US2685516A - Photographic developer composition - Google Patents

Photographic developer composition Download PDF

Info

Publication number
US2685516A
US2685516A US372192A US37219253A US2685516A US 2685516 A US2685516 A US 2685516A US 372192 A US372192 A US 372192A US 37219253 A US37219253 A US 37219253A US 2685516 A US2685516 A US 2685516A
Authority
US
United States
Prior art keywords
pyrazolidone
gallic acid
developer
developer composition
phenyl
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
US372192A
Inventor
Charles V Wilson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE530890D priority Critical patent/BE530890A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US372192A priority patent/US2685516A/en
Application granted granted Critical
Priority to GB22508/54A priority patent/GB767702A/en
Publication of US2685516A publication Critical patent/US2685516A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers

Definitions

  • This invention relates to photographic developers and particularly to methods for accelerating the development rate of photographic developing agents.
  • gallic acid is a very weak developing agent and the 3- pyrazolidone compounds are comparatively weak developing agents.
  • the activity of the resulting developing solution is much greater than expected from summing up the separate development activities of the compounds.
  • a further characteristic of the gallic acid-pyrazolidone developer compositions of the invention resides in the fact that the compositions behave as strong surface latent image developers as opposed to internal latent image developers, as long as they are free of silver halide solvents.
  • the developers also exhibit relatively little tendency for physical development. For these and other reasons, the developers of the invention are very useful in color development processes where a black-andwhite developer is required.
  • An additional unexpected feature of the developers containing gallic acid and the S-pyrazolidone compounds resides in the fact that similar developer compositions can be prepared, in which the pyrazoliclone is replaced by a conventional developing agent, for example, containing a mixture of N-methyl-p-aminophenol and gallic acid, which compositions do not exhibit the mentioned development acceleration efiect.
  • the 3-pyrazolidone developer compositions of the invention containing gallic acid can be readily converted to internal latent image developer compositions by merely adding a silver halide solvent such as sodium thiosulfate thereto.
  • the 3-pyrazolidone silver halide developing agents employed in the developer compositions together with gallic acid have the general structure ill in which the R groups each represent various substituents such as hydrogen, alkyl or aryl groups, for example, R1 can be hydrogen or a group such as alkyl preferably containing from 1 to a carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not, and R2, R3, R4 and R5 can be hydrogen atoms, or groups such as an alkyl group preferably of 1 to 4 carbon atoms or aryl such as phenyl.
  • R1 can be hydrogen or a group such as alkyl preferably containing from 1 to a carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not
  • R2, R3, R4 and R5 can be hydrogen atoms, or groups such as an alkyl group preferably of 1 to 4 carbon atoms or aryl such as
  • l-p- (p-hydroxyethylphenyl) -3-pyrazolidone 25.
  • the 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly efiicacious for use in the developer compositions of my invention inasmuch as they are more active developing agents than are compounds 1 to 12 which contain a single substituent or only hydrogen atoms in the 4-position of the pyrazolidone nucleus.
