EP0405237B1 - Photographic processing method - Google Patents
Photographic processing method Download PDFInfo
- Publication number
- EP0405237B1 EP0405237B1 EP90111253A EP90111253A EP0405237B1 EP 0405237 B1 EP0405237 B1 EP 0405237B1 EP 90111253 A EP90111253 A EP 90111253A EP 90111253 A EP90111253 A EP 90111253A EP 0405237 B1 EP0405237 B1 EP 0405237B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- stabilizing
- bleach
- fixing
- layer
- 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.)
- Expired - Lifetime
Links
- 238000003672 processing method Methods 0.000 title description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 8
- 239000007844 bleaching agent Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000417 fungicide Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 229940005740 hexametaphosphate Drugs 0.000 claims description 4
- 238000004061 bleaching Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical group 0.000 claims 1
- 229960004585 etidronic acid Drugs 0.000 claims 1
- 239000010410 layer Substances 0.000 description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 108010010803 Gelatin Proteins 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- QVLXDGDLLZYJAM-UHFFFAOYSA-N 2,5-dioctylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=C(CCCCCCCC)C=C1O QVLXDGDLLZYJAM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 229940044197 ammonium sulfate Drugs 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
-
- 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
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
Definitions
- the invention relates to a photographic processing method for color paper with the steps of developing, bleach-fixing and stabilizing
- the stabilization solution has the task of converting the chemicals remaining in the supervisory images, which originate from the material itself as well as from the processing solutions and which cannot be washed out due to the lack of watering, into a form that will remain in the image for a long time its quality is not affected.
- bleaching and fixing is usually carried out together in a bleach-fixing bath, the iron ammonium complex salt of ethylenediaminetetraacetic acid (FeNH4EDTA) being a common bleaching agent and ammonium or sodium thiosulfate being a common fixing agent.
- FeNH4EDTA ethylenediaminetetraacetic acid
- EP-B 158 369 describes an aqueous-free processing method from color development, bleach-fixing, stabilizing and drying, in which the bleach-fixing solution FeNH4EDTA, free EDTA, (NH4) 2S2O3 and (NH4) 2SO3 and the stabilizing solution acetic acid, formaldehyde, thiabenzazole, 1-hydroxyethane Contains -1,1-diphosphonic acid (HEDP) and potassium alum.
- the bleach-fixing solution FeNH4EDTA, free EDTA, (NH4) 2S2O3 and (NH4) 2SO3
- the stabilizing solution acetic acid formaldehyde, thiabenzazole, 1-hydroxyethane Contains -1,1-diphosphonic acid (HEDP) and potassium alum.
- Bleach-fix baths are regenerated in minilabs with the smallest possible volume per m2.
- Fe (NH4) 2DTPA) is used instead of FeNH4EDTA.
- the object of the invention is to provide a system in which the bleach-fixing bath and stabilizing bath are coordinated with one another in such a way that the abovementioned disadvantages do not occur and nonetheless colored top images of excellent quality - in particular with regard to color density, residual silver content and stability - are obtained.
- a compound of the formula Fe (X) 2DTPA in which X is alkali or ammonium, preferably Fe (NH4) 2DTPA or FeNa2DTPA, is used as the bleaching agent of the bleach-fixing bath and the stabilizing bath contains a fungicide, HEDP and a hexametaphosphate .
- the invention therefore relates to an aqueous-free process for producing colored top images by developing, bleach-fixing, stabilizing and drying, characterized in that the bleach-fixing bath as a bleaching agent is a compound of the formula Fe (X) 2DTPA, in which X is alkali or ammonium, and the stabilizing bath Contains fungicide, HEDP and a hexametaphosphate.
- the bleach-fixing bath as a bleaching agent is a compound of the formula Fe (X) 2DTPA, in which X is alkali or ammonium
- the stabilizing bath Contains fungicide, HEDP and a hexametaphosphate.
- the bleach-fixing bath preferably contains the bleaching agent in an amount of 0.1 to 0.5 mol / l.
- the stabilizing bath preferably contains 1x10 ⁇ 3 to 5x10 ⁇ 2 mol / l fungicide, 1x10 ⁇ 3 to 5x10 ⁇ 2 mol / l HEDP and 5x10 ⁇ 4 to 5x10 ⁇ 2 mol / l hexametaphosphate.
