JPH0570144B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method for processing silver halide color photographic materials (hereinafter abbreviated as "photosensitive materials"), and particularly to a stabilizing method that does not include a water washing step following a desilvering step. [Prior Art] In recent years, environmental conservation and water resource issues have become important in photofinishers that automatically and continuously develop photosensitive materials. It is desirable to reduce or eliminate the amount of flushing water used. For this reason, after the fixing or bleach-fixing process,
A technology has been proposed that directly performs stabilization treatment without washing with water. For example, JP-A-57-8542, JP-A No. 57-8542,
No. 132146, No. 57-14834, and No. 58-18631 each describe a technique of treatment with a stabilizing solution containing an isothiazoline derivative, a benzisothiazoline derivative, a polycarboxylic acid, a soluble iron complex salt, and an organic phosphonic acid. . Furthermore ^, as described in JP-A-58-134636, the amount of replenishment of the stabilizing solution that does not require water washing is approximately 25 ml to 2.5 ml per 1 m ² of photographic material, preferably 50 ml to 1. More preferably
It replenishes between 50ml and 200ml. However, in these techniques, image preservation deteriorates due to an increase in fixing and bleaching components introduced into the stabilizing solution by the photosensitive material, and in particular, when ferric salts of organic acids, which are bleaching agents, remain, long-term storage becomes difficult. The drawback is that it is less effective in suppressing the increase in yellow stain in uncolored areas. It has also been found that continuous processing increases edge contamination of photosensitive materials, which is a serious drawback, especially in color papers. It is an object of the present invention to provide a color stabilization processing method that does not substantially require a washing step after processing a photosensitive material with a processing solution having fixing ability. An object of the present invention is to provide a color stabilization processing method that reduces edge contamination. [Summary of the Invention] A method for processing a light-sensitive material according to the present invention is to process a silver halide color photographic light-sensitive material with a processing liquid having a fixing ability. In the processing method, the processing solution has a fixing ability and contains a thiosulfate;
A treatment method in which a portion of the thiosulfate is carried into the stabilizing solution, wherein Ba,
Mg, Ca, Al, Zn, Ni, Bi, Sn, Mn, Ce, Zr
1× water-soluble metal salt selected from the metal group consisting of
10 ^-4 to 1 x 10 ^-1 mol, and 0.002 to 1.0 mol of a compound that can release hydrogen ions after treatment, and there are two or more stabilizing liquid tanks, and the compound that can release hydrogen ions. is in a molar ratio of 2 to 1 to thiosulfate in the stabilizing solution in the final stabilizing solution tank.
It is characterized by being added ⁴ times as much as ×10. In a preferred embodiment of the present invention, the emulsion film surface PH after drying of the photosensitive material is 2.2 to 6.8, the metal group is composed of Mg, Ca, Bi, and Zn, and furthermore, after processing, hydrogen Examples of compounds capable of releasing ions include ammonium compounds. [Structure of the present invention] The present invention will be explained below. Contamination of the edges of photosensitive materials occurs even during normal washing, and is thought to be caused by color developing agents, bleaching agents, and silver, and can be prevented by washing for a long time. For this reason, in the method of direct stabilization treatment after fixing, various components accumulate in the stabilizing solution due to continuous treatment, making it difficult to wash out contaminant components. The inventor has discovered Ba, Mg, Ca, A
We have discovered that the above edge contamination can be reduced by using a water-soluble metal salt selected from the metal group consisting of , Zn, Ni, Bi, Sn, Mn, Ce, and Zr together with a compound that can release hydrogen ions after treatment. It is a thing,
At the same time, the specific water-soluble metal salt and hydrogen ion-releasing compound each have an effect of preventing yellow staining in uncolored areas during long-term storage.
We have discovered that it works even more effectively. Ba, Mg, Ca, added to the stabilizer of the present invention,
Water-soluble metal salts of A, Zn, Ni, Bi, Sn, Mn, Ce, and Zr have the property of dissolving in water, and specifically include sulfates, hydrochlorides, phosphates, and Salts with inorganic acids such as acid salts, acetates, citrates,
There are salts with organic acids such as oxalates, succinates, and maleates, complex salts with chelating agents, etc., but it is preferably contained in the stabilizing liquid as a metal chelate compound with a chelating agent. Although it is desirable to supply the metal chelate compound to the stabilizing liquid, it may be supplied separately. Preferred chelating agents include the following general formula []
Examples include chelating agents represented by ~[]. General formula [] MmPmO ₃ m General formula [] Mn+ ₂ PnO ₃ n+1 General formula [] A ₁ −R ₁ −Z−R ₂ −COOH General formula []

