JP2944204B2 - Low effluent replenishment system for color negative developer - Google Patents

Description

The present invention relates to a method for processing photographic silver halide color materials, and more particularly to replenishment of color developers for color negative films.

Color negative films are processed in an industry standard process designated C-41. Most C-41 systems are implemented on the basis that replenisher is added to the developer and excess developer is removed by overflow. In this way, the developer replenishes the chemicals depleted during processing to maintain the working concentration and seasoning products, such as bromide and iodide, entering the developer from the film. Achieve stable conditions that maintain ions and antifoggant fragments from the DIR coupler at acceptable levels. This C-41 system is 500-180
It is carried out at a developer replenishment rate of 0 ml / m ² (film to be processed).

Color paper is also processed in a replenishment system, which is based on silver bromide emulsions which contain little bromide or iodide. This enables a replenishment system that can replenish the developer with a more concentrated replenisher that does not cause overflow and little or no need to remove bromide and iodide. Such a system is described in European Patent Specification 0,17.
No. 3,203. Such concentrated replenishment sources can result in zero-overflow from the developer tank and plate-out of the seasoning product which is less detrimental to sensitometry. This involves reconditioning the sensitized coating to meet target sensitometry in the presence of relatively high levels of seasoning products. This is the main operation,
This is best avoided if relatively simple options are available as described in our invention. Even if the seasoning product is plated out constantly, there is another special case where the developing solution used already contains relatively synergistic inhibitors, so that they do not affect sensitometry. For example, if a sensitized material with a high silver chloride content was processed in a developer containing soluble sodium bromide (0.7 g /), the increase in chloride levels during use would be Will have little effect. This is similar to the method used in EP-A-0,173,203 for color paper developers. This is to some extent an artificial case, since high silver chloride coatings are best treated with much lower levels of bromide (about 20 mg /) for rapid processing. When seasoning products such as chlorides are plated out in the RA-4 method, sensitometry and processing rates are adversely affected.

Although it is known to use ion exchange resins to remove seasoning products from developers, such resins have never been used in systems having low replenishment rates as achieved by the present invention. Was. For example, "Developer Recycling-A New Generation" Meckl,
Journal of Imaging Technology, 13 , (1987), Issue 3,
Pages 85-89 describe a system in which the overflow from the color developer tank is transferred to a retention tank and then passed through an ion exchange resin to remove bromide ions. The solution thus treated is then transferred to a mixing tank, where
The replenisher components are added, and the newly formed solution is then transferred to a ready-to-use replenisher tank. The replenishment rate for the paper process is said to be 325 ml / m ² .

Japanese Patent Application No. 62-019842 describes a method for reducing the bromide ion concentration in a color developer for silver bromide color paper by applying an ion exchange resin to the back surface of the color paper. In turn, it absorbs bromide ions as it passes through the developer. This method is clearly undesirable because special and relatively expensive photographic paper must be used, which makes the paper more expensive and the method less universal. This method wastes an otherwise renewable ion exchange resin. Coating of such a material on a film (with a transparent substrate) appears to produce unacceptably degraded images.

Although relatively low replenishment rates have been proposed for developers for color paper, practical systems which achieve rates similar to the C-41 process have not been previously proposed.

According to the present invention, the color developer in the developer tank is
(I) flow through an in-line ion exchange resin system to remove developer seasoning products and return directly from the in-line ion exchange resin system to the developer tank; and (ii) a sufficiently small volume that does not substantially cause overflow. And a method for processing a photographic silver halide color negative film, which is replenished with a replenisher component.

In the present invention, the combination of extremely low replenishment rates and the use of in-line ion exchange resins is synergistic in that less replenisher is required so that the removal of seasoning products by the ion exchange resins is effective. Or have a synergistic effect. Thus, theoretically minimal chemistry addition can be used while still retaining the standard tank chemistry. This result indicates that the ion exchange resin is not only bromide ion,
Undesired levels of other seasoning products, for example,
It shows that the antifoggant released from the DIR coupler in the processed film is also removed.

Unlike the method described by Meckl mentioned earlier, in this method there is no dwell tank for developer overflow and also a mixing tank for the addition of make-up chemicals to the developer overflow to be processed There is no. Both features of the present invention result in a film process having exceptionally low replenishment rates.

