EP0330035B1 - Colour-photographic developer solution, and process for developing a colour-photographic material - Google Patents
Colour-photographic developer solution, and process for developing a colour-photographic material Download PDFInfo
- Publication number
- EP0330035B1 EP0330035B1 EP89102423A EP89102423A EP0330035B1 EP 0330035 B1 EP0330035 B1 EP 0330035B1 EP 89102423 A EP89102423 A EP 89102423A EP 89102423 A EP89102423 A EP 89102423A EP 0330035 B1 EP0330035 B1 EP 0330035B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- developer
- colour
- developer solution
- developing
- 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.)
- Expired - Lifetime
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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
Definitions
- the object of the invention was to provide a processing process in which the development time for color negative paper containing high chloride is further shortened.
- Optical brighteners polyalkylene glycols, surfactants, anti-limescale agents, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH.
- the developer solution can also contain up to 25 g of benzyl alcohol. However, less than 5 g of benzyl alcohol are preferred; it is preferably free of benzyl alcohol.
- Suitable antioxidants are e.g. Hydroxylamine and diethylhydroxylamine and sulfites, which are preferably used in an amount of up to 5 g.
- the ready-to-use solution can be prepared from the individual components or from so-called concentrates, with the individual components being dissolved in a much higher concentration in the concentrates.
- the concentrates are adjusted so that a so-called regenerator can be produced from them, ie a solution which has somewhat higher concentrations of the individual components than the ready-to-use solution, on the one hand, by further dilution and addition of a starter, preferably KCl, gives a ready-to-use solution and on the other hand, a developer solution in use is constantly added in order to replace the chemicals consumed during development or which are carried out of the developer solution by overflow or by the developed material. Chloride ions usually do not need to be added except for the freshly prepared developer, since chloride ions are released from the photographic material by the development.
- the developer composition according to the invention is so active that the development-inhibiting effect of e.g. KCl is easily overcome, so that an overflow-free regeneration is possible.
- Another object of the invention is a process for developing an exposed color photographic material, the light-sensitive emulsion layers of which contain silver halide grains with at least 80, preferably at least 95 mol% chloride, with the developer solution according to the invention, in particular a development process in which the development takes at most 40 seconds, preferably completed at most 20 seconds.
- the developer substance a) is preferably used exclusively.
- a color photographic negative paper the light-sensitive emulsion layers of which contain silver halide grains with at least 80 mol% of chloride, can be added in 15 seconds Develop temperatures of at most 38 ° C, the images produced being of excellent quality and comparable images obtained on the same color negative paper after 45 seconds by the RA-4 process. In particular, there is no need to accept any losses in the light resistance of the colors.
- development times of up to 5 seconds can be achieved.
- a commercially available high-chloride color paper (eg Kodak 2001 or Agfacolor type 9, with emulsions containing about 99.5 mol% Cl ⁇ and 0.5 mol% Br ⁇ ) was exposed imagewise , developed with the developer described below and in the usual way Bleached, fixed, washed and dried. Processing was set to type with respect to minimum densities, ⁇ -1 values, ⁇ -2 values and maximum densities.
- the aqueous developer contained the following substances per liter: 15 ml Benzyl alcohol 8.5 ml Diethylene glycol 1.0 g Diethylhydroxylamine 11.0 g CD-3 1.0 g K2SO3 44 g K3PO4 1.2 g KCl as well as surfactants, optical brighteners, stabilizers and anti-limescale in usual quantities and is adjusted to pH 11.6.
- Example 1 is repeated with a developer of the following composition: 11 ml Triethanolamine 6 ml an 85% by weight aqueous solution of diethylhydroxylamine 0.3 g K2SO3 5 g CD-3 25 g K2CO3 2.3 g KCl As well as surfactants, optical brighteners, stabilizers and anti-limescale in the usual amount and is adjusted to pH 10.1 with KOH.
- Example 1 is repeated, the use of benzyl alcohol and diethylene glycol being dispensed with.