[Chemical formula] In the formula, D represents a substituted or unsubstituted alkylene group, cycloalkylene group or phenylene group, -R ₇ OR ₇ -, -R ₇ OR ₇ OR ₇ -, -R ₇ ZR ₇ -, respectively, and Z represents >N-R ₇ -A ₆ , >N-A ₆ ,
R ₁ to R ₇ represent substituted or unsubstituted alkylene groups, A ₁ to _{A 6} are hydrogen atoms, -OH, -COOM, -
It represents PO ₃ M ₂ , M represents a hydrogen atom or an alkali metal atom, m represents an integer of 3 to 6, and n represents an integer of 2 to 20. General formula [] R ₈ N (CH ₂ PO ₃ M ₂ ) ₂ In the formula, R ₈ is a lower alkyl group, an aryl group, an arralkyl group, a nitrogen-containing 6-membered ring group [as a substituent -
OH, -OR, -COOM], M is a hydrogen atom,
Represents an alkali metal atom. General formula []

[Chemical formula] In the formula, R ₉ to _{R 11} are hydrogen atoms, -OH, lower alkyl (unsubstituted or as substituents -OH, -COOM,
_-PO3M2 ), _B1 to _B3 are hydrogen atoms, -OH, -COOM, _{-PO3M2 , -NJ2} , and J is _a hydrogen atom, lower alkyl, −C ₂ H ₄ OH,
-PO ₃ M ₂ , M represents a hydrogen atom or an alkali metal, and n and m represent 0 or 1. General formula []

[Chemical formula] In the formula, R ₁₂ and R ₁₃ are hydrogen atoms, alkali metals,
a substituted or unsubstituted C ₁ to C ₁₂ alkyl group, respectively;
Represents an alkenyl group or a cyclic alkyl group. General formula []

[C] In the formula, R ₁₄ is substituted or unsubstituted C ₁ to C ₁₂ , respectively.
alkyl group _{, C1-12} alkoxy group, _C1-12 monoalkylamino group _{, C2-12} dialkylamino group _, amino group, _{C1-24 allyloxy group} , _C6-24
(represents an arylamino group and an acyloxy group) _Q1 to _Q3 are -OH, substituted and unsubstituted _C1, respectively
~ _C12 alkoxy group, aralkyloxy group,
It represents an aryloxy group, _-OM3 ( _M3 is a cation), an amino group, a monophorino group, a cyclic amino group, an alkylamino group, a dialkylamino group, an arylamino group, or an alkyloxy group. General formula []

[ka] General formula []

[Chemical formula] In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -
OR ₁₉ ，−COOR ₂₀ ，

[Formula] or a substituted or unsubstituted phenyl group. _R19 , _R20 ,
R ₂₁ and R ₂₂ are each hydrogen atom or substitution,
Represents an unsubstituted alkyl group having 1 to 18 carbon atoms. General formula []

embedded image In the formula, R ₂₃ and R ₂₄ represent a hydrogen atom, a halogen atom, or a sulfonic acid group. General formula []

[Chemical formula] In the formula, R ₂₉ and R ₃₀ are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -CH ₂ COOH, -CH ₂ PO ₃ H ₂
or a salt thereof, X ₁ represents a hydroxyl group or a salt thereof, W ₁ , Z ₁ and Y ₁ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or It represents a salt thereof, an alkoxy group or an alkyl group. Also
m ₁ is 0 or 1, n ₁ is an integer of 1 to 4, l ₁ is 1 or 2, p ₁ is an integer of 0 to 3, and q ₁ is an integer of 0 to 2. Specific examples of the chelating agents represented by the above general formulas [] to [] include the following.

【table】 / \

HOOCCH ₂ CH ₂ CH ₂ CH ₂ COOH

[Table] ｜

PO ₃ H ₂

[Table] ｜

PO ₃ H ₂

【table】

[Table] ｜

PO ₃ H ₂

[Table] ｜

_NH2

[Table] ｜

OH

[Table] ｜ ｜

OH OH

【table】

【table】

【table】

〔Example〕

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 photosensitive material was prepared by sequentially coating the following layers on a polyethylene coated paper support from the support side. The polyethylene coated paper is made by adding anatase titanium oxide to a mixture of 200 parts by weight of polyethylene with an average molecular weight of 100,000 and a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of 0.80.
Added 6.8% by weight and formed a 0.035mm thick coating layer on the surface of high-quality paper with a weight of 170g/ ^m2 using an extrusion coating method, and a 0.040mm thick coating layer made only of polyethylene on the back side, and supported. As a body. The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied. First layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 95 mol % of silver bromide. sensitizing dye

2,5-di-tert-butyl sensitized using 2.5×10 ^-4 mol (using isopropyl alcohol as solvent) and dissolved and dispersed in a 1:1 mixture of dibutyl phthalate and dioctyl phthalate. α-[4- as hydroquinone and yellow coupler
(1-benzyl-2-phenyl 3,5-dioxo-1,2,4-triazolidyl)]-α-pivalyl-
Contains 2×10 ^-1 mol of 2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide per mol of silver halide, silver amount
It is applied at a concentration of 330mg/ ^m2 . 2nd layer: Di-t dissolved and decomposed in dibutyl phthalate
-Octylhydroquinone 300mg/m ² , 2-(2'-hydroxy-3',5'-di-t) as an ultraviolet absorber
-butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-
t-Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',
A gelatin layer containing 200 mg/m ² of a mixture of 5'-di-tert-butylphenyl)-5-chlorobenzotriazole is coated at 2000 mg gelatin/m ² . Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: sensitizing dye

