JPS62959A - Method for stabilizing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To inhibit the fading of a developed color image by carrying out stabilization with a specified dye stabilizing soln. in the final stage of color processing. CONSTITUTION:Stabilization is carried out with a dye stabilizing soln. of 3.0-9.0pH contg. a soluble iron salt and a chelating agent in a stage after a bleach-fixing or fixing stage. Washing is not practically carried out. An inorg. ferrous or ferric salt, iron carboxylate or an iron complex salt may be used as the soluble iron salt. In case of 3.0-9.0pH of the stabilizing soln., the fading preventing effect of the soluble iron salt is shown. The chelating agent is added so as to maintain the pH of the stabilizing soln. When the stabilizing soln. is used, the fading of a developed color image can be prevented without softening the gelatin film and the amount of washing water required can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for stabilizing dye images of silver halide color photographic materials.

As is well known, in silver halide color photographic materials, colored images are obtained by forming azomethine dyes and indoaniline dyes by a color development method.

It is well known that these pigments fade when exposed to ultraviolet rays or visible light.

These dyes fade even when stored in the dark. This fading is particularly accelerated under high temperature and high humidity. Fading of these colored images is a major defect in color photography,
Improvement of this defect has been strongly desired.

Conventionally, various methods have been known for preventing fading of colored images produced by silver halide color photographic materials in bright or dark places.For example, U.S. Pat. ,,． 7
Treatment with zinc solution of No. 88,474, No. 2. ,Q3
, 338, calcium, magnesium,
Treatment with cadmium salts, British Il! l#Access No. 909.
A method of treatment with a solution containing monosaccharide, disaccharide, hexitol, treatment with a solution containing formaldehyde and polycarboxylic acid, etc. are known, as described in No. 1124 and No. 1,001,446.

However, with these methods, the effects obtained are slight, and even if fading can be prevented, many of the compounds used soften the gelatin film and significantly weaken its mechanical strength.

For this reason, formaldehyde is sometimes used to prevent softening of the gelatin film, but formaldehyde is practically harmful and has the disadvantage of contaminating the white background.

Therefore, in order to prevent fading of the single-dye image and to remove the chemicals contained in the photographic material from the processing bath, it is necessary to perform a washing process using as much water as possible for a long time, which speeds up the processing and saves labor. In some cases, the stabilization process, which has a small effect as described above, is omitted for the purpose of optimization. In addition, for the same purpose and to reduce pollution load and cost, processing using each processing solution is usually carried out at high temperatures, shortening the washing processing time, and reducing the amount of washing water used to produce a single dye image. It can be said that the stabilization of is more impaired.

Further, a stabilization treatment method in which the water washing time is omitted is also known, for example, as described in U.S. Pat. In addition, since the stabilizing bath contains a large amount of sulfurous salts, the formed image dye is easily converted to leuco form, which has a large effect on the deterioration of color photographic images. A low PTT is not suitable as there is a risk of generating sulfur dioxide gas.

In this way, conventional color image stabilization processing can stabilize photographic images over a long period of time, speed up processing, save labor, and reduce pollution loads and water used for washing. There wasn't.

The present inventors have completed the present invention as a result of various studies on methods for preventing fading of colored images in bright or dark places. It is an object of the present invention to provide a stabilizing processing method for a single-dye image, which can significantly prevent fading of color, reduce the amount of washing water, and eliminate the need for washing.

Another object of the present invention is to provide a method for stabilizing a dye image using a stabilizing solution that has excellent stability in long-term use.

The above-mentioned object of the present invention is to provide a solution containing a soluble iron complex salt and having a pH of 3.0 to 9.0 in the final stage of color photographic processing.
This is achieved by a dye image stabilization processing method for a silver halide color photographic light-sensitive material, which is processed with a dye stabilizing solution (processing bath) containing a chelating agent.

