US3436222A - Process for preparing a photographic emulsion - Google Patents

Process for preparing a photographic emulsion Download PDF

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Publication number
US3436222A
US3436222A US435676A US3436222DA US3436222A US 3436222 A US3436222 A US 3436222A US 435676 A US435676 A US 435676A US 3436222D A US3436222D A US 3436222DA US 3436222 A US3436222 A US 3436222A
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United States
Prior art keywords
photographic
solution
silver halide
emulsion
polymeric
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US435676A
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English (en)
Inventor
Ramsis Gobran
Ronald F Ofstead
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3M Co
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Minnesota Mining and Manufacturing 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances

Definitions

  • gelatin Among the disadvantages of gelatin are variability in physical properties and chemical composition which lead to variations in the physical and photographic properties of the finished photographic emulsion; and variation in the susceptibility of the silver halides contained in these emulsions to sensitizing and desensitizing substances, developng agents and the like. Furthermore, gelatin products being brittle when dry, gelatin emulsion layers crack easily.
  • Another object of the invention is to provide lightsensitive photographic materials employing silver halide in which combinations of synthetic polymers are used, each polymer performing a selected function in compatibility with the other polymers present and with improved results.
  • Another object of the invention is to provide a novel process for the production of photographic emulsions.
  • Yet another object of the invention is to provide a unique method for production of photosensitive silver halide grains.
  • a still further object of the invention is to provide photographic materials using the emulsions of the invention.
  • the synthetic polymeric material for precipitation of silver halide and Ostwald ripening thereof is chosen from a class of synthetic polymers comprising water-soluble polymeric polyamine halide salts which act as source of halide ion for the formation of silver halide, and which also function as a protective colloid for precipitation of silver halide, and which permit Ostwald ripening to occur.
  • polyamines are polyethylenimine, polypropylenimine and polyaminoalkyl acrylates.
  • polymers when neutralized with a hydrohalic acid, form amine salts, unless all of the valence bonds of the amino groups are attached to carbon and such polymers are treated with an alkyl or aryl halide, in which case a quaternary ammonium structure results.
  • Polymeric polyamine salts and polymeric polyamine quaternary halides are included within the scope of the terms polymeric polyamine halide salts and halide salts of polymeric polyamine as used in the specification and claims of this application for Letters Patent.
  • the polymeric polyamines used in the invention can be further defined as containing from about 3 to 50 percent of amino nitrogen by weight, and preferably, from about 5 to 35 percent of nitrogen by weight. This corresponds broadly to an amino nitrogenzcarbon ratio of from about 1:1 to 1:30. Preferably the ratio is from about 1:2 to 1:20.
  • Polymers are known to consist of chains of atoms, the chains being of varying lengths. Thus, for example, when molecular weights of polymers are stated, they are average numbers which include lower and higher molecular Weight species.
  • the polymeric polyamines employed in the present invention are those having molecular weight sufiicient to act as a protective colloid, and broadly speaking, they have molecular weight ranging from about 1000 up to 100,000 or higher, on the average. In terms of repeating units, however, they can be characterized as having from about to 2000 or more repeating units.
  • Copolymers are also useful in the process of the invention, providing they meet these requirements, for example, copolymers of ethylenimine and propylenimine, and the like.
  • Copolymers in which one of the monomers contains no amino nitrogen are also useful; e.g., copolymers of polyethylenimine and polyethylene oxide can be used within the limits set forth. Such copolymers, and mixtures of polymers, are included within the scope of the term polymeric polyamine as used herein.
  • Some polymers in their lower molecular weight ranges as specified herein are of low viscosity and have little protective colloid action.
  • such polymers can be supplemented by adding to the solution in which precipitation of silver halide is to take place, non-gelatin, watersoluble polymers other than the polymeric polyamines, to increase the protective colloid action.
  • the above-mentioned second synthetic material which is used as a binder for the emulsion of the invention, is selected from a class of materials comprising synthetic or suitably modified (at least partially synthetic) naturally occurring polymers of vegetable origin which can be coated upon a supporting base from a water dispersion.
  • synthetic or suitably modified (at least partially synthetic) naturally occurring polymers of vegetable origin which can be coated upon a supporting base from a water dispersion.
  • These include water-soluble, film-forming polymers which can be crosslinked or otherwise rendered water-insoluble, or which form thermally reversible gels.
  • polymers of this type which form latices can be employed. They are selected according to their known characteristics, in order to provide optimum physical and mechanical characteristics in the final photographic products.
