EP0365955A2 - Bain de développement et procédé de développement d'un matériau photographique couleur - Google Patents
Bain de développement et procédé de développement d'un matériau photographique couleur Download PDFInfo
- Publication number
- EP0365955A2 EP0365955A2 EP89119136A EP89119136A EP0365955A2 EP 0365955 A2 EP0365955 A2 EP 0365955A2 EP 89119136 A EP89119136 A EP 89119136A EP 89119136 A EP89119136 A EP 89119136A EP 0365955 A2 EP0365955 A2 EP 0365955A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- developing
- bath
- developer
- mol
- development
- 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.)
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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
Definitions
- the development of the lowest layer is inhibited by the decrease in the concentration of the developer due to consumption in the upper layers and the increasing length of the diffusion path.
- insufficient development of this layer causes blue shadows to occur.
- the development bath of this process is regenerated in the course of the continuously carried out processing process in order to replace the developer substance consumed in the development process.
- the lowest possible regeneration rate is aimed at in order to limit the overflow quantity to a minimum, i.e. The smallest possible amount of liquid is used for regeneration. This requires a high developer concentration in the regenerator, which, however, is not possible due to the low solubility of the CD 3 developer used in this process, so that complete development of the bottom layer is problematic.
- the developer concentration in the use solution is lower than in the regenerator solution, while the halide concentration in the use solution is higher than in the regenerator solution.
- the layer with the unfavorable constellation of low color developer content and high halide content is loaded and developed during swelling.
- the invention relates to a color photographic developer bath for the development of imagewise exposed silver halide materials which have at least three light-sensitive silver halide emulsion layers different on a reflective layer support Spectral sensitivity, to which a cyan coupler, a magenta coupler and a yellow coupler are each spectrally assigned, characterized in that the development takes place in the development baths I and II, the developer content in the development bath I being greater than in the development bath I and II when the development baths are in use Halide content in developing bath I is smaller than in developing bath II.
- the concentrations of developer substance in developing bath I are preferably in the range from 0.01 to 0.03 mol / l, particularly preferably between 0.014 and 0.023 mol / l; in developing bath II in the range of 0.002 and 0.02 mol / l, particularly preferably between 0.005 and 0.01 mol / l.
- the concentration of halide in developing bath I is preferably 0.0015 to 0.015 mol / l, particularly preferably between 0.004 and 0.008 mol / l; in developing bath II in the range of 0.017 mol and 0.04 mol / l, particularly preferably between 0.02 and 0.03 mol / l.
- Another object of the invention is a method for developing an exposed color photographic material using developing baths I and II described above, characterized in that the residence time of the color photographic material in developing bath I is less than 50% of the total development time.
- the residence time of the color photographic material in developer bath I is preferably 10-20% of the total development time.
- This two-stage development achieves an optimal loading of the layer with a high developer concentration with a low halide content.
- the developer solution containing an optimal activity potential - high developer content with low halide content - is absorbed by the layer in the development stage I during the swelling, specifically in a limited residence time of ⁇ 50%, preferably 10-20% of the total development time.
- the development still beginning in development stage I, consumes a small amount of developer substance corresponding to the short residence time, so that the favorable ratio of high developer concentration and low halide content in the working solution of the first developer bath is largely retained.
- the color photographic material conditioned in this way is then finished in the second developer bath.
- the developer concentration in the second bath is substantially lower in the use state and the halide concentration is correspondingly higher than in the first development bath.
- the concentration ratios have also adjusted to the values of the second bath.
- regenerator feed is expediently based on the principle of level compensation. This ensures that no overflow occurs because the carry-over volume is equal to the feed volume of the regenerator solution.
- Suitable complexing agents for complexing calcium ions are, for example, aminopolycarboxylic acids, which are well known per se.
- aminopolycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, N, N'-bis- (2-hydroxybenzyl) -ethylenediamine-N, N'-diesiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid,
- calcium complexing agents are polyphosphates, phosphonic acids, aminopolyphosphonic acids and hydrolyzed polymaleic anhydride, e.g. Sodium hexametaphosphate, 1-hydroxyethane-1,1-diphosphonic acid, aminotrismethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid. 1-hydroxyethane-1,1-diphosphonic acid also acts as an iron complexing agent.
- Special iron complexing agents are e.g. 4,5-dihydroxy-1,3-benzenedisulfonic acid, 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid and 3,4,5-trihydroxybenzoic acid.
- the iron complexing agent is used in amounts of about 0.02 to about 0.2 moles per mole of developer substance.
- Particularly suitable primary aromatic amino developer substances are p-phenylenediamines and in particular N, N-dialkyl-p-phenylenediamines, in which the alkyl groups and the aromatic nucleus are substituted or unsubstituted.
- antioxidants are e.g. Hydroxylamine and diethylhydroxylamine and sulfites, which are preferably used in an amount of up to 5 g / l.
- Optical brighteners e.g. Polyalkylene glycols, surfactants, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH.
- the developer solution can contain benzyl alcohol or be free of benzyl alcohol.
- the developers according to the invention are, in particular, aqueous alkaline solutions which have a pH above 7, in particular from 9 to 13.
- known buffer substances such as alkali carbonates and alkali phosphates are used.
