US2698796A - Resin salts of couplers in mixed packet photographic emulsions - Google Patents

Resin salts of couplers in mixed packet photographic emulsions Download PDF

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Publication number
US2698796A
US2698796A US344896A US34489653A US2698796A US 2698796 A US2698796 A US 2698796A US 344896 A US344896 A US 344896A US 34489653 A US34489653 A US 34489653A US 2698796 A US2698796 A US 2698796A
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United States
Prior art keywords
salt
gelatin
emulsion
silver halide
coupler
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Expired - Lifetime
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US344896A
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English (en)
Inventor
Chechak Jonas John
Scheuring S Fierke
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE527645D priority Critical patent/BE527645A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US344896A priority patent/US2698796A/en
Priority to GB8536/54A priority patent/GB759869A/en
Priority to DEE8767A priority patent/DE1007623B/de
Priority to FR1134299D priority patent/FR1134299A/fr
Application granted granted Critical
Publication of US2698796A publication Critical patent/US2698796A/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
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex

Definitions

  • This invention relates to color photography and particularly to mixed packet photographic emulsions.
  • mixed grain photographic emulsions that is, photographic systems in which difierently sensitized silver halide grains are incorporated in a single photographic emulsion layer and used to produce differently colored photographic images in the layer.
  • Mixed grain systems have a number of advantages, chief among which is the simplicity of coating 21 single emulsion layer rather than several layers. Other advantages are the improved definition obtained by having the difierently sensitized particles juxtaposed in a single layer, and the simplification of processing which is gen erally obtained.
  • a second fault with the solvent system is the fact that the dye formed in the image is in solution in the solvent and is therefore in a more reactive state and is subject to more rapid fading and print-out than a dye in the solid state.
  • a third difficulty with the solvent system is the fact that dispersing agents are used for dispersion of the coupler and these sometimes adversely afiect the stability of the sensitized emulsion insofar as speed and contrast are concerned.
  • a further object is to provide a novel method of incorporating couplers in silver halide emulsions.
  • a still further object. is to provide a novel mixed packet emulsion.
  • a further object is to provide a novel method of incorporating couplers in mixed packet emulsions.
  • a further object is to'lprovide mixed packet emulsions free of organic coupler so vent.
  • couplers 2,698,796 Patented Jan. 4, 1955 having a suflicient number of solubilizing groups so that they can easily be put into aqueous solution, and precipitating the couplers with a polyvinyl resin containing pyridylamine nuclei, such as polyvinyl-N-(a-pyridybamine, to, give a precipitate completely insoluble in water even when the excess precipitant is washed out, but which is still sufi'iciently self-dispersibleso that a satisfactorily fine dispersion can be made without recourse to dispersing agents.
  • a polyvinyl resin containing pyridylamine nuclei such as polyvinyl-N-(a-pyridybamine
  • the fine dispersion of coupler salt is then added to a colloid-silver halide emulsion in the presence of a water-soluble saltof a polymer containing salt-forming acid groups, e. g. a methylmethacrylate-methacrylic acid copolymer, and a packet-forming component, e. g. a styrene-maleamic acid copolymer, to form particles of colloid, packet-forming component and silver halide containing the coupler salt.
  • a water-soluble saltof a polymer containing salt-forming acid groups e. g. a methylmethacrylate-methacrylic acid copolymer
  • a packet-forming component e. g. a styrene-maleamic acid copolymer
  • the invention depends upon the use of polyvinyl resins; These compounds are OSOwR in which R represents hydrogen or an alkyl group containing from lto 5 carbon atoms and R represents an alkyl group containing from 1 to 5 carbon atoms and the resin contains from 6% to 24% by weight of vinylpyrldyl amine units and from 40% to by weight of vinylpyridinium quaternary salt units.
  • Couplers can be incorporated according to our invention to form an emulsion in which dye images are pro prised by color forming development, or dyes may be incorporated in an emulsion to form a system In which dye images can be produced by bleaching the dyes in the presence of the silver image as described in Christensen U. S. Patent 1,517,049.
  • Couplers are suitable for use according to our invention: (1) SOaCI 4,6 dichloro 5 methyl 2 [2(2",4" diamylphenoxy)-5'- (3",5"-dich1orosulfonyl) benzamido ⁇ benzamido] phenol.
  • Compound 1 was prepared in the same way as Compound 11 of Salminen and Weissberger U. S. application Serial No. 344,884, filed concurrently herewith, using 3,5-dichlorosulfonylbenzoyl chloride instead of rn-chlorosulfonylbenzoyl chloride in the next to the last step.
  • Compound 2 was prepared as described in Salminen and Weissberger U. S. application Serial No. 344,884.