- example 1 Comparative example
- Example 2 yellow 242 243 240 purple 273 247 268 Blue green 284 246 271
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Für einen Großteil lichtempfindlicher Silberhalogenidaufzeichnungsmaterialien gibt es standardisierte Verarbeitungsprozesse, in denen fotografische Aufzeichnungsmaterialien beliebiger Provenienz typgerecht verarbeitet werden können, beispielsweise für die Herstellung von farbigen Aufsichtsbildern aus Farbnegativpapier unter Benutzung eines transparenten Farbnegativs, wobei das Farbnegativpapier wenigstens eine einen Gelbkuppler enthaltende blauempfindliche, wenigstens eine einen Purpurkuppler enthaltende grünempfindliche und wenigstens eine einen Blaugrünkuppler enthaltende rotempfindliche Silberhalogenidemulsionsschicht aufweist.For a large part of light-sensitive silver halide recording materials, there are standardized processing processes in which photographic recording materials of any provenance can be processed according to type, for example for the production of colored overlay images from color negative paper using a transparent color negative, the color negative paper containing at least one blue-sensitive, at least one magenta coupler containing a yellow coupler containing green sensitive and at least one cyan coupler containing red sensitive silver halide emulsion layer.
In dem weltweit durchgeführten Verarbeitungsprozeß für Farbnegativpapier, EP-2-Prozeß oder Agfacolor Prozeß AP 92 genannt, wird das bildmäßig belichtete Farbnegativpapier einer Farbentwicklung, einer Bleichung, einer Fixierung, einer Wässerung und einer Trocknung unterworfen, wobei Bleichung und Fixierung durch eine Bleichfixierung und die Wässerung durch eine Stabilisierung ersetzt sein können.In the worldwide processing process for color negative paper, EP-2 process or Agfacolor process called AP 92, the imagewise exposed color negative paper is subjected to color development, bleaching, fixing, washing and drying, bleaching and fixation can be replaced by bleaching fixation and washing can be replaced by stabilization.
Die Farbentwicklung benötigt 210 Sekunden. Um diese Zeit zu verkürzen, sind erhebliche Anstrengungen unternommen worden, ohne daß bisher ein neuer Prozeß Eingang in die Technik gefunden hätte, der unter Einsatz des bewährten Farbnegativpapiers, das im wesentlichen Silberbromidemulsionen mit nur geringen Chloridanteilen (<20 Mol-% Cl), zum Erfolg geführt hätte.The color development takes 210 seconds. In order to shorten this time, considerable efforts have been made without a new process having found its way into the technology which, using the proven color negative paper, essentially silver bromide emulsions with only low chloride contents (<20 mol% Cl), for Success.
Technisch angewendet wird in jüngster Zeit lediglich ein Verfahren, dessen Entwicklungszeit 45 Sekunden beträgt, das ein Farbnegativpapier benötigt, das überwiegend Silberchloridemulsionen (>95 Mol-% Cl) enthält und eine geänderte Entwicklerzusammensetzung aufweist (RA-4-Prozeß). Hierbei wird die bekannte Tatsache ausgenutzt, daß Chloridemulsionen schneller entwickelbar sind als Bromidemulsionen.Technically, only a method has recently been used, the development time of which is 45 seconds, which requires a color negative paper which predominantly contains silver chloride emulsions (> 95 mol% Cl) and has a changed developer composition (RA-4 process). Here, the known fact is exploited that chloride emulsions can be developed more quickly than bromide emulsions.
Aufgabe der Erfindung war es, einen Verarbeitungsprozeß bereitzustellen, bei dem die Entwicklungszeit für hochchloridhaltiges Farbnegativpapier weiter verkürzt wird.The object of the invention was to provide a processing process in which the development time for color negative paper containing high chloride is further shortened.
Es wurde nun gefunden, daß diese Aufgabe gelöst werden kann, wenn man einen Entwickler verwendet, dessen kennzeichnendes Merkmal die Kombination bestimmter Konzentrationen an sich bekannter Entwicklerbestandteile ist.It has now been found that this object can be achieved if a developer is used, the characteristic feature of which is the combination of certain concentrations of developer components known per se.
