Classifications

• • 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
• • 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
  • G03C1/42—Developers or their precursors
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/38—Fixing; Developing-fixing; Hardening-fixing

Definitions

• This invention relates to photographic compositions.
• Preferred embodiments of the invention concern photographic silver halide emulsions containing addenda that can serve as fog-inhibiting agents or as stabilizing agents obviating the necessity of conventional fixing.
• R R R R R R and R can be hydrogen atoms, hydrocar-bon radicals such as aryl radicals as illustrated by 3,226,839 Patented Nov. 30, 1965 phenyl radicals, alkyl-substituted phenyl and alkyl radicals and substituted alkyl radicals.
• R and R can also be acyl radicals having the formula wherein R is an alkyl radical.
• R and R together can also be the necessary carbon andhydrogen atoms to form an alkylene radical linking both'adjacentnitrogen-atoms to form a cyclic nucleus as illustrated-by the following moiety wherein R is an alkylene radical,
• R can be an acyl radical in addition to those substitutents described above for R
• the letter 11 can be an integer of at least 1, and generally 1 to 10, and preferably l to 3.
• the letter Y can be a carboxyl radical,a sulvfonate radical, a hydroxyl radical or an amino radical, including substituted amino radicals, of the formula wherein R is a hydrogen atom or an alkyl radical, and wherein R is a hydrogen atom, an alkyl radical or an acyl radical, their salts having the formula or a morpholino radical, Y being other than a carboxyl radical Whenn is 1 and R and R are hydrogen.
• Typical alkyl and alkylene radicals referred to above have 1 to'20 carbon atoms and moregenerally 1 to 4 carbon atoms.
• Illustrative alkyl radicals include methyl, ethyl, isopropyl, n-butyl, Z-ethylhexyl, n-decyl, stearyl, n-eicosyl and the like radicals.
• Alkylene radicals analogous to such alkyl radicals are suitable R substituents.
• the subject isothiourea derivatives are bases but can beutilizedas the salts of such acids as p-toluene sulfonicacid, nitric acid, perchloric acid, hydrochloric acid, vhydrobromic acid,-etc. as illustrated by the salt,
• the isothiourea derivatives of the invention can be .utilized in photographic silver halide emulsions .to reduce incubation fog. These addenda serve to stabilize emulsions under prolonged storage conditions orunder conditions of high temperature and humidity which typically occur in summer months or in tropical climates.
• the amount of the subject addenda that is used in photographic silver halide emulsions for anti-foggant purposes can be varied in accordance with usual practice, the amount utilized varying with the effect desired, degree of ripening, silver content of the emulsion, etc. Generally from about .001 to grams of the isothiourea per mole of silver halide are suitable for antifoggant purposes.
• the isothiourea derivatives of the invention can also serve as incorporated fixing agents. These addenda do not prevent development of exposed areas of the emulsion but protect the unexposed areas of the emulsion against print out after development of the emulsion. Thus with emulsions containing the addenda of the invention silver images can be formed and stabilized Without the use of a conventional fixing process.
• the subject addenda are stable and do not act as fixing agents in acidic or neutral media such as in emulsions. However, under aqueous alkaline conditions, such as often times prevail during the developing of photographic emulsions, the subject addenda become active fixing agents.
• the photographic element having the developed emulsion coated thereon can thereafter be immersed in a stronger alkaline bath for fixing. Under such conditions a soluble complex is formed with the silver halide in the unexposed and undeveloped areas of the emulsion.
• the subject addenda are used in photographic silver halide emulsions as fixing agents, at least one mole of the addenda is utilized for each mole of silver halide in the emulsion.
• the isothiourea derivatives of the invention can also serve in some silver halide emulsions to increase sensitivity, D and contrast in emulsions. These improved properties are also imparted to photographic silver halide emulsions when the isothiourea addenda of the invention are incorporated into gelatin layers coated adjacent to the photographic silver halide emulsions. 4
• the preparation of photographic silver halide emulsions such as are used with the addenda of this invention involves three separateoperations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess water-soluble salts, suitably by washing with water, and (3) the second digestion or after-ripening to obtain increased emulsion speed or sensitivity.
• the addenda of the invention can be added to the emulsion before the final digestion or after-ripening, or they can be added immediately prior to the coating.
• the addenda of the invention can be added to photographic emulsions using any of the well-known techniques in emulsion making. For example, they can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color-forming compounds (couplers) in a photographic emulsion. Techniques of this type are described in Jelley et al. US. Patent 2,322,027, imu'ed June 15, 1943, and Fierke et al. US. Patent 2,801,171, issued July 30, 1957.
