Method for minimising the aerial oxidation of photographic developers

Abstract: The invention concerns a method for decreasing the oxygen content of the atmosphere above photographic processing baths. The method consists of using a solid electrolyte which is a compound of bismuth, vanadium or another transition metal. The oxidation in air is thus minimised and the life of the bath is extended.

Description: The present invention concerns a method for improving the stability of photographic baths especially developers with respect to aerial oxidation. The efficacy of the development and of the developer depend on many factors, including the degree to which the developer has been used, or "seasoned". As it is used, the developer gains substances coming from the photographic film being processed, and is oxidized. Oxidation is the cumulative effect of the development (reduction of the silver halides) and contact with the air. The oxidation of the developer, that is, oxidation of the reducing substances which it contains, in particular the developing agents, impairs its efficacy and consequently requires the developer to be regenerated (or renewed) at regular intervals in order to maintain the sensitometric characteristics of the photographic films being processed and to prevent the formation of stain. In order to minimize the effects of aerial oxidation, which occurs even when the developer is not in use, large quantities of sulphite or bisulphite are usually incorporated in the developer (up to 100 g/l or more). Even with sulphite added, developers suffer the effects of aerial oxidation. Also, this oxidation results in the transformation of the sulphite into sulphate, which must be then eliminated to allow recycling the developer, or discharging it to the drains. EP-A-269 066 discloses a method of minimising the aerial oxidation of a photographic developer by reducing the oxygen content in the vicinity of the free surface of the bath through the use of a cap containing a metal salt. The object of the present invention is a method of solving the aforementioned problem, that is, a method which makes it possible to minimise the aerial oxidation of a photographic developer by reducing the oxygen content in the vicinity of the free surface of the bath of photographic developer. The method of the invention is characterised in that it comprises a step in which the atmosphere in the vicinity of the free surface of a photographic bath is put in contact with a cell comprising electrodes and a solid electrolyte which is conductive to O 2- ions, and which, in the presence of an electric current and at a temperature, such that the electrodes and the electrolyte can dissociate the oxygen into O 2- ions. This method, as shown by the following examples, makes it possible to obtain, in the vicinity of the surface of the bath, an atmosphere which is starved of oxygen, that is, an atmosphere containing less than 5% oxygen and advantageously less than 3% oxygen, instead of the normal oxygen content in atmospheric air, which is 21% (% by volume). The term "vicinity" in the present specification, is intended to designate the atmosphere which may contribute to the aerial oxidation of the developer. It will be understood that the vicinity may depend on such parameters as the volume, the ventilation or the geometry of the room where the processing equipment is installed. As mentioned above, the solid electrolyte is a substance which conducts O 2- ions in the presence of an electric current. Substances of this type, associated with electrodes, can extract oxygen from air or from oxygen-containing gaseous mixtures. Such solid electrolytes are described in Abraham et al US Patent 5 227 257, as being derivatives of Bi 4 V 2 O 11 with a gamma phase in which at least one of the elements Bi or V is partially replaced by a substitution element so that the structure of the gamma phase and the equilibrium of the charges are maintained. These derivatives of Bi 4 V 2 O 11 therefore have in particular the following formula: (Bi 2-x M x O 2 ) (V 1-y M' y O z ) where : M represents one or more metals substituting Bi and having an oxidation number less than or equal to 3; M' represents one or more elements substituting V and is selected from the class consisting of alkali metals, alkaline earth metals, metals of groups IIIa to Va, metals of groups IIIb to Vb of the periodic table, or rare earth metals. The limiting values of x, y and z are functions of the nature of M and M', and x plus y is greater than zero. Metals can be Zn, Cu, Ni, Co, Fe, Mn, Cd, Sb, In, Al, Ti, Sn, Ru, Nb, Ta, Pb, Cr. According to one embodiment, the compound has one of the formulae Bi 2 O 2 (V 1-y (M' y O z ) or (Bi 2-x M x O z )VO z , where M, M', x, y, z have the aforementioned meaning. When x is not equal to 0, M preferably represents a rare earth. When y is not equal to 0, M' preferably represents an alkali metal, an alkaline earth metal or a transition metal, such as Zn, Cu, Ni, Co, Fe, Mn, Cd, Sb, In, Al, Ti, Sn, Ru, Nb, Ta, Pb or Cr. According to one embodiment, the solid electrolyte has the formula: Bi 2 V 1-y M' y O 5.5-1.5y where M' is a transition metal such as Cu, Zu or Co, and y is a number