- Suitable fungicides are e.g. Benzoic acid, sorbic acid and isothiazolones.
- this precipitation in the stabilizing bath can be prevented by complexing agents of all known classes, for example by aminopolycarboxylic acids, aminopolyphosphonic acids, citric acid, polymaleic acid or phosphonobutane tricarboxylic acid.
- complexing agents of all known classes for example by aminopolycarboxylic acids, aminopolyphosphonic acids, citric acid, polymaleic acid or phosphonobutane tricarboxylic acid.
- a color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- a step wedge is exposed on the photographic material described above and processed as follows:
- the individual processing baths had the following composition:
- the total water consumption is 2 liters per m2.
- the step wedges thus obtained are subjected to storage at 60 ° C. and 90% relative humidity for 7 days.
- Material according to Example 1 is processed in an aqueous-free process.
- composition of the stabilizing bath A Composition of the stabilizing bath A
- Tank 1 800 ml stabilizing bath + 200 ml bleach-fixing bath
- Tank 2 960 ml stabilizing bath + 40 ml bleach-fixing bath
- Tank 3 992 ml stabilizing bath + 8 ml bleach-fixing bath
- Tank 4 998 ml stabilizing bath + 2 ml bleach-fixing bath
- the stabilizing bath consumption is 250 ml / m2.
- the stabilizing bath consumption corresponds to example 2.
- the stabilizing bath consumption corresponds to example 2.
- step wedges obtained with this process are stored together with the wedges of Examples 1, 2 and 3 under the specified conditions.
- the table shows that during the transition from processing with washing to a water-free process, a precipitate occurs in the first stabilizing solution tank, which is prevented by increasing the amount of aminopolycarboxylic acid, but this advantage must be bought with a significant increase in fog (increase D min ) .
- Sodium hexametaphosphate also prevents the formation of precipitates, but additionally also leads to a lowering of the fog compared to normally watered samples.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Detergent Compositions (AREA)
Description
Die Erfindung betrifft ein fotografisches Verarbeitungsverfahren für Colorpapier mit den Schritten Entwickeln, Bleichfixieren und StabilisierenThe invention relates to a photographic processing method for color paper with the steps of developing, bleach-fixing and stabilizing
Die Herstellung farbfotografischer Aufsichtsbilder wurde bisher nahezu ausschließlich von großen Entwicklungsanstalten vorgenommen, die die angelieferten Negativfilme entwickelten und unter Benutzung von Farbnegativpapier die farbigen Aufsichtsbilder herstellten. Der Vorteil der großen Entwicklungsanstalten liegt unter anderem darin, gut für eine Entsorgung der anfallenden verbrauchten Verarbeitungslösungen, insbesondere des Waschwassers für die Schlußwässerung sorgen zu können. Nachteilig ist, daß der Kunde oft längere Zeit auf seine Bilder warten muß.The production of color photographic supervisory images has so far been carried out almost exclusively by large development institutions, which developed the supplied negative films and produced the colored supervisory images using color negative paper. The advantage of the large development institutes is, among other things, that they can take good care of disposing of the used processing solutions, in particular the washing water for the final rinsing. The disadvantage is that the customer often has to wait a long time for his pictures.
Aus diesem Grunde wurden kleine Vorrichtungseinheiten entwickelt, die in Kundennähe installiert werden und dem Kunden die fertigen Bilder im Extremfall bereits eine Stunde nach dem Einliefern des belichteten Filmes aushändigen können. Diese Vorrichtungen wurden unter anderem durch die Entwicklung einer Prozeßvariante möglich, die auf die Schlußwässerung verzichtet und anstelle dessen die entwickelten, gebleichten und fixierten Bilder mit einer Stabilisierungslösung behandelt. Die neuen Vorrichtungen ("Minilab") kommen daher ohne Frischwasserzufuhr aus und produzieren auch kein Abwasser. Die verbrauchten Verarbeitungslösungen werden in Kanistern gesammelt und von Zeit zu Zeit entsorgt.For this reason, small device units have been developed that are installed close to the customer and, in extreme cases, can hand over the finished pictures to the customer just one hour after the exposed film has been delivered. These devices were made possible, among other things, by the development of a process variant which dispensed with the final rinsing and instead treated the developed, bleached and fixed images with a stabilizing solution. The new devices ("Minilab") therefore do not require fresh water and do not produce any wastewater. The used processing solutions are collected in canisters and disposed of from time to time.
