US2965484A - Mixed packet photographic emulsions - Google Patents

Mixed packet photographic emulsions Download PDF

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Publication number
US2965484A
US2965484A US573799A US57379956A US2965484A US 2965484 A US2965484 A US 2965484A US 573799 A US573799 A US 573799A US 57379956 A US57379956 A US 57379956A US 2965484 A US2965484 A US 2965484A
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United States
Prior art keywords
gelatin
silver halide
grains
sensitive
hydrophobic
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Expired - Lifetime
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US573799A
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English (en)
Inventor
Tulagin Vsevolod
Robert D Jackson
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GAF Chemicals Corp
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General Aniline and Film Corp
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Priority to BE556138D priority Critical patent/BE556138A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US573799A priority patent/US2965484A/en
Priority to GB9008/57A priority patent/GB811907A/en
Priority to DEG21762A priority patent/DE1055950B/de
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Publication of US2965484A publication Critical patent/US2965484A/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
    • 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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor

Definitions

  • the present invention pertains to hydrophobic silver halide grains, said grains dispersed in a highly non-water miscible liquid, water-sensitive or hydrophilic colloidal carriers containing such dispersions, and light sensitive emulsons containing a matrix of a water-sensitive or hydrophilic collofdal medium having dispersed therethrough immobile packets of a highly non-water miscible solvent surrounding hydrophobic silver halide grains with associated sensltizers and, if desired, color formers capable of yielding a dye image complementary in color to the light rays for which such hydrophobic silver halide grains are respectively sensitized, and methods for producing said grains and compositions.
  • sensitizer from layer to layer of color film has not been a particular problem.
  • a real problem arises if this phenomenon is permitted to ensue in so-called variable contrast paper.
  • two photographic emulsions of quite different contrast, each senstized to different regions of the spectrum, are intermixed.
  • the contrast of the image of such papers is controlled by the color of the exposing light. It is imperative in such materials to avoid migration of the sensitizers from grain to grain and also so-called contagious development wherein one exposed grain will cause several unexposed grains to become developable. In other words, it is essential that each emulsion function completely independently of the others present.
  • zein as the peptizing agent (colloid) in the formation of mixed grain packets.
  • the silver halide is formed in zein to produce oil soluble packets which are then dissolved in benzyl alcohol.
  • the resulting solution, to which sensitizers and/or color formers may be added, is then dispersed in a water receptive carrier, such as gelatin (U.S.P. 2,563,791).
  • a water receptive carrier such as gelatin
  • a f-urther advance in the packet 'concept was claimed in British Patent 711,488 and U-.S.'P. v2,698,795 and U-.S.P. 42,698,796, which turned upon the use, for iev# veloping the silver halide grains with associated sensitizeifs and color formers, if desired, of a copolymer of styrene and -maleic anhydride, on the one hand, and a water soluble polymer 'containing salt ⁇ forming acid groups, on thel other hand, such as a 'copolymer of methacrylic acid and methyl-a-methacrylate.
  • the colloidal carrier in this system is gelatin in which th'e silver halide is precipitated.
  • hydrophilic is meant that the sliver halides are preferentially wetted by water and even though obtained in a dry state, if dispersed in a water insoluble medium, would leave such medium and go into water or an aqueous solution if shaken therew th.
  • the vpattern Yfollowed by prior operators to effect and maintain the isolation of silver halidel grains in packets is- ⁇ self-evident from the above rsum.
  • the silver halide in normal photographic emulsions has an inherent propensity to segregate in the emulsion.
  • the idea has been, not to divest the silver halide grains of this natural propensity, but rather to imprison or entrap the grains through a hit or miss manner in a ce ⁇ l or enve'ope of 'a body foreign to the carrier matrix, such as a water insoluble or water soluble natural or synthetic resfn.
  • the silver halide .grains are separated from the aqueous mediuml by decantation, filtration or centrifugation.-
  • the isolated solid is re-'suspendedin a normally liquid (i.e., liquid at room temperature) inertY non-aqueous organic solvent, such as acetone, mcthylethyl ketone, benzene, ethyl acetate or the like, and thoroughly washed ktoremove any residual free water.
  • a normally liquid (i.e., liquid at room temperature) inertY non-aqueous organic solvent such as acetone, mcthylethyl ketone, benzene, ethyl acetate or the like, and thoroughly washed ktoremove any residual free water.
  • the solid in such solvent is then subjected to the action of a chemical reagent capable of rendering the surface of the gelatin envelope hydrophobic.
  • the latter treatment consists in closely associating the gelatin envelope of each silver halide grain with a hydrophobic moiety (see Schwartz- Ferry, Surface Active Agents, Interscience Publishers, Inc., New York, 1949, pages l7-20),'preferably, a long aliphatic chain, i.e., containing ten or more carbon atoms.
