JPS59173758A - Discriminating method of concentration of bromine ion - Google Patents

Abstract

PURPOSE:To maintain adequately the developing activity of developing soln. for continuous processing by making Br<->-contg. silver halide developing soln. acidic then adding water soluble silver salt thereto to prepare an adjusting soln., observing the developability of such soln. for a test piece having a silver halide- contg. layer and discriminating surely the Br<-> concn. in the developing soln. CONSTITUTION:A specified amt. of Br<->-contg. developing soln. is adjusted to 3- 4pH with acetic acid, etc. and thereafter the soluble silver halide (most preferably AgNO3) equivalent to the Br<-> at least two of the upper and lower limit of the permissible concn. of Br<-> and if necessary several points at the intermediate thereof is added thereto to prepare an adjusting soln. The developability of a test piece having a silver halide contg. layer by each adjusting soln. is observed. The silver halide layer of the test piece is developed and blackened by the adjusting soln. in which Ag<+> exists in Br<-> at the equiv. or above, but said layer is not developed at the equiv. or below. Whether the concn. of Br<-> in the developing soln. is within a permissible concn. or not and about how much said concn. exists are measurable at the quantitative determination accuracy of 2X 10<-4>mol/ l and therefore the quick, exact and correct control of the developing soln. is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for determining the concentration of bromide ions, particularly to a method for determining the concentration of bromide ions in a developer for silver halide photographic light-sensitive materials (hereinafter referred to as developer). .

(Prior Art) Generally, the developability of a developing solution for silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) is greatly influenced by the concentration of halogen ions, especially the concentration of bromide ions. When a photosensitive material is developed, halogen ions such as bromine ions are extracted and accumulated in the developer, so that the concentration thereof gradually changes and the developability is affected. Therefore, in order to maintain constant developability of the developer, it is necessary to maintain the concentration of halogen ions, especially bromide ions, within a certain range. Regarding the measurement and adjustment of the bromide ion concentration in the developer, there is a method using potentiometric titration with silver nitrate as the basic principle, as described in Japanese Patent Application Laid-Open No. 54-37731. Also known is a method in which bromine ions in a developer are oxidized and reacted with a coloring reagent, and the concentration of bromide ions in the developer is determined by absorbance measurement. However, this method has the disadvantage of requiring the use of large-scale and expensive equipment.

The kidnappers titrated an acidic developer with a water-based silver tester and detected the point at which silver halide formed in the developer started to be developed by the developer. A method for quantifying bromide ions was proposed in Japanese Patent Application No. 15600/1983. Although this method has the advantage of not requiring expensive equipment such as a potentiometric titrator, it does require a titration operation that requires skill. A method for determining the 0 degree bromide ion of the solution by adjusting the pi (to acidic) and observing the point at which development of silver halide produced in the solution starts in the presence of a water-soluble silver salt. In , the water-soluble silver salt concentration or bromide ion concentration prepared from the solution is 0.
A method for determining the bromide ion concentration has been proposed in which the bromide ion concentration in the solution is determined by comparing and observing the developability of silver halide in at least two test solutions with different concentrations ( (Japanese Patent Application No. 196415/1982). Although this method has the advantage of not requiring a titration operation that requires skill, it is not always clear how to determine the end point, and there are still points to be improved.

(Object of the Invention) Regarding the problem of detecting the bromide ion concentration, the object of the present invention is to maintain the bromide ion concentration, which is a factor that affects the performance of the developer, within a predetermined allowable range and to maintain the developing activity constant. Therefore, it is desirable to provide a method for determining 0 degrees of bromide ion, which can detect the bromide ion concentration range in a developer more reliably than conventional methods.

Another object of the present invention is to provide a simple, quick, and highly practical means for maintaining developer activity at an appropriate level during continuous processing of photosensitive materials by using the discrimination method of the present invention.

(Structure of the Invention) Generally, the developability of a developer for silver halogenide differs depending on the composition of the halogenated steel and the silver ion concentration in the developer, and silver chloride has better developability than silver bromide. The increase in developability due to the increase in silver ion concentration in the developer is known as a physical development phenomenon.

However, it is said that development of silver halide hardly occurs when a commonly used developing agent is used in a common developer in a state where the pI (pI) is lower than the medium age. It was not developed.

However, 5 the present inventors first brought the developer (original solution) to a pI state lower than neutrality, added a water-soluble silver salt to the developer (original solution) to prepare an adjustment solution, and It was discovered that silver halide is developed when the amount of ions is equal to or more than the amount of bromide ions.Furthermore, in the coexistence of chlorine ions,
It has also been found that when the amount of silver ions added exceeds the amount equivalent to the amount of bromide ions in the developer, silver halide is rapidly developed.