Die Stabilisierungslösung hat die Aufgabe, die in den Aufsichtsbildern verbleibenden Chemikalien, die sowohl aus dem Material selbst als auch aus den Verarbeitungslösungen stammen und die infolge der fehlenden Wässerung nicht mehr ausgewaschen werden, in eine Form zu überführen, die das Bild auch über lange Zeit in seiner Qualität nicht beeinträchtigt.The stabilization solution has the task of converting the chemicals remaining in the supervisory images, which originate from the material itself as well as from the processing solutions and which cannot be washed out due to the lack of watering, into a form that will remain in the image for a long time its quality is not affected.
Bleichen und Fixieren wird in Minilabs üblicherweise gemeinsam in einem Bleichfixierbad durchgeführt, wobei das Eisenammoniumkomplexsalz der Ethylendiamintetraessigsäure (FeNH₄EDTA) ein gebräuchliches Bleichmittel und Ammonium- oder Natriumthiosulfat ein gebräuchliches Fixiermittel sind.In minilabs, bleaching and fixing is usually carried out together in a bleach-fixing bath, the iron ammonium complex salt of ethylenediaminetetraacetic acid (FeNH₄EDTA) being a common bleaching agent and ammonium or sodium thiosulfate being a common fixing agent.
So beschreibt beispielsweise EP-B 158 369 ein wässerungsfreies Verarbeitungsverfahren aus Farbentwicklung, Bleichfixieren, Stabilisieren und Trocknen, bei dem die Bleichfixierlösung FeNH₄EDTA, freie EDTA, (NH₄)₂S₂O₃ und (NH₄)₂SO₃ und die Stabilisierlösung Essigsäure, Formaldehyd, Thiabenzazol, 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und Kaliumalaun enthält.For example, EP-B 158 369 describes an aqueous-free processing method from color development, bleach-fixing, stabilizing and drying, in which the bleach-fixing solution FeNH₄EDTA, free EDTA, (NH₄) ₂S₂O₃ and (NH₄) ₂SO₃ and the stabilizing solution acetic acid, formaldehyde, thiabenzazole, 1-hydroxyethane Contains -1,1-diphosphonic acid (HEDP) and potassium alum.
Diese Kombination aus Bleichfixierbad und Stabilisierbad weist Nachteile auf.This combination of bleach-fix bath and stabilizing bath has disadvantages.
Bleichfixierbäder werden in Minilabs mit einem möglichst geringen Volumen pro m² regeneriert.Bleach-fix baths are regenerated in minilabs with the smallest possible volume per m².
So ergibt sich ein wesentlich langsamerer Austausch der Badlösung als im Normalfall, besonders bei Minilabs mit relativ geringem Durchsatz an Colorpapier. Daraus folgt, daß das Sulfit der Badlösung durch den Luftsauerstoff oxidiert wird, die Stabilität des Thiosulfats nicht mehr gesichert ist und schließlich ein Niederschlag aus Schwefel ausfällt.This results in a much slower exchange of the bath solution than in the normal case, especially with minilabs with a relatively low throughput of color paper. It follows that the sulfite of the bath solution is oxidized by the atmospheric oxygen, the stability of the thiosulfate is no longer ensured and finally a precipitate of sulfur precipitates.
Diesen Mißstand kann man weitgehend beheben, wenn man anstelle von FeNH₄EDTA das Eisenammoniumsalz der Diethylentriaminpentaessigsäure (Fe(NH₄)₂DTPA) verwendet.This situation can largely be remedied if the iron ammonium salt of diethylenetriaminepentaacetic acid (Fe (NH₄) ₂DTPA) is used instead of FeNH₄EDTA.