  • the 4,4-dialkyl-3-pyrazolidone compounds are described and claimed in the Allen et al. U. S. patent application Serial No. 372,148 filedconcurrently herewith.
  • the w-hydroxyalkyHi -pyrazolidones for example, compounds 18 and 24 above, are also especially useful in concentrated formulas, in replenishers and in the presence of high salt concentrations where their increased solubility enables obtaining and holding adequate amounts of the pyrazolidone compound in solution.
  • the compounds are described and claimed in the Allen et a1.
  • U. S. patent application Serial No. 372,148 filed concurrently herewith and in the Reynolds and Tinker
  • U. S. patent application Serial No. 372,167 filed concurrently herewith.
  • Example 1 A fine-grain positive film was exposed behind a step wedge and separate strips were developed for a series of times in the following solutions Formula No.
  • Formula 6585 in which gallic acid was the sole developing agent, produced no development in times up to eight minutes at 68 F.
  • Formula 6586 containing l-phenyl-eA-dimethyl-li-pyrazolidone as a developing agent built up density very slowly.
  • Formula 6587 containing both agents, develops vigorously and density and contrast came up rapidly.
  • developer 6585 showed no image; developer 6586 gave a density at the fourth exposure step of 0.64. and a gamma of 0.88; and developer 6587 gave a density at the fourth step of 2.66 and a gamma of 2.0.
  • Example 2 The following developer compositions are useful as negative developers for color films:
  • the developers of this example can be used in any of the well-known processes of color development where a black-and-white developer is required.
  • the developers are especially useful in mixed grain color processes employing films such as disclosed in Mannes et al. U. S. Patent 2,388,855 or in the Carroll et al. U. S. Patent 2,614,925, October 21, 1952, wherein, for example,
  • developer compositions containing or free of silver halide solvents, are prepared from a mixture of at least one of the mentioned pyrazolidone compounds and gallic acid.
  • Particularly valuable developer compositions in addition to those exemplified above are those containing gallic acid and either a 1-tolyl-3-pyrazolidone such as 1-p-tolyl-3-pyrazolidone or l-ptolyl-4A-dimethyl-3-pyrazolidone or a l-(p-hydroxyalkylphenyl-4,4-dialkyl 3 pyrazolidone, such as l-(p-fi-hydroxyethylphenyl) AA-climethyl-S-pyrazolidone, or a l-(p-hydroxyalkylphenyl) -3-pyrazolidone such as 1-(p-B-hydroxyethylphenyl) -3-pyrazolidone.
  • a 1-tolyl-3-pyrazolidone such as 1-p-tolyl-3-pyrazolidone or
  • a photographic developer composition comprising an alkaline material, gallic acid, and a 3-pyrazolidone silver halide developing agent.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and 1-phenyl-3-pyrazolidone.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and a 4,4-dialkyl-3- pyrazolidone silver halide developing agent.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and l-phenyl-d/l-dimethyl-3-pyrazolidone.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and a 1- (w-hydroxyalkylphenyl) -3-pyrazolidone.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and 1- (p-B-hydroxyethylphenyl) -3-pyrazolidone.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and 1-(p-[3-hydroxyethylphenyl) -4,4-dimethyl-3-pyrazolidone.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and a 1-tolyl-3-pyrazolidone silver halide developing agent.
  • a photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and l-p-tolyl-3-pyrazolidone.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