According to one preferred embodiment of the present invention, the stabilization treatment of the present invention is a step subsequent to the bleach-fixing bath or the fixing bath, and substantially no washing treatment is performed.

The present invention will be explained in detail below.

Specific examples of the soluble iron salts contained in the stabilizer of the present invention include ferric chloride and ferric sulfate.

Inorganic ferric salts such as ferric nitrate, ferrous chloride, ferrous sulfate, ferrous nitrate, ferrous salts, ferrous carboxylate salts such as ferric acetate, ferric citrate, and There are various iron complex salts, and examples of compounds that form complex salts with iron ions include compounds represented by the following general formulas [I] to [X1].

General formula [I] P■03■ Beautiful; Hydrogen, alkali metal, ammonium l: An integer from 3 to 6.

General formula [II] Mn"aPnOin"nn: 2-
20 integers.

General formula [m] ]B-Ax-ZA*-0 formula [nI]
[ff], A and ~A6 are each substituted or unsubstituted alkylene group, Z is an alkylene group, cyclohexane group, phenylene group, -R-0-R-1)N-A, (A is hydrogen, carbonized Hydrogen, lower aliphatic carboxylic acid, lower alcohol), B, C%D%E%F, G is -OH.

-COOM, -POJt (M represents hydrogen, alkali metal, ammonium).

Ni Mayuzumi R,: -COOM, -PG(OM).

R2: hydrogen, C1 to C4 alkyl group, -(CHt)n
'C00M, 7 enyl group.

R3 dihydrogen, -COOM.

M = hydrogen, alkali metal, ammonium, m: 0 or 1
, n: an integer from 1 to 4, q: 0 or 1° General formula [Vl] RJ(CHtPOdb)tR4:
Lower alkyl group, aryl group, cyclohexane group, aralkyl group, nitrogen-containing 6-membered ring group, [10H1- as a substituent]
0Ri (Rs: Cx-C4, alkyl group), -PO
sll*, -CH, POsL, -N((:)l*POJ
t)x, -Cool,, -N(COOC00M)21M
Dihydrogen, alkali metals, ammonium.

General formula [■] R6, R7: hydrogen, lower alkyl group, -COOH.

-NJO (J is hydrogen, -〇H1 lower alkyl group, -CJ
40H) R6: hydrogen, lower alkyl group, -0■, -Nl2 (L is hydrogen, -OH, -COO, -CtHsl-CJJH,
-PO+11*)X%Y, Z: -OH, -C001
%PO3M1, hydrogen: hydrogen, alkali metals, ammonium.

n: 0 or an integer of 1 or more, ■: 0 or l.

General formula [■] 0M as-0-P-ORI.

layer R9, R1゜dihydrogen, alkali metal, ammonium.

CI to CUt substituted or unsubstituted alkyl groups, alkenyl groups, and cyclic alkyl groups.

R□1: C8-2 alkyl group, C8-12 alkoxy group, C8-2 monoalkylamino group.

C2~, 2 dialkylamino group, amino group, C8~,
aryloxy group, 24 arylamino group and amyloxy group to Cs.

Q1-Q, Ni0R1C1-114 alkoxy group, aralkyloxy group, amyloxy group, -am! (MS is a cation), amino group, morpholino group, cyclic amino group,
Indicates an alkylamino group, dialkylamino group, arylamino group, and alkyloxy group.

General formula [X] Rum5 C3: hydrogen, lower alkyl group, imine (lower alkyl group, optionally substituted with -COOCH*COONa), M: hydrogen, alkali metal, ammonium, n: 2-16
an integer of

R14~R+s: hydrogen, alkyl group [-O as a substituent
H,-0Cn"H,n"+, (n": 1~4),
-PO3M! , -COOP03M, -NR* (R is an alkyl group), -N(COOPOJ*)*].

M: Hydrogen, alkali metal, ammonium.

In addition to the compounds represented by these general formulas [I] to [X[], citric acid, glycine, etc. may also be mentioned. However, the compounds represented by the above general formula exhibit even more excellent effects.

