US3682634A - Method for developing photographic materials - Google Patents

Method for developing photographic materials Download PDF

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Publication number
US3682634A
US3682634A US74492A US3682634DA US3682634A US 3682634 A US3682634 A US 3682634A US 74492 A US74492 A US 74492A US 3682634D A US3682634D A US 3682634DA US 3682634 A US3682634 A US 3682634A
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stands
development
developing
quaternary ammonium
compounds
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US74492A
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English (en)
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Jozef Frans Willems
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C5/3056—Macromolecular additives

Definitions

  • R stands for an alkyl group comprising from 7 to 20 C- atoms or for the group X' is an anion, s
  • n stands for an integer from I to 250, n being at least 2 when R stands for alkyl, and
  • n stands for 2 when n is different from 1 and for an integer from 2 to 16 when n: l.
  • This invention relates to the development of photographic materials containing exposed silver halide, to new developing combinations and to photographic materials and solutions containing such combinations.
  • onium compounds such as quaternary ammonium, quaternary phosphonium and ternary sulphonium compounds are able to accelerate photographic development by agents which act as doubly or more highly charged negative ions for instance hydroquinone, hydroquinone derivatives, ascorbic acid, etc. whether as an additive to the developer or to the emulsion. It is further known (see for example T. H. James, Photographic Science and Technique, vol. 198 (1953) p. 36) that development by the singly ionized developer anions of hydroxylamine is markedly retarded by quaternary ammonium salts.
  • Q stands for a quaternary ammonium group either cyclic or acyclic such as the group wherein R,, R, and R, are aliphatic radicals such as methyl, ethyl, hydroxyethyl, propyl, benzyl, or the group wherein 2 stands for the non metallic atoms necessary to complete a heterocyclic nucleus such as pyridyl, a.- picolyl, morpholinyl, piperidyl and quinolyl,
  • X is an anion or acid radical for example halide, p-toluene sulphonate, alkyl sulphate, or perchlorate,
  • R stands for alkyl comprising from 7 to 20 carbon atoms or for the group it stands for an integer from 1 to 250, n being at least 2 when R stands for alkyl, and
  • x stands for 2 when n is different from 1 or for an integer from 2 to 16 when n: 1.
  • alkylmonopyridinium salts comprising no polyoxyalkylene groups retard development by N,N-dialkylhydroxylamines and polyoxyalkylene compounds comprising no quaternary ammonium groups as well as polyoxyalkylene compounds comprising pyridinium groups but no long chain aliphatic groups have so to say no effect at all on development by N,N-dialkylhydroxylamines and on the other hand that the compounds of use according to the present invention inhibit development by hydroxylamine itself and by monoalkylhydroxylamines.
  • HOCHzCH CHICHaOH HOCll-iClh CHzCHzOH A V w
  • Ttl tertiary bases as pyridines, picolines and trialkylamines such as trimethylamine, dimethylbenzylamine, dimethyllaurylamine, etc.
  • n is at least 2
  • the bisquaternary ammonium compounds wherein can be prepared according to the methods described in US. Patent 2,288,226 of Burt H. Carroll and Charles F. H. Allen issued June 30, 1942.
  • N,N-dialkyl hydroxylamines such as N,N- diethyl hydroxylamine, of which the oxidation products have the favourable property of leaving no residual stain in the silver image obtained, has been disclosed amongst others in US. Patent 2,857,276 of Edwin H. Land and Helen 1. Tracy issued Oct. 21, 1958.
  • N,N-dialkyl hydroxylamines that have been proposed for use as silver halide developing agents and of which the development activity is higher than of N,N-diethyl hydroxylamine include for example aminoalkyl hydroxylamines, more especially N,N-dialkylhydroxylamines having in at least one of the N-alkyl group an intralinear amino nitrogen atom, either cyclic or acyclic, examples of which can be found in US. Patent 3,287,125 of Milton Green, Adnan A. Sayigh and Henri Ulrich issued Nov.
  • alkoxyalkyl hydroxylamines more especially N,N-dialkylhydroxylamines of which at least one of the N-alkyl groups is substituted by alkoxy or alkoxyalkoxy, examples of which can be found in US. Patent 3,293,034 of Milton Green, Adnan A. Sayigh and Henri Ulrich issued Dec. 20, 1966 and sulphone hydroxylamines, more especially N,N-dialkylhydroxylamines having in at least one of the N-alkyl groups an intralinear sulphonyl (SO group, examples of which can be found in US. Patent 3,287,124 of Milton Green, Adrian A. Sayigh and Henri Ulrich issued Nov. 22, 1966.
  • SO group examples of which can be found in US. Patent 3,287,124 of Milton Green, Adrian A. Sayigh and Henri Ulrich issued Nov. 22, 1966.
  • a process for making photographic records which comprises treating a photographic material having layers containing developable silver salts with an aqueous alkaline solution in the presence of an N,N-dialkyl hydroxylamine developing agent and a quaternary ammonium compound as described above.
  • the invention also includes developer compositions comprising in addition to an N,N- dialkylhydroxylamine developing agent, a quaternary ammonium compound as described.
  • N,N-dia1kylhydroxylamine developing agent it is intended to embrace unsubstituted N,N-dialkyl hydroxylamines as well as derivatives thereof as described above.
  • the quaternary salts of use according to the present invention may be added to the developer or to the emulsion or to both simultaneously, the developing bath being preferred however.
  • the developing composition may comprise in addition to the N,N-dialkylhydroxylamine developing agents any of the common ingredients employed in developing compositions e.g. alkalies such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, trisodiurn phosphate, etc., silver halide solvents such as sodium thiosulphate, sodium thiocyanate or cyclic imides such as barbiturates and uracils, preservatives such as sulphites, bisulphites, metabisulphites and acids such as boric acid and citric acid.
  • alkalies such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, trisodiurn phosphate, etc.
  • silver halide solvents such as sodium thiosulphate, sodium thiocyanate or cyclic imides such as barbiturates and uracils
  • preservatives such as sulph
  • developer composition may comprise potassium bromide and water-softening agents such as poly phosphates and derivatives of ethylene diamine tetraacetic acid, antifoggants such as benzotriazole, S-nitro-benzotriaznle and 6-nitrobenzimidazole and wetting agents as well as other compounds known in the photographic development technique.
  • potassium bromide and water-softening agents such as poly phosphates and derivatives of ethylene diamine tetraacetic acid
