JPH06242559A - Processing method of halogenated silver photograph material - Google Patents

Abstract

PURPOSE: To facilitate and ensure the complete removal of bromide ion by continuously removing substantially all of the bromide ions from a developing soln. and treating this developing soln. by using a means for holding the developing soln. which does not substantially contain bromide ion during this operation. CONSTITUTION: Substantially all of the bromide ions are continuously removed from the developing soln. and the developing soln. is treated by using the means for holding the developing soln. which does not substantially contain the bromide ions during the operation of this method. Generally, the developing soln. is continuously taken out from a developing tank into a processing loop and the bromide ions formed during the development are removed from the developing soln. The treated soln. is thereafter returned to the tank. While the removal of the bromide ions is executable by the arbitrary adequate means including an ion exchange, elctrodialysis, dialysis and reverse osmosis, the removal by the ion exchange is more preferable.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to a method of processing silver halide photographic materials such as photographic film and photographic paper. In particular, it relates to a method of processing a color negative film. Color negative films are processed using an industry standard processing method called C-41. Most C-4
One method is based on a method in which a replenisher is added to a developer and then an excess developer is overflowed to be removed. In this way the developing solution becomes stable, under which conditions the chemicals consumed during processing are replenished to maintain the working concentration and are brought into the developing solution from seasoning products, eg films. Keep bromide and iodide ions and antifoggant fragments from the DIR coupler at acceptable levels.
The latest C-41 method is 500 ~ per 1 m ² of processed film.
Perform at a developer replenishment rate of 1800 mL. Color paper and black and white photographic materials can also be processed by the replenishment system.

Conventional developers contain bromide ions and additional bromide ions are introduced into the developing solution by reduction of silver bromide during the development process. Bromide ion levels in color negative developers have a significant effect on image development rate. All other things being equal, lower levels lead to faster development rates. CD4 (4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate) produced during development of color negative film
It is desirable to reduce runoff. One way to accomplish this is to reduce the CD4 concentration in the developer and supplement it elsewhere in the overall scheme to restore the required development activity. Low bromide ion levels in the developing solution may help in this regard. There is a minimum bromide ion level that can be reached by conventional replenishment methods, and it is necessary to remove bromide ion by artificial means to reduce the level beyond this point. However, this makes it difficult to accurately adjust the level of bromide ions due to different film types and different aging methods and different removal methods.

[0003]

According to the present invention there is provided a method of processing a silver halide photographic material wherein substantially all bromide ions are continuously removed from the developing solution and during the operation of said method. A method is provided which comprises treating the developing solution with a means for retaining the developing solution substantially free of bromide ions.

Preferably, the bromide ion is substantially absent from the developer or developer replenisher used in the method of the present invention, and the bromide ion produced by the reduction of silver bromide during development is the bromide ion developed. It is substantially completely removed as it is produced so that it does not effectively participate in the reaction. The method of the present invention is applicable to the processing of any silver halide photographic material such as color negative film, color photographic paper and black and white materials. The method of the present invention is very suitable for the processing of color negative films, especially by the C-41 process. Examples of color negative films that can be processed include commercially available films and Resear.
ch Disclosure Item 17643, December 1978, pages 22-31, Ke
nnethMason Publications of Emsworth, Hampshire, Un
The films listed in the ited Kingdom issue are listed.

Generally, the developing solution is continuously withdrawn from the developing tank into the processing loop to remove bromide ions formed during development from the developing solution and the processed solution is then returned to the tank. Removal of bromide ions can be accomplished by any suitable means including ion exchange, electrodialysis, dialysis and reverse osmosis, with ion exchange removal being preferred. Whatever the removal means, it is preferable to have sufficient performance to remove substantially all latent bromide. The method of the present invention can be used in the low effluent replenishment system for color negative developers described and claimed in our PCT / EP90 / 01854.