Specific examples of the compounds represented by the general formulas [I] to [X[] include the following.

Below margin (1) lla*PiO+t (2) Na
5PsO0 (3) Il, P, O, (4) R, P
So,.

(5) Na, P, 00 u- POsHt POsH
tposot PO,H.

C1, C00fl CHI −
Coo)lI (39) (4G)C4
Hs CCoon osut (45) (4B) H CI+ Ctl, PO, H, CI, OH CH2 0Jt 0■ fl-OsP CPOJ* /N% C,H@H (6G).

UOC■tcH (OR) CH-OP (ONa)
tHOCH*CH*OP (OH)t (63) Q HOCHtCCL OP (OH)t (69)
.

HJ-COOCHt-OP (OH) placement (72)
.

HsCCOOP　(OH)y IJ)l 0H OR.

COOOP OCH*CH-CHs I OX 01 ( CtHiOp 0CJs ■ H OH OH0H OCRs OCRs The soluble siliceous salt used in the present invention is stabilized in a stable bath.
It can be added in the range of IP' mol to IX 10-'' mol, preferably 4X 1 G'' mol to IX, 1 G-
It can be added in a range of F moles. In addition, in a continuous treatment method in which the treatment process consists of multiple stabilizing baths and is self-injected and replenished from the final bath, the desired amount of the above-mentioned soluble iron salt added is based on the concentration in the final bath of the stabilizing bath. be.

The stabilizing solution (stabilizing bath) according to the present invention has a pH of 3.0 to 9.0.
be. If the pH is less than 3.0, the fading prevention effect of the dye by the soluble iron salt will be impaired, and even if the pH exceeds 9.0,
In addition, fading and color prevention of pigments are impaired. In the case of unexploded
Preferably, the pH is 4.5 to B.5, and a particularly desirable pH is in the range of 6.0 to 8.0.A buffer is added to the stabilizer of the present invention to create a buffer action. It is desirable to keep it intact.

- As the buffering agent, compounds such as acetic acid, sodium acetate, boron, phosphoric acid, and sodium hydroxide are preferable, but the iron complex forming agent may be used in an amount equal to or more than the iron ion to provide buffering ability.

The stabilizing liquid used in the present invention contains a soluble iron salt.

Various chelating agents are added in addition to the iron complex salt. Examples of these include aminopolycarboxylate, aminopolyphosphonic acid, phosphonocarboxylic acid, alkylidene diphosphonic acid (e.g. l-hydroxyethylidene-1,1-diphosphonic acid), polyphosphate, pyrophosphoric acid, metaphosphoric acid. , gluconate, etc. These chelating agents are added in an amount necessary to maintain the pH of the stabilizing bath according to the present invention and within a range that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation.

According to the present invention, softening of the gelatin film is not caused,
Fading of the dye image can be prevented, and furthermore, in the present invention, by processing in a stabilizing bath containing iron ions,
Even if a small amount of other chemicals remains in the photographic material, the stability of the dye image can be greatly improved. For this reason, the water washing process can be shortened or eliminated. Compounds such as iron complex salts of ethylenediaminetetraacetate, which are used as bleaching agents in color photographic processing, have been thoroughly washed out by washing with water; however, as a result of studies conducted by the present inventors, it has been found that such soluble iron ions are It has been found that the dye image can be much more stabilized if the dye is present in an appropriate concentration range.

In color photographic processing, when processing is performed in a processing bath containing an organic acid ferric complex salt, the stabilization treatment is a processing step subsequent to the processing bath containing the organic acid ferric complex salt. Salt is automatically brought in and replenished by the photosensitive material. This allows processing without containing soluble iron salts in the stable replenisher. At the same time, the conventional water washing process can be made unnecessary. Of course, in order to maintain the concentration of soluble iron salts within the concentration range of the present invention, it is necessary to control the amount brought in by the photographic light-sensitive material from the organic acid ferric complex salt-containing processing solution and the amount of replenishment of the stabilizing solution. Due to the presence of soluble iron salts, other chemical components in the organic acid ferric salt complex-containing processing solution (for example, thiosulfate, 'M sulfate, etc.) may affect the fading properties of the dye image below a certain concentration. However, I found that the stability improved.