  • antifoggants such as benzotriazole, S-nitro-benzotriaznle and 6-nitrobenzimidazole and wetting agents as well as other compounds known in the photographic development technique.
  • the amount of quaternary ammonium compound used according to the present invention 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 amount of onium compound incorporated into the developing bath can vary between very wide limits and depends on the particular N,N-dialkylhydroxylamine used.
  • the optimum concentration for any onium compound of use according to the invention can best be determined by employing a series of concentrations in several batches of the same developer and determining the speed obtained before and after incorporation of the said compound in the usual manner which is of course well known to those skilled in the art.
  • the quaternary ammonium compound is used in amounts ranging between 0.01 and 20 millimoles per litre.
  • the development acceleration obtained with the products according to the present invention can be combined with a chemical sensitization by means of chemical sensitizing 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 Patents 493,464 filed Jan. 24, 1950 and 568,687 filed June 18, 1958 both by Gevaert Photo- Producten N.V., the iminoaminomethane sulphinic acid compounds described in the British Patent 789,823 filed Apr. 29, 1955 by Gevacrt Photo-Producten N.V. or precious metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds.
  • chemical sensitizing agents such as sulphur-containing compounds e.g. allyl isothiocyanate, allyl thiourea, or sodium thiosulphate
  • reducing agents such
  • N,N-dialkyl hydroxylamines can also be used in combination with stabilizing agents for silver halide emulsions, such as mercury compounds and the compounds described in Belgian Patents 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo- Producten N.V. and in combination with sensitizing and stabilizing cadmium salts in the light-sensitive material as well as in the developer.
  • stabilizing agents for silver halide emulsions such as mercury compounds and the compounds described in Belgian Patents 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo- Producten N.V.
  • novel developing combination of the invention may be used in conventional or wet development of silver halide emulsions, in diffusion transfer processes, both dye and silver, in such photographic processes known as stabilization processing wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver print, etc.
  • an exposed silver halide emulsion is treated with a liquid processing composition while in superposed relationship with an image-receiving material.
  • the exposed silver halide is developed to silver and the unexposed silver halide is converted into a complex silver salt which is transferred to the image-receiving material and there reduced to silver to form a positive print.
  • the processing composition normally includes a silver halide solvent, such as sodium thiosulphate, sodium thiocyanate, cyclic imides such as barbiturates or uracils, which forms with silver halide a soluble complex as is well known in the art of forming silver images by transfer, and may also include a film-forming material such as sodium carboxymethyl cellulose or hydroxyethyl cellulose, starch or gum for increasing the viscosity of the ccmposition as, for instance, in the case of in-camera silver complex dilfusion transfer processing.
  • a silver halide solvent such as sodium thiosulphate, sodium thiocyanate, cyclic imides such as barbiturates or uracils, which forms with silver halide a soluble complex as is well known in the art of forming silver images by transfer
  • a film-forming material such as sodium carboxymethyl cellulose or hydroxyethyl cellulose, starch or gum for increasing the viscosity of the ccm
  • the development accelerators of use according to the invention may be employed in solution or they may be initially incorporated in a layer of the photosensitive material e.g. a silver halide emulsion layer or other colloid layer in water-permeable relationship therewith.
  • a layer of the photosensitive material e.g. a silver halide emulsion layer or other colloid layer in water-permeable relationship therewith.
  • silver complex diffusion transfer processes they may also be incorporated in a layer of the imagereceiving material, which during processing, is in superposed relationship with the photosensitive silver halide material.
  • EXAMPLE 1 The other strips are developed in baths having the same composition as bath A but containing moreover one of the compounds listed in the table below in the amounts given.
  • a photosensitive element was prepared comprising on a paper support a silver bromoiodide emulsion layer con taining per kg. an amount of silver halide corresponding to g. of silver nitrate.
  • the photosensitive element and an image-receiving element which comprises a silver receptive layer containing development nuclei dispersed in a matrix of colloidal silica coated on a water-impervious support according to the practice described in US. Pat. 2,823,122 of Edwin H. Land issued Feb. 11, 1958, were advanced in superposed relationship between a pair of pressure applying rollers to spread between them in a thin layer the following processing composition:
  • Bath A plus 1.75 mllllmole of compound 2 u. 04 n. 04 u. 04 0. is 1.3;. Bath A plus 1.76 millimole of compound 4 0. 04 0. 04 0. (M 0.1! 0. 85 Bath A plus 1.75 millimole of compound 3... 0. 04 0. 04 0. 06 0. 28 1.50 Beth A plus 1.75 mllllmole of compound 6 0. 04 0. 04 0. 04 0.12 0. 91 Bath A plus 1.75 mlllimole of compound 1 0. 04 0. 04 0.05 0. 43 1. 77 Bath A plus 0.31 millimole of compound 12.. 0. 04 0. 04 0. 04 0.22 1. 44
  • Photographic developing method which comprises developing an exposed silver halide emulsion layer of a ternary ammonium groups or comprising pyridinium photographic material with an aqueous alkaline composition in the presence of a N,N-dialkylhydroxylamine developing agent and a quaternary ammonium compound corresponding to the general formula:
  • Q stands for a quaternary ammonium group either cyclic or acyclic
  • R stands for an alkyl group comprising from 7 to 20 C- atoms or for the group X- is an anion
  • n stands for an integer from 1 to 250, n being at least 2 when R stands for alkyl
  • Photographic developing method according to claim 1, wherein the said quaternary ammonium compound is present in the said aqueous composition in an amount comprised between 0.01 and 20 millimoles per litre.
  • Photographic developing method according to claim 1, wherein said method is used for making images according to the silver complex diffusion transfer process.
  • Photographic developing composition for developing an exposed silver halide emulsion layer of a photographic material comprising in aqueous alkaline solution in addition to an N, N-dialkylhydroxylamine developing agent, a quaternary ammonium compound corresponding to the general formula:

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Pyridine Compounds (AREA)
US74492A 1969-10-27 1970-09-22 Method for developing photographic materials Expired - Lifetime US3682634A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5256869 1969-10-27

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US3682634A true US3682634A (en) 1972-08-08

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US (1) US3682634A (de)
JP (1) JPS4913579B1 (de)
BE (1) BE756391A (de)
CA (1) CA940365A (de)
DE (1) DE2047474A1 (de)
FR (1) FR2068210A5 (de)
GB (1) GB1315498A (de)
NL (1) NL7014368A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5492841A (en) * 1994-02-18 1996-02-20 E. I. Du Pont De Nemours And Company Quaternary ammonium immunogenic conjugates and immunoassay reagents
EP0731381B1 (de) * 1995-02-21 1999-12-08 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten, photographischen Silberhalogenidmaterials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8530457D0 (en) * 1985-12-11 1986-01-22 Ciba Geigy Ag Processing halogens

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5492841A (en) * 1994-02-18 1996-02-20 E. I. Du Pont De Nemours And Company Quaternary ammonium immunogenic conjugates and immunoassay reagents
EP0731381B1 (de) * 1995-02-21 1999-12-08 Agfa-Gevaert N.V. Entwicklerlösung und Verfahren zum Entwickeln eines belichteten, photographischen Silberhalogenidmaterials

Also Published As

Publication number Publication date
BE756391A (nl) 1971-03-22
DE2047474A1 (de) 1971-06-09
CA940365A (en) 1974-01-22
JPS4913579B1 (de) 1974-04-01
NL7014368A (de) 1971-03-25
GB1315498A (en) 1973-05-02
FR2068210A5 (de) 1971-08-20

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