US3549370A - Quaternary ammonium bisulfites,sulfites or pyrosulfites as developer preservatives - Google Patents

Quaternary ammonium bisulfites,sulfites or pyrosulfites as developer preservatives Download PDF

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Publication number
US3549370A
US3549370A US646176A US3549370DA US3549370A US 3549370 A US3549370 A US 3549370A US 646176 A US646176 A US 646176A US 3549370D A US3549370D A US 3549370DA US 3549370 A US3549370 A US 3549370A
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Prior art keywords
developer
water
phenyl
sulfites
pyrosulfites
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US646176A
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English (en)
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Donald J Sykes
Harry Kroll
Theron R Finch
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Philip A Hunt Chemical Corp
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Philip A Hunt Chemical Corp
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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
    • 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
    • G03C5/305—Additives other than developers
    • 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
    • G03C5/383—Developing-fixing, i.e. mono-baths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/167—X-ray

Definitions

  • a developing solution for silver halide gelatin layers which solution includes a conventional developing agent or agents and other conventional constituents such as restrainers, anti-foggants, sequestrants, silver halide solvents and gelatin hardeners, and which for the preservative uses a quaternary ammonium bisulfite, sulfite or pyrosulfite of the formula:
  • each of R R R and R is selected from the class consisting of alkyls of one to four carbon atoms
  • hydroxyalkyls of two to four carbon atoms benzyl and phenyl.
  • the invention embraces the use of the foregoing chemical compositions (a) in working solutions of photographic developers, (b) in liquid developer concentrates, that is to say, liquid compositions which are intended to be diluted, as with Water, to form working solutions, (c) in liquid replenishers for developers, these constituting solutions more concentrated than Working solutions and which are intended to be added to working solutions that are at least in part exhausted so as to bring them back to working strength, (d) in combined developer/fixers of working strengths, these constituting socalled monobaths in which both developing and fixing takes place, and (e) in monobath concentrates which are intended to be diluted, as with water, to form monobath Working solutions.
  • preservatives as, for example, for preventing oxidation of the developing agents.
  • the preservatives heretofore conventionally employed were alkali metal sulfites, alkali metal bisulfites, hydroxyalkylamine-sulfur dioxide addition products, and ascorbic acid and its isomers.
  • the alkali metal sulfites and/or alkali metal bisul fites are effective preservatives but are of limited solubility in ice water. Developers which contain high proportions of hydroxyalkylamine-sulfur dioxide addition products tended to have a high viscosity and hence were difiicult to pour and measure accurately and to mix smoothly and easily with diluents such as Water.
  • the quaternary ammonium bisulfites sulfites and pyrosulfites of the present invention have the following generalized structure:
  • each of R R R and R is selected from the class consisting of alkyl of 1 to 4 carbon atoms, hydroxyalkyls, i.e. HO(CH where nequals 2, 3, or 4 carbon atoms, benzyl and phenyl.
  • N,N,N triskis (methyl), N (2 hydroxyethyl) ammonium bisulfite HOCHzCHz (CHa)aNHSOa (13) N,N,N,N-tetrakis (2-hydroxyethyl) ammonium bisulfite (HOCH CH NHSO Compounds illustrated in Examples 7 through 13 can be employed as the pyrosulfite or sulfite in place of the bisulfite without altering the scope or spirit of the invention.
  • the foregoing compounds can be prepared by passing gaseous or liquid sulfur dioxide through a solution of the corresponding quaternary ammonium hydroxide solution.
  • the compound to be prepared is tetramethyl ammonium pyrosulfite the solution is of tetramethyl ammonium hydroxide.
  • the compound to be prepared is N,N,N-triskis (Z-hydroxyethyl), N-methyl ammonium pyrosulfite
  • the solution is of N,N,N-triskis (Z-hydroxyethyl), N-methyl ammonium hydroxide, etc.
  • Quaternary ammonium bisulfites, sulfites and pyrosulfites such as have been described above are well known to the art. However, by way of illustration, there follows a description of a process for manufacturing tetramethyl ammonium pyrosulfite.
