US2275727A - Photographic emulsion - Google Patents

Photographic emulsion Download PDF

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Publication number
US2275727A
US2275727A US321592A US32159240A US2275727A US 2275727 A US2275727 A US 2275727A US 321592 A US321592 A US 321592A US 32159240 A US32159240 A US 32159240A US 2275727 A US2275727 A US 2275727A
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United States
Prior art keywords
emulsion
surface active
emulsions
photographic
chain
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Expired - Lifetime
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US321592A
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English (en)
Inventor
Burt H Carroll
Charles F H Allen
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
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Priority to US321592A priority Critical patent/US2275727A/en
Priority to GB269/42A priority patent/GB556457A/en
Application granted granted Critical
Publication of US2275727A publication Critical patent/US2275727A/en
Priority to FR949228D priority patent/FR949228A/fr
Anticipated expiration legal-status Critical
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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

Definitions

  • This invention relates to photographic emulsions and more, particularly to photographic emulsions of the silver halide type.
  • surface active substances such as aqueous dispersing or wetting agents, for example, of the cationic sulfonium salt type.
  • surface active substances are classified as anionic and cationic, or non-ionic, depending upon whether or not the substances ionize, and if so, depending upon whether the anion or the cation is surface active.
  • Surface active materials are sometimes referred to as capillary active materials, lipophylic materials or materials which possess interface modifying properties.
  • Our new method of sensitizing emulsions is an improvement over the known methods of enhancing sensitivity, since the speed increases attained by our 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.
  • Patents 2,075,046, 2,075,047 and 2,075,048, each dated March 30, 1937) the supersensitizing effect is confined more or less to a single spectral region, the sensitization attained in our new emulsions extends throughout the entire region in which the spectral sensitizer acts (and is fairly uniform in degree throughout the entire region), while at the same time the sensitivity in the violet and blue region (where the spectral sensitizer does not act) is also enhanced to about the same degree.
  • An object of our invention is to provide new photographic emulsions.
  • a further object is to provide emulsions sensitized with a supersensitizing combination of a sensitizing dye and a surface active material of the cationic sulfonium salt type.
  • a further object is to provide a process for preparing such emulsions. 1
  • a cationic surface active sulfonium salt 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 be thoroughly incorporated in the emulsion.
  • the surface active material 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 after the sensitizing dye, although in some cases, as hereinafter set forth, it is advantageous to incorporate the sensitizing dye before incorporating the surface active substance.
  • 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 a solution 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 our invention, the surface active substances are also advantageously incorporated in the washed, finished emulsions.
  • the surface active substances are also advantageously incorporated in the washed, finished emulsions.
  • the surface active substance can be added to the emulsion during the preparation thereof, i. e. during the precipitation, the first digestion, or the second digestion (the ripening). After preparing the emulsions in the presence of the surface active substance, the sensitizing dyes can be incorporated in the so-prepared emulsions.
  • sulfonium salt surface active substances we have found that those which do not contain a hydrogen atom on the sulfonium sulfur atom (i. e. the so-called ternary sulfonium types) are advantageously employed.
  • the sulfonium 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.
  • One or more aromatic rings, such as a benzene ring, for example, can take the place of one or more of the eight or more atoms.
  • benzene ring can take the place of one atom, while a naphthalene ring (two benzene rings fused together) can take the place of two atoms.
  • the atoms attached to the eight or more atoms in the chain can be hydrogen, oxygen, sulfur, carbon or halogen, for example. Any aromatic ring system in the chain can carry simple substituents.
  • cationic sulfonium salt surface active substances having a sulfonium 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, 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 desirable, if such sulfonium salts are employed. For this reason, we ordinarily prefer to employ surface active substances containing anions other than halides. Perchlorates and p-toluenesulfonates are advantageously employed.
  • 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:
  • Nonyl CHa(CH2) a- (nine atom chain) Decyl, CH3--(GH2)9- (ten atom chain) Lauryl, CHs(CI-I2) 11 (twelve atom chain) Cetyl, CHs-(CHz) 15- (sixteen atom chain) Heptoxymethyl, CHs-(CHz) s-OCH2 (nine atom chain) Undecoxymethyl, CH3(CH2)1 -OCH2 (thirteen atom chain) Heptylthiomethyl, CH3-(CH2) aSCH2- (nine atom chain) Carbnonoxymethyl,
  • 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 mg. of spectral sensitizer per liter of emulsion containing about 0.25 grammole 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 emulsions where smaller amounts of sensitizing dyes usually give optimum sensitization.
  • the optimum concentration, as above referred to, of a sensitizing dye (i. e. the concentration at which greatest sensitivity occurs) can be readily determined in a manner well known to those skilled in the art by measuring the sensitivity of a series of emulsions containing diiferent concentrations of the sensitizing dye.
  • Our invention is directed particularly to the silver halide developing-out emulsions customarily employed in the art, including the gelatino-silverchloride, the gelatino-silver-bromide and the gelatino-silver-bromiodide developing-out emulsions, for example.