The present invention is based on the above-mentioned findings, and is based on the solubility product of silver halide (particularly silver bromide in the present invention). On the variable axis (hereinafter abbreviated as Ag+-Br- concentration axis), the developer (original solution) whose bromine ion concentration (hereinafter referred to as (:Br-)) is to be detected is brought to an acidic region and a water-soluble silver salt is added. By adding a predetermined amount of a solution (hereinafter referred to as Ag+ solution), for example, a silver nitrate solution, at least at two levels of known concentration, at least two levels located at at least two levels on the Ag+-Br''- concentration axis are added. Adjustment solutions with fixed conditions, that is, test solutions are prepared, and comparison is made between which of the test solutions to see whether development behavior in accordance with the detection described above appears for silver halide that is inevitably produced in one solution. When using a method of interpolatively determining the concentration range in which (Br-) exists in the developing solution by observing, the present invention includes comparative observation of silver halide inevitably generated in the solution. This method replaces the comparative observation of the development behavior of silver halide on a test piece having at least one silver halide-containing layer in advance.This greatly simplifies the operation while maintaining detection accuracy.

Furthermore, the addition of ascorbic acid and/or its salts to the conditioning solution significantly speeds up the development behavior.

The present invention will be explained in more detail.

First, regarding the development activity of the target developer, the lower limit of the allowable bromide ion concentration range is [Br-:lDb, the upper limit is Car-]n
If tr, these can be obtained experimentally, and furthermore, if the optimum concentration is [:Br-]Do, it is known from the needle setting specifications of the developer. These three types differ depending on the developer formulation or the photosensitive material to be processed.

Furthermore, if the bromide ion concentration in the target developer is [Br-]D, [Br-]D is the above-mentioned [Br""IDL, [Br
-: IDU and (Ilr-) no K H Ag” -
It is unknown at what point on the Br-concentration axis. However, it is in one of the following ranges.

(1) [Br-)D< [Br-)DL (2)
[:Br-]nL-[Br-]D-4(Br-)DU(
3) CBr-]Dtr < [Br-)n The first practical embodiment of the present invention is an embodiment in which at least two test solutions at at least two levels are prepared using only the Ag+ solution.

゛For example, collect the current i solution (:Br-)D to a certain view vD, and add [Br-]DLX VD, [Br-]
Ag equivalent to the amount of bromide ions in Dtr
+ solution and make it correspond to the above sampled developer solution to test solution S]
? Prepare Il, 5DIJ, etc.

In that case, (Br-)n is [Br-:
When ln <[Br'lDL, 5IIL, 5D
Both TJ are in the Ag + J residual σ degree range, and SDL and S
The test piece immersed in DU was developed and blackened (
2) l:Br-]Dx, 4(13r-]D4[
Br"-: In the case of b: +tr, SDL is Br-excess,
SDU has Ag+ excess and the test piece is developed only for SDU, or if [Br-)ntr < [Br-)n in (3), both 5DIL and SDU have Br- excess and the test piece is not developed.

Therefore, by comparing and observing the behavior of the test solutions SDL, s,..., it can be determined that in this example, ld (Br-lD) is out of the permissible bromide ion concentration range for development activity or is within the range. It is determined whether the amount exceeds or exceeds the amount.

If the test solution for Br-:Ino K is applied at the same time, in the case of (2) above, (Br-]n is the optimum concentration [
Br″″〕D.

It is determined whether it is on the lower limit side or on the upper limit side.

Furthermore, in the same manner as above, instead of the allowable upper and lower limits, an arbitrary number of detection concentration sections are generally set, and an arbitrary number of test liquids 51 (i: 2, 3.4, etc.) corresponding to the upper and lower limits are set.・・・
By comparing and observing that sl does not develop the test piece and Si develops the test piece, if [Br-)n is prepared, the concentration range corresponding to 5i-1 and SiK is determined. It is determined that the temperature is in the intensity section on the variable axis of Ag-Br, which is determined by the lower limit and upper limit of .

In the present invention, the minimum unit of the concentration division, that is, the bromide ion quantitative accuracy is 2 XIO"" mol / 13,
It satisfies the necessary accuracy for practical use.

Next, a second embodiment of the present invention is a different mode in which an Ag+ solution and a Br- solution are used in combination when preparing a test solution located at at least two levels on the Ag+-Br- concentration axis.

