EP1061416A1 - Colour photographic developer concentrate - Google Patents

Colour photographic developer concentrate Download PDF

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Publication number
EP1061416A1
EP1061416A1 EP00201918A EP00201918A EP1061416A1 EP 1061416 A1 EP1061416 A1 EP 1061416A1 EP 00201918 A EP00201918 A EP 00201918A EP 00201918 A EP00201918 A EP 00201918A EP 1061416 A1 EP1061416 A1 EP 1061416A1
Authority
EP
European Patent Office
Prior art keywords
concentrate
colour
developer
hydroxylamine
comparison
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.)
Ceased
Application number
EP00201918A
Other languages
German (de)
French (fr)
Inventor
Gustav Tappe
Matthias Porger
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
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
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of EP1061416A1 publication Critical patent/EP1061416A1/en
Ceased legal-status Critical Current

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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
    • 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
    • G03C2200/00—Details
    • G03C2200/44—Details pH value
    • 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
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/266—Supplying of photographic processing chemicals; Preparation or packaging thereof of solutions or concentrates

Definitions

  • the developer solution for developing colour photographic materials is prepared from or, in the case of continuous operation, replenished with concentrates which contain the necessary constituents.
  • one concentrate contains the antioxidant, an auxiliary solvent and an optical brightener
  • a second concentrate contains the colour developer substance, for example CD 3 (N-ethyl-N-(2-methylsulfonylaminoethyl)-3-methyl-p-phenylenediamine)
  • a third concentrate contains the buffer substance, alkali and a water softener.
  • the first concentrate is alkaline (approx. pH 10)
  • the second is strongly acidic and thus stable with regard to colour developer concentration
  • the third is strongly alkaline.
  • a small quantity of sulfite is generally added to the concentrate of the colour developer substance for stabilisation purposes.
  • the quantity of sulfite must not be too large as it otherwise has a negative impact on sensitometry (inhibition of development and thus reduction of colour densities).
  • Two one-part concentrates are currently commercially available, a) Monoline® RA-4 CD-R from Tetenal, a two-phase concentrate with a solid, undissolved phase deposited at the bottom and b) TriPhase® RA-4 CD-R from Trebla, a three-phase concentrate with undissolved constituents in the middle phase (c.f. also US 5 891 609).
  • the object of the invention was to provide a two-part concentrate for a colour developer, neither part of which contains any undissolved constituents, from which parts a regenerating solution may rapidly be produced and which parts comprise a single phase.
  • part 1 of the two-part concentrate containing the antioxidant, the auxiliary solvent, the optical brightener, the colour developer substance and 0.001 to 1 mol of hydroxylamine or a monoalkylated hydroxylamine or the salts thereof per litre of concentrate.
  • hydroxylamine or monoalkylated hydroxylamine or the salts thereof are used, particularly preferably hydroxylammonium sulfate.
  • Monoalkylated hydroxylamine is preferably of the formula HO-NH-R in which
  • the colour of the stored concentrates is unchanged in comparison with the fresh preparations.
  • a colour developer working solution was then prepared from these concentrates. 35 ml of part 1, 17.5 ml of part 2 and 35 ml of part 3 were used per litre. The pH is adjusted to 10.2 with potassium hydrogen carbonate. 2 g of potassium chloride were added per litre. The preparation is light yellow and clear and thus matches the preparation made from the fresh, unstored concentrates.
  • Photographic materials were processed in these two preparations.
  • the two processed materials in fresh, unstored concentration or in stored concentrate) exhibit no sensitometric differences (Table 1).
  • Part 2 is identical to part 3 of Example 1.
  • the colour of the stored concentrate, part 1 is distinctly darkened and deep brown in comparison with the fresh preparations.
  • a colour developer working solution was then prepared from these concentrates. 28 ml of part 1 and 35 ml of part 2 were used per litre. The pH is adjusted to 10.2 with potassium hydrogen carbonate. 2 g of potassium chloride are added per litre. The preparation is dark and turbid, while the preparation made from the fresh, unstored concentrates is light in colour and clear.
  • Example 2 As Example 2, but the part 1 concentrate is adjusted to pH 3.
  • the colour of the stored part 1 concentrate is distinctly darkened and deep brown in comparison with the fresh preparations.
  • the preparation is dark and turbid, while the preparation made from the fresh, unstored concentrates is light in colour and clear.
  • Example 2 but the sulfite is omitted from the part 1 concentrate.
  • the colour of the stored concentrate, part 1 is distinctly darkened and deep brown.
  • Example 3 As Example 3, but the sodium disulfite is replaced by 5 g of hydroxylammonium sulfate.
  • the colour of the stored concentrate, part 1 is unchanged in comparison with the fresh preparation.
  • Example 2 but with 150 g of caprolactam instead of the polyethylene glycol and additionally with 5 g of hydroxylammonium sulfate.
  • the colour of the stored concentrate, part 1 is unchanged in comparison with the fresh preparation.
  • Part 2 is identical to part 3 of Example 1.
  • the colour of the stored concentrate, part 1 is identical to that of the fresh preparation. (Yellow fog of processed material) Yellow D min x 1000 fresh stored Example 1 (Comparison) 114 116 Example 2 (Comparison) 114 137 Example 3 (Comparison) 115 155 Example 4 (Comparison) 113 132 Example 5 (Invention) 114 116 Example 6 (Invention) 113 115 Example 7 (Invention) 114 116 (CD 3 loss due to storage of concentrate for 1 week at 60°C) CD 3 content [g/l] fresh stored Example 1 (Comparison) 5.0 4.8 Example 2 (Comparison) 5.0 4.1 Example 3 (Comparison) 5.0 3.8 Example 4 (Comparison) 5.0 4.3 Example 5 (Invention) 5.0 4.8 Example 6 (Invention) 5.0 4.7 Example 7 (Invention) 5.0 4.9

