US2618553A - Hardened particle mixed grain photographic emulsion - Google Patents

Hardened particle mixed grain photographic emulsion Download PDF

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Publication number
US2618553A
US2618553A US789294A US78929447A US2618553A US 2618553 A US2618553 A US 2618553A US 789294 A US789294 A US 789294A US 78929447 A US78929447 A US 78929447A US 2618553 A US2618553 A US 2618553A
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United States
Prior art keywords
color
coupler
emulsion
silver
sensitive
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Expired - Lifetime
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US789294A
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English (en)
Inventor
Baines Harry
Davey Edward Philip
Teal Eric Fred
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to improvements in color photographic material especially suitable for the production of three-color subtractive pictures.
  • the invention relates to photographic material of the type in which a support carries three differentially color-sensitised emulsions containing color couplers, i. e. bodies which are capable of combining with the oxidation product of the developing agent used for developing the exposed silver salt to metallic silver with the production of coloring matter in the region where the silver is developed. Subsequent removal of metallic silver without removal of coloring matter leaves substantially clear transparent dye images.
  • these three emulsions so made could be coated as layers one above the other and then there is formed, for instance under the action of blue light, a yellow color, and at the places acted on by red and green light the corresponding complementary colors.
  • they may be treated in a suitable manner, for instance by tanning, so that they can be mixed without the three compounds (halogensilver and color-formers) uniting to form one homogeneous layer or film. In any case, the unused silver halide and the silver formed are simultaneously removed.
  • the first consideration is obviously that a very cheap form of manufacture be used as otherwise large prints become prohibitive in cost. It is clearly not necessary, for instance, that the emulsion for this purpose should have a high speed or exceptionally fine grain. It is essential, of course, that the color separation should be of a high order. It is also essential for this class of work that the processing be especially simple. While a long and complicated processing of small color films or one or two color prints can be tolerated for commercial purposes, this is not so in the case of the commercial production of large quantitles of prints all of large and difiering sizes.
  • One object of our invention is to overcome all the aforesaid difficulties.
  • Another object of our invention is to provide a three-color sensitive material which is simple and cheap to manufacture.
  • Another object of our invention is to provide a three-color sensitive material which gives three-color prints of satisfactory and commercially valuable color rendition.
  • Another object of our invention is to provide a commercially useful color sensitive material for subtractive three-color photography in which the sensitive emulsions remain distinct and separate when coated as a single layer in one coating operation.
  • Another object of our invention is to provide a mixture of three differentially color sensitive silver halide emulsions, each containing the .appropriate color former, which mixture yields color prints of a high order of color separation when exposed and processed in a simple manner.
  • a sensitive color photographic element by coating on a single support a layer consisting of a mixture of three sets of differentially color sensitive particles of emulsions of silver halide in hardened gelatine binder and containing three color couplers respectively, preferably without any added binder between the particles or with only a small quantity of a water-soluble colloid binder between the particles.
  • a layer consisting of a mixture of three sets of differentially color sensitive particles of emulsions of silver halide in hardened gelatine binder and containing three color couplers respectively, preferably without any added binder between the particles or with only a small quantity of a water-soluble colloid binder between the particles.
  • gelatine By hardened gelatinewemean that the gelatin should be sufficiently hardened that it is insoluble either in boiling water or at least in water :which is just sufficiently hot to dissolve the .water-soluble colloid (usually gelatine) if one is used. While gelatine is preferred for the water- .soluble colloid (when oneis used) other watersoluble colloids may be used.
  • three differentially color sensitized emulsions made of silver halide with the appropriate color couplers in hardened gelatine are each flrstproduced in the form of spray-dried particles and then a dispersion of these three sets of particles isformed in plain water and then'this dispersion is coated as a single layer.
  • Each particle consists of a minute portion of hardened gelatine-silver halide emulsion mixed -with the color coupler. If a gelatine solution is used instead of plain water, the melting point of 'the gelatine is advantageously about 30 0. below that of the hardened gelatine, for instance, the melting point of theformer may be 25-35 C.
  • the method of performing the invention is illustrated as follows. Three well hardened gelaitino silver chloride. emulsions each containing its appropriate color coupler arefirstmade. Each emulsion is then converted into a powder consisting of dried particles, and for this purpose the 'liquid emulsionmay be fed into a drying chamber and on to the underside of aninverted bowl shaped disc rotating therein at high speed, the
  • Thethree sets of dried particles so obtained may then be dispersed in plain water and then the dispersions mixed together and the mixture coated on paper as a single layer.
  • the color couplers ar advantageously dissolved in a high boiling organic solvent and then added to a gelatine solution and the mixture is emulsified for instanceby passing through a colloid mill, then this color coupler dispersion is added to the photographic emulsion. If no such high boiling solvent is present in the emulsion, the dried particles obtained are not so satisfactory. Sufficient high boiling solvent must be present to prevent crystallization of the color coupler when the spray drying step is performed,