For example, when using [Br-)nr, t, [Br-]nv as the base %i K, take a constant mother Vp of developer solution which is [Br-]n, and divide it into one ([er-] nv −[
Add an equivalent amount of Br- solution to Br-:)Dr, )
By adding an equivalent amount of Ag+ solution to the 8DL and SDU described in the first embodiment, a test solution equivalent in terms of analytical function to the 8DL and SDU described in the first embodiment can be obtained.

In this second embodiment as well, upper and lower limits of the above-mentioned arbitrary detection 0 degree section are set, and an arbitrary number of test liquids corresponding thereto are prepared, and [or-: A method of capturing ID can be used.

This second embodiment is highly practical in the field of photo labs, since processing errors are reduced by using different types of chemical solutions, and a developing solution with a known bromine concentration can be used as a Br solution.

If the dominant ion excess in the sample solution is small and development is difficult to proceed, it is possible to supplement a small amount of Ag+ solution to promote development and shorten the time required for confirmation. In this case, it is desirable to prepare a calibration curve in advance and check it.

The test piece used in the present invention needs to have at least one layer containing silver halide. As the silver halide, at least one type or a combination of two or more of silver bromide, silver chloride, silver halobromide, and silver halochloride can be used.

From the viewpoint of developability, among the silver halides, silver chloride and/or
It is preferable to use silver halochloride or silver halochloride. Particularly preferred are silver halochlorides in which the proportion of silver chloride and/or halogen is more than 50%, and pure silver is most preferred.

Halogenated coins (ri) contained in the test piece used in the present invention
It may be polydisperse or monodisperse. There is also no particular restriction on the size of the crystals, but a grain size of 0.1 to 2 μm is preferred. Furthermore, there is no particular restriction on the crystal form.

Since the test piece used in the present invention is not used as a light-sensitive material, a general sensitization treatment is not necessarily required. However, a Ka image is necessary for development. It is preferable to carry out a sensitization treatment or a fogging treatment.These treatments include sulfur sensitization, gold sensitization, reduction sensitization, dye sensitization, etc. used in partially photosensitive materials.

A preferred embodiment of the test strip according to the invention has at least one layer containing a silver halide emulsion on one side of the support. Various polymeric resin materials are suitable for the support, such as cellulose acetate, polyethylene terephthalate, polycarbonate or polystyrene. Furthermore, paper supports used in photographic light-sensitive materials can be used, and paper supports are convenient because they can be easily distinguished by the degree of reflection. It is preferable that the paper support is coated with polyethylene or the like.

The layer containing the silver halide emulsion of the test piece according to the present invention is preferably a layer made of a hydrophilic colloid, and various hydrophilic colloids can be used as the hydrophilic colloid, but gelatin is preferable. preferable. The test piece can also be provided with various layers. For example, it is preferable to provide a rattan retention layer as the uppermost layer in order to adjust the developability.

Additives used in photographic materials and/or other fields can be added to the layers provided on the test strip for the purpose of adjusting developability and other physical properties.

For example, it is preferable to add a hardening agent because it stabilizes development and improves the physical stability of the layer.

In the present invention, the method for collecting a certain amount of developer is to pour the developer into a container with a label corresponding to the amount to be collected up to the mark, or to collect a set amount using a measuring cylinder. Use a method such as collecting a set amount using a pipette, using a syringe-type sample collection device, or preferably using a syringe-type sample collection device that can collect a fixed amount with a stopper. However, the manner in which the developer is collected is not limited to this.

It is desirable to perform the operation of the present invention avoiding direct sunlight. For this purpose, it is desirable to perform the operation indoors.

More preferably, the operation is performed in a room with low illumination light. Furthermore, if a room with low illumination cannot be used, it is desirable to use a dark box to shield the sample area from excessive light. For ease of operation, it is preferable to have an opening at the top of the dark box for inserting a test liquid tube, etc., and an opening at the bottom of the dark box that can be opened and closed for testing the test liquid. However, the form of the dark box is not limited to this.

To adjust the pH of the collected developer, such as acid and/or strong acid, weak salt, etc., as well as a developing agent when it is necessary to add it, may be added directly to the collected developer sample.
Alternatively, it may be added to the developer sample after being dissolved in water or a suitable solvent.

The water-soluble silver salt added to the developer sample whose pH has been lowered to acidic can be in the form of either a water-soluble or suitable solution or a solid containing water-soluble silver groups. In particular, it is preferable to use a standard water-soluble silver salt aqueous solution with a defined concentration.