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

Abstract

A two-part colour photographic developer concentrate in which part 1 contains at least one antioxidant, at least one auxiliary solvent, at least one optical brightener and at least one colour developer substance and part 2 contains at least one buffer substance, alkali and at least one water softener, may be produced by part 1 additionally containing 0.001 to 1 mol of hydroxylamine or a monoalkylated hydroxylamine or the salts thereof per litre of concentrate.

Description

The developer solution for developing colour photographic materials, in particular for developing colour photographic paper, is prepared from or, in the case of continuous operation, replenished with concentrates which contain the necessary constituents.
It is conventional to provide three different concentrates, as certain constituents of the developer bath are not mutually compatible on extended storage. Thus, for example, one concentrate contains the antioxidant, an auxiliary solvent and an optical brightener, a second concentrate contains the colour developer substance, for example CD 3 (N-ethyl-N-(2-methylsulfonylaminoethyl)-3-methyl-p-phenylenediamine) and a third concentrate contains the buffer substance, alkali and a water softener.
The first concentrate is alkaline (approx. pH 10), the second is strongly acidic and thus stable with regard to colour developer concentration and the third is strongly alkaline. A small quantity of sulfite is generally added to the concentrate of the colour developer substance for stabilisation purposes. The quantity of sulfite must not be too large as it otherwise has a negative impact on sensitometry (inhibition of development and thus reduction of colour densities).
There has been no lack of attempts to develop stable, one-part colour developer concentrates as handling errors during preparation or replenishing of a developer solution may consequently be avoided.
Two one-part concentrates are currently commercially available, a) Monoline® RA-4 CD-R from Tetenal, a two-phase concentrate with a solid, undissolved phase deposited at the bottom and b) TriPhase® RA-4 CD-R from Trebla, a three-phase concentrate with undissolved constituents in the middle phase (c.f. also US 5 891 609).
In both cases, the presence of undissolved constituents is disadvantageous for the purposes of handling the concentrate. Especially when preparing the regenerating solution, problems may occur because the undissolved constituents dissolve only poorly.
The object of the invention was to provide a two-part concentrate for a colour developer, neither part of which contains any undissolved constituents, from which parts a regenerating solution may rapidly be produced and which parts comprise a single phase.
This object is achieved by part 1 of the two-part concentrate containing the antioxidant, the auxiliary solvent, the optical brightener, the colour developer substance and 0.001 to 1 mol of hydroxylamine or a monoalkylated hydroxylamine or the salts thereof per litre of concentrate.
Preferably, 0.005 to 0.3 mol of hydroxylamine or monoalkylated hydroxylamine or the salts thereof are used, particularly preferably hydroxylammonium sulfate.
  • Part 1 preferably has a pH of 1.5 to 6.
  • Part 2 of the two-part concentrate corresponds to the previous part 3, comprising the buffer substance, alkali and water softener.
    • Monoalkylated hydroxylamine is preferably of the formula HO-NH-R in which
    R
    means C1-C10-alkyl, hydroxy-C1 -C10-alkyl, C1-C10-alkoxy-C1 -C10-alkyl, carboxy-C2-C10-alkyl, dicarboxy-C1 -C10-alkyl, carboxyhydroxy-C1 -C10-alkyl, hydroxy-C1 -C5-alkyl-(oxy-C1 -C5-alkyl)n, C1 -C5-alkoxy-C1 -C5-alkyl-(oxy-C1-C5-alkyl)n or aryl and
    n
    means a number from 1 to 4.
    Examples
    The following Examples describe concentrated (parts 1, 2 and 3, or parts 1 and 2), from which developer solutions were prepared in the stated manner. A portion of each of the concentrates was stored for 1 week at 60°C before use and then compared with the freshly produced concentrates. Table 1 shows the differences in yellow fog of a material based on silver chloride emulsions which was processed with these developer solutions.
    Example 1 (Comparison) Part 1
    Polyethylene glycol, average MW 400 300 ml
