-increasing agents
US3649287A (en) * 1965-01-25 1972-03-14 Agfa Gevaert Nv Method of incorporating photographic ingredients into a photographic colloid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2360290A (en) * 1941-07-31 1944-10-10 Eastman Kodak Co Preventing formation of color fog in emulsions
GB804971A (en) * 1954-03-09 1958-11-26 Polaroid Corp Improvements in or relating to photography
CA606417A (en) * 1960-10-04 R. Blout Elkan Photographic products
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA606417A (en) * 1960-10-04 R. Blout Elkan Photographic products
US2360290A (en) * 1941-07-31 1944-10-10 Eastman Kodak Co Preventing formation of color fog in emulsions
GB804971A (en) * 1954-03-09 1958-11-26 Polaroid Corp Improvements in or relating to photography
US2983606A (en) * 1958-07-14 1961-05-09 Polaroid Corp Processes and products for forming photographic images in color

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3649287A (en) * 1965-01-25 1972-03-14 Agfa Gevaert Nv Method of incorporating photographic ingredients into a photographic colloid
US3630730A (en) * 1970-06-01 1971-12-28 Eastman Kodak Co Diffusion transfer processes and elements comprising dye developers and bis-sulfonyl alkane speed-increasing agents

Also Published As

Publication number Publication date
GB1060241A (en) 1967-03-01
BE644383A (es) 1964-06-15
DE1188944B (de) 1965-03-11

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