US2685514A - Direct positive photographic development process - Google Patents

Direct positive photographic development process Download PDF

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Publication number
US2685514A
US2685514A US371946A US37194653A US2685514A US 2685514 A US2685514 A US 2685514A US 371946 A US371946 A US 371946A US 37194653 A US37194653 A US 37194653A US 2685514 A US2685514 A US 2685514A
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US
United States
Prior art keywords
bromide
emulsion
methyl
silver halide
developer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US371946A
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English (en)
Inventor
Grant M Haist
Harold D Russell
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Eastman Kodak Co
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Eastman Kodak Co
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Filing date
Publication date
Priority to BE530882D priority Critical patent/BE530882A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US371946A priority patent/US2685514A/en
Priority to FR1143615D priority patent/FR1143615A/fr
Application granted granted Critical
Priority to GB22509/54A priority patent/GB767703A/en
Publication of US2685514A publication Critical patent/US2685514A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • G03C1/48546—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent
    • G03C1/48553—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent the fogging agent only present in the developer
    • 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
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • G03C1/48546—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent

Definitions

  • An internal latent image emulsion that is, one which forms the latent image mostly inside the silver halide grains, as described on pages 295 and 297 of Mess The Theory of the PhotographicProcess, 1942, is especially useful for the process of our invention.
  • Most of the internal latent image emulsions are silver bromoiodide emulsions of high iodide content, preferably containing at least %20% of the halide as iodide.
  • Burtons emulsion is an emulsion of this type, having a silver iodide content of approximately 40% of the content of silver halide. It is not absolutely essential, however, for the emulsion to contain silver iodide.
  • An internal latent image emulsion made as described in Davey and Knott U. S. Patent No. 2,592,250, may also be used according to our invention.
  • This emulsion is prepared by first forming in the absence of ammonia and in one or more stages, silver salt grains Iconsisting at least partly of asilver salt which is more soluble in Water than silver bromide, subsequently converting the grains to silver bromide or silver bromoiodide and if the silver iodide content of the emulsion is less than 6% calculated on the total silver halide, treating such grains with an iodine compound to bring the silver iodide up to at least 6%, ripening preferably in the absence of ammonia and then either Washing out some of the soluble salts or Washing out the Whole of the soluble salts, followed bythe addition of soluble salts such as soluble chloride or bromide.
  • An example of an emulsion made in this Way is as follows:
  • An internal latentlimage type of silver halide emulsion may be defined as one which, when a test portion is exposed to a light intensity scale for a fixed time between V100 and l second, and developed for 4 minutes at 20 C. in the ordinary surface developer (Example I) exhibits a maxl- F mum density not greater than 1/5 the maximum density obtained when the same emulsion is equally exposed and developed for 3 minutes at C. in an internal type developer (Example Il).
  • the maximum density obtained with the surface developer is not greater than 174,0 the maximum density obtained when the same emulsion is developed in the internal type developer.
  • an internal latent image emulsion when developed in an internal type developer (Example Il) exhibits a maximum density at least 5, and preferably at least 10, times the maximum density obtained when the same emulsion is exposed in the same way and developed in a surface developer (Example I).
  • Our process is carried out by exposing the internal latent image emulsion layer to an object or image and then placing the exposed emulsion layer directly in a silver halide developing solution containing one or more hydrazines such as those mentioned hereinafter and in addition, containing one or more of the above-mentioned effective Quaternary ammonium compounds as well as developing agent.
  • the hydrazine can be incorporated into the internal latent image emulsion in which case the exposed emulsion layer is developed in a developer solution containing one or more of the mentioned effective Quaternary ammonium compounds as Well as a developing agent.
  • Developing agents suitable for use in the process of our invention include the usual phenolic or aminophenol type developing agents such as N-methyl-p-aminophenol sulfate, hydroquinone, catechol, 2-methyl hydroquinone, Z-chlorohydroquinone, p-aminophenol, and pyrogallol.
  • 3- pyrazolidone developing agents are veryy useful in our developer compositions, for example, 1 (p I3 hydroxyethylphenyl) 3- pyrazolidone, l phenyl- 3 pyrazolidone, 1 ptolyl 3 pyrazolidone, 1 phenyl 2 acetyl- S-pyrazolidone, and particularly the 1-aryl-4,4- dialkyl-S-pyrazolidones such as 1-phenyl-4,4-dimethyl 3 pyrazolidone, l (p--hydroxyethylphenyl) 4,4 dimethyl 3 pyrazolidone and 1 p tolyl 4,4 dimethyl 3 pyrazolidone described in Allen et al. U. S. patent application Serial No. 372,148 led August 3, 1953, and in the Reynolds and Tinker U. S. patent application Serial No. 372,167, filed August 3, 1953.
  • Particularly eficacious developer compositions are those containing, in addition to the indicated eifective Quaternary ammonium compounds, a mixture of developing agents such as a mixture of N-methyl-p-aminophenol and hydroquinone, or a mixture of lhydroquinone and a 3-pyrazolidone developing agent.
  • a mixture of developing agents such as a mixture of N-methyl-p-aminophenol and hydroquinone, or a mixture of lhydroquinone and a 3-pyrazolidone developing agent.
