US2271623A - Photographic emulsion - Google Patents

Photographic emulsion Download PDF

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Publication number
US2271623A
US2271623A US321595A US32159540A US2271623A US 2271623 A US2271623 A US 2271623A US 321595 A US321595 A US 321595A US 32159540 A US32159540 A US 32159540A US 2271623 A US2271623 A US 2271623A
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United States
Prior art keywords
surface active
emulsion
emulsions
photographic
silver
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Expired - Lifetime
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US321595A
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English (en)
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Burt H Carroll
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes

Definitions

  • This invention relates to photographic emulsions and more particularly to photographic emulsions of the silver halide type.
  • My new method of sensitizing emulsions is an improvement over the known methods of enhancing sensitivity, since the speed increases attained by my new method are complementary to the speed increases that can be attained by the prior methods.
  • the surface-active substances act on the emulsion in unknown manner to increase its effective sensitivity.
  • the sensitivity is increased by about the same amount at any wavelength within the range of its spectral sensitivity, although in spectrally sensitized emulsions there is frequently observed an appreciable increase in relative sensitivity for longer wavelengths.
  • An object of my invention is to provide new photographic emulsions.
  • a further object is to provide emulsions sensitized with a.
  • a further object is to provide a process for preparing such emulsions.
  • the surface active substance can be incorporated in any suitable form, e. g. in the form of a solution in a suitable solvent, such as water or methyl alcohol.
  • the surface active material should b thoroughly incorporated in the emulsion.
  • the surface active substance can be added to the finished emulsion or at any stage of the preparation of the emulsion.
  • the surface "active substance can be incorporated in the emulsion before, simultaneously with, or,
  • sensitizing dye before incorporating the surface active material.
  • the methods of incorporating sensitizing dyes in emulsions are, of course, well known to those skilled in the art. Ordinarily, it is advantageous to employ asolution of the sensitizing dye in a suitable solvent, e. g. methyl alcohol. Ethyl alcohol or "acetone may be employed in cases where the solubility of the sensitizing dye in methyl alcohol is very low.
  • sensitizing dyes are ordinarily incorporated in the washed finished emulsions, and in accordance with my invention, the surface active substances are advantageously also incorporated in the washed finished emulsions.
  • the surface active substance canbe added to the emulsion during the preparation thereof, i. e. during the precipitation, the first digestion or the second digestion (the ripening).
  • the sensitizing dyes can be incorporated in the so-prepared emulsion.
  • I include particularly those having at least one lipophylic quaternary ammonium cation containing four separate alkyl groups (alcohol radicals) attached to the quaternary ammonium nitrogen atom, as well as those having at least one lipophylic quaternary ammonium cation in which the quaternary ammonium.
  • nitrogen atom is one of the nuclear atoms of a heterocyclic ring (the nuclear atoms of which advantageously consist of carbon and nitrogen atoms), said ring being devoid of fusedon aromatic rings.
  • ammonium cation advantageously should contain at least one organic group containing a chain of at least eight members.
  • such members are from the group consisting of carbon, oxygen, nitrogen and sulfur atoms.
  • aromatic rings such as a benzene ring for example, can take the place of one or more ofthe eight or more atoms.
  • a benzene ring can take the place of one atom
  • a naphthalene ring two benzene rings fused together
  • the atoms attached to the eight or more atoms in the chain can be hydrogen, oxygen, carbon, or halogen for example. Any aromatic ring system in the chain can carry simple substituents.
  • the organic group containing a chain of eight or more atoms can be attached directly to the ammonium nitrogen atom or indirectly thereto by means of a group of atoms.
  • cationic ammonium salt surface active substances especially the quaternary type, having an ammonium cation containing a lipophylic organic group which contains a chain composed of from nine to twelve members selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and aromatic ring systems, are advantageously employed.