    Diethylhydroxylamine, 85 wt.% aqueous solution (DEHX solution) 120 ml
    Optical brightener 20 g
    Water to make up to 1000 ml
    pH 10
    Part 2
    CD 3 280 g
    Sodium disulfite 10 g
    Water to make up to 1000 ml
    pH 1
    Part 3
    Potassium hydroxide 65 g
    Potassium carbonate 600 g
    EDTA 3 g
    Water to make up to 1000 ml
    pH 14
    The colour of the stored concentrates is unchanged in comparison with the fresh preparations.
    A colour developer working solution was then prepared from these concentrates. 35 ml of part 1, 17.5 ml of part 2 and 35 ml of part 3 were used per litre. The pH is adjusted to 10.2 with potassium hydrogen carbonate. 2 g of potassium chloride were added per litre. The preparation is light yellow and clear and thus matches the preparation made from the fresh, unstored concentrates.
    Photographic materials were processed in these two preparations. The two processed materials (in fresh, unstored concentration or in stored concentrate) exhibit no sensitometric differences (Table 1).
    Example 2 (Comparison)
    In this Example, parts 1 and 2 from Example 1 were combined to form a new part 1 of the following composition. Since not all the substances from part 1 of Example 1 dissolve at pH 1, the pH value was raised.
    Part 2 is identical to part 3 of Example 1.
    Part 1
    Polyethylene glycol of an average MW of 400 375 ml
    DEHX solution 150 ml
    Optical brightener 25 g
    CD 3 250 g
    Sodium disulfite 6.2 g
    Water to make up to 1000 ml
    pH 5
    The colour of the stored concentrate, part 1, is distinctly darkened and deep brown in comparison with the fresh preparations.
    A colour developer working solution was then prepared from these concentrates. 28 ml of part 1 and 35 ml of part 2 were used per litre. The pH is adjusted to 10.2 with potassium hydrogen carbonate. 2 g of potassium chloride are added per litre. The preparation is dark and turbid, while the preparation made from the fresh, unstored concentrates is light in colour and clear.
    Example 3 (Comparison)
    As Example 2, but the part 1 concentrate is adjusted to pH 3.
    The colour of the stored part 1 concentrate is distinctly darkened and deep brown in comparison with the fresh preparations.
    The preparation is dark and turbid, while the preparation made from the fresh, unstored concentrates is light in colour and clear.
    Example 4 (Comparison)
    As Example 2, but the sulfite is omitted from the part 1 concentrate.
    The colour of the stored concentrate, part 1, is distinctly darkened and deep brown.
    Example 5 (According to the invention)
    As Example 3, but the sodium disulfite is replaced by 5 g of hydroxylammonium sulfate.
    The colour of the stored concentrate, part 1, is unchanged in comparison with the fresh preparation.
    Example 6 (According to the invention)
    As Example 2, but with 150 g of caprolactam instead of the polyethylene glycol and additionally with 5 g of hydroxylammonium sulfate.
    The colour of the stored concentrate, part 1, is unchanged in comparison with the fresh preparation.
    Example 7 (According to the invention) Part 1
    Triethanolamine 250 ml
    HADS 120 g
    Optical brightener 25 g
    CD 3 250 g
    Hydroxylammonium sulfate 5 g
    Water to make up to 1000 ml
    pH 3
    Part 2 is identical to part 3 of Example 1.
    The colour of the stored concentrate, part 1, is identical to that of the fresh preparation.
    (Yellow fog of processed material)
    Yellow Dmin x 1000
    fresh stored
    Example 1 (Comparison) 114 116
    Example 2 (Comparison) 114 137
    Example 3 (Comparison) 115 155
    Example 4 (Comparison) 113 132
    Example 5 (Invention) 114 116
    Example 6 (Invention) 113 115
    Example 7 (Invention) 114 116
    (CD 3 loss due to storage of concentrate for 1 week at 60°C)
    CD 3 content [g/l]
    fresh stored
    Example 1 (Comparison) 5.0 4.8
    Example 2 (Comparison) 5.0 4.1
    Example 3 (Comparison) 5.0 3.8
    Example 4 (Comparison) 5.0 4.3
    Example 5 (Invention) 5.0 4.8
    Example 6 (Invention) 5.0 4.7
    Example 7 (Invention) 5.0 4.9
    It is evident that only the two-part concentrates according to the invention achieve the performance of the three-part concentrate with regard to yellow fog and stability.