  • the flask was stoppered again ':and the mixture refluxed at such a rate as to maintain the temperature of the distilling vapors at 78-80 C. After about 30 mins. the elimination of alcohol became very slow, and the remaining half of the amine was added.i It required a total heating time of 1.5-2.5 hrs. before all ofthe alcohol waseliminated; 40-50 cc. was collected. ; The reaction mixture was cooled with running water until 200 cc. of hen- Iene could be added safely and was well-stirred to prevent The yellumping while the mixture. was cooledftciflO" C. low precipitate was filtered, washed figithSOO cc.
  • F'COMPOUND 5 Ethyl -a-(p-nitr0benzpyl) acetoacetate .In,-a,--l-.liter:beakenwas placed 33 g. (0.25 mole) of ethyl acetoacetate and 100 cc. of water. The mixture was cooled to 15 in running water. Then solutions of 46 g. (0.25 mole) of p-nitrobenzoyl chloride in 100 cc. of acetone and 20 g. (0.50 mole) of sodium hydroxide in 100 cc. of water were added simultaneously with stirring and cooling to keep the temperature below 23. The additions required twenty minutes.
  • the water-soluble polymer when mixed with the gelatin of the dispersion acts as a modifying agent so that small packets containing appropriately sensitized silver halide and color-forming coupler can be formed.
  • the polymeric packet-forming component consists of a polymeric carbon chain having recurring phenyl groups and carboxylic" acid groups and preferably also carboxylic acid amide groups or imide groups or both and is used as the water-soluble salt such as the ammonium, sodium, potassium or lithium salt.
  • the polymeric packet-forming component is preferably an interpolymer of styrene and an a e-unsaturated carboxylic acid, part of whose carboxyl groups have been converted to amide derivatives or both, such as interpolymers of styrene-maleic acid, styrene-acrylic acid, styrene-methacrylic acid, or styrene-itaconic acid.
  • Suitable polymers of styrene with maleic acid or its derivatives which may be used as the polymeric packetforming component according to our invention are described in Godowsky U. S. application Serial No. 156,066, filed April 15, 1950.
  • the polymers illustrated in Examples 2 and 3 of the Godowsky application areespecially suitable for use according to our invention.
  • the packet emulsion in its single layer or single color form consists of particles or packets of gelatin associated with polymeric packet-forming component containing silver halide and coupler salt, the packets being dispersed in an aqueous medium containing additional gelatin or another film-forming water-soluble polymer.
  • the coupler may be made in dispersion in gelatin or in solution in water, added to the silver halide emulsion or to the water-soluble salt such as the salt of methylmethacrylate-methacrylic acid copolymer, and then the.
  • pyridyl)-amine resin in 1% acetic acid solution was then added producing a white precipitate.
  • the mixture was stirred for 5 minutes, filtered, washed and dried to a moist cake. 20 cc. of water and 38 cc. of 10% gelatin solution were added and the mixture stirred at 40 C. until the lumps were broken down and finally dispersed by running through a colloid mill.
  • a third set of packets was made as in A except that a blue-sensitive emulsion and the yellow coupler N0. 3 were used.
  • t t it 1 Film coatings were made by mixing the three components .as follows and coating 25 cc. per square foot of surface:
  • the coating was then placed in an acetic acid stop bath for 5 minutes .and then washed, the reduced silver bleached and fixed in the usual manner.
  • the azo dyes such as No. 7 and No. 8 are incorporated in an emulsion in a manner similar to that used by the couplers except that the hydrolysis step is omitted. Excellent packets containing the dyes are obtained and coatings containing these packets are processed by the silver dye bleach process.
  • one or more couplers may be incorporated in packets and the remaining coupler or couplers may be incorporated in separate layers in dispersion in a coupler solvent or directly incorporated in the gelatin of the emulsion.
  • two packets of different couplers may be incorporated in a single gelatin layer and a third coupler incorporated in another layer either directly in the emulsion or in dispersion in .a solvent for the coupler.
  • all three couplers may be in packet dispersion or two of the couplers may be in packets and the third coupler incorporated in a surrounding silver halide emulsion in the same layer.
  • Antistain agents other than dioctyl hydroquinone may be used in the emulsion such as diamylhydroquinone and didodecylhydroquinone.
  • a color-forming photographic emulsion which comprises dispersing in gelatin a salt of a coloring material selected from the class consisting of color couplers and polyazo dyes containing at least one salt-forming acid group with a polyvinyl resin containing pyridylamine groups and pyridinium quaternary salt groups and having the recurring structure:
  • a mixed packet photographic emulsion which comprises dispersing in gelatin a salt of a coloring material selected from the class consisting of color couplers and polyazo dyes containing at least one salt-forming acid group with a polyvinyl resin containing pyridylamine groups and pyridinium quaternary salt groups and having the recurring structure where R is selected from the class consisting of hydrogen and alkyl groups containing from 1 to 5 carbon atoms and R represents an alkyl group containing from 1 to 5 carbon atoms, said resin containing from 6% to 24% by weight of vinyl pyridylamine units .and from 40% to by weight of vinyl pyridinium quaternary salt units, mixing with the dispersion thus formed a gelatino-silver halide emulsion sensitive to one region but less than all regions ofthe visible spectrum to form an emulsion of gelatin containing dispersed silver halide and coloring material-polyvinyl resin salt, adding to said last-ment