determined as a function of M' and the degree of oxidation of the metals. Preferably, y is between 0.05 and 0.5 and advantageously between 0.08 and 0.25. These substances are designated in the literature under the generic name Bimevox, or depending on the metal associated with bismuth, under the name Bicuvox, Bicovox, Biznvox, etc. Figure 1 depicts schematically a device for implementing the method of the invention. This device comprises a tank 10 containing a photographic developer 11. The free surface of this developer is in contact with atmospheric air. A cell 12 comprising the solid electrolyte is placed in the vicinity of the free surface; each face of the cell 12 is connected to electrodes 14a and 14b, themselves connected to a current source (16); a pipe (13) and a pump (not shown) permits evacuation of the oxygen extracted from the atmospheric air by the solid electrolyte. The cell is placed in a heating source 12b in order it to operate at the desired temperature. A pump 15 circulates the air to be treated. Figure 2 depicts another embodiment of the invention, comprising a tank 20 containing a developer 21, a cell 22 containing Bimevox, a circuit 23 for pumping air above the surface of the developer, with a pump 23a, an oxygen gauge 23b and a condenser 23c for cooling the gaseous fluid after it has passed through the cell 22, a pipe 24 for evacuating oxygen and a circuit 25 for the developer with a pump 25b. Figure 3 depicts a cell such as 22 in Figure 2, comprising a heating chamber 30 capable of producing temperatures of up to 700°C or more, a ceramic or alumina wall 31, a slug 32 consisting of Bimevox, with electrodes 34a and 34b in the form of metallic grids set in the body of the slug but visible on each face of the slug. The solid electrolyte exhibits O 2- conductivity when its temperature is of at least 250°C, advantageously between 250 and 700°C and more advantageously between 300 and 600°C, and when it has a voltage across it. A source producing a current density of 100 to 1500 mA/cm 2 at a voltage of 1 to 30 V and advantageously 2 to 15 V is used. Under these conditions, a solid electrolyte slug enables oxygen to be extracted from the atmospheric air above the surface of a developer, at a rate of between 100 and 1000 ml/hour with a slug with a surface area of approximately 2 cm 2 . The oxygen content of the atmosphere in the vicinity of the free surface of the developer can thus be reduced by a factor of 10 until the initial content (21% by volume) is reduced to less than 2% by volume. The risk of aerial oxidation of the developer is therefore reduced accordingly. The cell containing the solid electrolyte is placed with respect to the surface of the bath so as to be able to reduce the oxygen content of the atmosphere likely to be in contact with this surface. The cell can be placed at a greater or lesser distance from the surface depending on whether a suction device is used which forces the ambient atmosphere to circulate throughout the cell. Because the operating temperature of the solid electrolyte is around 250 to 500°C, it is preferred that the cell not be in the immediate vicinity of the surface of the bath. According to another embodiment, the polarity of the electrodes of the device depicted in Figure 1 is reversed so that, instead of reducing the oxygen content of the atmosphere, it is increased so as to oxidise the oxidisable substances contained in the photographic processing bath. It is possible, after a certain period of use, to destroy certain constituents of the bath before discharging it to the drains. Preparation of the bimevox material The procedure is in accordance with the operating method described in Abraham US patent 5,227,257, that is by direct synthesis in solid phase, from Bi 2 O 3 (99% Aldrich), V 2 O 5 (99.6% Aldrich) and CuO (99% Aldrich), or another oxide such as CoO or ZnO, depending on circumstances. The constituents of this mixture are crushed in stoichiometric proportions. Bi 2 O 3 is first heated to 600°C for 6 hours until all traces of carbonate are eliminated. The crushed mixture is then heated for 12 hours at 700°C and is left to cool at a rate of 20°C/hour. The structure and formula (Bi 2 V 0.9 Cu 0.1 O 5.35 ) are checked by X-ray diffraction and pellets of this material are produced by compacting. EXAMPLE 1A 600 ml of a colour developing solution for Kodak Ektachrome E-6® processing was introduced into a closed tank. The developer was maintained at a temperature of 50°C and stirred vigorously in order to simulate maximum aerial oxidation. By means of a loop and a pump, the conditions of circulation of the developer in the tank, at a rate of 50 ml/minute, were also reproduced. The volume of air in the tank above the surface of the developer was approximately 1000 ml. In accordance with the arrangement in the diagram in Figure 1, a cell comprising a solid electrolyte of formula Bi 2 V 1-y Cu y O 0.5-1.5y with y = 0.1 prepared in accordance with the operating method described above was placed above the surface of the developer. The Bicuvox material was in the form of compacted cylindrical pellets, 16 mm in diameter and 5 mm thick with, two conductive metallic grids inserted in