Der Nachteil einer Kombination dieses vorteilhaften Bleichfixierbades mit einem nachfolgenden Stabilisierbad, das HEDP enthält, besteht darin, daß im Gebrauchszustand des Stabilisierbades ein Niederschlag entsteht. Die durch Einschleppung im Stabilisierbad entstehende Konzentration des DTPA kann diesen Niederschlag nicht verhindern. Ebensowenig gelingt das mit den in manchen Stabilisierbädern im Bereich von 0,2 bis 2 g/l enthaltenen Aminopolycarbonsäuren.The disadvantage of a combination of this advantageous bleach-fixing bath with a subsequent stabilizing bath which contains HEDP is that in the state of use a precipitate is formed in the stabilizing bath. The concentration of DTPA created by the introduction in the stabilizing bath cannot prevent this precipitation. This is also not possible with the aminopolycarboxylic acids contained in some stabilizing baths in the range from 0.2 to 2 g / l.
Aufgabe der Erfindung ist es, ein System zur Verfügung zu stellen, bei dem Bleichfixierbad und Stabilisierbad so aufeinander abgestimmt sind, daß die vorerwähnten Nachteile nicht auftreten und dennoch farbige Aufsichtsbilder hervorragende Qualität - insbesondere hinsichtlich Farbdichte, Restsilbergehalt und Stabilität - erhalten werden.The object of the invention is to provide a system in which the bleach-fixing bath and stabilizing bath are coordinated with one another in such a way that the abovementioned disadvantages do not occur and nonetheless colored top images of excellent quality - in particular with regard to color density, residual silver content and stability - are obtained.
Diese Aufgabe wird dadurch gelöst, daß als Bleichmittel des Bleichfixierbades eine Verbindung der Formel Fe(X)₂DTPA, worin X Alkali oder Ammonium bedeutet, vorzugsweise Fe(NH₄)₂DTPA oder FeNa₂DTPA, eingesetzt wird und das Stabilisierbad ein Fungizid, HEDP und ein Hexametaphosphat enthält.This object is achieved in that a compound of the formula Fe (X) ₂DTPA, in which X is alkali or ammonium, preferably Fe (NH₄) ₂DTPA or FeNa₂DTPA, is used as the bleaching agent of the bleach-fixing bath and the stabilizing bath contains a fungicide, HEDP and a hexametaphosphate .
Gegenstand der Erfindung ist daher ein wässerungsfreies Verfahren zur Herstellung farbiger Aufsichtsbilder durch Entwickeln, Bleichfixieren, Stabilisieren und Trocknen, dadurch gekennzeichnet, daß das Bleichfixierbad als Bleichmittel eine Verbindung der Formel Fe(X)₂DTPA, worin X Alkali oder Ammonium bedeutet, und das Stabilisierbad ein Fungizid, HEDP und ein Hexametaphosphat enthält.The invention therefore relates to an aqueous-free process for producing colored top images by developing, bleach-fixing, stabilizing and drying, characterized in that the bleach-fixing bath as a bleaching agent is a compound of the formula Fe (X) ₂DTPA, in which X is alkali or ammonium, and the stabilizing bath Contains fungicide, HEDP and a hexametaphosphate.
Vorzugsweise enthält das Bleichfixierbad das Bleichmittel in einer Menge von 0,1 bis 0,5 Mol/l. Vorzugsweise enthält das Stabilisierbad 1x10⁻³ bis 5x10⁻² Mol/l Fungizid, 1x10⁻³ bis 5x10⁻² Mol/l HEDP und 5x10⁻⁴ bis 5x10⁻² Mol/l Hexametaphosphat. Geeignete Fungizide sind z.B. Benzoesäure, Sorbinsäure und Isothiazolone.The bleach-fixing bath preferably contains the bleaching agent in an amount of 0.1 to 0.5 mol / l. The stabilizing bath preferably contains 1x10⁻³ to 5x10⁻² mol / l fungicide, 1x10⁻³ to 5x10⁻² mol / l HEDP and 5x10⁻⁴ to 5x10⁻² mol / l hexametaphosphate. Suitable fungicides are e.g. Benzoic acid, sorbic acid and isothiazolones.