  • a'color-forming photographic emulsion which comprises dispersing in gelatin a polyvinyl-N-(a-pyridyl) amine salt of a color coupler containing at least one salt-forming acid group, mixing with the dispersion thus formed a gelatino-silver halide emulsion to form an emulsion of gelatin containing dispersed silver halide and polyvinyl-N-(a-pyridyl) aminecoupler salt, adding to said last-mentioned emulsion a water-soluble salt of the copolymer of methyl methacrylate and methacrylic acid and a solution of a polymeric carbon chain compound having recurring phenyl groups,
  • a mixed packet photographic emulsion which comprises dispersing in gelatin a polyvinyl-N-(a-pyridyl) amine salt of a color coupler containlng at least one salt-forming acid group, mixing with the dispersion thus formed a gelatino-silver halide emulsion sensitive to one region but less than all regions of the visible spectrum to form an emulsion of gelatin containing dispersed silver halide and polyvinyl-N-(a-pyridyl) aminecouplei' salt, adding to said emulsion a water-soluble salt of the copolymer of methyl methacrylate and methacrylic acid and a solution of a polymeric carbon chain compound having recurring phenyl groups, carboxyl groups and amide-groups appended thereto and stirring to form a dispersion of particles of gelatin, polymeric carbon-chain compound, silver halide, and polyvinyl-N- (a-pyridyl) amine-
  • the method of making a mixed packet photographic emulsion which comprises dispersing in gelatin the polyvinyl N-(a-pyridyl) amine salt of 4,6-dichloro-5-methyl- 2 [2' ⁇ (2",4 diamylphenoxy) 5-(3,5-dichlorosulfonyl)-benzamido ⁇ -benzamido]-phenol, mixing with the dispersion thus formed a red-sensitive gelatino-silver halide emulsion to form an emulsion of gelatin containing dispersed silver halide and coupler salt, adding to said emulsion the ammonium salt of styrene-maleic acid anhydride copolymer and a solution of the copolymer of methylmethacrylate and methacrylic acid and stirring to form a dispersion of particles of gelatin, styrene-maleic acid anhydride copolymer, silver halide and polyvinyl- -(a-pyrid
  • a light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin reacted with a water-soluble salt of an interpolymer of styrene, said interpolymer containing at least a carboxylic acid group of the groups selected from the class consisting of carboxylic acid and carboxylic acid amide groups, said particles or packets containing a salt of polyvinyl-N-(a-pyridyl) amine and a color coupler containing at least one salt-forming acid group, and silver halide sensitive to at least one region but less than all regions of the visible spectrum, and at least one separate set of packets or discrete particles of gelatin reacted with said interpolymer, polyvinyl-N-(a-pyridyl) amine salt of a color coupler different from said first-mentioned color coupler, and silver halide sensitive to a region of the visible spectrum different from that to which said first-mentioned silver halide is sensitive.
  • the method of making a color-forming photographic emulsion which comprises dispersing in gelatin a polyvinyl-N-(a-pyridyl) amine salt of a polyazo dye containing at least one salt-forming acid group, mixing with the dispersion thus formed a gelatino-silver halide emulsion to form an emulsion of gelatin containing dispersed silver halide and polyvinyl-N-(a-pyridyl) amine-dye salt, adding to said last-mentioned emulsion a water-soluble salt of a polymer containing salt-forming acid groups and a solution of a polymeric carbon chain compound having recurring phenyl groups, carboxyl groups and amide groups appended thereto and stirring to form a dispersion of particles of gelatin, polymeric carbon chain compound, silver halide, and polyvinyl-N-(a-pyridyl) amine-dye salt in gelatin.
  • a light-sensitive mixed packet photographic emulsion comprising packets or discrete particles of gelatin reacted with a water-soluble salt of an interpolymer of styrene, said interpolymer containing at least a carboxylic acid group of the groups selected from theclass consisting of carboxylic acid and carboxylic acid amide groups, said particles or packets containing a salt of polyvinyl-N- (a-pyridyl) amine and a polyazo dye containing at least one salt-forming acid group, and silver halide sensitive to at least one region but less than all regions of the visible spectrum, and at least one separate set of packets or discrete particles of gelatin reacted with said interpolymer, polyvinyl-N-(a-pyridyl) amine salt of a polyazo dye different from said first-mentioned polyazo dye, and silver halide sensitive to a region of the visible spectrum different from that to which said first-mentioned silver halide is sensitive.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US344896A 1953-03-26 1953-03-26 Resin salts of couplers in mixed packet photographic emulsions Expired - Lifetime US2698796A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE527645D BE527645A (en(2012)) 1953-03-26
US344896A US2698796A (en) 1953-03-26 1953-03-26 Resin salts of couplers in mixed packet photographic emulsions
GB8536/54A GB759869A (en) 1953-03-26 1954-03-24 Method of making photographic emulsions for colour photography
DEE8767A DE1007623B (de) 1953-03-26 1954-03-25 Verfahren zur Herstellung einer farbenphotographischen Emulsion, vorzugsweise einer farbenphotographischen Mischemulsion
FR1134299D FR1134299A (fr) 1953-03-26 1954-03-26 Procédé de préparation de produits photosensibles et nouveaux produits obtenus