  • the anion may be any acid radical, such as chloride, bromide, iodide, p-toluenesulfonate, perchlorate or alkylsulfate for example.
  • introduction of halide anions into photographic silver halide emulsions alters the halide concentration in the emulsion and compensating changes in the emulsion may be necessary, if such ammonium salts are employed.
  • Perchlorates and p-toluenesulfonates are advantageously employed;
  • Tetraalkyl quaternary ammonium salts which can be represented by the following general formula:
  • R, R, R" and R' represent an organic lipophylic group containing a chain of at least eight members selected from the group consisting of carbon represented by the following general formula:
  • R represents an organic lipophylic group containing a chain of at least eight members selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and aromatic ring systems and x represents an acid radical or anion.
  • R represents an alkyl group, such as methyl, ethyl, butyl or benzyl for example, one of the groups R and R" represents an organic lipophylic group containing a chain of at least eight members selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms,
  • R and R represents hydrogen or a low molecular weight alkyl group, such as methyl, ethyl or butyl, and x represents an acid radical or anion.
  • R i R wherein one of the groups R and R represents an organic lipophylic group, containing a chain of at least eight members selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atomsand aromatic ring systems, while the other of the R and R groups represents hydrogen or a low molecular weight alkyl group, such as methyl, ethyl, butyl or benzyl for example, and X represents an acid radical or anion.
  • nc--c-cm HrC- / ⁇ nx I N wherein one of the groups R and R represents an organic lipophylic group containing a chain benzyl, and X represents an acid radical or anion.
  • one of the R and R groups represents an organic lipophylic group containing a chain of at least eight members selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and aromatic ring systems while the other of theR and R groups represents a low molecular weight alkyl group such as methyl, ethyl, butyl or benzyl and X represents an acid radical or anion.
  • organic lipophylic groups containing a chain of at least eight members selected from the group consisting of carbon atoms,-oxygen atoms, sulfur atoms and aromatic ring systems:
  • the quantity of surface active agent which is mostv advantageously employed varies with the nature of the surface active agent and with the nature of the emulsion. Ordinarily the most advantageous concentration was found to be between about 20 mg. and about 200 mg. of the surface active agent per gram-mole of silver halide in the amulsion, although greater or smaller concentration can be employed. I have found that excesses of the surface active agent are advantageously avoided, since excesses produce fog in the emulsions. For surface active agents containing a lipophylic group containing achain of eight to ten members, I have found that as much as about 400 mg.
  • surface active agent per mole of silver halide in the emulsion can ordinarily be employed without encountering excessive fog, while with surface active agents containing a lipophylic group containing a chain of eleven to twelve or more members, I have found that not more than about 200 mg. of surface active agent per mole of silver halide should ordinarily be employed.
  • the optimum range of concentration for any particular surface active agent is ordinarily fairly narrow and can best be determined by employing a series of concentrations of the surface active agents, separately in several batches of the same emulsion and determiningthe sensitivity of the several emulsions, before and after incorporation of the surface active agent, in a conventional manner, well known to those skilled in the art.
  • the method of determining sensitivity of emulsions comprises coating the emulsion onto a glass plate to a suitable thickness and drying the coated emulsion, and then testing the resulting photographic plate in a wedge spectrograph and a sensitometer, whereby spectral sensitivity and speed of the emulsion on the plate is determined.
  • the spectral sensitizers are advantageously employed in about their optimum concentration which ordinarily lies between about 3 mg. and 20 mg. of spectral sensitizer per liter of emulsion containing about 0.25 mole of silver halide, although concentrations above or below the optimum concentration can be employed.
  • concentration of sensitizing dye to the concentration of silver halide in the emulsion is advantageously larger than in the coarser grain emulsion, where smaller amounts of sensitizing dye usually give optimum sensitization.