Gegenstand der Erfindung ist daher eine farbfotographische Entwicklerlösung, die in einem Liter gebrauchsfertiger, wäßriger Lösung
- a) 4 bis 15 g des Entwicklers der Formel
- b) 0 bis 2,0 g des Entwicklers der Formel
- c) 8 bis 35 g PO₄³⁻-Ionen, insbesondere als K₃PO₄ oder K₂HPO₄
- d) mindestens 0,2 g Oxidationsschutzmittel
- e) 0,5 bis 5,0 g KCl
- f) 0 bis 0,5 g KBr
- a) 4 to 15 g of the developer of the formula
- b) 0 to 2.0 g of the developer of the formula
- c) 8 to 35 g PO₄³⁻ ions, especially as K₃PO₄ or K₂HPO₄
- d) at least 0.2 g antioxidant
- e) 0.5 to 5.0 g KCl
- f) 0 to 0.5 g KBr
Als weitere Bestandteile kommen optische Aufheller, Polyalkylenglykole, Tenside, Kalkschutzmittel, Stabilisatoren, z.B. heterocyclischen Mercaptoverbindungen oder Nitrobenzimidazol und Mittel zur Einstellung des gewünschten pH-Wertes in Frage. Die Entwicklerlösung kann ferner bis zu 25 g Benzylalkohol enthalten. Bevorzugt sind aber weniger als 5 g Benzylalkohol; vorzugsweise ist sie benzylalkoholfrei.Optical brighteners, polyalkylene glycols, surfactants, anti-limescale agents, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH. The developer solution can also contain up to 25 g of benzyl alcohol. However, less than 5 g of benzyl alcohol are preferred; it is preferably free of benzyl alcohol.
Geeignete Oxidationsschutzmittel sind z.B. Hydroxylamin und Diethylhydroxylamin sowie Sulfite, die vorzugsweise in einer Menge bis zu 5 g eingesetzt werden.Suitable antioxidants are e.g. Hydroxylamine and diethylhydroxylamine and sulfites, which are preferably used in an amount of up to 5 g.
Die gebrauchsfertige Lösung kann aus den einzelnen Bestandteilen oder aus sogenannten Konzentraten hergestellt werden, wobei in den Konzentraten die einzelnen Bestandteile wesentlich höher konzentriert gelöst werden. Die Konzentrate sind so eingestellt, daß sich aus ihnen ein sogenannter Regenerator herstellen läßt, d.h. eine Lösung, die etwas höhere Konzentrationen an den einzelnen Bestandteilen als die gebrauchsfertige Lösung aufweist, einerseits durch weiteres Verdünnen und Zugabe eines Starters, vorzugsweise KCl eine gebrauchsfertige Lösung ergibt und andererseits ständig einer in Gebrauch befindlichen Entwicklerlösung zugesetzt wird, um die beim Entwickeln verbrauchten oder aus der Entwicklerlösung durch Überlauf oder durch das entwickelte Material ausgeschleppten Chemikalien zu ersetzten. Chloridionen brauchen dabei üblicherweise nicht zugesetzt werden außer beim frisch angesetzten Entwickler, da Chloridionen aus dem fotografischen Material durch die Entwicklung freigesetzt werden.The ready-to-use solution can be prepared from the individual components or from so-called concentrates, with the individual components being dissolved in a much higher concentration in the concentrates. The concentrates are adjusted so that a so-called regenerator can be produced from them, ie a solution which has somewhat higher concentrations of the individual components than the ready-to-use solution, on the one hand, by further dilution and addition of a starter, preferably KCl, gives a ready-to-use solution and on the other hand, a developer solution in use is constantly added in order to replace the chemicals consumed during development or which are carried out of the developer solution by overflow or by the developed material. Chloride ions usually do not need to be added except for the freshly prepared developer, since chloride ions are released from the photographic material by the development.
Die erfindungsgemäße Entwicklerzusammensetzung ist so aktiv, daß die entwicklungshemmende Wirkung von z.B. KCl ohne weiteres überwunden wird, so daß eine überlauffreie Regenerierung möglich ist.The developer composition according to the invention is so active that the development-inhibiting effect of e.g. KCl is easily overcome, so that an overflow-free regeneration is possible.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Entwicklung eines belichteten farbfotografischen Materials, dessen lichtempfindliche Emulsionsschichten Silberhalogenidkörner mit mindestens 80, vorzugsweise mindestens 95 Mol-% Chlorid enthalten, mit der erfindungsgemäßen Entwicklerlösung, inbesondere ein Entwicklungsverfahren, bei dem die Entwicklung in höchstens 40 Sekunden, vorzugsweise höchstens 20 Sekunden abgeschlossen ist.Another object of the invention is a process for developing an exposed color photographic material, the light-sensitive emulsion layers of which contain silver halide grains with at least 80, preferably at least 95 mol% chloride, with the developer solution according to the invention, in particular a development process in which the development takes at most 40 seconds, preferably completed at most 20 seconds.