    Claims (4)

    1. Two-part colour photographic developer concentrate in which part 1 contains at least one antioxidant, at least one auxiliary solvent, at least one optical brightener and at least one colour developer substance and part 2 contains at least one buffer substance, alkali and at least one water softener, characterised in that part 1 additionally contains 0.001 to 1 mol of hydroxylamine or a monoalkylated hydroxylamine or the salts thereof per litre of concentrate.
    2. Developer concentrate according to claim 1, characterised in that part 1 additionally contains 0.005 to 0.3 mol of hydroxylamine or a monoalkylated hydroxylamine or the salts thereof per litre of concentrate.
    3. Developer concentrate according to claim 1, characterised in that part 1 contains N-ethyl-N-(2-methylsulfonylaminoethyl)-3-methyl-p-phenylenediamine as colour developer substance.
    4. Developer concentrate according to claim 1, characterised in that part 1 has a pH of 1.5 to 6.
    EP00201918A 1999-06-17 2000-05-29 Colour photographic developer concentrate Ceased EP1061416A1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19927601 1999-06-17
    DE19927601A DE19927601A1 (en) 1999-06-17 1999-06-17 Color photographic developer concentrate

    Publications (1)

    Publication Number Publication Date
    EP1061416A1 true EP1061416A1 (en) 2000-12-20

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    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP00201918A Ceased EP1061416A1 (en) 1999-06-17 2000-05-29 Colour photographic developer concentrate

    Country Status (2)

    Country Link
    EP (1) EP1061416A1 (en)
    DE (1) DE19927601A1 (en)

    Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2910251A1 (en) * 1978-03-15 1979-09-20 Minnesota Mining & Mfg COLOR DEVELOPER FOR COLOR PHOTOGRAPHIC RECORDING MATERIAL, METHOD FOR ITS MANUFACTURING AND ITS USE
    DE3801536A1 (en) * 1988-01-20 1989-07-27 Agfa Gevaert Ag PHOTOGRAPHER COLOR DEVELOPER
    JPH08248600A (en) * 1996-03-11 1996-09-27 Konica Corp Color developing solution for silver halide color photographic sensitive material improved in safety and preservability, etc.

    Patent Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2910251A1 (en) * 1978-03-15 1979-09-20 Minnesota Mining & Mfg COLOR DEVELOPER FOR COLOR PHOTOGRAPHIC RECORDING MATERIAL, METHOD FOR ITS MANUFACTURING AND ITS USE
    DE3801536A1 (en) * 1988-01-20 1989-07-27 Agfa Gevaert Ag PHOTOGRAPHER COLOR DEVELOPER
    JPH08248600A (en) * 1996-03-11 1996-09-27 Konica Corp Color developing solution for silver halide color photographic sensitive material improved in safety and preservability, etc.

    Non-Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Title
    PATENT ABSTRACTS OF JAPAN vol. 1997, no. 01 31 January 1997 (1997-01-31) *

    Also Published As

    Publication number Publication date
    DE19927601A1 (en) 2001-01-11

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