Patented Aug. 3, 1954 PHOTOGRAPHIC DEVELOPER COMPOSITION Charles V. Wilson, Rochester, N. Y., assignor to Eastman Kodak CompanygRochester, N. Y., a corporation of New Jersey No Drawing. Application August 3, 1953, Serial No. 372,192
9 Claims. 1
This invention relates to photographic developers and particularly to methods for accelerating the development rate of photographic developing agents.
I have discovered a method for accelerating the development activity of developing agents which are themselves weak developing agents for silver halide even under the most favorable conditions of development. For example, gallic acid is a very weak developing agent and the 3- pyrazolidone compounds are comparatively weak developing agents. However, I find that when these developing agents are combined in a single developing solution, the activity of the resulting developing solution is much greater than expected from summing up the separate development activities of the compounds. -A further characteristic of the gallic acid-pyrazolidone developer compositions of the invention resides in the fact that the compositions behave as strong surface latent image developers as opposed to internal latent image developers, as long as they are free of silver halide solvents. The developers also exhibit relatively little tendency for physical development. For these and other reasons, the developers of the invention are very useful in color development processes where a black-andwhite developer is required.
An additional unexpected feature of the developers containing gallic acid and the S-pyrazolidone compounds resides in the fact that similar developer compositions can be prepared, in which the pyrazoliclone is replaced by a conventional developing agent, for example, containing a mixture of N-methyl-p-aminophenol and gallic acid, which compositions do not exhibit the mentioned development acceleration efiect.
The 3-pyrazolidone developer compositions of the invention containing gallic acid can be readily converted to internal latent image developer compositions by merely adding a silver halide solvent such as sodium thiosulfate thereto.
The 3-pyrazolidone silver halide developing agents employed in the developer compositions together with gallic acid have the general structure ill in which the R groups each represent various substituents such as hydrogen, alkyl or aryl groups, for example, R1 can be hydrogen or a group such as alkyl preferably containing from 1 to a carbon atoms, or an aryl group of the benzene or naphthalene series substituted or not, and R2, R3, R4 and R5 can be hydrogen atoms, or groups such as an alkyl group preferably of 1 to 4 carbon atoms or aryl such as phenyl.
The following compounds are representative of 3-pyrazolidone silver halide developing agents which are useful in the developer compositions of the invention:
. 1-phenyl-3-pyrazolidone l-p-tolyl-3-pyrazolidone 5-phenyl-3-pyrazolidone 5-methyl-3-pyrazolidone 1-p-chlorophenyl-3-pyrazolidone 1-phenyl-5-phenyl-3-pyrazolidone l-m-tolyl-3-pyrazolidone 1-phenyl-5-methyl-3-pyrazolidone 1-p-tolyl-5-phenyl-3-pyrazolidone l0. 1-m-tolyl-3-pyrazolidone 11. 1-p-methoxyphenyl-3-pyrazolidone 12. 1-acetamidophenyl-3-pyrazolidone l3. 1-phenyl-2-acetyl-4A-dimethyl 3 pyrazo1i-- done 7 l4. 1-phenyl-4,4-dimethyl-3-pyrazolidone 15. 1 m aminophenyl 4 methyl-i-propyl 3- pyrazolidone 16. 1-o-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone l7. 1 m acetamidopheny1-4,4-diethyl-3-pyrazolidone 18. l-p(c hydroxyethylphenyl) -4,4-dimethyl-3- pyrazolidone 19. 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone 20. l-p-methoxyphenyl 4,4 diethyl-3-pyrazolidone 21. l-p-tolyl-4,4-dimethyl-3-pyrazolidone 22. 1-(7 hydroxy 2 naphthyl) -4-methyl-4-npropyl-3-pyrazolidone 23. 1-p-diphenyl-4,4-dimethyl-3-pyrazolidone 24. l-p- (p-hydroxyethylphenyl) -3-pyrazolidone 25. l-o-tolyl-S-pyrazolidone 26. l-o-tolyl-A-dimethyl-3-pyrazolidone The 4,4-dialkyl-3-pyrazolidone compounds 13 to 23 and 26 above are particularly efiicacious for use in the developer compositions of my invention inasmuch as they are more active developing agents than are compounds 1 to 12 which contain a single substituent or only hydrogen atoms in the 4-position of the pyrazolidone nucleus. The 4,4-dialkyl-3-pyrazolidone compounds are described and claimed in the Allen et al. U. S. patent application Serial No. 372,148 filedconcurrently herewith. The w-hydroxyalkyHi -pyrazolidones, for example, compounds 18 and 24 above, are also especially useful in concentrated formulas, in replenishers and in the presence of high salt concentrations where their increased solubility enables obtaining and holding adequate amounts of the pyrazolidone compound in solution. The compounds are described and claimed in the Allen et a1. U. S. patent application Serial No. 372,148 filed concurrently herewith and in the Reynolds and Tinker U. S. patent application Serial No. 372,167 filed concurrently herewith.