• the solvent should be selected so that it has no harmful effect upon the emulsion in accordance with usual practice, and generally solvents or dilu'ents which are miscible with water are to be preferred.
• the emulsions of the invention can include the usual photographic emulsion addenda including chemical sensitizers, optical sensitizers, stabilizers or antifoggants, plasticizers, hardeners, coating aids, and the like.
• silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
• gelatin In the preparation of the silver halide dispersions employed for preparing silver halide emulsions, there can be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred.
• colloids which can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Low'e US. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 1926% as described in US.
• Patent 2,768,154 issued October 23, 1956; or containing cyanoacetyl groups such as the vinyl alcohol-vinyl cyanoac'etate copolymer as described in Unruh, Smith and Priest US. Patent 2,808,331;, issued October 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in Illingsworth, Dann and Gates US. Patent 2,852,382, issued September 19, 1958. If desired, compatible mixtures of two or more of these colloids can be employed for dispersing the silver halide in its preparation.
• Typical supports for photographic elements of the invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethyleneterephthalate film and related films of resinous materials, as well as glass, paper, Wood, metals and others.
• Typical isothiourea derivatives of the invention were incorporated into a high speed negative-type gelatinosilver bromoiodide emulsion which was sulfur and gold sensitized.
• the emulsion was coated on cellulose acetate film supports at a coverage of about 355 mg. of silver and about 840 mg. of gelatin per square foot.
• the prepared photographic elements were then exposed, both initially and after 1 and 2 weeks storage at 120 F.
• EXAMPLE 2 Additional addenda of the invention were incorporated into a photographic high speed negative-type gelatino silver bromoiodide emulsion panchromatically sensitized with a cyanine dye and coated on a cellulose acetate film support and tested as described in Example 1 except the test samples, after exposure in the sensitometer, were developed for minutes at 68 F. in a developer having the formula:
• Table B further illustrates the antifoggant properties of the subject isothiourea derivatives.
• EXAMPLE 3 The determination of the antifoggant properties of several additional addenda of the invention was carried out by the general procedure described in Example 1.
• the emulsion was a fast negative-type gelatino-silver bromoiodide emulsion which was gold and sulfur sensitized and coated on a cellulose acetate film support as described in Example 1.
• the results of the tests are summarized by the data set out in Table C below.
• Table C 120 F., 50% RH. Original Test Cone. of Addenda Addenda 1 Week 2 Weeks Speed Fog Speed Fog Fog Control 0 100 08 123 21 50 2. 7 97 07 138 11 26 o 5. 2 97 07 135 l0 22 Compound 4- 0. 87 O7 107 .12 24 Compound 5. 0. 09 97 08 135 16 34 Control t- 0 100 11 110 28 Compound 4. O. 54 97 07 71 14 Compound 9 0. 15 97 08 110 19 o 0.
• EXAMPLE 4 A 4.0 gram portion of Compound 2 and 5.0 grams of gelatin were dissolved in 40.0 ml. of hot water. To the resulting mixture was added 4.0 ml. of a concentrated negative-type medium speed gelatino-silver bromoiodide emulsion of the type described by Trivelli and Smith in the Phot. Jour., vol. 79, pp. 330331 (1939), and the resulting emulsion coated on a cellulose acetate film support. The resulting photographic element was then exposed to an image, developed for 2 minutes at 68 F. in the developer described in Example 2 and then immersed in 10% tetramethylammonium hydroxide for 1 minute.
• the resulting photographic emulsion was then coated on a 40-pound photographic paper support with a waterproof backing that had previously been soaked in a 5% solution of Compound 2 and partially dried on a heated coating block.
• the coated paper was then exposed to an image and immersed for 2 minutes in a solution containing 2.5% sodium hydroxide and 10% sodium sulfate, after which the paper was light stable without washing.
• This example illustrates the use of a photographic silver halide emulsion containing both an isothiourea fixer derivative of the invention and a 3- pyrazolidone developer, and the developing and fixing of this emulsion by immersing in an aqueous alkaline solution having a pH greater than 7.
• EXAMPLE 7 To 20.0 ml. of a 10% gelatin solution was added 20.0 ml. of a 15% solution of Compound 2. To the resulting solution was added 5.0 ml. of the concentrated negativetype medium speed gelatino-silver bromoiodide emulsion referred to in Example 4. To the resulting emulsion was added 2.0 ml. of 10% l-phenyl-3-pyrazolidone in ethanol and 4.0 ml. of a 10% aqueous solution of Lascorbic acid. The emulsion was then coated on a cellulose acetate film support. After exposure to an image,
• the coated emulsion was immersed in a 10% tetramethylammonium hydroxide solution for 15 seconds whereupon the film had developed and cleared producing an image of good quality and light stability.
• EXAMPLE 8 EXAMPLE 9 A high speed negative-type gelatino-silver bromoiodide emulsion similar to that described in Example 1 containing Compound 2 was coated on a photographic paper support at a coverage of 70 mg. of silver per square foot, 0.245 gram of Compound 2 per square foot also being present in the coated emulsion.