  • the film-forming binder cap if desired, be present during precipitation of the halide, or can be added to the precipitated and ripened grains of silver halide after these are formed. At least a part of the polymeric polyamine protective colloid present during precipitation of the silver halide grains can have been removed, if desired, prior to or after addition of the binder.
  • the synthetic polymeric polyamines employed in this invention may be treated (neutralized) with either a hydrohalic acid or with an organic halogen compound reactive towards amines, to form the polymeric polyamine halide salt.
  • a hydrohalic acid or with an organic halogen compound reactive towards amines include hydrochloric, hydrobromic and hydriodic acid, as well as methyl iodide, methyl bromide, ethyl iodide, and the like.
  • An important characteristic of such a salt is believed to be the uniform array or spacing of halide ions along the polymer chain. This appears to aid in preventing clumping and to promote formation of uniform silver halide grains during precipitation.
  • Chloride, bromide, iodide or combinations of these anions may be employed in this invention by choice of the appropriate hydrohalic acid, or reactive organic halogen compound used to quaternize the synthetic polymeric polyamine, in order to prepare silver halide photographic emulsions of desired silver halide composition.
  • film-forming synthetic binder for the photographic emulsion is determined by the physical and chemical properties desired in the ultimate photographic products.
  • a film-forming material or a combination of film-forming materials is selected which is compatible with the polymeric polyamine halide salt and which may be readily crosslinked or otherwise rendered water-insoluble.
  • the film remains in or is treated to place it in condition in which it is permeable to or swelled by the solvent of the developer.
  • crosslinking or insolubilization may be achieved by the use of agents known in the art, for example, as disclosed in United States Patents 3,113,026; 2,720,468; 2,671,022; 2,646,411 and 2,376,371.
  • agents known in the art for example, as disclosed in United States Patents 3,113,026; 2,720,468; 2,671,022; 2,646,411 and 2,376,371.
  • Other crosslinking or insolubilizing agents which can be employed are formaldehyde, mucochloric acid and tris-(laziridinyl)-phosphine oxide.
  • Such synthetic polymeric film-forming binders are hydroxyethyl cellulose, hydroxypropylcellulose, polyvinylprrolidone and the like.
  • the filmforming binder employed can be gelatin if desired.
  • the precipitation of silver halide grains may be effected in the presence of the quaternized or neutralized synthetic polymeric polyamine salt alone or in the presence of both the polymeric polyamine salt and the filmforming polymer, depending upon the choice of synthetic materials employed and upon the subsequent operations desired in the emulsion preparation.
  • Adjuvants for light-sensitive emulsions such as sensitizers and sensitizing dyes, fog inhibitors, developing agents and the like, all of which are well-known to the art, can also be present in the emulsions of the invention.
  • Crosslinking agents, surfactants or hardeners can likewise be employed in the usual way.
  • the process of the invention is the following: An aqueous mixture containing the polymeric polyamine halide salt (quaternized or neutralized) which may contain the film-forming polymer, for example, containing polyvinyl alcohol, and while maintaining the mixture containing the polyamine halide salt in the dark, is combined with soluble silver salt, e.g., silver nitrate, in desired amount with proper stirring to insure substantial homogeneity of the resulting emulsion.
  • soluble silver salt e.g., silver nitrate
  • An excess of the polymer salt may be present, but generally the amount of halide salt used is not less than that which is stoichiometrically equivalent to the amount of soluble silver salt employed.
  • the emulsion After formation of the silver halide by reaction with the halogen anions of the polymeric polyamine salt, the emulsion may be coated as such or it may be maintained at an elevated temperature, say 50-60 C., for Ostwald ripening.
  • suflicient halide ion can be provided by the halide salt of the polymeric polyamine, so that Ostwald ripening can be accomplished.
  • the precipitation of silver halide and ripening can be accomplished in the absence of the film-forming binder if desired. Furthermore, if desired, substantially all of the polymeric polyamine can be removed following the formation of silver halide grains of desired size. In these cases, the film-forming binder is added separately, with agitation to insure a homogeneous dispersion of silver halide grains. Because no inorganic cations are present from the silver halide formation, washing of the emulsion is unnecessary.
  • the fluid emulsions thus prepared can be coated upon a flexible or rigid supporting base, for example, baryta paper, and dried in the dark at room temperature.
  • photographic taking films can be made using appropriate glass sheets or transparent plastic film base material instead of the paper. These photographic materials have high sensitivity and excellent photographic characteristics. When made with synthetic polymers they also have physical properties superior to those of emulsions prepared using gelatin. Light-sensitive materials prepared in this way can be exposed and developed in the usual manner using the common developing agents.