Grundsätzlich läßt sich zwar dieser Niederschlag im Stabilisierbad durch Komplexbildner aller bekannten Klassen verhindern, z.B. durch Aminopolycarbonsäuren, Aminopolyphosphonsäuren, Citronensäure, Polymaleinsäure oder Phosphonobutantricarbonsäure. Da jedoch die meisten davon die Wirkung des im Stabilisierbad üblicherweise enthaltenen HEDP als Eisenmaskierungsmittel behindern und somit die bei Tropenlagerung entstehende Vergilbung nicht genügend unterdrücken, bleibt, wie überraschend gefunden wurde, nur die Klasse der Phosphor- und der Phosphonsäuren als geeignet übrig, im optimalen Fall Natriumhexametaphosphat.Basically, this precipitation in the stabilizing bath can be prevented by complexing agents of all known classes, for example by aminopolycarboxylic acids, aminopolyphosphonic acids, citric acid, polymaleic acid or phosphonobutane tricarboxylic acid. However, since most of them hinder the effect of the HEDP usually present in the stabilizing bath as an iron masking agent and thus do not sufficiently suppress the yellowing that occurs when stored in the tropics, it was surprisingly found that only the classes of phosphoric and phosphonic acids remain suitable, in the optimal case Sodium hexametaphosphate.
Ein farbfotografisches Aufzeichnungsmaterial, welches für das erfindungsgemäße Verarbeitungsverfahren geeignet ist, wurde hergestellt, indem auf einen Schichtträger auf beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.A color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.
-
1. Schicht (Substratschicht):
0,2 g Gelatine1st layer (substrate layer):
0.2 g gelatin -
2. Schicht (blauempfindliche Schicht): blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g AgNO₃ mit
1,38 g Gelatine
0,95 g Gelbkuppler Y
0,29 g Trikresylphosphat (TKP)2nd layer (blue-sensitive layer): blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO₃ with
1.38 g gelatin
0.95 g yellow coupler Y
0.29 g tricresyl phosphate (CPM) -
3. Schicht (Schutzschicht)
1,1 g Gelatine
0,06 g 2,5-Dioctylhydrochinon
0,06 g Dibutylphthalat (DBP)3rd layer (protective layer)
1.1 g gelatin
0.06 g 2,5-dioctyl hydroquinone
0.06 g dibutyl phthalate (DBP) -
4. Schicht (grünempfindliche Schicht)
grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO₃ mit
1,08 g Gelatine
0,41 g Purpurkuppler M
0,08 g 2,5-Dioctylhydrochinon
0,34 g DBP
0,04 g TKP4th layer (green-sensitive layer)
Green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgNO₃ with
1.08 g gelatin
0.41 g purple coupler M
0.08 g 2,5-dioctyl hydroquinone
0.34 g DBP
0.04 g CPM -
5. Schicht (UV-Schutzschicht)
1,15 g Gelatine
0,6 g UV-Absorber der Formel
0,04 g TKP5th layer (UV protective layer)
1.15 g gelatin
0.6 g UV absorber of the formula
0.04 g CPM -
6. Schicht (rotempfindliche Schicht)
rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO₃ mit
0,75 g Gelatine
0,36 g Blaugrünkuppler C
0,36 g TKP6th layer (red-sensitive layer)
Red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.3 g AgNO₃ with
0.75 g gelatin
0.36 g cyan coupler C
0.36 g CPM -
7. Schicht (UV-Schutzschicht)
0,35 g Gelatine
0,15 g UV-Absorber gemäß 5. Schicht
0,2 g TKP7th layer (UV protective layer)
0.35 g gelatin
0.15 g UV absorber according to the 5th layer
0.2 g CPM -
8. Schicht (Schutzschicht)
0,9 g Gelatine
0,3 g Härtungsmittel H der folgenden Formel
0.9 g gelatin
0.3 g of curing agent H of the following formula
Die Kuppler entsprachen folgenden Formeln:
Ein Stufenkeil wird auf das oben beschriebene fotografische Aufzeichnungsmaterial aufbelichtet und wie folgt verarbeitet:
Die einzelnen Verarbeitungsbäder hatten die folgende Zusammensetzung:The individual processing baths had the following composition:
mit Wasser auffüllen auf 1 liter ; pH 10
make up to 1 liter with water; pH 10
Mit Wasser auf 1 Liter auffüllen und auf pH 5,0 stellen.
Make up to 1 liter with water and adjust to pH 5.0.