  • a hydrophobic radical on the one hand, and a group readily reactive with amines, on the other hand, such as long chain acid anhydrides, acid chlorides, sul fonyl chlorides, isocyanates or chlorocarbonates.
  • Such long chain aliphatic compounds are those normally ernployed in modifying surface ⁇ properties.
  • such compounds are tetradecyl isocyana-te, hexadecyl isocyanate, myristyl isocyanate, myristic anhydride, palmityl anhydride, Vrnyr-istoyl chloride, -palmitoyl lchloride, stearoyl chloride, -myristylsulfonyl chloride, palmityh si'ilfon-yl chloride, stearylsulfonyl chloride, decylchloro- It has been Examples of carbonate, hexadecylchlorocarbonate, tetradecylchlorocarbonate, and the like.
  • the treatment with these reagents is effected in normally liquid, inert organic solvents, such as, acetone, benzene, ethyl acetate, butyl acetate, methylethyl ketone and the like.
  • the silver halide grains are not rendered hydrophobic in the event that the reagent employed is relatively inert to amines, i.e., a carboxylic acid, per se, such as myristic acid.
  • the excess of the hydrophobating reagent is removed by washing with an organic solvent, such as acetone, and gradually replaced with another organic solvent which is to -be the final carrier for the transformed silver halide and which is an oily, non-water miscible liquid, such as benzyl alcohol, phenyl ethyl alcohol, 'y-phenylpropyl alcohol or the like, phthalic acid esters, i.e., dibutyl phthalate, di--ethoxyethyl phthalate, tricresyl phosphate, triphenyl phosphate, or a combination of such solvents.
  • an organic solvent such as acetone
  • the silver halide grain in such solvent is now added to non-aqueous solutions of color formers, sensitizing dyes, stabilizers and other adjuncts usual in the manufacture of photographic emulsions.
  • the color formers employed are of the type capable of forming azomethine, quinoneimine or azine dyes on color development, i.e., they contain a phenolic hydroxy or reactive methylene group, are oil soluble and preferably contain an aliphatic chain of at least carbon atoms.
  • Illustrative of color formers in this category are those described in Schneider et al., U.S.P. 2,186,849, without, however, a water solubilizing group being present in the color former molecule.
  • the non-aqueous packets thus obtained are then dispersed in an aqueous solution of a water permeable colloid, such as gelatin, gum arabic, starch, polyvinyl alcohol, or carboxymethyl cellulose, with or without the aid of dispersing agents, as the occasion may demand and the operator may see tit to use.
  • a water permeable colloid such as gelatin, gum arabic, starch, polyvinyl alcohol, or carboxymethyl cellulose
  • the Water soluble carrier should be capable of gelation so that once cast or gelled, a rigid matrix is obtained.
  • thislprocedure would permit theseparate sensitization of hydrophobic grains to the blue, green and red region of the spectrum along with color formers capable of giving a dye complementary in color to that of the spectral region to which the grains are sensitized.
  • the different packets may then be dispersed in one and the same water permeable colloid and the resulting emulsion coated and dried.
  • a single exposure and color development with a primary aromatic amino developer such as the Ndialkyl-p-phenylenediamines, i.e., N-diethyl-p-phenylenediamine, 3-methyl-4-diethylaminoaniline, N--hydroxyethyl-N-ethyl-p-phenylenediamine and the like would produce images in the various ⁇ primary colors with adequate color separation being a.s ⁇ sured.
  • a further advantage resides in the fact that a drastic discontinuity between the packet and the matrix helps to isolate each individual packet and make it independent of chemical processes which may be taking place in an adjacent packet. Furthermore, it is possible to prepare packets of uniform size distribution and of almost any specified size.
  • DIGESTION PROCEDURE Example I 50% acetone(by volume) followed by two washings ⁇ with acetone, using 150 ml. of solvent each time.
  • the Washes were removed by decantation.
  • the silver halide may then be made hydrophobic as :subsequently described. i
  • Example II To 1000 grams of a melted added 100 ml. of 1% gelatin silver halide were trypsin as in Example I. After removall of ⁇ the digested gelatin, the precipitated silver halide was washed' with two 2,00 rnl. portions of 50% ethanol' followed by two washings with 95% alcohol, using 150-ml. each time. The product was then made hydrophobic as subsequently described.
  • Example lll The silver halide isolated by enzymatic ⁇ digestion as in Examplel was suspended in a solution of 2.5 grams of myristic anhydride dissolved in 100 ml. of acetone.
  • Themixture was tumbled inlasmall roller mill for several hours and then allowed to stand until the silver halide Vhad settled.
  • the acetone solution was decanted and the precipitate washed with two 150 ml. portions of fresh acetone.
  • the damp. cake. was suspended in 30 rnl. of phenyl ethyl alcoholand stirred vigorously for 3 minutes in a small Waring blender.
  • the resulting milky oil containing the hydrophobic silver halide is ready to be incorporated in packet or mixed grain photographic emulsions.
  • Example IV The silver halide obtained according to Example I was stirred up with a solution of 5.0 grams of myristic isocyanate in 100 ml. of acetone for l0 hours. The suspension was allowed to settle and the precipitate washedl twice with 200 ml. portions of acetone. The damp c-ake of hydrophobic silver halide was then dispersed in tricresyl phosphate to be used in the preparation of mixed grain photographic emulsions.
  • Example V Example Vl 'Ihe procedure was the same as in Example III, exceptingr that the.y hydrophobic character was imparted to the silver halideerains by treatment. with octadooyl chlorocarbonate.
  • Example VII The, procedure was the same as in Example V, excepting that tetradecylsulfonyl chloride was employed to render the silver halide grains hydrophobic.