  • tetramethyl ammonium hydroxide dissolved in methanol e.g., a 24% solution of tetramethyl ammonium hydroxide in methanol
  • a gas-distributing apparatus e.g., a bubbling ring at the bottom, a stirrer and a thermometer.
  • gaseous sulfur dioxide is bubbled through the gas distributor into the bottom of the reaction flask containing he methanol solution of tetramethyl ammonium hydroxide.
  • the reaction is carried out at atmospheric pressure.
  • the reaction flask should be cooled to prevent the temperature from rising beyond 60 C.
  • Any mole ratio of sulfur dioxide to quaternary ammonium hydroxide can be employed, varying, for example, as widely as from one-thousandth part of sulfur dioxide to one part of quaternary ammonium hydroxide, to equal parts of each.
  • tetramethyl ammonium bisulfite When the tetramethyl ammonium bisulfite is dissolved in an alkaline aqueous solution, it is converted into the sulfite, namely, tetramethyl ammonium sulfite.
  • the quaternary ammonium bisulfite, sulfite and pyrosulfiite novel preservative compounds of the present invention have the same stabilizing effect for photographic developing agents, to wit, inhibition of oxidation, as is conventionally supplied by alkali metal sulfites, bisulfites, hydroxyalkylamine sulfur dioxide addition products, ascorbic acid and its isomers presently known in the art, and said novel preservative compounds are used, pursuant to the present invention, to formulate stable photographic developers, e.g., working solutions and liquid concentrates, that are stable against oxidation, such developers being inclusive of a photographic developing agent, and including conventional alkali-buffer systems, such, for instance, as quaternary ammonium hydroxides, alkali metal carbonates, tetraborates, metaborates, hydroxides and the family of hydroxyalkylamines, either separately or in combination.
  • stable photographic developers e.g., working solutions and liquid concentrates
  • alkali-buffer systems
  • the present invention embraces the use of these novel preservative compounds in photographic treating solutions where they may act as preservatives in combination with all manners of known alkalis and alka i buffer systems.
  • the present invention includes the use with the aforesaid novel preservative compounds of all developing agents, particularly silver halide developing agents, which are well known to the art.
  • An exemplificative partial list of photographic developing agents suitable for use separately or in combination with the new novel preservative compounds in working baths, concentrates and monobaths includes: hydroquinone, chloro-hydroquinone, bromo-hydroquinone, p-phenylene-diamine and all its derivatives, n-monomethyl-p-aminophenol sulfate, l-phenyl- 3-pyrazolidone and all its derivatives including 4,4-dimethyl-1-phenyl-3-pyrazolidone.
  • Other developing agents can be employed without altering the scope of this invention.
  • Developers so formulated may contain the known photographic developer addenda, i.e., restrainers; viz alkali metal chlorides, alkali metal bromides, alkali metal iodides; antifoggants: viz. benzotriazole, S-methylbenzotriazole, 6-nitrobenzimidazole, l-phenyl-S-mercapto tetrazole, Z-anthraquinone-sulfonic acid; sequestering agents: viz ethylenediamine tetraacetic acid and sodium hexametaphosphate; silver halide solvents: viz alkali metal thiosulfate and thioglycolates: various co-solvents: viz diethylene glycol; and gelatin hardening agents; viz formaldehyde and glutaraldehyde, as well as their bisulfate adducts.
  • antifoggants viz. benzotriazole, S-methylbenzotriazo
  • processing compositions and particularly developing compositions including developing agents, are not restricted solely to use with gelatin layers. They may be employed equally well, for instance, in silver-halide containing gelatin layers including gelatin extenders, such as carboxymethylated soy protein, or succinoylated hydroxyethyl cellulse, which replace a part of the gelatin in the photographic emulsion layer.
  • gelatin extenders such as carboxymethylated soy protein, or succinoylated hydroxyethyl cellulse, which replace a part of the gelatin in the photographic emulsion layer.
  • novel preservative compounds alkali buffer systems, and, if desired, restrainers, anti-foggants, sequestering agents, silver halide solvents, co-solvents, and gelatin hardening agents, that high quality photographic developers and developer/fixers with excellent stability have been prepared.