Der Gesamtwasserverbrauch beträgt 2 Liter pro m².The total water consumption is 2 liters per m².
Die damit erhaltenen Stufenkeile werden einer Lagerung bei 60°C und 90 % relativer Feuchte über 7 Tage unterworfen.The step wedges thus obtained are subjected to storage at 60 ° C. and 90% relative humidity for 7 days.
Ergebnisse siehe Tabelle.Results see table.
Material gemäß Beispiel 1 wird in einem wässerungsfreien Prozeß verarbeitet.
Entwickler und Bleichfixierbad entsprachen Beispiel 1Developer and bleach-fixing bath corresponded to example 1
Mit Wasser auf 1 Liter auffüllen, auf pH 5,0 stellen.Make up to 1 liter with water, adjust to pH 5.0.
Herstellung des Gebrauchszustandes in den vier zu einer Kaskade zusammengefaßten Stabilisierbadtanks:
Tank 1 : 800 ml Stabilisierbad + 200 ml Bleichfixierbad
Tank 2 : 960 ml Stabilisierbad + 40 ml Bleichfixierbad
Tank 3 : 992 ml Stabilisierbad + 8 ml Bleichfixierbad
Tank 4 : 998 ml Stabilisierbad + 2 ml BleichfixierbadProduction of the use condition in the four stabilizing bath tanks combined into a cascade:
Tank 1: 800 ml stabilizing bath + 200 ml bleach-fixing bath
Tank 2: 960 ml stabilizing bath + 40 ml bleach-fixing bath
Tank 3: 992 ml stabilizing bath + 8 ml bleach-fixing bath
Tank 4: 998 ml stabilizing bath + 2 ml bleach-fixing bath
Der Stabilisierbadverbrauch beträgt 250 ml/m².The stabilizing bath consumption is 250 ml / m².
Die mit diesem Prozeß erhaltenen Stufenkeile werden gemeinsam mit den in Beispiel 1 gewonnenen Keilen gelagert. Ergebnisse siehe Tabelle.The step wedges obtained with this process are stored together with the wedges obtained in Example 1. Results see table.
Material und Verarbeitung mit Ausnahme des Stabilisierbades entsprachen Beispiel 2.Material and processing with the exception of the stabilizing bath corresponded to Example 2.
Mit Wasser auf 1 Liter auffüllen und auf pH 5,0 stellen.
Make up to 1 liter with water and adjust to pH 5.0.
Der Gebrauchszustand der 4 Stabilisierbadtanks wurde wie in Beispiel 2 hergestellt.The condition of use of the 4 stabilizing bath tanks was produced as in Example 2.
Der Stabilisierbadverbrauch entspricht Beispiel 2.The stabilizing bath consumption corresponds to example 2.
Lagerung gemeinsam mit den Keilen der Beispiele 1 und 2 unter den angegebenen Bedingungen. Ergebnisse siehe TabelleStorage together with the wedges of Examples 1 and 2 under the specified conditions. Results see table
Material und Verarbeitung mit Ausnahme des Stabilisierbades entsprachen Beispiel 2.Material and processing with the exception of the stabilizing bath corresponded to Example 2.
Mit Wasser auf 1 Liter auffülen und auf pH 5,0 stellen.
Make up to 1 liter with water and adjust to pH 5.0.
Der Gebrauchszustand der 4 Stabilisierbadtanks wurde wie in Beispiel 2 hergestellt.The condition of use of the 4 stabilizing bath tanks was produced as in Example 2.
Der Stabilisierbadverbrauch entspricht Beispiel 2.The stabilizing bath consumption corresponds to example 2.
Die mit diesem Prozeß erhaltenen Stufenkeile werden gemeinsam mit den Keilen der Beispiele 1, 2 und 3 unter den angegebenen Bedingungen gelagert.The step wedges obtained with this process are stored together with the wedges of Examples 1, 2 and 3 under the specified conditions.
Von den Stabilisierbädern der Beispiele 2, 3 und 4 wurden jeweils aus Tanks Proben entnommen und 4 Tage lang bei Raumtemperatur stehengelassen. Über das eventuelle Auftreten eines Niederschlags siehe Tabelle.