Multiple stabilizing baths are used to maintain the desired concentration.□
It is preferable to carry out the treatment while replenishing the water by a countercurrent method.

It is important to process the stabilizing bath according to the present invention at the final stage after color development, and it is desirable to directly enter the drying process. It is also possible to perform rinsing or washing with water to remove such compounds, or apply a treatment solution containing an oxidizing agent such as hydrogen peroxide or persulfate, or immerse it in a treatment bath. In addition, for bleaching solutions and bleach-fixing solutions that contain organic acid ferric complex salts as a bleaching agent, it is desirable to directly stabilize them after processing, but organic acid ferric complex salts may be added to the stabilizing solution by photographic light-sensitive materials. Stabilization treatment can also be carried out through rinsing or washing with water to an extent that does not prevent the amount carried into the concentration range of the present invention.

The stabilization treatment of the present invention is carried out at the final stage of color treatment, but the stabilization treatment can be carried out using a single stabilization bath. However, for the above-mentioned reasons, when stabilizing treatment is performed subsequent to bleach-fixing or fixing solution treatment, it is preferable that the stabilizing bath according to the present invention is composed of multiple baths and has a multi-bath processing format.Furthermore, the present invention The number of tanks provided to achieve the above objective is determined by the amount carried in by the photographic light-sensitive material from the organic acid ferric complex-containing processing bath in order to bring the soluble iron salt concentration in the final stabilizing bath to the desired value. It is closely related to the amount of replenishment of the stabilizing solution, and the smaller the ratio of the amount of replenishment to the amount brought in, the more tanks are required, and the larger the ratio, that is, the greater the amount of replenishment, the fewer the number of cypresses. It will be over.

In general, depending on the concentration of the organic acid ferric chain salt-containing bath, when the amount of replenishment is about 3 to 5 times the amount brought in, it is preferable to process with 2 to 8 tanks, for example. When the amount is 50 times, the objective can be achieved preferably by treatment using 2 to 4 tanks.

The stabilizing bath according to the present invention can be used as long as it is a buffer solution adjusted to a pH range of 3-0 to 9.0, and various buffers can be used. , borax, phosphate, monocarboxylate, dicarboxylate, polycarboxylate, oxycarboxylate, amino acid, aminocarboxylate, primary phosphate, secondary phosphate, tertiary phosphate
Phosphate, sodium hydroxide, potassium hydroxide, etc. can be mentioned.

In addition, commonly known stabilizing bath additives include (1) optical brighteners, surfactants, preservatives, anti-pie agents, organic sulfur compounds, onium salts, formalin, hardeners such as aluminum, chromium, etc. There are various metal salts, etc., and the amount of these compounds added is within the range necessary to maintain the pH of the stabilizing bath according to the present invention and does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. What kind of compound?

It can be used in any combination.

Desirable compounds to be added to the stabilizing bath of the present invention include, in addition to soluble iron salts, buffers such as acetic acid and sodium acetate, 5-chloro-2-methyl-4-isothiazoline-3-
Examples include anti-pyre agents such as 1,2-benzisothiazolin-3-one and thiabendazole, trace amounts of formaldehyde, hardening agents such as aluminum salts and magnesium salts, and optical brighteners.

However, according to the processing method of the present invention, these additive compounds can efficiently stabilize the dye image and omit the water washing process, so long as the buffering capacity is sufficient from the viewpoint of pollution load and cost measures. The more dilute it is, the better.