  • the quaternary ammonium bisulfite, sulfite and pyrosulfite novel preservatives enable developers and developer/fixers to be formulated that can be packaged and stored in highly concentrated liquid forms. This is the result of the high degree of solubility of quaternary ammonium bisulfites, sulfites and pyrosulfites in water in comparison with the lesser solubility of conventional alkali metal sulfites or bisulfites and other prior art preservatives.
  • Quaternary ammonium bisulfites, sulfites and pyrosulfites allow for greater developer system solubility, i.e., the solubility of the system including the preservative and developing agents and hardener and/or anti-foggant, and/ or sequestrants, etc.
  • Concentrates of developers and of developer/fixers embodying the present invention are of a low order of viscosity that is particularly conducive to trouble-free mixing and is quite unlike some known concentrates of developers and developer/fixers employing as the preservative agent hydroxyalkylamine-sulfur dioxide addition products. These latter are considerably more viscous.
  • a developer concentrate containing an alkanolamine sulfur dioxide addition product as the preservative in an amount of g. per ml. of developer concentrate, along with proportionate amounts of developing agent and buffering agent has a viscosity of 5250 centipoises at room temperature. This obviously makes preparation of a working developer bath extremely difiicult.
  • novel preservative compounds of the present invention are highly compatible with the other constitutents of developing compositions, i.e., are inert thereto.
  • one of the advantages of employing quaternary ammonium bisulfites, sulfites and pyrosulfites is that in combination with known gelatin hardening agents, namely, aldehydes and dialdehydes, a particularly stable developer concentrate and/or working solution results.
  • novel preservative compound of the present invention can be used effectively in connection with aldehyde and dialdehyde gelatin hardening agents to form a particularly stable developer concentrate and/or working developer solution.
  • Specific aldehydes and dialdehydes useful in the present invention and mentioned by way of example are formaldehyde, glyoxal, glutaraldehyde, succinic dialdehyde, maleic dialdehyde, their derivatives and their bisulfite addition products.
  • Tetramethyl ammonium bisulfite solution i.e., 55
  • the solution prepared as per Example I produces an excellent working developer for both film and paper.
  • Eastman Kodak Plus-X Pan Film, at film having a gelatin silver halide emulsion layer is processed with the developer of Example I at 68 :F. for only 2 minutes to yield excellent results.
  • Eastman Kodak Kodabromide F-Z paper a paper coated with a photographic gelatin containing silver bromide, is developed with the developer of Example I at 68 F. for 60 seconds to produce excellent results. Both the film and the paper are fixed in a rapid acid fixing bath for 3 minutes at 68 F. and are washed for 15 minutes at 68 F., then being dried in the normal manner.
  • the developing solution of Example I can be packaged in any convenient way.
  • This formulation will effectively develop photographic printing paper similar to Kodabromide F-2 at 68 F. for 1 minute. Fixing and washing is as described in Example I.
  • Ethylenediamine tetraacetic acid 1.0 g. Tetramethyl ammonium bisulfite (55% solution)58.0 g. Hydroquinone--20.0 g.
  • Glutaraldehyde (50% )8.0 g. 4-methyl-l-phenyl-3-pyrazolidone--2.0 g. BenZotriazole-0.50 g. 6-nitrobenzimidazole--0.20 g.
  • Thisstable, hardening formulation will develop both double and single coated X-ray filmin 70 seconds at 90 F.
  • the developed X-rays are fixed in a standard, rapid, acid ammonium thiosulfate fixer, such as is used for automatic processing of X-ray film, for 35 seconds and washed for 60 seconds at 90 F. and dried.
  • the developer prepared from Example V will develop Plus-X Pan film to a gamma of 0.82 in minutes at 68.
  • F. Kodabromide F-2 paper is developed in 2 minutes at 68 F. Both materials are fixed in a rapid acid fixer for 3 minutes and washed in running water for 15 minutes at 68 F. and dried in any conventional manner.