  • the optimum concentration, as above referred to, of a sensitizing dye can be readily determined in a mannerwell known to those skilled in the art by measuring the sen- My invention is directed particularly to the silver-halide developing-out emulsions customarily employed in the art, including the gelatino- A silverchloride, the gelatino-silver-bromide and the gelatino-silverbromiodide developing-out emulsicns, for example.
  • my invention can be employed with silver halide emulsions wherein the carrier is other than gelatin, for example a resinous or cellulosic substance which has substantially no deleterious eifect on the light-sensitive materials in the emulsions.
  • sensitizing dyes only those which are non-acidic can be employed in practicing my invention.
  • sensitizing dyes such as Congo red, which disperse in water to give a colored anion, i. e. acidic sensitizing dyes, appear to interfere with the surface active agent, with the result that neither the acid dye nor the surface active substance exert a. substantially beneficial effect on the emulsion.
  • non-acidic sensitizing dyes I include all the known neutral and basic sensitizing dyes, i. e. those sensitizing dyes which do not give colored anions. Some of these non-acidic sensitizing dyes, such as the cyanine dyes, give colored cations.
  • non-acidic sensitizing dyes are the sensitizing cyanine dyes (see, for example United States Patents 1,846,300; 1,846,301; 1,846,302; 1,846,303 and 1,846,304 each dated February 23, 1932, United States Patent 1,861,836, dated June 7, 1932, United States Patent 1,939,201, dated December 12, 1933, United States Patent 1,942,- 854, dated January 9, 1934, United States Patent 1,957,869, dated May 8, 1934, United States Patent 1,962,124, dated June 12, 1934, United States Patent 1,969,446, dated August 7, 1934, United States Patent 1,973,462, dated September 11, 1934; United States Patent 1,990,507, dated February 12, 1935, United States Patent 2,094,580, dated October 5, 1937, United States Patent 2,112,140, dated March 22, 1938 and French Patent 757,813, published January 5, 1934), the sensitizing merocyanine dyes (see United States Patent 2,078,233, dated April 27, 1937, United States Patent 2,078,233
  • Photographic elements can be made from emulsions prepared in the above manner by coating the emulsions to a suitable thickness on a suitable support and drying the coated emulsion, in a manner well known to those skilled in the art.
  • Suitable supports are, of course, glass, photographic paper support and photographic film support.
  • the photographic film support may, of course, be of cellulose acetate, cellulose nitrate or any other suitable cellulose derivative, or be of any suitable resinous material, such as a polyvinyl acetal resinous material for example.
  • My new emulsions are advantageously coated on glass support.
  • Nonyl pyridinium perchlorate 1,200 0.96 .10 445 0.86
  • n-Nonyl pyridinium perchlo- 1 000 1.03 .05 Do rate, 30 mg./liter. Do do ay -N-methyl pyridinium 1,100 1.03 .05
  • Curve A represents the spectral sensitivity of a gelatino silver bromiodide emulsion (about 0.25 mole of silver halide per liter of emulsion) containing sensitizing dyes such as thiacarbocyanine dyes and 2'-cyanine dyes as described in Mees U. S. Patent 2,158,882, granted May 16, 1939.
  • Curve B represents the spectral sensitivity of the same dyed emulsion but containing in addition a cationic surface active salt in accordance with the present invention in the concentration of approximately 15 mg. per liter of emulsion.
  • the sulfonates, bromides and other derivatives may be satisfactorily produced by known methods; hence, reference to a description thereof is unnecessary.
  • a photographic silver halide emulsion sensitized with a cationic surface active ammonium salt 1.
  • a photographic silver halide developing-out emulsion sensitized with a cationic surface active ammonium salt 1.
  • a photographic gelatino-silver-halide emulsion sensitized with a cationic surface active ammonium salt 4.
  • a photographic gelatino-silver-halide developing-out emulsion sensitized with a cationic surface active ammonium salt 4.
  • x 5 A photographic gelatino-silver-halide emulsion sensitized with a supersensitizing combination of at least one non-acidic sensitizing dye together with a cationic surface active ammonium salt.
  • a photographic gelatino-silver-halide emulsion sensitized with a cationic surface active quaternary ammonium salt 8.
  • a photographic gelatino-silver-halide developing-out emulsion sensitized with a cationic surface active quaternary ammonium salt 9.
  • An undyed gelatino silver halide emulsion containing, at least, one cationic surface active ammoniuma salt in a concentration equal to less than 400 milligrams per gram-mole of silver halide in the emulsion.