The treatment temperature during the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C, and the treatment time is preferably as short as possible from the viewpoint of rapid processing, but usually 20 seconds to 10 minutes. , most preferably 1 minute to 5 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the first stage tank be treated for a shorter time and the second stage tank be treated for a longer time, especially 20% to 50% of that of the front stage tank. It is preferable to perform the treatments sequentially with increasing treatment times by 5%. After the stabilization treatment according to the present invention, there is no need for washing with water at all, but rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. are necessary. You can do it as you like.

In this way, the processing method of the present invention can be applied to color paper, reversal color paper, color positive film, color negative film, and color reversal film.

It can also be used to process color X-ray films and the like.

Incidentally, when the stabilizing bath of the present invention contains a soluble silver salt, silver can also be recovered from the bath.

Silver recovery methods include ion exchange resin method, metal replacement method,
Electrolysis method, silver sulfide precipitation method, etc. can be used.

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A Sakura color paper sample was subjected to stepwise exposure using a conventional method, and after one-color development, bleach-fixing, and washing with water, the sample was divided into seven parts, each of which was divided into (I) and (■) shown in Table 1 below. After being immersed in the prescribed solution at 33°C for 1 minute, it was dried to obtain a test sample.

Table-1 used.

Measure the maximum concentration of blue and red of the above sample, and
After being stored in a constant temperature and humidity chamber at a relative humidity of 80% for 60 days, the concentration was measured again and the rate of decrease in each concentration was determined. The results are shown in Table-2.

Table 2 As is clear from Wheat-2, Sample No. 1 produced by the method of the present invention
It can be seen that in (m) to (Vf), the fading of the dye, especially the fading of the red density, was significantly reduced, and the fading prevention effect was remarkable. In addition, in the samples treated with the stabilizer according to the present invention, the fading of the blue, green, and red densities is small and occurs evenly, so there is no loss of color balance, and the visual fading rate is higher than the fading rate measured by density measurement. It can be seen that it becomes significantly smaller.

Example 2 The method was the same as Example 1, and the sample after washing with water was divided into 6 parts.
Each was immersed in a solution having the formulations (1) to (Vl) shown in Table 3 below at 33°C for 1 minute, and then dried to provide a test sample.

Table-3 Measure the red intermediate density (D-1, 5') of the sample.

After being stored in a constant temperature and humidity chamber at 80° C. and 80% relative humidity for 60 days, the concentration was measured again and compared. The red intermediate density was expressed as the percentage decrease in density.

The results are shown in Table 4.

Table 4 As can be seen from the results in Table 4, if the pH of the stabilizer is lower than the range of the present invention, the color fading due to preservation of the red density will be large, which is undesirable, and if the pH is too high than the range of the present invention, The decrease in red intermediate density becomes large. In addition, the p of the stabilizing solution
When n is a desirable value within the range of the present invention, a red intermediate density is a desirable value and fading due to storage is prevented. In addition, when measuring the minimum blue concentration of the obtained sample, it was found that even in the desired pH range, the minimum blue concentration was
The higher the H, the more desirable results were obtained.

Example 3 Sakura Color Baber (in roll form) (manufactured by Konishiroku Photo Industry Co., Ltd.) was subjected to a continuous replenishment process (referred to as running process) using an automatic processor after printing. The drilling process and the composition of the processing liquid at this time are as follows.

Standard processing step 1, color development 33℃ 3 minutes 30 seconds 2, bleach fixing 33℃ 1 minute 30 seconds 3, stabilization treatment
25℃~3Q'C 3 minutes 4, drying 75℃~8
0°C for about 2 minutes Processing solution composition [Color developer tank solution] [Red developer replenisher] [Bleach-fix tank solution] [Bleach-fix replenisher A] [11 White fixer replenisher B] Does the above apply to an automatic processor? Fill the color developer tank solution, bleach-fix tank solution, and the following stable solution, and add the above color developer replenisher, bleach-fix replenisher A, B, and stable replenisher to a metered cup every 3 minutes before processing the color paper. I did a running test while replenishing it. The amount of replenishment was 324 layers per rn' of color vapor to the color developing tank, and 25 layers each of bleach-fixing replenishers A and B to the bleach-fixing tank.