  • our invention can be employed with silver halide emulsions wherein the carrier is other than gelatin, for example, a resinous or cellulosic derivative substance which has substantially no deleterious effect on the light-sensitive materials in the emulsions.
  • sensitizing dyes only those which are non-acidic can be employed in practicing our 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 we include all the known neutral and basic sensitizing dyes, i. e. those sensitizing dyes which do not give colored anions. Some 01 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,
  • sensitizing merocyanine dyes see United States Patent 2,078,233, dated April 27, 1937,'United States Patent 2,089,729, dated August 10, 1937, United States Patent 2,153,169, dated Aprfl 4, 1939 and United States Patents 2,177,401, 2,177,402, and 2,177,403, dated October 24, 1939
  • the sensitizing hemi-cyanine dyes see-United States Patent 2,166,736, dated July 18, 1939
  • sensitizing hemioxonol dyes see United States Patent 2,165,339, dated July 11, 1939 and French Patent 841,632, published May 24, 1939.
  • the process of our invention is subject to variation, particularly as respects the nature and quantity of surface active substance employed, the nature and quantity of the spectral sensitizer employed, it any, the nature of the silver halide emulsion employed, and the manner the surface'active substance and the spectral sensitizer (if any) in the emulsions, the following example will serve to illustrate the manner of obtaining our new emulsions. This example is not intended to limit our invention.
  • Example 1 Into one liter of fiowable, washed, finished gelatino-silver-bromide developing-out emulsion containing about 0.25 gram-moles of silver halide were incorporated slowly,with stirring, a methyl alcoholic solution of 2,2'-dimethyl-8-methyl- 3,4,3',4'-dibenzothiacarbocyanine chloride. Suflicient of the alcoholic solution was added to incorporate about 15 mg. of the 'carbocyanine chloride in the emulsion.
  • a 1% (by weight) aqueous solution or lauryldimethyl-sulfonium-p-toluenesulfonate were added slowly and with stirring, a 1% (by weight) aqueous solution or lauryldimethyl-sulfonium-p-toluenesulfonate.
  • Sufiicienhot the aqueous solution was added to incorporate about 50 mg. of the ptoluenesulfonate in the emulsion.
  • Photographic elements can be made from 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 and be 01' any suitable resinous material, such as polyvinyl acetal resin, for example.
  • Our new emulsions are advantageously coated on glass support.
  • Nonyldi'methylsulfonium p toluenesulfonate was the specific salt employed as the addition agent in this example. This salt was incorporatedinto a sensitized emulsion by procedure comparable to that already described. The nonyldimethylsulfonium p-toluenesulfonate was added in an amount between 20-100 mg. per liter of emulsion. This compound appeared to exhibit very little tendency to cause fog and consequently high concentrations may be employed.
  • control referred to is the emulsion without the sulfonium salt.
  • control contains a sensitizing dye.
  • the controls were processed and otherwise handled in exactly the same manner as the emulsions containing the sulfonium salts.
  • nium p-toluenc suliouate 20 mg./liter.
  • iouium p-Toiuene suliouate 100 mg./llter. 73 u-Octyl dimcthyl sul- 645 0.78 .08 250 0.61
  • the sulfonium compound described herein may be obtained from various sources and by various methods provided the products are of sufficient purity and otherwise possess qualities rendering them capable of meeting photographic specifications.
  • the surface active sulfonium salts may be made by various published methods disclosed in patents and other disclosures (see for example United States Patent 2,090,890, dated August 24, 1937, and United States Patent 2,121,823, dated June 28, 1938). Hence, it is unnecessary to discuss the preparation of these compounds herein, since such surface active sulfonium salts per se form no part of the present invention.
  • a photographic silver halide developing-out emulsion sensitized with a cationic surface active sulfonium salt 1.
  • a photographic silver halide emulsion sensitized with a cationic surface active ternary sulfonium salt is provided.
  • a cationic surface active ternary sulfonium salt the cation of which contains at least one organic group containing a chain of from 9 to 10 members selected from the group consisting of carbon atoms, sulfur atoms, oxygen atoms, nitrogen atoms and benzene nuclei.
  • a photographic gelatino-silver-halide developing-out emulsion sensitized with a nonacidic sensitizing dye and containing, in a concentration of from about 20 to about 200 milligrams per gram-mole of silver halide in the emulsion, a cationic surface active ternary sulfonium salt, the cation of which contains at least one organic group containing a chain of from 9 to '10 members selected from the group consisting of carbon atoms, sulfur atoms, oxygen atoms, nitrogen atoms and benzene nuclei.
  • a photographic gelatino-silver-halide de veloping-out emulsion sensitized with a nonacidic sensitizing dye and containing, in a concentration of from about 20 to about 200 milligrams per gram-mole of silver halide in the emulsion, a cationic surface active n-nonyl dimethyl sulfonium salt.
  • a photographic gelatino-silver-halide developing-out emulsion sensitized with a nonacidicsensitizing dye and containing, in a concentration of from about 20 to about 200 milligrams per gram-mole of silver halide in the emulsion, acationic surface active n-decyl dimethyl sulfonium salt.
  • a photographic geZatino-silver-halide developing-out emulsion sensitized with a nonacidic sensitizing dye and containing, in a concentration of from about '20 to about 200 milligrams per gram-mole of silver halide in the emulsion, a cationic surface active n-octyl dimethyl sulfonium 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US321592A 1940-02-29 1940-02-29 Photographic emulsion Expired - Lifetime US2275727A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US321592A US2275727A (en) 1940-02-29 1940-02-29 Photographic emulsion
GB269/42A GB556457A (en) 1940-02-29 1942-01-07 Improvements in and relating to sensitive photographic materials
FR949228D FR949228A (fr) 1940-02-29 1945-08-11 émulsions photographiques