  • the color couplers used are those having non-diffusing properties such as those of the kind described and claimed in United States specification No. 2,322,627.
  • the sensitizing dyes used are advantageously those known to have little tendency to wander, such as those described in United States specification No. 2,282,116.
  • a support [0 is provided with a single layer of gelatine H containing closely adjacent particles in the form of two sets, one set l2 being sensitized hardened gelatino silver chloride particles and the second set [3 being differently sensitized hardened gelatino silver halide particles each of the particles containing the appropriate color couplers.
  • the particles are for clarity shown as of oval shape, but of course, this is only diagrammatic since all particles are approximately spherical in shape and the sets do not differ substantially in shape from one another.
  • the drawing illustrates a two-color coating only, but it will be understood that three differently sensitized particles may be mixed or that a two-particle layer may be overcoated with the usual gelatino-silver halide emulsion sensitive to a single color and containing an appropriate color 19- (t-Butylphenoxy) -ethyl p-benzoylacetamino)-benzenesulphonate (see United States specification No. 2,289,805) grams l5 Dibutyl phthalate ccs 30 Dibutyl oxalate ccs -30 Solution is effected by heating. Then add the solution to a mixture of 500 cos. of 10% aqueous gelatine and 15 cos.
  • the green and red sensitive emulsions are made in like manner except that they were sensitized respectively with 0.015 grams of 5-[(2-ethyll(2)-benzoxazolylidene) ethylidenel 3 nheptyl-l-phenyl-2-thiohydantion and 0.025 gram of 5 [4 (2 ethyl- 1 -(2) -benzothiazolylidene) butenylidenel 3 n heptyl-2-thio2:4(3:5)- oxazoledione, and instead of the color coupler dispersion formula as given above, there were used respectively, 10 grams of 1-phenyl-3- palmitylamino-5-pyrazolone (see United States specification No.
  • Each of these three emulsions were then separately converted to a dry powder by feeding on to the underside of an inverted bowl shaped disc rotating at high speed in a drying chamber as described above. Each emulsion was thus converted into a fine dense powder having particles about 80% of which were under 20s in diameter and about of which were 5 1 or less.
  • the three powdered emulsions so obtained were then mixed in proportions, which on test showed that the best speed balance was obtained, and the mixture was dispersed in plain water and coated on paper.
  • the sensitive material so obtained could be used as a printing paper for making three-color prints from three-color negatives.
  • the particles obtained in the foregoing ex- 1 ample could be dispersed in warm water without rupturing their envelope or gelatine, and could even be put into boiling water without doing so, but such a degree of hardening is not necessary. It is sufficient for the envelope to remain intact at the coating and mixing temperature, normally about 40 C.
  • the dispersion is made in dilute gelatine or water: if normal gelatine strengths of about 6% are used, the viscosity is very high and the coating very difilcult.
  • Our invention gives commercially useful results if only two sets of particles are dispersed in water and coated as one layer and then the third emulsion is coated as a second layer either as particles or as an ordinary coating.
  • the method of making a mixed grain photographic element having at least a silver halide emulsion layer capable of reproducing at least two different colors of the visible spectrum comprises dispersing in a gelatino-silver chloride emulsion sensitive to a primary color region of the visible spectrum and containing sufficient gelatin hardening agent to render the emulsion insoluble in water at 40 C.
  • a solution of a color coupler in a high boiling organic solvent for said coupler similarly dispersing in at least one other gelatino-silver halide emulsion selected from the group consisting of gelatinosilver chloride, silver bromide, and -silver bromoiodide, sensitive to a primary color region of the spectrum difierent from said first men- 6 tioned region, and similarly hardened, a solution of a color coupler different from said first-mentioned coupler, each of said emulsions being sensitive to a difierent primary color region of the visible spectrum and each of said color couplers being capable of coupling with the oxidation product of a primary aromatic amino developing agent to produce a different dye image, separately spray drying each of said emulsions to form separate dry powders insoluble in water at 40 C., and dispersing said powders in the same aqueous medium to form an emulsion of separate particles sensitive to difierent spectral regions and containing
  • each of the color couplers is dissolved in a coupler solvent comprising at least 50% of dibutyl phthalate.
  • a mixed grain multi-color emulsion layer comprising a mixture of at least two sets of separate and distinct particles, each set of particles being sensitive to a different primary color, at least one of said sets of particles comprising a gelatino-silver chloride emulsion containing a solution of a non-diffusing color coupler in a high-boiling organic solvent, the other set of particles comprising a gelatinosilver halide emulsion selected from the group consisting of gelatino-silver chloride, -silver bromide, and -silver bromoiodide, and containing a solution of a nondiiiusing color coupler in a high-boiling organic solvent, each of said particles being insoluble in water at 40 C. and about 80% of said particles being less than 20 in diameter, and each set of said particles containing a different color coupler capable of coupling with the oxidation product of a primary aromatic amino developing agent to form a different dye image.
US789294A 1946-12-09 1947-12-02 Hardened particle mixed grain photographic emulsion Expired - Lifetime US2618553A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB36366/46A GB632804A (en) 1946-12-09 1946-12-09 Improvements in colour photographic materials