For the stabilization treatment, the stabilization treatment baths of the automatic developing machine were configured into 1, 3, and 6 tanks, and were modified to enable continuous processing.

If the stabilization processing baths of each automatic processor are composed of multiple tanks, the stabilization processing baths of each automatic processing machine are arranged in the direction of the flow of the photosensitive material from the first tank to the third tank,
The first to sixth tanks are stabilizing tanks, each of which is refilled from the final tank, the overflow liquid from the final tank flows into the hinoki cypress in the previous stage, and this overflow liquid also flows into the hinoki hinoki in the previous stage. A tank countercurrent system was adopted.

Continuous processing was carried out until the total amount of bleach-fixing replenishers A and B used was three times the tank capacity of the bleach-fixing solution.

Measure the presence or absence of precipitation in the frontmost tank of the stabilization treatment bath,
The red intermediate density of the sample obtained at the end of the running process (
D-15) was measured, and then the sample was left at 80° C. and 80% relative humidity for 60 days, and the red intermediate density was measured again.

The results are shown in Table-5.

The amount of bleach-fix solution added to the stabilizer per color paper was 50 ml.

Stabilizing solution (replenishment solution) Table 5 As is clear from Table 5 above, in the comparison treatment (1), the tank liquid remains even after replenishing a large amount of washing water. ! Algae and a small amount of sediment were observed to grow on the walls, which also adhered to the color vapor and caused malfunctions. In addition, there is a large decrease in the intermediate red color density due to the storage test of the sample.On the other hand, in the stabilization treatments (2) to (10) according to the present invention, no precipitation is observed in the stabilizing solution, and the decrease in the red color concentration due to the storage test is small. Recognize. However, even with the stabilization treatment of the present invention, if the bleach-fix solution is directly stabilized and the amount of replenishment is less than 100 times the amount brought in by the photosensitive material, the color will be red if the stabilization solution tank is 1 hinoki. Although the anti-fading effect can be obtained to some extent, it is considerably impaired. This is probably due to the fact that components other than the ferric complex salt in the bleach-fix solution are not diluted. When performing stabilization treatment in the next step directly from the liquid, the stabilizing liquid consists of multiple tanks of two or more cypresses, and the replenisher is replenished from the final bath and is processed in a countercurrent method in which it sequentially overflows to the previous tank. It has been found that a higher effect of preventing dye image fading according to the present invention can be obtained.

In addition to this example, the iron complex salt of ethylenediaminetetraacetate was removed from the stable replenisher, but iron ions were brought in from the bleach-fix solution, and almost the same effect as in this example was obtained. In addition, in the three-tank treatment of samples (7) and (8) in this example, the processing time was set to 20 seconds for the first tank, 40 seconds for the second tank, and 2 minutes for the third tank. ), 10 seconds in the 1st tank, 10 seconds in the 2nd tank, 20 seconds in the 3rd tank, 4
The processing time was set to 30 seconds for the 54th tank, 50 seconds for the 54th tank, and 1 minute for the 6th tank.

Example 4 It was found that the liquids (1) to (2) of Example 1 and the liquids of Examples 2 to (2) contained a chelating agent, and therefore could withstand long-term use without the formation of precipitates.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi (and 1 other person)

Claims (2)

[Claims] (1) Contains soluble iron salt and has a pH of 3.0 to 9.0
A method for stabilizing a silver halide color photographic light-sensitive material, which is characterized in that the stabilization treatment is carried out at the final stage of color processing using a dye stabilizer containing a chelating agent. (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the stabilization treatment is a step subsequent to a bleach-fixing bath or a fixing bath, and substantially no washing treatment is performed. Stabilization treatment method.