  • solution A Five parts of solution A are added to 62.5 parts of solution B. While stirring, the mixture is acidified to a pH between pH 2 and pH 7 by the addition of 48 percent hydrobromic acid, following the pH change with a glass electrode pH meter. To the above mixture is then added 0.3 part of boric acid in 2 parts of water, slowly and with good stirring. The remainder of the operations are carried out in the darkroom. Five parts of solution C are added with good stirring over a period of 30 seconds, and the mixture is thereafter stirred thoroughly for 5 minutes.
  • a non-ionic surfactant e.g., Polytergent J-300, a polyethoxylated higher alcohol, containing approximately 9 moles of ethylene oxide
  • a non-ionic surfactant e.g., Polytergent J-300, a polyethoxylated higher alcohol, containing approximately 9 moles of ethylene oxide
  • EXAMPLE 2 For comparative purposes, systems similar to those of the invention, that is, using polyethylenimine as in Example 1, but forming the silver halide grains in the conventional way, were prepared as follows:
  • photographic prints obtained were of poor quality, possessing a high fog level and lacking in definition.
  • photographic emulsions prepared employing synthetic polymeric amines which have been quaternized with an acid other than a hydrohalic acid, and in which the halide ion for silver halide formation was introduced in the form of an alkali metal halide yield photographic products unsuitable for practical photographic uses.
  • EXAMPLE 3 Following the procedure of Example 1, 10 parts of solution A are mixed well with 8 parts of 48 percent aqueous hydrobromic acid. To this is added 100 parts of 3 percent aqueous cellulose ether solution (Klucel G, available from the Hercules Powder Co.), with good mixing. The various mixing, coating and drying steps are carried out at 25 C. After preparation of the polymer mixture, further operations are conducted in a darkroom. Ten ml. of solution C are added to the well-stirred polymer solution. Five parts of 5 percent acetone solution of mucochloric acid, 3 parts of 37 percent aqueous formaldehyde solution and 3 parts of surfactant solution (as in Example 1) are then added with stirring. The emulsion thus prepared is coated upon baryta paper. After airdrying, the paper is stored in light-proof containers. Excellent photographic prints are made upon such printing paper.
  • EXAMPLE 4 Nine parts of a 50 percent aqueous solution of polyproplyenimine (M. W. about 20-40,000) are acidified to pH 4 with 48 percent hydrobromic acid. To this solution are added parts of a 10 percent aqueous solution of polyvinyl alcohol, with good stirring. Thereafter, all operations are conducted with the exclusion of light. A solution of 5.4 parts of solution C (Example 1) is added to the well-stirred polymer mixture. A water solution of a hardener for polyvinyl alcohol, and 4 parts of surfactant solution (as in Example 1) are added with thorough stirring. The emulsion thus prepared is coated upon baryta paper, and the coating is air-dried. Thereafter, the paper is stored in light-proof containers.
  • Example 5 The procedure of Example 1 is employed, except that poly-N-hydroxyethyl ethylenimine is employed. A solution of 5 parts of poly-N-hydroxyethyl ethylenimine (M. W. ranging from about 1040,000), 50 percent solids in Water, is added to 62.5 parts of solution B. While stirring, the solution is acidified with 48 percent hydrobromic acid to a pH value between pH 2 and pH 7. To this solution is added slowly and with good stirring, an aqueous solution of a hardner. Thereafter, operations are carried out in the dark, and 4.7 parts of solution C (the calculated amount) and a small amount of an aqueous solution of a non-ionic surfactant are added with good stirring.
  • M. W. ranging from about 1040,000 50 percent solids in Water
  • the emulsion thus prepared is coated on baryta paper and on subbed polyester film. These coatings were airdried and then stored in light-proof containers. When exposed in a standard camera, and developed using the normal photographic and fixing methods, excellent negatives and prints were obtained.
  • EXAMPLE 6 Ostwald ripening of silver halide grains by the process of the invention is shown as follows: The solutions described in Example 1 are employed. To parts of solution A are added a sufiicient amount of 48 percent hydrobromic acid to bring the solution to between about pH 2 and pH 7. In the dark, and while stiring, 5 pats of solution C are added over a period of about 60 seconds with rapid agitation. The stirring speed is then reduced to gentle agitation and the mixture is heated at 60 C. for 40 minutes. Samples of the mixture are removed after 10, 20, 30 and 40 minutes of ripening. Electron micrographs of these samples show octahedral silver bromide crystals with maximum diameters as follows:
  • Example 1 The procedure of Example 1 is followed except that solution A is not used. Instead, 12 parts of a polymeric poly quaternary amine bromide, made by completely quaternizing poly-4-vinylpyridine (M.W. about 5-40,000) by reaction with ethyl alpha-bromoacetate, are added to 62.5 parts of solution B. The addition of a small amount of 48 percent hydrobromic acid suffices to acidify the mixture.
  • the process thereafter follows Example 1. Paper coated with the emulsion thus prepared can be exposed to light through a negative and developed with the ordinary metol-hydroquinone developing agents.
  • a method for preparing a photographic emulsion containing silver halide crystals which comprises preparing an aqueous solution of a halide salt of a polymeric polyamine having a molecular weight greater than about 1000 and containing about 3 to percent by Weight of amino nitrogen, and adding thereto an aqueous solution of a soluble silver salt.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
US435676A 1965-02-26 1965-02-26 Process for preparing a photographic emulsion Expired - Lifetime US3436222A (en)