The present invention can be engineered to remove halide ions at the rate at which they occur. Further, the antifoggant fragmet is similarly removed. Thus, the present invention allows for a theoretical minimum chemical charge to the C-41 developer in a single developer tank arrangement using both in-line ion exchange resin and concentrated replenisher addition.

One of the main advantages of the present invention is the significant reduction in effluents caused by its use. Kodak VR in C-41
400 Normally developer replenishment rate for the film is 1675ml / m ² with respect to 35 mm, which is the new C-41 LORR
The (low replenishment rate) method has now been reduced to about 841 ml / m ² . The present invention increases this speed by 5 for 35 mm film.
It is reduced to 6.0~117ml / m ^2. Since the added volume is very greatly reduced, the displaced volume is likewise reduced. In fact, no overflow occurs and only the effluent comes from the volume of developer carried over to the bleach tank. This is about 18.7~56.0ml / m ² with respect to 35mm film.
Chemical effluent is the same concentration as in methods commonly refilled, its volume was reduced to about 841ml / m ² ~ about 56.0 mL / m ^2.

Another advantage of the present invention is that the required chemical input can be reduced by reducing the effluent, and a relatively large percentage of the chemical is used to produce the image. Based on CD4 (4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulphate), the chemical input is 70 times higher than this C-41 LORR replenisher.
%Few. This offers advantages in terms of the costs of the development and printing operations, and in terms of manufacturing costs.

Yet another advantage of the present invention is that the system can handle a wide range of application conditions. The color developing agent can be added separately from the other components, and since its level in the use tank does not depend on the level of antioxidant, it can withstand low usage conditions relatively easily. Since the bromide, CD4 and antioxidant levels can be controlled independently of each other, accurate tank chemistry can be maintained for all application conditions. This is not possible with conventional methods that include all of these components in the same replenisher. For these reasons, a process replenished with the system described in the present invention should have no process failure.

The system in the present invention is also ideally suited to be controlled by a replenisher management unit that could account for different film types and usage conditions and adjust the chemical input.

In the accompanying drawings: FIG. 1 shows a developer tank having an inlet and an outlet,
FIG. 2 is a control chart relating to the method described in the example.

FIG. 1 shows a developer tank to which an activator solution and a solid CD4 color developing agent are added. If there is transport of the developer over the film and the volume may be reduced by evaporation, the reduction in height is compensated for by water. An ion exchange cartridge is mounted in the tank shown, and the developer is preferably circulated through it only when there is a film to be processed, for example by a pump.

The ion exchange resin can be of the anionic type (for anion exchange) or amphoteric type or a mixture thereof. Preferred types of anionic resins are crosslinked,
For example, based on a polystyrene matrix crosslinked with 3% to 5% divinylbenzene. Its strong basicity is derived from quaternary ammonium groups. Suitable anion exchange resins are the following: IRA 400 Rohm and Haas Dowex 1-x8 Dow Chemical and Duolite A113 Diamond Shamrock ion exchange resins are preferably through which the contents of the color developer tank are passed. Placed in cartridges that are pumped continuously or as needed. that is,
It will be appreciated that in the event of fatigue, it may be discarded or regenerated.

The replenisher may be in the form of a solution or a solid. However, the exact form must be such that under normal conditions of use, substantially no overflow will occur at normal replenishment rates.

In one embodiment of the invention, the replenisher component is added as an activator solution and a solution of the color developing agent; in another embodiment, the color developer is added as a solid.
In yet another embodiment, the replenisher component may be added as three separate solutions having the following composition: Part A 470 g of potassium carbonate / 11 g of potassium hydroxide / 106 g of diethylenetriaminepentaacetic acid pentasodium salt / 43 g of sodium pyrosulfite The approximate replenishment rates for the above three-part replenisher would be as follows: Part A 16.8-49.5 ml / m ² film Part B 1.87 / Part B Hydroxylamine sulfate 272 g / Part C Sodium pyrosulfite 16.5 g / CD4 472 g / 6.56.5 ml / m ² film Part C 3.5-6.5 ml / m ² film The present invention can also be used to carefully control tank chemistry levels to values other than those in normal use tank chemistry. This is desirable for non-standard sensitometry, eg, for special uses where relatively high sensitivity is required.

Films to be processed are commercially available or
Research Disclosure Item 17643 December 1978,22-3
Page 1 (Kenneth Mason Publications of Emsworth, Hampsh
ire, United Kingdom publication) can be any camera speed color negative film.

