US3767403A - Tetra-alkyl p-phenylene diamine with aromatic primary amino color developing agent - Google Patents

Tetra-alkyl p-phenylene diamine with aromatic primary amino color developing agent Download PDF

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Publication number
US3767403A
US3767403A US00178811A US3767403DA US3767403A US 3767403 A US3767403 A US 3767403A US 00178811 A US00178811 A US 00178811A US 3767403D A US3767403D A US 3767403DA US 3767403 A US3767403 A US 3767403A
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United States
Prior art keywords
colour
phenylene diamine
developing agent
primary amino
alkyl
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Expired - Lifetime
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US00178811A
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English (en)
Inventor
T Ghys
J Willems
Veelen G Van
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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
    • G03C5/30—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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

  • ABSTRACT A photographic colour developing composition for silver halide material is described which comprises besides the aromatic primary amino colour developing agent a tetraalkyl p-phenylene diamine compound of the formula I Rf wherein each of R R and R is C,C alkyl or R together with R represent the atoms necessary to close a pyrrolidine ring, and
  • R is C C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R -substituent
  • R,-R being a C C alkyl group carrying a solubilizing group.
  • the tetraalkyl p-phenylene diamine compound increases the activity of the colour developing agent without effecting to a noteworthy extent the fog and gradation of the silver halide material.
  • The. present invention relates to a process for the colour development of photographic silver halide materials containing exposed silver halide and to developing compositions used therein.
  • R stands for c,-c alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in orthoposition to the amino group carrying the R substituent, one of R R R and R being a C -C alkyl group carrying a solubilizing group which includes such groups droxyl.
  • photographic developing compositions for developing, in the presence of a colour forming coupler, an exposed silver halide emulsion layer' of a photographic element comprise, in addition to an aromatic primary amino colour developing agent, a tetraalkyl-p-phenylene diamine derivative as represented by the above general formula.
  • the present invention also provides a process for the production of photographic colour images which comprises treating a photographic material having a layer containing developable silver halide with an aqueous alkaline solution in the presence of a colour forming coupler, an aromatic primary amino colour developing agent and a tetraalkyl-p-phenylene diamine derivative corresponding to the above general formula.
  • the ratio of tetraalkyl-p-phenylene diamine derivative corresponding to the above general formula to aromatic primary amino colour developing agent used in accordance with the present invention can vary within wide limits. A strong superadditive effect is obtained already with a ratio of 50 mg of tetraalkyl-p-phenylene diamine derivative to 3 g of colour developing agent.
  • the amount of the tetraalkyl-pphenylenediamine derivative is comprised between l0 mg and l g per litre.
  • tetraalkyl-p-phenylene diamine compounds of the above general formula can be used in processes wherein the colour-forming couplers are dissolved in the developer as well as in processes wherein the colour-for ming couplers are incorporated in the photographic element. They can be used in negative processes as well as in reversal processes.
  • tetraalkyl-p-phenylene diamine compounds of the above general formula are effective not only when used in the colour developing solution comprising the aromatic primary amino colour developing agent but also when used in a supplemental alkaline treating solu- 3 tion included in the colour processing directly after the colour development step.
  • the compounds corresponding to the above general formula are used to advantage in producing colour images using any of the well known aromatic primary amino colour developing agents more particularly N,N-dialkyl-p-phenylene diamines and derivatives thereof, e.g., the toluene analogues. All of these colour developing agents have an unsubstituted amino group which enables the oxidation product of the developing agent to couple with the colour forming couplers to form a dye image.
  • aromatic primary amino colour developing agents are N,N-diethyl-p-phenylene diamine, 2-amino-5-diethylaminotoluene, N-butyl-N-sulphobutyl-p-phenylene diamine, 2-amino-5-[N-ethyl-N (B-methylsulphonamido)ethyl] aminotoluene, N-ethyl-N-B- hydroxyethyl-p-phenylene diamine, etc.
  • These developing agents are usually used in the salt form such as the hydrochloride or sulphate.
  • Alkali, alkali metal sulphites, alkali metal halides, thickening agents such as carboxymethyl cellulose for making viscous developers, and any of the other additives included in colour developing solutions such as hydroxylamine and derivatives such as N,N-diethylhydroxylamine may be used in the colour developers employed in the colour development process of the present invention.
  • a photographic multilayer colour element containing a red-sensitized, a green-sensitized and a bluesensitive silver halide emulsion layer wherein on colour development, by the use of appropriate colour couplers, a cyan, magenta and yellow dyestuff image are formed, respectively.
  • Other multicolour elements have the three differently sensitized silver halide grains dispersed in a single emulsion layer, e.g., an emulsion layer of the mixed packet type as described in U.S. Pat. No. 2,698,794 or an emulsion layer of the mixed grain type as described in U.S. Pat. No. 2,592,243.
  • the colour forming couplers may be soluble colour couplers used in the colour developer or non-diffusible colour couplers incorporated in the photographic element.
  • naphtholic or phenolic couplers are used to form the cyan dye image, indazolone or pyrazolone couplers to form the magenta dye image, and open chain ketomethylene couplers to form the yellow dye image.