  • Example VIII 0.60 gram of 25% phenyl ethyl alcohol silver halide suspension prepared according to Example III was added to 30 ml. of 10% ⁇ gelatin andthe resulting mixture stirred vigorously for minutes. A dispersion was obtained consisting of minute oily droplets, 2 to 4 microns in diameter containing embedded hydrophobic silver halide crystals..
  • Example 0.0902 gram ofV yellow coupler (NhacetylAbenzoyiaootamidoshlfahilaoilide) was dissolved is. a mixtuo. of; 2.0 grams of; trioiosyl phosphate. alos 2-O, gratos of.. benzyl alcohol to which was added 0.274 gram of 24%.
  • hydrophobic Silver Chlorido ⁇ Suspended ihy phenyl ethyl alcohol and the whole rhixod thoroughly- T-.his mixture.. was. thon dispersed.
  • Example X1 To 0.0764 gram of l-hydroxy-N-myrilstyl naphtharnidel and .007 mg. of a red sensitizing dye dissolved in a mixture ot 1.0 gram of phenyl ethyl alcohol plus 1.0 gram of the product sold by Atlas Powder Company as Span was added with good stirring 0.274 gram of 24% hydrophobic silver chloride suspended in( phenyl ethyl alcohol. This mixture was then dispersed in 30 rnl. of 10% gelatin by stirringl until the sizeY of the droplets were 5 to 10 microns. Y
  • Example XII To 0.0882 gram of l-phenyl-3-stearoylamino-S-pyrazolone and .01 mg. of a green sensitizing dye dissolved in a mixture of 5.71 grams of phenyl ethyl alcohol,
  • Example XIII To 0.152 gram of yellow coupler (4f-benzoylacetamido- N4caproylsulfanilanilide) dissolved in a Amixture of 5.71 ml. of phenyl ethyl alcohol and 0.63 ml. of tricresyl phosphate was added 0.397 gram of 34.5% hydrophobic silver chloride phenyl ethyl alcohol suspension and the whole thoroughly stirred. This mixture was dispersed in 30 ml. of a 10% solution of gelatin in a small Waring blender. Agitation was continued until a particle size of 5 to l0 microns was achieved.
  • yellow coupler (4f-benzoylacetamido- N4caproylsulfanilanilide) dissolved in a Amixture of 5.71 ml. of phenyl ethyl alcohol and 0.63 ml. of tricresyl phosphate was added 0.397 gram of 34.5% hydrophobic silver
  • Example XIV One part of the emulsion from Exemple IX was added to one ⁇ part of the emulsion from Example XI, and the resulting mixture gently stirred for 5. minutes. This mixed emulsion was coated on suitable lm base, dried and exposed through a step wedge and developed ina developing solution of the following composition to form a negative colored image:
  • Example XV One part of the green sensitive emulsion prepared in Example XII was added to one part of the blue sensitive emulsion from Example Xlil. The mixture was gently agitated for 3 minutes and then coated on suitable ilm base and exposed through a blue and green filter. Develcpment was carried out as described in Example XIV. Satisfactory color separation of magenta and yellow images. Wis. obtained in the Portions. of ⁇ theooaiihe exposed. to green and blue light, respectively. v
  • Example XVI Example X VII One part of the emulsion from Example IX, one part of the emulsion from Example X and one part of the emulsion from Example XI were added together and the resulting mixture gently stirred for a period of minutes. The mixed emulsion was coated on a film base, dried,
  • Example XVIII The procedure is the same as in Example XIV, excepting that the color developing agent is N-diethyl-p-phenylenediamine.
  • a base may be coated sequentially with a red sensitized emulsion (Example XI), a green sensitized emulsion (Example IX) and a blue sensitive emulsion (Example X).
  • This monopack iilm layer may be exposed and processed with the usual primary aromatic amino color developers to the three complementary colored images.
  • a light-sensitive photographic emulsion comprising a hydrophilic colloid carrier having dispersed therethrough immobile packets of an oily, non-water miscible solvent surrounding light-sensitive silver halide grains which have been rendered hydrophobic by treating a light-sensitive gelatin silver halide photographic emulsion with a proteolytic enzyme in order to digest the gelatin carrier and produce silver halide grains each surrounded ⁇ by a hull of adsorbed gelatin, separating the light-sensitive grains and their adsorbed gelatin hulls from the digested gelatin and treating by intimately associating the gelatin hulls and said grains with an aliphatic compound having a hydrocarbon cha-in of at least 10 carbon atoms and a ⁇ substituent selected from the group consisting of acid anhydrides, acid chlorides, sulfonyl chlorides, isocyanates and chlorocarbonates.
  • the process of rendering silver halide grains hydrophobic which comprises treating a light-sensitive gelatin silver halide photographic emulsion with a proteolytic enzyme in order to digest the gelatin carrier and produce silver halide grains each surrounded by a hull of adsorbed gelatin, separating the light-sensitive grains and their adsorbed gelatin hulls from the digested gelatin and treating by intimately associating the gelatin hulls and said grains with an aliphatic compound having a hydrocarbon chain of at least 10 carbon atoms and a substituent selected from the group consisting of acid anhydrides, acid chlorides, sulfonyl chlorides, isocyanates and chlorocarbonates.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Pyridine Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US573799A 1956-03-26 1956-03-26 Mixed packet photographic emulsions Expired - Lifetime US2965484A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE556138D BE556138A (xx) 1956-03-26
US573799A US2965484A (en) 1956-03-26 1956-03-26 Mixed packet photographic emulsions
GB9008/57A GB811907A (en) 1956-03-26 1957-03-19 Improvements relating to photographic emulsions
DEG21762A DE1055950B (de) 1956-03-26 1957-03-23 Lichtempfindliche Halogensilber-Gelatine-Aggregate und Verfahren zu ihrer Herstellung