- the pH in developing bath I is higher than in developing bath II.
- Color photographic material is developed whose silver halide emulsions generally contain at least 70 mol% bromide.
- the silver halide emulsion layers of a color photographic material which the invented according to the two-stage development according to a rapid development according to the RA-4 process with a development period of 45 seconds, at least 80, preferably at least 95 mol% of chloride should be present.
- the ready-to-use solutions can be prepared from the individual components or from so-called concentrates, the individual components being dissolved in the concentrates in a much higher concentration.
- the concentrates are adjusted so that a so-called regenerator can be produced from them, i.e. a solution which has somewhat higher concentrations of the individual components than the ready-to-use solution, on the one hand results in a ready-to-use solution by further dilution and addition of a starter, preferably KCl or KBr, and on the other hand is constantly added to a developer solution in use to prevent the development to replace used chemicals or chemicals carried over from the developer solution by overflow or by the developed material.
- a starter preferably KCl or KBr
- halide concentration in the development baths I and II changes accordingly.
- the halide concentrations given above refer to the use of halide-free developer regeneration solutions.
- the photographic material is stopped, bleached, fixed, washed and dried as usual, bleaching and fixing can be combined for bleach-fixing, and the washing can be replaced by a stabilizing bath. If the bleach or bleach-fix bath is sufficiently acidic, the stop bath can also be dispensed with.
- a step wedge is exposed onto the color photographic material described above and processed under the usual processing conditions as follows: developer 210 s 38 ° C Bleach-fixer 90 s 38 ° C Watering 210 s 33 ° C dry
- An exposed step wedge is developed according to the invention in developers I and II.
- the bleach-fix bath solution in use has the same composition as in the comparative example.
- the comparison shows that the values of the shoulder gradation and the maximum density of the underlying yellow layer obtained in the comparative example are too low in relation to the purple and cyan values in terms of color balance.
- the processing according to the invention favors the development of the yellow layer below, so that the higher values of the shoulder gradation and the maximum density result in a much better color balance.
- a color photographic recording material was produced by coating on a support on both tig with polyethylene coated paper the following layers were applied in the given order. The quantities indicated relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given.
- the couplers used have the following formula:
- a step wedge is exposed onto the color photographic material described above and processed under the usual processing conditions as follows: developer 45 s 35 ° C Bleach-fixer 45 s 35 ° C Watering 90 s 33 ° C dry
- composition of the baths developer Tank solution regenerator Condition of use water 960 ml 960 ml Diethylene glycol 30 ml 30 ml Iso-nonyl-phenoxipolyglycidol 0.5 g 0.5 g 4,5-dihydroxy-1,3-benzenedisulfonic acid 0.5 g 0.5 g Ethylenediaminetetraacetic acid 2 g 2 g Potassium sulfite 0.1 g 0.3 g N, N-diethylhydroxyamine, 85% by weight 2 ml 8 ml Sodium chloride 3 g 0.3 g CD3 3 g 10 g Potassium carbonate 20 g 20 g PH value 10.1 11.3
- the bleach-fix bath tank solution has the same composition as in Example 1, but with a pH of 5.5 (correction with acetic acid).
- An exposed step wedge is developed according to the invention in developers I and II.
- the state of use was generated with the same regeneration rate / m2 and the same developer / regenerator composition as in the comparative example.
- Processing conditions Developer I 6 s 27 ° C Developer II 39 s 35 ° C Bleach-fixer 45 s 35 ° C Watering 90 s 33 ° C dry
- the bleach-fix bath tank solution has the same composition as in the comparative example.
- the comparison shows that the values of the shoulder gradation and the maximum density of the underlying yellow layer obtained in the comparative example are too low in relation to the purple and cyan values in terms of color balance.
- the processing in the example according to the invention favors the development of the yellow layer below, so that the higher values of the shoulder gradation and the maximum density result in a much better color balance.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3836778 | 1988-10-28 | ||
DE3836778 | 1988-10-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0365955A2 true EP0365955A2 (fr) | 1990-05-02 |
Family
ID=6366116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89119136A Withdrawn EP0365955A2 (fr) | 1988-10-28 | 1989-10-14 | Bain de développement et procédé de développement d'un matériau photographique couleur |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0365955A2 (fr) |
JP (1) | JPH02171748A (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1899767A2 (fr) * | 2005-07-05 | 2008-03-19 | Thomson Licensing | Color film developer composition and process therefor |
-
1989
- 1989-10-14 EP EP89119136A patent/EP0365955A2/fr not_active Withdrawn
- 1989-10-27 JP JP27878189A patent/JPH02171748A/ja active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1899767A2 (fr) * | 2005-07-05 | 2008-03-19 | Thomson Licensing | Color film developer composition and process therefor |
EP1899767A4 (fr) * | 2005-07-05 | 2008-06-25 | Thomson Licensing | Color film developer composition and process therefor |
Also Published As
Publication number | Publication date |
---|---|
JPH02171748A (ja) | 1990-07-03 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 19891014 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE FR GB IT |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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18W | Application withdrawn |
Withdrawal date: 19910410 |
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R18W | Application withdrawn (corrected) |
Effective date: 19910410 |