In the present invention, the test piece can be immersed in the test solution and subjected to a secondary treatment after the reaction to facilitate discrimination. The secondary processing is, for example, a method such as reinforcement.

The water-soluble silver salt used in the present invention refers to a silver salt having a larger solubility product than silver chloride, such as silver formate, silver chlorate, silver heptadide, silver nitrate, silver acetate, silver tartrate, and silver citrate. , silver benzoate, silver sulfate, etc. Particularly in the present invention, silver formate, silver chlorate, silver fluoride, and silver nitrate are preferably used, and silver nitrate is most preferably used.

In the present invention, the pH of the developer is adjusted to acidic to make the developing performance inactive, and then K, for example, using the difference in reaction rate or reaction area between silver chloride and silver bromide, is used to generate bromine ions. It is also true that the concentration range is determined. In the method for determining bromide ion straightness of the present invention, ' is the pi of a solution containing bromide ions and a silver halide developing agent.
(The lower limit of the range is not particularly limited, but preferably approximately pH 3, more preferably pH
It is 4.

For pH adjustment, acids and/or salts such as strong acid and weak base salts can be used. Is the nucleic acid and/or the salt free of bromide ions and also a substance that promotes the fermentation of halogenated substances? Selected from substances that do not contain

For example, it is desirable to use acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, etc. or easily soluble carboxylic acids and their strong and weak base carriers for this purpose.

In the present invention, a developing agent of a commonly used developer for photosensitive materials may be added to a developer sample taken from a developing bath to prepare a test solution. For example, as a developing agent for black and white, hydroquinone, Phenidone and metol are preferred, but not limited to these. As the developing agent for color photosensitive materials, paraphenylenediamine-based agents are preferred. The main drug based on phenylenediamine is:
For example, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-reminor N-ethyl-N-β-
Methoxyethylaniline, 3-β-methanesulponamidoethyl-4-amino-N, N-diethylaniline soluble, 3-methoxy-4-amino-N-β-hydroxyethylaniline, 3-methoxy-4-amino -N-ethyl/L/-N-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-diethylaniline, 4
-amino-N, N-dimethylaniline, N-ethyl-N
-β-[β-(,β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-
N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and carriers thereof such as sulfate, hydrochloride, sulfite tm, p-)luenesulfonate and the like.

The developing agent to be added is preferably used within a predetermined range as an appropriate amount so that the appearance of development can be clearly identified. The amount of the developing agent added is preferably 0.01.9 to 100 g per developer sample 11, and more preferably 0.01.9 to 100 g per developer sample.
It is particularly preferable to add in an amount of 1 g to xoy, ir>.

It has been found that in the addition or presence of ascorbic acid and/or its salt according to the present invention, the developability of silver oxide is particularly improved. The effect is particularly great when ascorbic acid or a salt thereof is added to a developer containing a nokuraphenylenediamine-based color developer. Ascorbic acid and its salts have the same effect in both the L-type and the D-type.
It is preferable to add in the range of g to 11. 1g more
It is particularly preferable to add in the range of ~10 g.

Examples of the developer for photosensitive materials to which the present invention can be applied include a developer for X-ray photosensitive materials, a developer for Lith photosensitive materials,
This includes, but is not limited to, developers for general black and white photosensitive materials, developers for color negative photosensitive materials, developers for color paper photosensitive materials, developers for color reversal photosensitive materials, and developers for direct positive photosensitive materials. It's not a thing.

Since the bromide ion concentration [:Br-]D in the developer is a measure of the appropriateness of the replenishment amount of the developer replenisher, when implementing the method of the present invention, it is necessary to If the present invention is applied to such devices, it becomes possible to automatically adjust the replenishment amount of developer replenisher using these devices and equipment. It is also possible to manually adjust the replenishment amount of the developer replenisher based on the results obtained by the (Br-]p discrimination method of the present invention. In other words, according to the present invention, it is possible to By preparing simple instruments and reagents that require little burden on the target, it is possible to achieve great results by being able to accurately and easily identify (Br-:ln) in the developing solution (Example) ) Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereby.

Example 1 2 m of the sodium bromide-containing color developer samples (A, B, C, and D) shown in Table 1 below were collected into 10 test tubes each, and the pH of the developer samples was adjusted using acetic acid. Adjusted to 4.0. To each sample, 2 d of water bath solutions (1, 2, 3, and 5) containing silver nitrate shown in Table 2 below were added to 2 of the 10 water-dead samples A, B, C, and D, respectively.
A set of samples was made.