  • Tetramethyl ammonium bisulfite (55% solution)--30.0 g. Hydroquinone10.0 g.
  • Tetramethyl ammonium bisulfite 5 5 solution l0.0 g.
  • This bath will develop miniature film, such as Plus-X Pan film in 10 minutes at 68 F. to a gamma of 0.65. Fixing, washing and drying are done in the conventional manner.
  • Viscosity equals 17.5 centipoises at 68 F.
  • Part A plus B and C when combined and diluted with tap water to 1500 ml. will produce a developer that will process X-ray film as is described in Example IV.
  • N,N,N-triskis (methyl), N-(Z-hydroxyethyl) ammonium bisulfite (58% solution)-25.0 g.
  • the developer produced above will develop Plus-X pan film in 2 minutes at 68 F. Conventional fixing, washing, and drying follow.
  • the developing agent includes a mixture of hydroquinone and a compound selected from the class consisting of l-phenyl- 3 pyrazolidone, 4 methyl-1-phenyl-3-pyrazolidone, and 4,4-dimethyl-1-phenyl-3-pyrazolidone.
  • D-72 is an Eastman Kodak developer containing sodium sulfite, hydroquinone, n-monomethyl-paminophenol sulfate (Metol), sodium carbonate and potassium bromide. One part by volume of D-72 is mixed with two parts by volume of water.
  • Developer D-76 is an Eastman Kodak developer and includes essentially the same constituents in varying proportions as D72, except that borax is substituted for sodium carbonate.
  • EXAMPLES OF PHOTOGRAPHIC EFFECTS ON EASTMAN KODAK BLUE BRAND X-RAY FILM Norm Developer D-19 is an Eastman Kodak developer and includes hydroquinone, sodium carbonate, sodium hydroxide, Metol and sodium sulfite,
  • a method of developing an exposed gelatin-silver halide photographic emulsion layer comprising treating the emulsion layer with an aqueous bath including a developing agent and a preservative constituting a compound selected from the class consisting of quaternary ammonium bisulfites, sulfites and pyrosulfites of the formulae:
  • R2 R2 R2 N 11803 N 803- and N 5205" R R3 R3 R4 R4 2 R4 2 in which each of R R R and R is selected from the class consisting of alkyls of l to 4 carbon atoms, hydroxyalkyls of 2 to 4 carbon atoms, benzyl and phenyl.
  • the developing agent includes at least two compounds selected from the class consisting of hydroquinone, chloro-hydroquinone, bromo-hydroquinone, p-phenylenediamine and derivatives thereof, n-monomethyl-p-aminophenol sulfate, and l-phenyl-3-pyrazolidone and derivatives thereof.
  • the bath includes a buffer selected from the class consisting of hydroxides, carbonates, borates and hydroxyalkylamines.
  • R R R and R is selected from the class consisting of alkyls of 1 to 4 carbon atoms, hydroxyalkyls of 2 to 4 carbon atoms, benzyl and phenyl.
  • the preservative is selected from the class consisting of (a) tetramethyl ammonium bisulfite,
  • a developer as set forth in claim 13 which includes a silver halide solvent.
  • a developer as set forth in claim 13 which includes a gelatin hardener selected from the class consisting of aldehydes and dialdehydes.
  • a developer as set forth in claim 14 which includes a buffer selected from the class consisting of hydroxides, carbonates, borates and hydroxyalkylamines.
