US3532499A - Amino - n - oxides as development accelerators in photography - Google Patents

Amino - n - oxides as development accelerators in photography Download PDF

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Publication number
US3532499A
US3532499A US573801A US3532499DA US3532499A US 3532499 A US3532499 A US 3532499A US 573801 A US573801 A US 573801A US 3532499D A US3532499D A US 3532499DA US 3532499 A US3532499 A US 3532499A
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development
mole
oxide
oxides
compounds
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US573801A
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English (en)
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Jozef Frans Willems
Francis Jeanne Sels
Joseph Louis Demunck
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Agfa Gevaert NV
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Agfa Gevaert NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
    • C07D295/24—Oxygen atoms
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
    • 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
    • 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
    • Y10S430/15—Lithographic emulsion

Definitions

  • This invention relates to the development of photographic silver halide emulsions in the presence of substances infiuencing the development and combinations of these substances with known development accelerators.
  • each of R and R represents an alkyl radical e.g. methyl, an aralkyl radical e.g. benzyl, or together represent the atoms required for completing an heterocyclic ring e.g. a morpholine, a pyrrolidine, or a piperidine ring,
  • R represents an alkyl radical e.g. ethyl or an aralkyl radical e.g. benzyl,
  • R represents alkyl and aralkyl
  • R represents a hydrogen atom or a substitutent such as an alkyl radical or an aralkyl radical
  • X- represents an anion
  • R represents a bivalent organic radical such as an alkylene radical or an alkylenephenylenealkylene radical
  • Z represents the atoms required for forming an heterocyclic ring system
  • Compounds corresponding to one of these general formulae are i.e. the compounds resulting from the alkylation of tertiary amino-N-oxides such as trimethylamino- N-oxide, triethylamino-N-oxide, tributylamino-N-oxide, monomethyldiethylamino- N oxide, dodecyldimethylamino-N-oxide, cetyldimethylaminio-N-oxide, pyridine-N- oxide, a-, 5-, or 'y-picoline-N-oxide, chloropyridine-N- oxide, quinoline-N-oxides, lepidine-N-oxides, and amino- N-oxides derived from other heterocyclic nitrogen compounds.
  • tertiary amino-N-oxides such as trimethylamino- N-oxide, triethylamino-N-oxide, tributylamino-N-oxide, monomethyldie
  • Suitable alkylating agents are, e.g., alkyl bromides, alkyl tolusulphonates, alkylmethyl sulphonates, aralkyl bromides, 1,2-dibromomethane, 1,4-dibromobutane, p-xylylene dibromide, N,N'-bis-(2-bromoethyl)-succinamide, bis-(2-bromoethyl)-sulphone, bis (2 bromoethyl)-sub phide, bis (2 bromoethyl) ether, and N,N-bis-(10- bromohendecanoyl -ethylenediamine.
  • Preparation 4 In a 100 cm. flask fitted with a condenser 0.05 mole of tetrarnethylene dibromide is mixed with 0.12 mole of triethylamine-N-oxide in 15 cm. of acetone. After having been refluxed for 5 hours the precipitate is filtered by suction and Washed with chloroform and afterwards with ether. Melting point: explodes on the Kofler hot bench at 200 C.
  • Preparation 8 In a 100 cm. flask fitted with a condenser 0.1 mole of hexamethylene dibromide is mixed with 0.2 mole of pyridine-N-oxide in 40 cm. of acetonitrile. After having been refluxed for 2 hours the formed precipitate is filtered by suction. The precipitate is recrystallised from ethanol. Melting point: 162 C.
  • Preparation 9 In a 100 cm. flask fitted with a condenser 0.1 mole of n-hexylmethyl sulphonate is mixed with 0.1 mole of pyridine-N-oxide in 50 cm. of acetonitrile. After refluxing the solution for 6 hours, the solvent is evaporated in vacuo and the waxy residue is washed with a mixture of ether and ethyl acetate (50:50).
  • the onium derivatives of the amino-N-oxides influencing the rate of development are preferably added to the light-sensitive silver halide emulsions in dissolved form in water or a mixture of water and water-miscible organic solvents, which do not impair the photographic characteristics of the emulsion.
  • condensation products can also be incorporated into the emulsion by im'bibition by treating it with a solution containing these products or by d ffusion from an adjacent water-permeable layer comprising these products.
  • the onium derivatives of the amine-N-oxides used according to the present invention can be added to the light-sensitive silver halide emulsion during different preparation steps of the light-sensitive material. For example they can be incorporated therein by a separate addition or they can be added as a mixture with one or more ingredients used in the formation of the silver halide grains, during the physical or chemical ripening or during another step preceding the coating of the emulslon.
  • the said derivatives are preferably used in combination with -water-soluble alkylene oxide condensation products as described e.g. in the United States patent specifications 1,970,578 by Conrad Schoeller and Max Wittwer issued Aug.
  • polyoxyalkylene compounds i.e. alkylene oxide condensation products together with the onium derivatives of the amine-N-oxides as described above can be added to the composition of the silver halide emulsion of to a water-permeable layer, which together with the emulsion layer forms part of a water-permeable element.
  • the said derivatives are preferably added to the emulsion after the chemical ripening and just before the coating of the emulsion.
  • the alkylene oxide condensation products and/or the onium derivatives of the amine-N-oxides can also be added to the developing bath.
  • the optimum amount of alkylene oxide condensation product and onium derivatives of amine-N-oxides according to the above formulae depends on the very compound, on the nature of the colloid binder of the silver halide grains and on the amount and type of silver halide in the emulsion.
  • the above alkylene oxide condensation products are added to the light-sensitive material in an amount of mg. of 10 g. per mole of silver halide.
  • the amount of onium derivative incorporated into the light-sensitive material preferably ranges between 5 mg. and 5 g. per mole of silver halide.
  • the derivative is used preferably in an amount varying between 5 mg. to 5 g. per litre.