  • hydrazines useful in the developer compositions include those amongtle et al. U. S. Patent 2,618,656, November 18, 1952, and in the Weissberger U. S. patent application Serial No. 159,139 filed April 29, 1950, now Patent No. 2,663,732, such as the following:
  • The' water-soluble salts of the hydrazines are, of
  • An internal type developer that is, onewhich. ⁇ develops an image inside the grains of 'an internal latent image emulsion is thefollowing:
  • Example II G I-Iydroquinone n-lvethyl-p-aminophenol sulfate 15. Sodium sulte (anhydrous) 50i Potassium bromide 10 Sodium hydroxide Sodium thiosulfate (crystals) 20 Water to 1 liter. Development time, 3 min. at 20C.
  • Example III An emulsion made asdescribed. inthe Davey and Knott application Serial No. 82,914 was coated on a support, dried and exposed on an intensity scale sensitometer tia-3000? Kelvin tung- Isten illumination ⁇ anddeveloped. for. from 1. toy 2. minutes at 75 F. ina solution', ofthe following composition:
  • N -methyl-p-aminophenol su1fate.. 5.0 Hy-droquinoneY 10.0 p- (,f3-Methylsulionamidoethyl).v phenyl hydrazine hydrochloride 2.0 Sodium sulte (desiccated) 75.0. Trisodium phosphate, cryst 75.0 Diglycolic acid 13.4 5methyl benzotriazole 0.2. Sodium hydroxide 15.0l
  • ExampleIII andi developed for 1 to 2 minutes at 75 F. in a solution of the following composition:
  • Sodium carbonate monohydrate 4010 Benzotriazole 012' 3-methyl-2--phenethyl isoquinolinium bromide Water 13o-make 1,0 liter.
  • Example VI A portion of the emulsion used in Example III was ⁇ coated and exposed as in Example III developed for 1 to 2 minutes at 75 F. in af solu tion of the following' composition:
  • Example VII A portion of the emulsion used in Example III was coated and exposed as in Example 111 and developed for 1 to 2 minutes at 75 F. in a solution of the following composition:
  • a photographic developing composition comprising an aqueous alkaline solution containing a mixture of a silver halide developing agent, a compound selected from the group consisting or S-methyl-Z--phenethylisoquinolinium bromide, 2-benzyl-S-methyl-isoquinolinium bromide, l-,B- phenethyl-,B-picolinium bromide, l--phenethylquinolinium bromide and 1--phenethyl lepidinium bromide, and a hydrazine having the general formula wherein D represents a divalent mononuclear arylene group of the benzene series, n represents a positive integer of from 1 to 5, and R represent-s an alkyl group oi from 1 to 4 carbon atoms.
  • the photographic developer composition of claim 1 wherein the designated hydrazine has the general formula wherein D represents a divalent mononuclear arylene group of the benzene series and R represents an alkyl group oi from 1 to 4 carbon atoms.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a silver halide developing agent, 3- methyl-2--phenethylisoquinolinium bromide, and a hydrazine having the general formula wherein D represents a divalent mononuclear arylene group of the benzene series, n represents a positive integer of from 1 to 5, and R represents an alkyl group of from 1 to 4 carbon atoms.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and N-methyl-p-aininophenol silver halide developing agents, p-(- methylsulfonamidoethyl)phenylhydrazine, and 3-methyl-2--phenethylisoquinolinium bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and a B-pyrazolidone silver halide developing agent, p-(-methylsulionamidoethyl)phenylhydrazine, and S-methyl- 2-B-phenethylisoquinolinium bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and l-phenyl-S-pyrazolidone silver halide developing agents, p-(- methylsulfonamidoethyl)phenylhydrazine, and 3-methyl-Z--phenethylisoquinolinium bromide.
  • a photographic developer composition comprising an-aqueous alkaline solution containing a mixture of hydroquinone and 1-phenyl-/l,4- dimethyl-B-pyrazolidone silver halide developing agents, p- (-methylsulfonamidoethyl) phenylhydrazine, and 3-methyl-Z--phenethylisoquinolinium bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and 1-p-tolyl-4,4 dimethyl-B-pyrazolidone silver halide developing agents, p- ,S-methylsulfonamidoethyl) phenylhydrazine, and 3-methy1-2-phenethylisoquinolini um bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of a silver halide developing agent, 2- benzyl-S-methylisoquinolinium bromide, and a hydrazine having the general formula wherein D represents a divalent mononuclear arylene group of the benzene series, n represents a positive integer of from 1 to 5, and R represents an alkyl group of from 1 to 4 carbon atoms.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and N-methyl-paminophenol silver halide developing agents, p- (-methylsulfonamidoethyl) phenylhydrazine and Z-benzyl-S-methylisoquinolinium bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and a B-pyrazolidone silver halide developing agent, p-(-methylsulonamidoethyl) phenylhydrazine and 2-benzyl-3- methylisoquinolinium bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of hydroquinone and i-phenyl-Iipyrazolidone silver halide developing agents, pmethylsulfonamidcethyl) phenylhydrazine and 2-benzyl-S-methylisoquinolinium bromide.
  • a photographic developer composition comprising an an aqueous alkaline solution containing a mixture or hydroquinone and 1-phenyl-4,4 dimethyl-3-pyrazolidone silver halide developing agents, p-(,6-methylsulfonamidoethyl)phenylhydrazine and 2-benzy1-3-methylisoquinolinium bromide.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of 'hydroquinone and 1-p-tolyl-4,4dimethyl-S-pyrazolidone silver halide developing agents, p- (-methylsulfonamidoethyl) phenylhydrazine and 2 benzyl-3-methylisoquinolinium bromide.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US371946A 1953-08-03 1953-08-03 Direct positive photographic development process Expired - Lifetime US2685514A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE530882D BE530882A (enrdf_load_stackoverflow) 1953-08-03
US371946A US2685514A (en) 1953-08-03 1953-08-03 Direct positive photographic development process
FR1143615D FR1143615A (fr) 1953-08-03 1954-08-02 Procédé pour l'obtention d'images positives directes et révélateurs pour la miseen oeuvre de ce procédé
GB22509/54A GB767703A (en) 1953-08-03 1954-08-03 Improvements in direct positive photographic processes