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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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US321595A 1939-03-30 1940-02-29 Photographic emulsion Expired - Lifetime US2271623A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9899/39A GB527296A (en) 1939-03-30 1939-03-30 Improvements in the manufacture of dyes and of photographic emulsions

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US2271623A true US2271623A (en) 1942-02-03

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FR (1) FR949227A (cs)
GB (1) GB527296A (cs)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2454043A (en) * 1944-04-04 1948-11-16 Ilford Ltd Gelatino-silver halide photographic elements containing higher fatty alcohols
US2490745A (en) * 1948-01-13 1949-12-06 Eastman Kodak Co Cellulose carboxylic ester silver halide emulsions sensitized with benzothiazole and benzoselenazole quaternary salts
US2490760A (en) * 1946-04-15 1949-12-06 Eastman Kodak Co Water spot prevention in photographic film
US2784090A (en) * 1952-11-08 1957-03-05 Eastman Kodak Co Stabilization of emulsions sensitized with onium compounds
US2831766A (en) * 1954-05-17 1958-04-22 Eastman Kodak Co Gelatin coating compositions
US2886437A (en) * 1955-12-01 1959-05-12 Eastman Kodak Co Photographic emulsions sensitized with alkylene oxide polymers and quaternary ammonium compounds
US2940855A (en) * 1957-11-27 1960-06-14 Eastman Kodak Co Sensitization of photographic emulsions
US2945762A (en) * 1955-10-12 1960-07-19 Eastman Kodak Co Supersensitization of photographic emulsions using triazines
US2950196A (en) * 1955-10-12 1960-08-23 Eastman Kodak Co Supersensitization of photographic emulsions using triazines
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3093479A (en) * 1958-12-12 1963-06-11 Eastman Kodak Co Use of quaternary ammonium compounds for stabilizing processed photographic elements
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3441413A (en) * 1964-07-07 1969-04-29 Fuji Photo Film Co Ltd Photographic elements having gelatinous coating compositions containing amphoteric surface active agents
US3481742A (en) * 1964-07-11 1969-12-02 Fuji Photo Film Co Ltd Silver halide photographic emulsion
US3619199A (en) * 1968-10-31 1971-11-09 Gaf Corp Photographic coating formulation
US4184871A (en) * 1974-04-18 1980-01-22 Mitsubishi Chemical Industries Ltd. Photosensitive composition for electrophotography
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
US6156419A (en) * 1997-05-02 2000-12-05 Iford Imaging Switzerland Gmbh Recording sheets for ink jet printing
US7235284B1 (en) 1997-03-20 2007-06-26 Ilford Imaging Switzerland Gmbh Recording sheets for ink jet printing
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2454043A (en) * 1944-04-04 1948-11-16 Ilford Ltd Gelatino-silver halide photographic elements containing higher fatty alcohols
US2490760A (en) * 1946-04-15 1949-12-06 Eastman Kodak Co Water spot prevention in photographic film
US2490745A (en) * 1948-01-13 1949-12-06 Eastman Kodak Co Cellulose carboxylic ester silver halide emulsions sensitized with benzothiazole and benzoselenazole quaternary salts
US2784090A (en) * 1952-11-08 1957-03-05 Eastman Kodak Co Stabilization of emulsions sensitized with onium compounds
US2831766A (en) * 1954-05-17 1958-04-22 Eastman Kodak Co Gelatin coating compositions
US2945762A (en) * 1955-10-12 1960-07-19 Eastman Kodak Co Supersensitization of photographic emulsions using triazines
US2950196A (en) * 1955-10-12 1960-08-23 Eastman Kodak Co Supersensitization of photographic emulsions using triazines
US2886437A (en) * 1955-12-01 1959-05-12 Eastman Kodak Co Photographic emulsions sensitized with alkylene oxide polymers and quaternary ammonium compounds
US2940855A (en) * 1957-11-27 1960-06-14 Eastman Kodak Co Sensitization of photographic emulsions
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3093479A (en) * 1958-12-12 1963-06-11 Eastman Kodak Co Use of quaternary ammonium compounds for stabilizing processed photographic elements
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3441413A (en) * 1964-07-07 1969-04-29 Fuji Photo Film Co Ltd Photographic elements having gelatinous coating compositions containing amphoteric surface active agents
US3481742A (en) * 1964-07-11 1969-12-02 Fuji Photo Film Co Ltd Silver halide photographic emulsion
US3619199A (en) * 1968-10-31 1971-11-09 Gaf Corp Photographic coating formulation
US4184871A (en) * 1974-04-18 1980-01-22 Mitsubishi Chemical Industries Ltd. Photosensitive composition for electrophotography
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US7235284B1 (en) 1997-03-20 2007-06-26 Ilford Imaging Switzerland Gmbh Recording sheets for ink jet printing
US6156419A (en) * 1997-05-02 2000-12-05 Iford Imaging Switzerland Gmbh Recording sheets for ink jet printing
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

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Publication number Publication date
FR949227A (fr) 1949-08-24
GB527296A (en) 1940-10-07
BE466375A (cs)

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