Innerhalb der angegebenen Mengen der Entwickler a) und b) ist es aus Gründen optimaler Lichtbeständigkeit vorteilhaft, daß das Gewichtsverhältnis a):b) größer als 4:1 ist. Vorzugsweise wird ausschließlich die Entwicklersubstanz a) eingesetzt.Within the stated amounts of developers a) and b), it is advantageous for reasons of optimal light resistance that the weight ratio a): b) is greater than 4: 1. The developer substance a) is preferably used exclusively.
Mit dem erfindungsgemäßen Entwickler gelingt es, ein farbfotorafisches Negativpapier, dessen lichtempfindliche Emulsionsschichten Silberhalogenidkörner mit mindestens 80 Mol-% Chlorid enthalten, in 15 Sekunden bei Temperaturen von höchstens 38 °C zu entwickeln, wobei die erzeugten Bilder von ausgezeichneter Qualität und vergleichbar Bildern sind, die auf dem gleichen Farbnegativpapier nach dem RA-4-Prozeß in 45 Sekunden erhalten werden. Insbesondere müssen bei der Lichtbeständigkeit der Farben keine Einbußen hingenommen werden.With the developer according to the invention, a color photographic negative paper, the light-sensitive emulsion layers of which contain silver halide grains with at least 80 mol% of chloride, can be added in 15 seconds Develop temperatures of at most 38 ° C, the images produced being of excellent quality and comparable images obtained on the same color negative paper after 45 seconds by the RA-4 process. In particular, there is no need to accept any losses in the light resistance of the colors.
Bei einer Erhöhung der Entwicklungstemperatur können Entwicklungszeiten bis 5 Sekunden erreicht werden.If the development temperature is increased, development times of up to 5 seconds can be achieved.
Ein handelsübliches hochchloridhaltiges Colorpapier (z.B. Kodak 2001 oder Agfacolor Typ 9, mit Emulsionen, die etwa 99,5 Mol-% Cl⊖ und 0,5 Mol-% Br⊖ enthalten) wurde bildmäßig belichtet, mit dem nachfolgend beschriebenen Entwickler entwickelt und in üblicher Weise gebleicht, fixiert, gewaschen und getrocknet. Die Verarbeitung wurde bezüglich Minimaldichten, γ-1-Werten, γ-2-Werten und Maximaldichten jeweils auf Typ eingestellt.A commercially available high-chloride color paper (eg Kodak 2001 or Agfacolor type 9, with emulsions containing about 99.5 mol% Cl ⊖ and 0.5 mol% Br ⊖ ) was exposed imagewise , developed with the developer described below and in the usual way Bleached, fixed, washed and dried. Processing was set to type with respect to minimum densities, γ-1 values, γ-2 values and maximum densities.
Der wäßrige Entwickler enthielt pro Liter die folgenden Substanzen:
sowie Tenside, optische Aufheller, Stabilisatoren und Kalkschutzmittel in üblicher Menge
und ist auf pH 11,6 eingestellt.The aqueous developer contained the following substances per liter:
as well as surfactants, optical brighteners, stabilizers and anti-limescale in usual quantities
and is adjusted to pH 11.6.
Entwicklungszeit: 15 Sekunden/38°C.Development time: 15 seconds / 38 ° C.
Beispiel 1 wird mit einem Entwickler folgender Zusammensetzung wiederholt:
Sowie Tenside, optische Aufheller, Stabilisatoren und Kalkschutzmittel in üblicher Menge und ist mit KOH auf pH 10,1 eingestellt.Example 1 is repeated with a developer of the following composition:
As well as surfactants, optical brighteners, stabilizers and anti-limescale in the usual amount and is adjusted to pH 10.1 with KOH.
Entwicklungszeit 45 Sekunden/35°C.Development time 45 seconds / 35 ° C.
Beispiel 1 wird wiederholt, wobei auf den Einsatz von Benzylalkohol und Diethylenglykol verzichtet wird.Example 1 is repeated, the use of benzyl alcohol and diethylene glycol being dispensed with.