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US371946A US2685514A (en) 1953-08-03 1953-08-03 Direct positive photographic development process

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BE (1) BE530882A (enrdf_load_stackoverflow)
FR (1) FR1143615A (enrdf_load_stackoverflow)
GB (1) GB767703A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840471A (en) * 1956-09-06 1958-06-24 Francis G Berry Photographic film developer
US3062643A (en) * 1959-05-22 1962-11-06 Eastman Kodak Co Photographic diffusion transfer process
US3719494A (en) * 1970-10-30 1973-03-06 Eastman Kodak Co Silver halide emulsion containing a dihydroaromatic quaternary salt nucleating agent and the use thereof
US4486528A (en) * 1980-06-20 1984-12-04 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic element with redox dye releasers
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0254280B1 (en) * 1986-07-22 1993-12-29 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic material

Non-Patent Citations (1)

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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840471A (en) * 1956-09-06 1958-06-24 Francis G Berry Photographic film developer
US3062643A (en) * 1959-05-22 1962-11-06 Eastman Kodak Co Photographic diffusion transfer process
US3719494A (en) * 1970-10-30 1973-03-06 Eastman Kodak Co Silver halide emulsion containing a dihydroaromatic quaternary salt nucleating agent and the use thereof
US4486528A (en) * 1980-06-20 1984-12-04 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic element with redox dye releasers
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators

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Publication number Publication date
FR1143615A (fr) 1957-10-03
BE530882A (enrdf_load_stackoverflow)
GB767703A (en) 1957-02-06

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