  • the development acceleration and the increase of dot definition and of the development latitude obtained with the products according to the present invention can be combined with a chemical sensitisation by using in combination with the above-mentioned onium derivatives of amine-N-oxides chemical sensitising agents such as sulphur-containing compounds e.g. allyl isothiocyanate, allyl thiourea, or sodium thiosulphate, reducing agents such as the tin compounds described in the Belgian patent specification 493,464 filed Jan. 24, 1950 and 568,687 filed June 18, 1958 by Gevaert Photo-Production, N.V., the iminoaminomethane sulphinic acid compounds described in the British patent specification 789,823 filed Apr.
  • chemical sensitising agents such as sulphur-containing compounds e.g. allyl isothiocyanate, allyl thiourea, or sodium thiosulphate
  • reducing agents such as the tin compounds described in the Belgian
  • the products influencing the development according to the present invention can also be used in combination with stabilising agents for silver halide emulsions, such as mercury compounds and the compounds described in the Belgian patent specifications 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo-Producten N.V., and in combination with sensitising and stabilising cadmium salts in the light-sensitive material as well as in the developer.
  • stabilising agents for silver halide emulsions such as mercury compounds and the compounds described in the Belgian patent specifications 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo-Producten N.V.
  • the onium compounds of amine-N-oxides either or not in combination with polyoxyalkylene compounds may be used to improve the developing characteristics of various types of emulsions. So, they may be used in combination with optically sensitised emulsion as well as with not optically sensitised emulsions e.g. X-ray emulsions as well as orthochromatic and panchromatic emulsions, and emulsions sensitive to infrared radiation.
  • Various silver salts may be used as light-sensitive salt e.g. silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • Said compounds may be used in emulsions for colour photography, emulsions of the mixed packet type, or emulsions of the mixed grain type. They can also be used in emulsions, which form latent images predominantly on the surface of the silver halide crystal, or in emulsions, which form latent images predominantly inside the silver halide crystal. They may be used in silver halide emulsions for application in the silver halide diffusion transfer process or other transfer processes based on silver halide photography, in which e.g. the diffusion of a developer, a coupler, or a dye is applied.
  • derivatives of tetra-azaindenes having the following general for- 7 8 mula can be used as fog-inhibiting compounds in the Boric acid g. light-sensitive material: Potassium bromide-0.5 g.
  • Such compounds can be prepared by starting from 1 15 6 359 mole of fl-ketoester of an u-ethoxymethylene-fi-ketoester with 1 mole of a suitable 3-amino-l,2,4-triazole.
  • the combination of the alkylene oxide derivatives in- 95 fluencing the development and onium derivatives of amine- Sodium heXametaphOSphat-e 1 N oxides according to the present invention can prefer- Anhydrous sodium sulphite 20 ably be used in the development of silver chloride and Anhydrous Sodium carbonate 20 silver bromochloride emulsions with a hydroquinone-formpotassium bromide 5 aldehyde-bisulphite developer.
  • Hydmquinone 4 4 The following examples illustrate the invention.
  • the development accerelators listed in Table 2 are EXAMPLE 1 added to samples of this solution.
  • the table also de- A washed gelatin silver iodobromide emulsion (94.5 notes the densities obtained after different development mole percent of silver bromide and 5.5 mole percent of times.
  • silver iodide (average grain size of the silver halide: EXAMPLE 3 0.8g) of the negative type is ripened at 45 C.
  • the emulsion ready for coating contains per kg. g. of silver halide, 75 g. of gelatin, 30 mg. of optical sensitising agent according to the following structural for- The amounts of compounds influencing the develop- 50 ment, defined in Table 3, are added before the coating step to samples of a green-sensitised gelatin silver chlorobromide emulsion (35 mole percent of bromide) commula' CH prising 5-methyl-7-hydroxy-s-triaz0lo-(l,5-a)-pyrimidine,
  • the latex-plasticizer H Br consists of a latex of a 20% by Weight aqueous dispersion N+ N of poly(ethyl acrylate) prepared according to known (Q2115 (132m techniques of emulsion polymerisation by carrying out the polymerisation in the presence of 8% by Weight (calculated on the monomer) of an emulsifying agent 50 of s'methyl 7 hydloxy's'tnazolo(15a)- of one of the followin types the condensation g product the of triacetate support and dried.
  • test strips are prei i or i Sodmm salt an alkyibenzene pared by adding to samples of the above-mentioned emulg g 2 gg; g z z the alkyl radlcal contams from sions prior to the coating step the development accele- Subse 32 thne'mulsion Stri s are harden d rators in the amounts listed in the table hereinafter. formaldghyde yeach time applied the Same: a a
  • the dot sharpness is judged of visually by comparison Borax-4O g. to standard materials, which is decreasing value of dot 9 sharpness quality are defined with the numbers 1, 2, 3, and 4.
  • R represents a bivalent organic radical such as an alkylene or an alklene-phenylene-alkylene
  • Z represents the atoms required for forming a pyridine or quinoline nucleus.
  • each of R and R represents an alkyl radical, an aralkyl radical, or together the atoms required for completing an heterocyclic ring,
  • R represents an alkyl radical or an aralkyl radical
  • R represents an alkyl radical or an aralkyl radical
  • R represents a hydrogen atom, an alkyl radical or an aralkyl radical
  • a photographic light-sensitive silver halide material according to claim 3 containing in addition to an onium derivative of an amino-N-oxide a polyoxyalkylene compound and a fog-inhibiting compound of the following general formula:
  • each of R' and R' represents a hydrogen atom, an derivative is present in a developing bath in an amount alkyl, aralykl or aryl radical, and varying from 5 mg. to 5 g. per litre.
  • R 3 represents a ydrogen atom, an alkyl, a carboxy, References Cited or an alkoxycarbonyl group. 5.
  • an onium UNITED STATES PATENTS derivative is present in the light-sensitive material in a 5 3,129,100 4/1964 Grabhisfer et range of 5 mg. to 5 g. per mole of silver halide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • 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)
  • Pyridine Compounds (AREA)
US573801A 1965-10-07 1966-08-22 Amino - n - oxides as development accelerators in photography Expired - Lifetime US3532499A (en)