In addition, a test piece (hereinafter referred to as a test piece) was prepared by coating a silver cyclide emulsion having the composition shown in Table 3 below on waterproof polyethylene paper (lighter paper).

0.1 g of silver chloride crystal was added to each of the above-mentioned sets of samples A, B, C, and D to which silver nitrate was added. After 30 seconds after adding the silver chloride crystal, a sample was taken into a cell for measuring optical strength, and the transmittance optical power was increased by 1 using white light.

Also, 1 for each of the other sets of samples 7'-+B+C and D.
The above-mentioned test paper was immersed in a book, and 30 seconds later, the test paper was taken out, fixed, washed with water, dried, and the optical reflection density was measured using white light. The results are shown in Table 4.

Table 1 Table 2 The composition of the color negative developing solution used is as follows.

Hydroxylamine Wbm2FA 2.
0 g4-amino-3-methyl-N-ethyl-N-(β
-Hydroxyethyl)aniline (Kodak CD-4
) 4.75 g potassium carbonate
37.51! pH 10.10 Add water to adjust to 11.

Table 3 below ゛All 9 whites Table 4 As is clear from the results of this example, the present invention has a higher concentration of the developer as determined by test paper compared to a comparative example in which crystals of the incubator were added to the developer. It can be seen that it is not affected by coloring, etc., and there is a large difference in developability due to the equivalence relationship between bromide ions and silver ions, making it easy to distinguish bromide ion images.

Example 2 Example 10 Sample A made according to the method of the present invention.

Developer samples (A, B, C
.

D) L-ascorbic acid into 2rnl 10 Il+p
A set of samples A/, e#, c/ and D' were prepared, and the same experiment as in Example 1 was conducted. Sample of the present invention not containing L-ascorbine ÷ A, B, C and D and L
- Sample A1 of the invention containing ascorbic acid. B/
, c/and D' are shown in Table 5.

As is clear from the results of this example in Table 5, the effects of the present invention are further significantly enhanced in examples in which ascorbic acid is added.

(Effects of the Invention) As the objects of the present invention have been achieved, the performance evaluation of the developer, which has a significant impact on the image quality of photosensitive materials, is quick and easy, and the image quality and yield are improved in current toilets, etc. led to an increase.

Agent Yoshimi Kuwahara

Claims (9)

[Claims] (1) After bringing a stock solution containing bromide ions and a silver chloride developing agent into an acidic region, the bromide ion of the stock solution is determined by the developability of the prepared solution containing a water-soluble iron salt to 710 silver In the method of determining 0 degrees, the bromide ion 0 degree of the original solution is determined by the developability of the adjustment solution with respect to the silver halide of a test piece having at least one layer containing silver halide. Characteristic method for determining bromine ion concentration. (2) The silver hydrogenide of the silver halide containing material of the test piece is at least one selected from silver halide, silver bromide, silver halobromide, and silver halobromide. A method for determining bromide ion concentration according to claim 1, characterized in that: (3) The method for determining the degree of bromide ion according to item 1 or 2, wherein the water-soluble solid is silver nitrate. (4) The method for determining bromide ion concentration according to claim 1, 2 or 3, wherein the raw solution is mixed with a developer for silver halide photographic light-sensitive materials. (5) After bringing the stock solution containing bromide ions and silver halide developing agent into an acidic region, the bromide ion tonicity of the stock solution is determined by the developability for silver halide of the adjustment solution to which all water-soluble silver is added. A method for determining 0 degree bromide ion, characterized in that the adjustment solution contains ascorbic acid and/or its additive. (6) In the method of determining the bromide ion concentration of the stock solution based on the developability of the prepared solution containing no ascorbic acid and/or its salt with respect to silver halide, of the test piece having a containing layer.
6. The method for determining bromide ion concentration according to claim 5, wherein the degree of bromide ion in the raw solution is determined based on the developability of the adjustment solution with respect to silver halide. (7) The silver halide in the silver halide-containing layer of the test piece is any one or a combination of two or more of silver chloride, silver bromide, silver halochloride, and silver halobromide. A method for determining bromide ion concentration according to claim 6. (8) The method for determining bromide ion concentration according to claim 5, 6, or 7, characterized in that the water-soluble silver salt is silver nitrate. (9) The method for determining bromide ion concentration according to claim 5, 6, 7, or 8, wherein the stock solution is a developer for halogenated photographic light-sensitive materials. .