  • a developer as set forth in claim 14 which is a liquid concentrate containing a high proportion of a preservative selected from said class, the preservative on an S0 basis being present in at least equal molar ratio to the total number of mols of the developing agent.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US646176A 1966-11-23 1967-06-15 Quaternary ammonium bisulfites,sulfites or pyrosulfites as developer preservatives Expired - Lifetime US3549370A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US59647466A 1966-11-23 1966-11-23
US64617667A 1967-06-15 1967-06-15
GB21221/68A GB1207583A (en) 1966-11-23 1968-05-03 Processing of photographic silver halide
DE19681772404 DE1772404A1 (de) 1966-11-23 1968-05-10 Photographischer Entwickler
BE715118 1968-05-14
FR154048 1968-06-06
US9002470A 1970-11-16 1970-11-16

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US90024A Expired - Lifetime US3705806A (en) 1966-11-23 1970-11-16 Polyquaternary ammonium bisulfites,sulfites and pyrosulfites as developer preservatives

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BE (1) BE715118A (https=)
DE (1) DE1772404A1 (https=)
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GB (1) GB1207583A (https=)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294911A (en) * 1979-06-18 1981-10-13 Eastman Kodak Company Development of light-sensitive quinone diazide compositions using sulfite stabilizer
US4310613A (en) * 1979-05-29 1982-01-12 Mitsubishi Paper Mills, Ltd. Liquid processing composition for silver complex diffusion transfer process
US4467027A (en) * 1981-05-25 1984-08-21 Konishiroku Photo Industry Co., Ltd. Process of developing posi-type lithographic printing plate with inorganic alkali solution
US4686002A (en) * 1986-07-18 1987-08-11 Syntex (U.S.A.) Inc. Stabilized choline base solutions
US4987060A (en) * 1989-04-03 1991-01-22 Minnesota Mining And Manufacturing Company Concentrated photographic developer composition and method of making it
US5863713A (en) * 1997-04-07 1999-01-26 Aviles; John Jay Process repeatedly regenerates developers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1397732A (en) * 1971-07-26 1975-06-18 Mundipharma Ag Stabilized choline salicylate compounds
US4147776A (en) 1971-07-24 1979-04-03 Mundipharma, Ag Stabilized choline salicylate compounds
US4118231A (en) * 1972-03-08 1978-10-03 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials containing antistatic agents
US3857710A (en) * 1972-12-22 1974-12-31 Gen Film Dev Corp High contrast, high capacity monobath processing method and composition for monochrome film
IL61497A (en) * 1980-11-16 1985-06-30 Hanetz Photographic Processes Developer for lith or line films and process for its use
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
WO2007053235A1 (en) * 2005-11-04 2007-05-10 Sachem, Inc. Cation-exchange displacement chromatography process and cationic organic compounds for use as displacer compounds in cation-exchange displacement chromatography process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB430916A (en) * 1932-12-24 1935-06-27 Ig Farbenindustrie Ag Improvements relating to photographic baths
US3022168A (en) * 1958-06-28 1962-02-20 Pharmacia Ab Photographic developer
GB958678A (en) * 1959-09-04 1964-05-21 Kodak Ltd Photographic developer concentrates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB430916A (en) * 1932-12-24 1935-06-27 Ig Farbenindustrie Ag Improvements relating to photographic baths
US2030336A (en) * 1932-12-24 1936-02-11 Agfa Ansco Corp Photographic developer
US3022168A (en) * 1958-06-28 1962-02-20 Pharmacia Ab Photographic developer
GB958678A (en) * 1959-09-04 1964-05-21 Kodak Ltd Photographic developer concentrates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310613A (en) * 1979-05-29 1982-01-12 Mitsubishi Paper Mills, Ltd. Liquid processing composition for silver complex diffusion transfer process
US4294911A (en) * 1979-06-18 1981-10-13 Eastman Kodak Company Development of light-sensitive quinone diazide compositions using sulfite stabilizer
US4467027A (en) * 1981-05-25 1984-08-21 Konishiroku Photo Industry Co., Ltd. Process of developing posi-type lithographic printing plate with inorganic alkali solution
US4686002A (en) * 1986-07-18 1987-08-11 Syntex (U.S.A.) Inc. Stabilized choline base solutions
US4987060A (en) * 1989-04-03 1991-01-22 Minnesota Mining And Manufacturing Company Concentrated photographic developer composition and method of making it
US5863713A (en) * 1997-04-07 1999-01-26 Aviles; John Jay Process repeatedly regenerates developers

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Publication number Publication date
US3705806A (en) 1972-12-12
BE715118A (https=) 1968-09-30
DE1772404A1 (de) 1971-04-01
FR1567793A (https=) 1969-04-08
GB1207583A (en) 1970-10-07

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