• a photographic element having two layers coated on photographic paper was also prepared wherein Compound 2 dispersed in a gelatin undercoat at a concentration of :195 gram per square foot having coated thereon a layer of the described gelatino-silver bromoiodide emulsion free of Compound 2.
• a control gelatino-silver bromoiodide emulsion tree of Compound 2 was also prepared. A sample of each coating was then exposed in an Eastman Ib sensitometer, processed in an X-ray developer for 25 seconds at 32 C., and then fixed, washed and dried in the usual manner.
• the developer had the following formula:
• Table E illustrates the improvement in D imparted by the isothiourea addenda of the invention when utilized with thio sensitizers.
• the color reversal process utilized is described below.
• the exposed film was developed in a developer having the following composition:
• the element was again washed and treated once again with the clearing and fixing bath identified above.
• the element was again washed and treated in a stabilizing bath having the following composition:
• Triton-X 100 1.9., an alkylaryl polyether alcohol (octylphenoxy polyethoxy ethanol).
• EXAMPLE 1 l A high speed gelatino-silver bromoiodide emulsion which was optically sensitized in the region of 5000 to 6000 angstroms and containing dispersed therein a pyrazolone coupler suitable for forming a magenta image with oxidized color developer, e.g., coupler Nos. 7, etc., of Fierke et al., U.S. Patent 2,801,171 (column 2), was prepared. The prepared emulsion was divided into several portions, one portion coated on a cellulose acetate film support without further emulsion addenda, and other portions coated on the film support with a thio sensitizer and a mixture of the thio sensitizer and Compound 1.
• Table F illustrates the antifoggant properties of the subject isothiourea derivatives in emulsions containing thio sensitizers used in color photography.
• EXAMPLE 12 A high speed gelatino-silver bromoiodide emulsion which was optically sensitized in the region of 6000 to 7000 angstroms and containing dispersed therein a phenolic coupler. suitable for forming a cyan image with oxidized color developer, e.g., coupler Nos. 1 to 6 of Fierke et al. U.S. Patent 2,801,171 (column 2) in a solvent such as tri-o-cresylphosphate, was prepared.
• Table G further illustrates the antifoggant properties of the subject thiourea derivatives.
• EXAMPLE 13 Additional addenda of the invention were incorporated into a photographic high speed negative-type gelatinosilver bromoiodide emulsion panchromatically sensitized with a cyanine dye and coated on a cellulose acetate film support and tested as described in Example 2.
• the results of the sensitometeric tests are summarized by the data set out in Table H below wherein the speeds and concentration units are as described by the data in Table A.
• R R R R and R are selected from the group consisting of (a) hydrogen, (b) alkyl, and
• R and R are selected from the group consisting (a) hydrogen, (b) alkyl, P y
• n is an integer of 1 to 10;
• Y is selected from the group consisting of (a) amino
• R R R R and R are selected from the group consisting of (a) hydrogen, (b) alkyl, and p y
• R and R are selected from the group consisting of (a) hydrogen, (b) alkyl, (c) phenyl, and (d) acyl having the formula 0 Rilwherein R is alkyl; (3) n is an integer of l to 10; and (4) Y is selected from the group consisting of (a) amino, (b) carboxyl, (c) sulfonyl, and (d) hydroxyl; Y being other than carboxyl when n is 1 and R and R are hydrogen atoms.
• a photographic silver halide emulsion as described in claim 18 which contains a coupler compound selected from the class consisting of phenolic, pyrazolone and open-chain reactive methylene compounds capable of forming a dye with the oxidation product of an aromatic primary amine silver halide color developing agent.
• a photographic silver halide emulsion containing about .001 to 10 grams per mole of silver halide of an isothiourea derivative having the formula wherein n isan integer of 2 to 4 and R is alkyl.
• a photographic silver halide emulsion containing about .001 to 10 grams per mole of silver halide of an isothiourea derivative having the formula wherein n is an integer of 2 to 4.
• a photographic silver halide emulsion containing about .001 to 10 grams per mole of silver halide of an isothiourea derivative having the formula wherein n is an integer of 2 to 4.
• C--S-OH;4CHQOH EN 32 A photographic silver halide emulsion containing about .001 to 10 grams per mole of silver halide of an isothiourea derivative having the formula C -S-C HgC HgNH2 EN 33.
• a photographic emulsion support selected from the group consisting of cellulose acetate film, polystyrene film, polyethyleneterephthalate film and paper having coated thereon a photographic silver halide emulsion as described in claim 18.

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• Physics & Mathematics (AREA)
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• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (39)

Citations (5)

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  • BE BE621606D patent/BE621606A/xx unknown
• 1961
  • 1961-08-25 US US133769A patent/US3220839A/en not_active Expired - Lifetime
• 1962
  • 1962-08-23 DE DEE23426A patent/DE1281845B/de active Pending
  • 1962-08-27 GB GB32149/65A patent/GB1019224A/en not_active Expired
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