  • the compounds corresponding to the above general formula may also be used to activate colour development, by means of aromatic primary amino colour developing agents, of radiographic colour materials, for example of the kind described in U.S. Pat. application Ser. Nos. 852,236 and 852,246.
  • U.S. Pat. application Ser. No. 852,236 a method is described and claimed for the production of colour radiographs according to which in a recording material comprising one or more silver halide emulsions a developable silver image is formed by means of directly or indirectly recorded penetrating radiation the said material being processed in such a way that at least two images of contrasting colour and of opposite gradation are obtained.
  • U.S. Pat. application Ser. No. 852,246 a method is described and claimed according to which monochromic radiographic images are produced, optionally together with a silver image, thus offering more visual retrieval of information than corresponding black-and-white radiographic images.
  • the said elements can be developed in the presence of development accelerators.
  • development accelerators can be used either in a silver halide emulsion layer of the photographic element or in the developing composition itself. They include alkylene oxide compounds of various types for example alkylene oxide condensation products or polymers as described in U.S. Pat. Nos. 1,970,578; 2,240,472; 2,423,549; 2,441,389; 2,531,832 and 2,533,990 and in United Kingdom Pat. Specification Nos.
  • development accelerating compounds are onium and polyonium compounds preferably of the ammonium, sulphonium and phosphonium type, including onium polyoxyalkylene salts especially polyoxyalkylene bispyridinium salts examples of which can be found in U.S. Pat. No. 2,944,900, etc.
  • EXAMPLE 1 An exposed multilayer colour photographic negative film carrying three differently sensitized emulsion layers containing cyan, magenta, and yellow colour formers respectively was developed for 6 min. at 24C in a colour developer, made up according to the following recipe water 900 ml sodium hexametaphosphate 1 g sodium sulphite (anh.) 4 g N,N-diethyl-p-phenylene diamine hydrochloride 2.7 g sodium carbonate (anh.) 25 g sodium hydroxide 0.5 g potassium bromide 2.2 g hydroxylamine hydrochloride 1.2 g water to make 1000 ml (pH 10.7) On completion of the development step the photo- 5 graphic material was rinsed and transferred for 2 min.
  • a colour developer made up according to the following recipe water 900 ml sodium hexametaphosphate 1 g sodium sulphite (anh.) 4 g N,N-diethyl-p-phenylene diamine hydrochloride
  • an acid hardening fixer of the following composition water 800 ml sodium thiosulphate (anh.) 200 g sodium bisulphite 12 g glacial acetic acid 12 m1 borax 20 g potassium alum 15 g water to make 1,000 ml (pH 3.9)
  • the photographic material was then washed and transferred for 3 min. to a silver bleach bath of the following composition water 800 ml potassium bromide 15 g potassium ferricyanide 75 g potassium aluminium sulphate 15 g sodium acetate 5 g acetic acid 10 g water to make 1000 ml (pl-I 3.65)
  • the sensitometric results obtained are listed in the following table as compared with the results obtained when one of the compounds listed in the table below are added to the colour developer in an amount of 0.2
  • EXAMPLE 2 A radiographic colour material comprising a polyethylene terephthalate support and on both sides thereof a high-speed gelatin silver bromoiodide emulsion comprising a colour coupler, was exposed through a wedge and colour processed to yield a coloured wedge print. Development occurred by treatment of the exposed material for 27 sec. at 40C in a colour developer comprising N-ethyl-N-B-hydroxyethyl-p-phenylene diamine as colour developing agent and one of the superadditive black-and-white developing agents listed in the table below.
  • the sensitometric results obtained are listed in the table below.
  • the values given for the speed are relative values measured at density 1 above fog.
  • the value of 100 was given to the speed of the material developed in a developer comprising no superadditive developing agent.
  • the values given for the gradation were measured behind a red filter between density 0.25 and 2.0 above the fog value.
  • R R and R stands for C C alkyl or R together with R represents the atoms necessary to close a pyrrolidine ring, and R stands for C C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R substituent,
  • Ii -R being a C -C alkyl group carrying a solubilizing group which is a member of the group consisting of carboxyl, sulpho, ionizable sulphonarnide, and hydroxyl.
  • a process of producing photographic colour images which comprises treating a developable silver halide emulsion layer in the presence of a colour coupler with a developer composition which comprises an aromatic primary amino colour developing agent and a tetraalkyl p-phenylene diamine compound corresponding to the general formula:
  • each .of R R and R stands for C C alkyl or R, together with R represents the atoms necessary to close a pyrrolidine ring, and R stands for C -C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group carrying the R substituent, one of R -R, being a C2-C6 alkyl group carrying a solubilizing group which is a member of the group consisting of carboxyl, sulpho, ionizable sulphonarnide, and hydroxyl.
  • a process of producing photographic colour images which comprises treating a developable silver halide emulsion layer in the presence of a colour coupler with a colour developing composition comprising an aromatic primary amino colour developing agent and then treating the developed emulsion layer with an alkaline composition comprising a tetraalkyl-pphenylene diamine compound corresponding to the formula:
  • each of R,, R and R- stands for C -C alkyl or R, together with R represents the atoms necessary to close a pyrrolidine ring, and R stands for C -C alkyl or ethylene or propylene linked to the C-atom of the phenylene ring in ortho position to the amino group thereof.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00178811A 1970-12-01 1971-09-08 Tetra-alkyl p-phenylene diamine with aromatic primary amino color developing agent Expired - Lifetime US3767403A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB5706270A GB1365300A (en) 1970-12-01 1970-12-01 Colour development of photographic silver halide elements