When ion exchange is used as the removal method,
The ion exchange resin is preferably anionic (for exchanging anions). A preferred type of anionic resin is a polystyrene matrix, for example 3% to 5%.
The base material is one crosslinked with divinylbenzene. This strong basicity results from the quaternary ammonium groups. Examples of suitable anionic exchange resins are: IRA 400 Rohm and Haas Dowex 1-X8 Dow Chemical, and Duolite A113 Diamond Shamrock Ion exchange resins are preferably arranged in cartridges and passed through the cartridge. Pump the contents of the developer tank continuously or as needed. As is well known, ion exchange resins are either discarded or regenerated when exhausted.

A small amount of replenisher added to the developing solution has a pH of 1
It may be in the form of a solution of 0.09 and has the following composition: potassium carbonate 37.5 g / L sodium bromide 0.45 g / L Anti-cal 6.5 g / L sodium sulfite 4.85 g / L hydroxyl Amine sulfate salt 3.4 g / L CD4 5.9 g / L Here, Anti-cal is a pentasodium salt of diethylenetriaminepentaacetic acid.

The method of the present invention allows the use of developing solutions containing lower levels of color developer as compared to the solutions used in standard C-41 processing. A suitable level is 10% to 100% of the color developer used in standard processing, preferably standard C
It is 25% to 50% of the color developing agent used for the -41 process.

The method of the present invention has many advantages, some of which are listed below: The present invention allows the use of low levels of CD4 in the developing solution, and the CD4 level in the effluent also decreases proportionally. 2. Complete removal of bromide ions can be easily and reliably ensured by any method. 3. There is no need for control as the bromide ion level is effectively zero. The same is true for iodide ion levels. 4. Image structure advantages are obtained with a zero bromide developer. 5. The development time can be shortened because a zero bromide developer is used. 6. High developability allows for reduced silver levels, reduced coupler levels and / or the use of small grain size emulsions.

The present invention will be described with reference to the accompanying drawings. FIG. 1 shows a developing tank to which an activator solution and a solid-phase CD4 color developing agent are added. Water is used to replenish that level because there is a developer solution that is shipped with the film and there is a volume loss due to evaporation. An ion exchange cartridge is attached to the tank as shown and a developer is circulated through the cartridge, preferably only when there is a processed film, for example using a pump.

The ion exchange resin used is preferably anionic as described above and is preferably placed in a cartridge as described above. The replenisher may be a solution or a solid phase and can be added in one of the above methods.

The present invention is further illustrated by the following example: Example 1 In this example, bromide ion is added to C-4 as shown in FIG.
1 Removed from developer. When the solution after the ion exchange treatment was analyzed, the results shown in FIG. 2 were obtained. FIG. 2 shows a plot of the concentrations of (1) sodium bromide, (2) sodium sulfite, (3) sodium sulfate, and (4) CD4 against the number of bed volume. The volume of one bed was equal to the volume of resin beads in the column and was about 50 ml. The resin used is IRA 400 (Rohm and
Haas). It was regenerated with 10 bed volumes of potassium carbonate solution (5%) and then washed with 5 bed volumes of water. In this way, the resin and the column are prepared for use, then the developer from the developer tank is passed through the column and a sample is taken before returning to the developer tank, and the color developing agent (CD4), sodium bromide, sodium sulfite and sulfuric acid are collected. Analyzed for sodium. The initial concentrations of these components are shown in Figure 2 at zero bed volume. These represent untreated C-41 developers. From FIG. 2, as the volume of C-41 developer that passes through the resin increases, the bromide ion concentration remains very close to zero. Thus, ion exchange can be used to remove all bromide ions from the developer, keeping the developer substantially free of bromide ions during its operation. Bromide ions generated by the development of silver halide emulsions are removed by this method. If the developer used is replenished, the developer replenisher will also be substantially free of bromide ions.