Entwicklungszeit 15 Sekunden/38°C.Development time 15 seconds / 38 ° C.
Es wurden folgende Maximaldichten erhalten:
Claims (7)
- A colour photographic developer solution which contains - per litre ready-to-use solution -a) 4 to 15 g of a developer corresponding to the formula
b) 0 to 2.0 g of a developer corresponding to the formula
c) 8 to 35 g PO₄⁻³ ionsd) at least 0.2 g antioxidante) 0.5 to 5.0 g KClf) 0 to 0.5 g KBrand other typical constituents and which is adjusted to a pH value of 10.4 to 12.9. - A colour photographic developer solution as claimed in claim 1, the ratio by weight of a:b being greater than 4:1.
- A colour photographic developer solution as claimed in claim 1, characterized in that it does not contain the developer b).
- A process for developing an exposed colour photographic material of which the photosensitive emulsion layers contain silver halide crystals containing at least 80 mol-% chloride, characterized in that the developer solution claimed in claim 1 is used.
- A developing process as claimed in claim 5, characterized in that development is complete in at most 40 seconds.
- A developing process as claimed in claim 5, characterized in that development is complete in at most 20 seconds.
- A developing process as claimed in claim 5, characterized in that the silver halide crystals contain at least 95 mol-% chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3805699 | 1988-02-24 | ||
| DE3805699A DE3805699A1 (en) | 1988-02-24 | 1988-02-24 | PHOTOGRAPHIC COLOR DEVELOPER SOLUTION AND METHOD FOR DEVELOPING A COLOR PHOTOGRAPHIC MATERIAL |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0330035A2 EP0330035A2 (en) | 1989-08-30 |
| EP0330035A3 EP0330035A3 (en) | 1989-12-06 |
| EP0330035B1 true EP0330035B1 (en) | 1993-04-14 |
Family
ID=6348015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89102423A Expired - Lifetime EP0330035B1 (en) | 1988-02-24 | 1989-02-13 | Colour-photographic developer solution, and process for developing a colour-photographic material |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0330035B1 (en) |
| JP (1) | JPH025048A (en) |
| DE (2) | DE3805699A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8804606D0 (en) * | 1988-02-26 | 1988-03-30 | Kodak Ltd | Method & apparatus for processing photographic colour materials |
| JPH087418B2 (en) * | 1988-10-03 | 1996-01-29 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JPH0820718B2 (en) * | 1988-10-03 | 1996-03-04 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JP2949879B2 (en) * | 1991-02-20 | 1999-09-20 | コニカ株式会社 | Processing method of silver halide color photographic light-sensitive material |
| DE4114481A1 (en) * | 1991-05-03 | 1992-11-05 | Agfa Gevaert Ag | ENVIRONMENTALLY IMPROVED DEVELOPMENT PROCESS FOR PHOTO MATERIALS AND SUITABLE DEVELOPER SOLUTION |
| US7172854B2 (en) | 2003-11-10 | 2007-02-06 | Konica Minolta Photo Imaging, Inc. | Photographic color developer solution and processing method by use thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5895345A (en) * | 1981-12-01 | 1983-06-06 | Konishiroku Photo Ind Co Ltd | Formation of dye image |
| FR2554935A1 (en) * | 1983-11-15 | 1985-05-17 | Kis France Sa | COMPOSITION TO REVEAL COLOR PHOTOGRAPHS |
| CA1314424C (en) * | 1986-01-24 | 1993-03-16 | Sheridan E. Vincent | Photographic color developing compositions which are especially useful with high chloride photographic elements |
-
1988
- 1988-02-24 DE DE3805699A patent/DE3805699A1/en not_active Withdrawn
-
1989
- 1989-02-13 DE DE8989102423T patent/DE58904034D1/en not_active Expired - Fee Related
- 1989-02-13 EP EP89102423A patent/EP0330035B1/en not_active Expired - Lifetime
- 1989-02-22 JP JP1040461A patent/JPH025048A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0330035A3 (en) | 1989-12-06 |
| DE58904034D1 (en) | 1993-05-19 |
| DE3805699A1 (en) | 1989-09-07 |
| JPH025048A (en) | 1990-01-09 |
| EP0330035A2 (en) | 1989-08-30 |
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