each pellet. The surfaces of the pellet were polished with an abrasive, so as to leave the mesh of the metallic grille showing on each face of the pellet. The assembly was placed in a refractory chamber provided with heating, and was connected to the electrical circuit (current source 16 in Figure 1). The cell was raised to a temperature of 500°C and had a voltage (2 V, 200 mA) across it, enabling an oxygen concentration of approximately 2% to be attained. After 18 hours, the developing agent and sulphite contents of the developer were measured, and its coloration was examined. The results are set out in Table I. EXAMPLE 1B (comparative) The operating method of Example 1A was repeated, except that a cell was not used and the developer was therefore in contact with atmospheric air. After 18 hours, a strong brown colouring, and a very marked reduction in the concentration of developing agent and sulphite (see Table I) were noted. Example Developing agent g/l Sulphite g/l Coloration 1A 5.06 (-4%) 2.0 (-15%) clear 1B (comparative) 1.94 (-70%) 0.615 (-59%) brown Example 2A The operating method of Example 1A was repeated, except that the E6 colour developer was replaced with ascorbic acid black and white developer whose formula was as follows, and was given in Research Disclosure, August 1993, publication No 35249, page 543, "High Potassium Developing Solutions": K 2 CO 3 100 g/l K 2 SO 3 50 g/l Benzotriazole 0.2 g/l HMMP 2.5 g/l KBr 4 g/l Ascorbic acid 32 g/l Anti-calcium agent 4.3 g/l pH 10.2 at 20°C The results obtained are set out in Table II. EXAMPLE 2B (comparative) The operating method of Example 2A was repeated, except that the cell with solid electrolyte was omitted. The results obtained are set out in Table II. Example Developing agent g/l Sulphite g/l Coloration 2A 37.9 (-0%) 8.9 (-4%) clear 2B (comparative) 29.8 (-20%) 6.2 (-25%) brown It can be seen that the reference developer, in the absence of the cell, exhibits a significant reduction in the concentrations of developing agent and sulphite.

Claims: Method of treating a photographic bath comprising a step in which the atmosphere in the vicinity of the free surface of the photographic bath is put in contact with a cell comprising electrodes and a solid electrolyte, characterised in that the solid electrolyte is a substance which is conductive to O 2- ions in the presence of an electric current and at a temperature which are such that the electrodes and the electrolyte can dissociate the oxygen into O 2- ions. Method according to Claim 1, characterised in that the solid electrolyte is a derivative of Bi 4 V 2 O 11 with a gamma phase in which at least one of the elements Bi or V is at least partly replaced by another element so that the structure of the gamma phase of Bi 4 V 2 O 11 is maintained as well as the equilibrium of the charges. Method according to Claim 1, characterised in that the solid electrolyte has the formula (Bi 2-x M x O 2 ) (V 1-y M' y O z ) where M represents one or more metals substituting Bi and having an oxidation number less than or equal to 3; M' represents one of more elements substituting V and selected from the class consisting of an alkali metal, an alkaline earth, a metal of groups IIIa to Va, a metal of groups IIIb to Vb of the periodic table, or a transition metal ; the limiting values of x, y, z being functions of the nature of M and M', and x plus y is greater than zero. Method according to Claim 1, characterised in that the solid electrolyte has the formula Bi 2 V 1-y M' y O 5.5-1.5y where M' represents a transition metal and y is determined as a function of M' and the degree of oxidation of the metals. Method according to Claim 4, characterised in that y is a number between 0.05 and 0.5. Method according to Claim 4, characterised in that M' is copper, cobalt or zinc. Method according to one of Claims 1 to 6, characterised in that the photographic bath is a developer. Method according to Claim 7, characterised in that the developer is a black and white developer comprising a developing agent of the ascorbic acid type, or of the hydroquinone type. Method according to Claim 7, characterised in that the developer is a colour developer comprising a developing agent of the aromatic primary amine type. Method according to Claim 7, characterised in that the developer is a developer containing an inorganic developing agent. Method according to one of Claims 1 to 10, characterised in that the atmosphere in the vicinity of the free surface of the photographic bath is put in contact with the solid electrolyte, at a temperature of between 250 and 700°C. Method according to one of Claims 1 to 11, characterised in that a voltage of between 1 and 30 V and a current density of between 100 and 1500 mA/cm 2 are applied to the solid electrolyte.

Inventors: BOIVIN JEAN-CLAUDE FREDDY ROBE, MAIRESSE GAETAN JEAN-MARIE, MARTIN DIDIER JEAN, NOWOGROCKI GUY JEAN, PONCELET OLIVIER JEAN CHRISTIA, BOIVIN, JEAN-CLAUDE FREDDY ROBERT, MAIRESSE, GAETAN JEAN-MARIE, MARTIN, DIDIER, JEAN, NOWOGROCKI, GUY JEAN, PONCELET, OLIVIER JEAN CHRISTIAN
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1998
Main classification: G03C5
IPC codes: G03C5, G03D13, B01D53, C25B1, G03D3, G03C7