Example 2 High-speed magenta emulsion and magenta coupler (Iso 4
00-speed), a series of single layer coatings containing standard C-
41 developer (a) and inventive developer (b) containing zero bromide ions and half-level CD4 of C-41.
Processed in (d). The composition of the developer is as follows.

Standard 4.5 g / liter CD4 developer, 1.3 g / L NaBr Inventive 2.25 g / liter CD4 developer, 0.
0 g / L NaBr The developer of the present invention was used for processing at three types of developing times (0.5 minutes (b), 0.75 minutes (c) and 1.0 minutes (d)). The standard processing development time was 2.5 minutes. In all cases the development temperature was 37.8 ° C.

The results are shown in FIG. In FIG. 3, the standard (a) is shown by a dotted line, and the results (b) to (d) of the present invention are shown by a solid line. FIG. 3 shows that for the inventive developer a development time of about 45 seconds is approximately equal to standard C-41 processing.
Thus, for zero bromide treatment, similar sensitometry can be obtained with low CD4 levels in a much shorter time than the standard 2.5 minutes normally required.

Example 3 Several single layer coatings were prepared with a standard C-41 developer and some inventive developers containing a conventional quarter level of color developing agent and having a zero bromide ion concentration. Processed. The standard developer has a CD-4 concentration of 4.5 g / L, while the developer of the present invention has a CD-4 concentration of 1.125.
It was g / L. In all cases development was done at 37.8 °. The results are shown in Fig. 4. FIG. 4 is a graph of dye density versus relative exposure. In FIG. 4, the curve a) is 1.
For standard C-41 developer containing 3 g / L sodium bromide; curve b) is 1.125 g / L
Of CD-4 and zero bromide ion of the invention; curve c) is 1.125 g / L.
Of CD-4, zero bromide ion and 0.002 g / L of 5-methylbenzotriazole of the present invention. The development times were a) 2.5 minutes and b) and c) were 2.08 minutes, respectively.

From FIG. 4 it can be seen that the developer of curve c) is well compatible with the C-41 developer (curve a).

Additional Embodiments 1. The method of claim 1 wherein the silver halide photographic material is a color negative film. 2. Item 2. The method according to Item 1, wherein the color negative film is processed by C-41 processing. 3. Method according to any one of the preceding clauses, characterized in that the bromide ion removal means is ion exchange, electrodialysis, dialysis and / or reverse osmosis. 4. Item 4. The method according to Item 3, wherein the bromide ion removing means is an ion exchange method. 5. Item 5. The method according to Item 4, wherein an anion exchange resin (for anion exchange) is used. 6. Item 6. The method according to Item 5, wherein the anion exchange resin is based on a polystyrene matrix crosslinked with 3% to 5% of divinylbenzene. 7. Item 3. The method according to Item 2, wherein the developing solution contains a low level of the color developing agent as compared with the level present in the standard C-41 processing method. 8. Item 8. The method according to Item 7, wherein the reduction level of the color-developing agent is in the range of 25% to 50% of the developer present in the standard C-41 processing method.

[Brief description of drawings]

FIG. 1 is a diagram of a developer tank having an inlet and an outlet.

FIG. 2 is a graph of concentration (g / L) with respect to the number of bed volumes, showing that bromide was removed by ion exchange in Examples.

FIG. 3 is a graph of dye density versus logarithmic relative exposure showing the results of Example 2.

FIG. 4 is a graph of dye density vs. relative exposure logarithm showing the results of Example 3.

 ─────────────────────────────────────────────────── ───Continued from the front page (72) Inventor Paul Mary Maggie Finchley N, England 12 7 Ejay, Holden Road 49, Tudor Lodge 2 (72) Inventor Nigel Richard Wildman Middlesex H2, England 6 Eldy North Harlow, Bearwood Road 47

Claims (1)

[Claims] 1. A method of processing a silver halide photographic material, wherein substantially all bromide ions are continuously removed from the developing solution and is substantially bromide ion-free during operation of the method. Treating the developing solution with a means for retaining the method.