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US344896A US2698796A (en) 1953-03-26 1953-03-26 Resin salts of couplers in mixed packet photographic emulsions

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BE (1) BE527645A (en(2012))
DE (1) DE1007623B (en(2012))
FR (1) FR1134299A (en(2012))
GB (1) GB759869A (en(2012))

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2835580A (en) * 1955-11-10 1958-05-20 Eastman Kodak Co Photographic emulsion with vinyl alcohol-n-allylcyanoacetamide copolymer continuous phase
US3000740A (en) * 1955-10-01 1961-09-19 Gevaert Photo Prod Nv Photographic material
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2422680A (en) * 1944-06-01 1947-06-24 Du Pont Process for preparing hydrophilic color-former silver halide dispersions
US2463794A (en) * 1944-08-30 1949-03-08 Du Pont Preparation of colloid color former silver halide dispersions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3000740A (en) * 1955-10-01 1961-09-19 Gevaert Photo Prod Nv Photographic material
US2835580A (en) * 1955-11-10 1958-05-20 Eastman Kodak Co Photographic emulsion with vinyl alcohol-n-allylcyanoacetamide copolymer continuous phase
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

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Publication number Publication date
BE527645A (en(2012))
DE1007623B (de) 1957-05-02
FR1134299A (fr) 1957-04-09
GB759869A (en) 1956-10-24

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