The following examples are included for a better understanding of the invention. The word 'Kodak' is a trademark.

EXAMPLES A seasoning test was performed for several months to determine the basic procedure and the chemical addition and ion exchange rates.
The three components of the replenishment system are: (i) activator (ii) addition of solid or concentrated CD4 (iii) in-line ion exchange for the developer tank (i) activator which has the composition shown in Table 1 Have.

Table 1 Composition of film activator K ₂ SO ₃ (anhydrous) 24.0 g / hydroxylamine sulfate 13.4 g / diethylenetriaminepentaacetic acid pentasodium salt (41% solution) 6.5 ml / K ₂ CO ₃ 37.5 g / pH 11.6 This solution Is a "bag-in-the-box collapsible" (collapsip) often used for closed containers, i.e. wines and other liquids which are susceptible to decomposition by the atmosphere.
ble) kept in plastic containers. A regular replenisher tank can be tolerated for a short time (day), but for a relatively long time (week), the absorption of carbon dioxide from the air lowers the pH of the activator, thereby reducing the developer tank.
It was found that the pH could not be maintained. These problems have been prevented by the use of collapsible containers. The activator was added once a week at a rate of 37.4-117 ml / m ² (35 mm film to be processed), depending on the average throughput of the film. The total average film throughput was about 62 linear meters / day at VR400 exposed to average customer concentration.

(Ii) Addition of solid CD4 The addition rate of solid CD4 was calculated from a computer model of the replenishment system. In fact, this is
Slight reduction in CD4 was taken into account. The rate of addition is as follows: VR400 1.4-1.9 g / m ² VR100 0.65-0.94 g / m ² Solid CD4 was added at said rate in proportion to the amount of film processed. In practice, this was done by removing some of the developer, adding a weighed amount of solid CD4 to it, and returning it to the developer tank.

The seasoning test described above was performed with the addition of solid CD4, but CD4 concentrate can be used as well with similar results.

(Iii) In-line ion exchange IRA400, a strong anionic resin available from Rohm and Haas, was used. Ion exchange rate with respect VR400 film was 196 ml / m ^2.
The resin was regenerated with 5% potassium carbonate, washed with deionized water, and then connected in series with the developer tank. About 40
0 g of resin was included in a simple flow-through cell with a capacity of about 500 ml. The flow through the resin cell is controlled by a conventional refill pump that is switched on as the film passes through the processor, along with a refill pump for the activator. Solution flow from the developer tank through the cartridge occurs only as the film passes through the processor. The processed solution is then returned directly to the developer tank. This ensures a controlled removal rate of bromide ions and other seasoning products. The film passed through the processor at about 62 m / day for 35 mm film. Resin cells of the dimensions described here take about one week or 35
mm With VR400 seasoning film, it lasts between 300 and 385 linear m.

An analytical sample was taken from the developer tank to monitor the level of the chemical reaction and to evaluate whether the chemical reaction was controlled. The method was performed on sensitometric control strips throughout the three month seasoning test.
A plot of the control parameters is shown in FIG. It can be seen that the method controls during the entire test, even if this test is also a practice to learn to determine the correct addition and ion exchange rates.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/44 G03C 5/31

Claims (7)

(57) [Claims] 1. The method according to claim 1, wherein the color developing solution in the developing solution tank is:
Flow through the in-line ion exchange resin system to remove developer seasoning products and return directly from the in-line ion exchange resin system to the developer tank; and (ii) a sufficiently small replenisher that does not substantially cause overflow. A method of processing a photographic silver halide color negative film, which is supplemented with components. 2. The method of claim 1 wherein said replenisher component is added as one or more solid or concentrated solutions. 3. The processing method according to claim 1, wherein the ion exchange resin is of an anionic type. 4. The processing method according to claim 1, wherein the solution from the developing tank is pumped through a container containing an ion exchange resin and is returned directly to the developing solution tank. . 5. The processing method according to claim 1, wherein the developer is treated with the ion exchange resin only while the film is being processed. 6. The processing method according to claim 1, wherein the developer is treated with an ion exchange resin when necessary. 7. The treatment method according to claim 1, wherein said ion exchange resin is based on a crosslinked polystyrene matrix and contains a quaternary ammonium group.