Publications (1)

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US (1) US3767403A (enrdf_load_stackoverflow)
BE (1) BE774949A (enrdf_load_stackoverflow)
CH (1) CH579787A5 (enrdf_load_stackoverflow)
DE (1) DE2156479A1 (enrdf_load_stackoverflow)
FR (1) FR2117091A5 (enrdf_load_stackoverflow)
GB (1) GB1365300A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007593A1 (de) * 1978-08-01 1980-02-06 Agfa-Gevaert AG Farbfotografisches Entwicklungsverfahren

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265502A (en) * 1961-06-21 1966-08-09 Gevert Photo Producten N V Photographic developing compositions
GB1149794A (en) * 1966-12-14 1969-04-23 Ilford Ltd Photographic silver halide colour development
US3615525A (en) * 1967-05-24 1971-10-26 Agfa Gevaert Nv Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265502A (en) * 1961-06-21 1966-08-09 Gevert Photo Producten N V Photographic developing compositions
GB1149794A (en) * 1966-12-14 1969-04-23 Ilford Ltd Photographic silver halide colour development
US3615525A (en) * 1967-05-24 1971-10-26 Agfa Gevaert Nv Derivative of 6-amino-1 2 3 4-tetrahydroquinoline as superadditive in developing composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007593A1 (de) * 1978-08-01 1980-02-06 Agfa-Gevaert AG Farbfotografisches Entwicklungsverfahren

Also Published As

Publication number Publication date
FR2117091A5 (enrdf_load_stackoverflow) 1972-07-21
GB1365300A (en) 1974-08-29
BE774949A (nl) 1972-05-05
DE2156479A1 (de) 1972-06-08
CH579787A5 (enrdf_load_stackoverflow) 1976-09-15

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