Example 1 A fine-grain positive film was exposed behind a step wedge and separate strips were developed for a series of times in the following solutions Formula No.
Water cc. 100 100 100 Gallic acid "grams. 0. 34 i 0. 34 l-Phenyl-4,4-dimethyl-S-pyrazolidoue grams 0. 04 0. 04 Sodium sulfite, anhydrous .d 2. 5 2. 5 2. 5 Sodium carbonate, monohydrate. do 2.5 2. 5 2. 5 Acetic acid, to adjust pH to 10.0.
Formula 6585, in which gallic acid was the sole developing agent, produced no development in times up to eight minutes at 68 F. Formula 6586, containing l-phenyl-eA-dimethyl-li-pyrazolidone as a developing agent built up density very slowly. Formula 6587, containing both agents, develops vigorously and density and contrast came up rapidly. In a comparison of density produced in eight minutes at 68, developer 6585 showed no image; developer 6586 gave a density at the fourth exposure step of 0.64. and a gamma of 0.88; and developer 6587 gave a density at the fourth step of 2.66 and a gamma of 2.0.
These data illustrate the pronounced acceleration in development obtained by use of the pyrazolidone-gallic acid developer.
Example 2 The following developer compositions are useful as negative developers for color films:
(1) Without sulfite Grams/liter Sodium hexametaphosphate 0.5 Sodium carbonate monohydrate 25.0
Water to make 1.0 liter.
The developers of this example can be used in any of the well-known processes of color development where a black-and-white developer is required. The developers are especially useful in mixed grain color processes employing films such as disclosed in Mannes et al. U. S. Patent 2,388,855 or in the Carroll et al. U. S. Patent 2,614,925, October 21, 1952, wherein, for example,
is shown a two-layer film, one layer containing blue-sensitive silver halide, the other containing a mixture of green and red-sensitive silver halide grains. When the developers immediately above are used in the color process of the patents as the negative developer for such a film it is observed, particularly with the formula free of sulfite, that physical development effects are minimized with the result that the color developed images have increased saturation because of decreased physical development in the negative developer of the invention.
Results similar to those exemplified above are obtained when developer compositions, containing or free of silver halide solvents, are prepared from a mixture of at least one of the mentioned pyrazolidone compounds and gallic acid. Particularly valuable developer compositions in addition to those exemplified above are those containing gallic acid and either a 1-tolyl-3-pyrazolidone such as 1-p-tolyl-3-pyrazolidone or l-ptolyl-4A-dimethyl-3-pyrazolidone or a l-(p-hydroxyalkylphenyl-4,4-dialkyl 3 pyrazolidone, such as l-(p-fi-hydroxyethylphenyl) AA-climethyl-S-pyrazolidone, or a l-(p-hydroxyalkylphenyl) -3-pyrazolidone such as 1-(p-B-hydroxyethylphenyl) -3-pyrazolidone.
It will be understood that my invention as specified by the claims hereinafter, includes the mentioned developer compositions in either the liquid form exemplified above, or in the dry powder form such as packaged developer formulas suitable for dissolving in water to form a liquid developer. Such dry compositions include the mentioned 3-pyrazolidone compounds, gallic acid, and an alkaline material such as sodium carbonate, caustic alkali or sodium perborate.
What I claim is:
1. A photographic developer composition comprising an alkaline material, gallic acid, and a 3-pyrazolidone silver halide developing agent.
2. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and 1-phenyl-3-pyrazolidone.
3. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and a 4,4-dialkyl-3- pyrazolidone silver halide developing agent.
4. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and l-phenyl-d/l-dimethyl-3-pyrazolidone.
5. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and a 1- (w-hydroxyalkylphenyl) -3-pyrazolidone.
6. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and 1- (p-B-hydroxyethylphenyl) -3-pyrazolidone.
7. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and 1-(p-[3-hydroxyethylphenyl) -4,4-dimethyl-3-pyrazolidone.
8. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and a 1-tolyl-3-pyrazolidone silver halide developing agent.
9. A photographic developer composition comprising an aqueous alkaline solution containing a mixture of gallic acid and l-p-tolyl-3-pyrazolidone.
No references cited.