Die Tabelle zeigt, daß beim Übergang von der Verarbeitung mit Wässerung zu einem wässerungsfreien Verfahren ein Niederschlag im ersten Stabilisierlösungstank auftritt, der zwar durch Erhöhung der Menge an Aminopolycarbonsäure unterbunden wird, daß dieser Vorteil aber mit einer erheblichen Schleiererhöhung (Anstieg Dmin) erkauft werden muß.The table shows that during the transition from processing with washing to a water-free process, a precipitate occurs in the first stabilizing solution tank, which is prevented by increasing the amount of aminopolycarboxylic acid, but this advantage must be bought with a significant increase in fog (increase D min ) .
Natriumhexametaphosphat verhindert ebenfalls die Niederschlagsbildung, sogt aber zusätzlich sogar für eine Schleiererniedrigung gegenüber normal gewässerten Proben.Sodium hexametaphosphate also prevents the formation of precipitates, but additionally also leads to a lowering of the fog compared to normally watered samples.
Claims (2)
- A no-rinse process for the production of colour photographs by development, bleaching/fixing, stabilization and drying, characterized in that the bleaching/fixing bath contains a compound with the formula Fe(X)₂DTPA, where X is an alkali metal or ammonium, as bleaching agent while the stabilizing bath contains a fungicide, hydroxyethanediphosphonic acid and a hexametaphosphate.
- A process as claimed in claim 1, characterized in that Fe(NH₄)₂DTPA or FeNa₂DTPA is used as the bleaching agent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3920922A DE3920922A1 (en) | 1989-06-27 | 1989-06-27 | PHOTOGRAPHIC PROCESSING METHOD |
DE3920922 | 1989-06-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0405237A1 EP0405237A1 (en) | 1991-01-02 |
EP0405237B1 true EP0405237B1 (en) | 1994-09-14 |
Family
ID=6383617
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90111253A Expired - Lifetime EP0405237B1 (en) | 1989-06-27 | 1990-06-14 | Photographic processing method |
Country Status (4)
Country | Link |
---|---|
US (1) | US4987058A (en) |
EP (1) | EP0405237B1 (en) |
JP (1) | JPH0339738A (en) |
DE (2) | DE3920922A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5543272A (en) * | 1993-02-17 | 1996-08-06 | Fuji Photo Film Co., Ltd. | Photographic composition having fixing capacity and a method for processing using the same |
US5945262A (en) * | 1995-12-14 | 1999-08-31 | Agfa-Gevaert, N.B. | Correcting liquid for a silver imaged lithographic printing plate |
KR100414642B1 (en) * | 2000-06-20 | 2004-01-13 | 김찬근 | Combination structure of soundproof and fireproof door and door frame with flat plane when combination of frame and door |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5814834A (en) * | 1981-07-21 | 1983-01-27 | Konishiroku Photo Ind Co Ltd | Method for stabilizing silver halide color photosensitive material |
US4601975A (en) * | 1983-12-23 | 1986-07-22 | Konishiroku Photo Industry Co., Ltd. | Method for processing light-sensitive silver halide color photographic material |
JPS63129341A (en) * | 1986-11-19 | 1988-06-01 | Fuji Photo Film Co Ltd | Silver halide color reversal photographic sensitive material |
EP0296854B1 (en) * | 1987-06-24 | 1993-08-18 | Konica Corporation | Method for processing light-sensitive silver halide color photographic material |
-
1989
- 1989-06-27 DE DE3920922A patent/DE3920922A1/en not_active Withdrawn
-
1990
- 1990-06-13 US US07/537,942 patent/US4987058A/en not_active Expired - Fee Related
- 1990-06-14 DE DE59007107T patent/DE59007107D1/en not_active Expired - Fee Related
- 1990-06-14 EP EP90111253A patent/EP0405237B1/en not_active Expired - Lifetime
- 1990-06-26 JP JP2165820A patent/JPH0339738A/en active Pending
Also Published As
Publication number | Publication date |
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DE59007107D1 (en) | 1994-10-20 |
EP0405237A1 (en) | 1991-01-02 |
US4987058A (en) | 1991-01-22 |
DE3920922A1 (en) | 1991-01-03 |
JPH0339738A (en) | 1991-02-20 |
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