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212896A (en) * 1961-06-07 1965-10-19 Eastman Kodak Co Dry processing of photographic emulsions
US3755177A (en) * 1969-02-04 1973-08-28 Xerox Corp Process of making liquid electrostatic developers containing gelatin
US5399480A (en) * 1993-09-14 1995-03-21 Eastman Kodak Company Attachment of gelatin-grafted polymer particles to pre-precipitated silver halide grains

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2527261A (en) * 1944-10-30 1950-10-24 Ilflord Ltd Production of photographic silver halide emulsions from gelatinanion soap complexes
US2544640A (en) * 1949-06-10 1951-03-13 Eastman Kodak Co Mixed grain photographic emulsions
US2618553A (en) * 1946-12-09 1952-11-18 Eastman Kodak Co Hardened particle mixed grain photographic emulsion
US2698794A (en) * 1950-04-15 1955-01-04 Eastman Kodak Co Mixed packet photographic emulsions
US2728662A (en) * 1947-08-13 1955-12-27 Eastman Kodak Co Method of preparing photographic emulsions
US2763552A (en) * 1950-04-15 1956-09-18 Eastman Kodak Co Modifiers for photographic packet emulsions
US2768079A (en) * 1954-01-25 1956-10-23 Eastman Kodak Co Method of preparing washed photographic emulsions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2527261A (en) * 1944-10-30 1950-10-24 Ilflord Ltd Production of photographic silver halide emulsions from gelatinanion soap complexes
US2618553A (en) * 1946-12-09 1952-11-18 Eastman Kodak Co Hardened particle mixed grain photographic emulsion
US2728662A (en) * 1947-08-13 1955-12-27 Eastman Kodak Co Method of preparing photographic emulsions
US2544640A (en) * 1949-06-10 1951-03-13 Eastman Kodak Co Mixed grain photographic emulsions
US2698794A (en) * 1950-04-15 1955-01-04 Eastman Kodak Co Mixed packet photographic emulsions
US2763552A (en) * 1950-04-15 1956-09-18 Eastman Kodak Co Modifiers for photographic packet emulsions
US2768079A (en) * 1954-01-25 1956-10-23 Eastman Kodak Co Method of preparing washed photographic emulsions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3212896A (en) * 1961-06-07 1965-10-19 Eastman Kodak Co Dry processing of photographic emulsions
US3755177A (en) * 1969-02-04 1973-08-28 Xerox Corp Process of making liquid electrostatic developers containing gelatin
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

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DE1055950B (de) 1959-04-23
GB811907A (en) 1959-04-15

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