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US2618553A true US2618553A (en) 1952-11-18

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US (1) US2618553A (sl)
BE (1) BE478554A (sl)
CH (1) CH275176A (sl)
FR (1) FR962814A (sl)
GB (1) GB632804A (sl)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852383A (en) * 1955-09-01 1958-09-16 Eastman Kodak Co Preparation of photographic packet emulsions by a water-in-oil system
US2965484A (en) * 1956-03-26 1960-12-20 Gen Aniline & Film Corp Mixed packet photographic emulsions
US3276869A (en) * 1961-05-09 1966-10-04 Polaroid Corp Capsular product coated with silver halide and containing a color-providing substance
US5399480A (en) * 1993-09-14 1995-03-21 Eastman Kodak Company Attachment of gelatin-grafted polymer particles to pre-precipitated silver halide grains
US5441865A (en) * 1993-01-07 1995-08-15 Eastman Kodak Company Gelatin-grafted-polymer particles as peptizer for silver halide emulsions
GB2419679A (en) * 2004-11-02 2006-05-03 Eastman Kodak Co Photographic imaging material and method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1055155A (en) * 1912-07-01 1913-03-04 Rudolf Fischer Process of making photographs in natural colors.
US1903783A (en) * 1929-01-22 1933-04-18 Agfa Ansco Corp Production and application of layers sensitive to light
US2168182A (en) * 1936-12-09 1939-08-01 Agfa Ansco Corp Photographic material for color photography
US2186730A (en) * 1936-05-08 1940-01-09 Agfa Ansco Corp Multicolor photography
US2272191A (en) * 1939-12-29 1942-02-10 Eastman Kodak Co Dispersing mixtures of resins and coloring materials in gelatin
US2318597A (en) * 1941-01-03 1943-05-11 Eastman Kodak Co Photographic printing material
US2322027A (en) * 1940-02-24 1943-06-15 Eastman Kodak Co Color photography

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1055155A (en) * 1912-07-01 1913-03-04 Rudolf Fischer Process of making photographs in natural colors.
US1903783A (en) * 1929-01-22 1933-04-18 Agfa Ansco Corp Production and application of layers sensitive to light
US2186730A (en) * 1936-05-08 1940-01-09 Agfa Ansco Corp Multicolor photography
US2168182A (en) * 1936-12-09 1939-08-01 Agfa Ansco Corp Photographic material for color photography
US2272191A (en) * 1939-12-29 1942-02-10 Eastman Kodak Co Dispersing mixtures of resins and coloring materials in gelatin
US2322027A (en) * 1940-02-24 1943-06-15 Eastman Kodak Co Color photography
US2318597A (en) * 1941-01-03 1943-05-11 Eastman Kodak Co Photographic printing material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852383A (en) * 1955-09-01 1958-09-16 Eastman Kodak Co Preparation of photographic packet emulsions by a water-in-oil system
US2965484A (en) * 1956-03-26 1960-12-20 Gen Aniline & Film Corp Mixed packet photographic emulsions
US3276869A (en) * 1961-05-09 1966-10-04 Polaroid Corp Capsular product coated with silver halide and containing a color-providing substance
US5441865A (en) * 1993-01-07 1995-08-15 Eastman Kodak Company Gelatin-grafted-polymer particles as peptizer for silver halide emulsions
US5503972A (en) * 1993-01-07 1996-04-02 Eastman Kodak Company Gelatin-grafted-polymer particles as peptizer for silver halide emulsions
US5399480A (en) * 1993-09-14 1995-03-21 Eastman Kodak Company Attachment of gelatin-grafted polymer particles to pre-precipitated silver halide grains
US5543283A (en) * 1993-09-14 1996-08-06 Eastman Kodak Company Attachment of gelatin-grafted plymer particles to pre-precipitated silver halide grains
US5741633A (en) * 1993-09-14 1998-04-21 Eastman Kodak Company Attachment of gelatin-grafted polymer particles to pre-precipitated silver halide grains
GB2419679A (en) * 2004-11-02 2006-05-03 Eastman Kodak Co Photographic imaging material and method

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Publication number Publication date
BE478554A (sl)
FR962814A (sl) 1950-06-21
GB632804A (en) 1949-12-05
CH275176A (fr) 1951-05-15

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