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BE (1) BE676549A (enrdf_load_stackoverflow)
DE (1) DE1572205A1 (enrdf_load_stackoverflow)
GB (1) GB1128959A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607290A (en) * 1968-01-08 1971-09-21 Minnesota Mining & Mfg Polymer-containing silver halide photographic emulsions, preparation thereof and photographic elements produced therefrom
CN117487307A (zh) * 2023-11-17 2024-02-02 育才控股集团股份有限公司 一种abs复合抗菌塑料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2484423A (en) * 1945-10-30 1949-10-11 Eastman Kodak Co Process for the preparation of polyvinylamine salts
US2949442A (en) * 1955-05-04 1960-08-16 Eastman Kodak Co Process for preparing amphoteric copolymers and the resulting products
US3084132A (en) * 1958-06-25 1963-04-02 Du Pont Process for forming a stable distribution of silver halide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2484423A (en) * 1945-10-30 1949-10-11 Eastman Kodak Co Process for the preparation of polyvinylamine salts
US2949442A (en) * 1955-05-04 1960-08-16 Eastman Kodak Co Process for preparing amphoteric copolymers and the resulting products
US3084132A (en) * 1958-06-25 1963-04-02 Du Pont Process for forming a stable distribution of silver halide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607290A (en) * 1968-01-08 1971-09-21 Minnesota Mining & Mfg Polymer-containing silver halide photographic emulsions, preparation thereof and photographic elements produced therefrom
CN117487307A (zh) * 2023-11-17 2024-02-02 育才控股集团股份有限公司 一种abs复合抗菌塑料及其制备方法和应用
CN117487307B (zh) * 2023-11-17 2025-07-04 育才控股集团股份有限公司 一种abs复合抗菌塑料及其制备方法和应用

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GB1128959A (en) 1968-10-02
BE676549A (enrdf_load_stackoverflow) 1966-08-16
DE1572205A1 (de) 1970-01-02

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