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Application Number Priority Date Filing Date Title
GB42592/65A GB1121696A (en) 1965-10-07 1965-10-07 Improvements relating to the development of light-sensitive silver halide material

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US3532499A true US3532499A (en) 1970-10-06

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US (1) US3532499A (cs)
BE (1) BE686520A (cs)
DE (1) DE1522396A1 (cs)
FR (1) FR1498724A (cs)
GB (1) GB1121696A (cs)
NL (1) NL6612269A (cs)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770451A (en) * 1968-10-09 1973-11-06 Eastman Kodak Co Silver halide emulsions sensitized with dyes containing heterocyclic nitrogen atoms substituted with an -or group
US3972719A (en) * 1971-02-15 1976-08-03 Agfa-Gevaert N.V. Photographic developer compositions
USRE29168E (en) * 1968-10-09 1977-04-05 Eastman Kodak Company Photographic elements with light absorbing layers
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
US6218070B1 (en) 1993-03-30 2001-04-17 Agfa-Gevaert, N.V. Process to make ultrahigh contrast images

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0794456B1 (en) * 1996-03-07 2003-01-29 Agfa-Gevaert Method of reproducing an electronically stored medical image on a light-sensitive photographic material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129100A (en) * 1961-03-16 1964-04-14 Agfa Ag Developing accelerators for silver halide emulsion layers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129100A (en) * 1961-03-16 1964-04-14 Agfa Ag Developing accelerators for silver halide emulsion layers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770451A (en) * 1968-10-09 1973-11-06 Eastman Kodak Co Silver halide emulsions sensitized with dyes containing heterocyclic nitrogen atoms substituted with an -or group
USRE29168E (en) * 1968-10-09 1977-04-05 Eastman Kodak Company Photographic elements with light absorbing layers
US3972719A (en) * 1971-02-15 1976-08-03 Agfa-Gevaert N.V. Photographic developer compositions
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
US6218070B1 (en) 1993-03-30 2001-04-17 Agfa-Gevaert, N.V. Process to make ultrahigh contrast images

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Publication number Publication date
GB1121696A (en) 1968-07-31
DE1522396A1 (de) 1969-08-14
NL6612269A (cs) 1966-10-25
BE686520A (cs) 1967-03-07
FR1498724A (fr) 1967-10-20

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