Claims (1)

1. A PHOTOGRAPHIC DEVELOPER COMPOSITION COMPRISING AN ALKALINE MATERIAL, GALLIC ACID, AND A 3-PYRAZOLIDONE SILVER HALIDE DEVELOPING AGENT.
US372192A 1953-08-03 1953-08-03 Photographic developer composition Expired - Lifetime US2685516A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE530890D BE530890A (en) 1953-08-03
US372192A US2685516A (en) 1953-08-03 1953-08-03 Photographic developer composition
GB22508/54A GB767702A (en) 1953-08-03 1954-08-03 Improvements in photographic developer compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US372192A US2685516A (en) 1953-08-03 1953-08-03 Photographic developer composition

Publications (1)

Publication Number Publication Date
US2685516A true US2685516A (en) 1954-08-03

Family

ID=23467090

Family Applications (1)

Application Number Title Priority Date Filing Date
US372192A Expired - Lifetime US2685516A (en) 1953-08-03 1953-08-03 Photographic developer composition

Country Status (3)

Country Link
US (1) US2685516A (en)
BE (1) BE530890A (en)
GB (1) GB767702A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4409324A (en) * 1981-09-21 1983-10-11 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive materials
US4465762A (en) * 1981-03-03 1984-08-14 Fuji Photo Film Co., Ltd. Method for color developing color photographic silver halide light-sensitive material
US5534389A (en) * 1991-05-31 1996-07-09 Konica Corporation Processing method of black-and-white light-sensitive silver halide photographic material and processing agent for the same
US5776664A (en) * 1995-06-15 1998-07-07 Fuji Photo Film Co., Ltd. Silver halide photographic material
WO2007059901A1 (en) * 2005-11-22 2007-05-31 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung_E.V. Organic oxygen scavenger/indicator
US9580460B2 (en) 2000-11-20 2017-02-28 Alphabeta Ab Discordant helix stabilization for prevention of amyloid formation

Non-Patent Citations (1)

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

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465762A (en) * 1981-03-03 1984-08-14 Fuji Photo Film Co., Ltd. Method for color developing color photographic silver halide light-sensitive material
US4409324A (en) * 1981-09-21 1983-10-11 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive materials
US5534389A (en) * 1991-05-31 1996-07-09 Konica Corporation Processing method of black-and-white light-sensitive silver halide photographic material and processing agent for the same
US5776664A (en) * 1995-06-15 1998-07-07 Fuji Photo Film Co., Ltd. Silver halide photographic material
US9580460B2 (en) 2000-11-20 2017-02-28 Alphabeta Ab Discordant helix stabilization for prevention of amyloid formation
WO2007059901A1 (en) * 2005-11-22 2007-05-31 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung_E.V. Organic oxygen scavenger/indicator
US20080272336A1 (en) * 2005-11-22 2008-11-06 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Organic Oxygen Scavenger/Indicator
US8158019B2 (en) 2005-11-22 2012-04-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Organic oxygen scavenger/indicator

Also Published As

Publication number Publication date
GB767702A (en) 1957-02-06
BE530890A (en)

Similar Documents

Publication Publication Date Title
US2688548A (en) Photographic developer composition
US2688549A (en) Photographic developer composition
US2289367A (en) Photographic developer
US2588982A (en) Direct positive photographs using hydrazine in the emulsion
US2563785A (en) Direct positive photographs from hydrazine-containing developers
US3247201A (en) 1-carbocyclic aryl-2-tertiary amino-3, 4-hydrocarbon and carbocyclic aryl-3-pyrazolidones
US2497917A (en) Method of producing direct positive photographs having increased density
US3705035A (en) Diffusion-fast color-forming developing agents
CA1135555A (en) PHOTOGRAPHIC COLOUR DEVELOPER COMPOSITION CONTAINING A PHENYLENE DIAMINE DERIVATIVE AND AN .alpha. AMINO CARBONYL ANTIOXIDANT
US2685516A (en) Photographic developer composition
US3549370A (en) Quaternary ammonium bisulfites,sulfites or pyrosulfites as developer preservatives
US2592363A (en) P-phenylenediamine developer containing nu-alkylacetamido ethyl substituent
US2384593A (en) Antifoggant
US2271229A (en) Fog inhibitor for photographic developers
US2685515A (en) Photographic developer composition
GB1251558A (en)
US2449919A (en) 3-methylsulfonamido-4-amino dimethyl aniline photographic developer
US4035184A (en) Method of producing reversal color images
US3265502A (en) Photographic developing compositions
US2350138A (en) Nondiffusing acylacetyl sulphonamide coupler
US2753265A (en) Photographic developing compositions
US3740221A (en) Development of photographic material
US3615509A (en) Photographic fixer-developer containing compounds with p-aminophenol and dyeforming nuclei
US3276875A (en) Developing composition with pyrrolidone anti-sludging agent
US3043694A (en) Novel class of 3-indazolinone developing agent