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Cited By (10)

* 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
US2527263A (en) * 1945-11-19 1950-10-24 Ilford Ltd Photographic transfer materials bearing gelating anion soap complex silver halide layer
US2784090A (en) * 1952-11-08 1957-03-05 Eastman Kodak Co Stabilization of emulsions sensitized with onium compounds
US2848330A (en) * 1955-12-01 1958-08-19 Eastman Kodak Co Photographic emulsions sensitized with sulfonium salts and alkylene oxide polymers
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US4028110A (en) * 1974-02-28 1977-06-07 Agfa-Gevaert, N.V. Development of exposed lith-emulsions
US4076539A (en) * 1973-07-23 1978-02-28 Fuji Photo Film Co., Ltd. Process for preparing silver halide dispersions
US4125403A (en) * 1976-06-25 1978-11-14 Fuji Photo Film Co., Ltd. Heat developable light sensitive material

Cited By (10)

* 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
US2527263A (en) * 1945-11-19 1950-10-24 Ilford Ltd Photographic transfer materials bearing gelating anion soap complex silver halide layer
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
US2848330A (en) * 1955-12-01 1958-08-19 Eastman Kodak Co Photographic emulsions sensitized with sulfonium salts and alkylene oxide polymers
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US4076539A (en) * 1973-07-23 1978-02-28 Fuji Photo Film Co., Ltd. Process for preparing silver halide dispersions
US4028110A (en) * 1974-02-28 1977-06-07 Agfa-Gevaert, N.V. Development of exposed lith-emulsions
US4125403A (en) * 1976-06-25 1978-11-14 Fuji Photo Film Co., Ltd. Heat developable light sensitive material

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GB556457A (en) 1943-10-06
FR949228A (fr) 1949-08-24

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