[Chemical formula] 2.5-di-t-butyl sensitized using 2.5×10 ^-4 mol and dissolved and dispersed in a solvent consisting of a 1:1:1 mixture of dioctyl phthalate, dibutyl phthalate and tricresyl phosphate. 1-(2,4,
6-trichlorophenyl)-3-(2-chloro-5
−Octadecenyl succinimide analino)−
5-pyrazolone at 1.5x per mole of silver halide
It contains 10 ^-1 mol of silver and is coated with a silver content of 300 mg/m ² . In addition, as an antioxidant, 2, 2, 4
-Trimethyl-6-lauryloxy-7-tert-octylchroman was used at 0.3 mol per mol of coupler. 4th layer: Di-t dissolved and dispersed in dibutyl phthalate
- 30 mg/ ^m2 of octylhydroquinone and 2-(2'-hydroxy-3',5'-di-t) as a UV absorber.
-butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-
3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5-t-butylphenyl)-5-chloro-
Mixture of benzotriazole (2:1.5:1.5:
2) Gelatin in the gelatin layer containing 500mg/ ^m2
It is applied at a concentration of 2000mg/ ^m2 . Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide.The emulsion contains 500 g of gelatin per mol of silver halide, and has the following structure per mol of silver halide sensitizing dye

[Chemical formula] 2.5-di-t-butylhydroquinone and cyan coupler sensitized using 2.5×10 ^-4 mol and decomposed by dissolving in dibutyl phthalate.
4-dichloro-3-methyl-6-[γ-(2,4-
diamylphenoxy)butyramide]phenol and 4-chloro-2-(pentafluorobenzamide-5-[α-(2,4-di-t-pentylphenoxy)-iso-valeroamide]phenol:
The mixture was mixed at a ratio of 1:1 and contained 3.5×10 ^-1 mol per mol of silver halide, and was coated to give a silver amount of 280 mg/m ² . 6th layer: Gelatin layer, coated with gelatin at 1000mg/m ² . The silver halide emulsions used in each light-sensitive emulsion layer (1st, 3rd, and 5th layers) were prepared by the method described in Japanese Patent Publication No. 46-7772, and each was prepared using sodium thiosulfate pentahydrate. Chemically sensitized and 4-hydroxy-6-methyl-1,3,3a,7 as a stabilizer
-tetrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid. After exposing the color paper produced by the above method, continuous processing was performed using the following processing steps and processing solution until the total amount of stabilizing solution replenishment reached three times the stabilizing bath volume. Standard processing steps [1] Color development 33℃ 3 minutes 30 seconds [2] Bleach fixing 33℃ 1 minute 30 seconds [3] Stabilization 25℃~30℃ 2 minutes [4] Drying 90℃~100℃ approx. 2 Separation liquid composition

[Table] 〓ru.

[Table] 〓ru.
<Bleach-fix tank solution> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid Add water to bring the total volume to 1. <Bleach-fixing replenisher A> Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260g Potassium carbonate 42g Add water to bring the total volume to 1. The pH of this solution is 6.7±0.1. <Bleach-fix replenisher B> Ammonium thiosulfate (70% solution) 500ml Ammonium sulfite (40% solution) 250ml Ethylenediaminetetraacetic acid 17g Glacial acetic acid 85ml Add water to bring the total volume to 1. The pH of this solution is 4.6±0.1. <Stabilizer tank liquid or replenisher> Exemplary chelating agent [81] 3.0g 5-chloro-2-methyl-4-isothiazolin-3-one 0.03g 2-methyl-4-isothiazolin-3-one
0.03g 2-octyl-4-isothiazolin-3-one
Add 0.01g water to bring the total volume to 1, and adjust the pH to 7.5 with KOH. Fill an automatic processor with the above color developing tank liquid, bleach-fixing tank liquid, and stabilizing liquid, and the replenishment amount is 324 ml to the color developing tank and 324 ml to the bleach-fixing tank per 1 m ² of color paper. 25 ml each of replenishing solutions A and B, and 250 ml of stabilizing solution were added to the stabilization treatment bath. The stabilizing baths of the automatic processor are the first to third tanks in the direction of the flow of the photosensitive material.
A multi-vessel countercurrent system was used in which replenishment was performed from the final tank, overflow from the final tank was allowed to flow into the previous tank, and this overflow liquid was also allowed to flow into the previous tank. After continuous treatment, take 12 pieces, one from each of stable tanks 1 to 3, add compounds No. 1 to 12 shown in Table 1, respectively, and adjust the pH of each tank to 7.5 with KOH.
After adjustment with H ₂ SO ₄ , the color developing tank solution and the bleach-fixing tank solution were also taken, and the color paper was developed and used as a sample. The emulsion surface pH of the sample was measured using a composite integrated electrode and an ion analyzer manufactured by Orion. In addition, the sample was rolled into a roll, and the degree of edge contamination was measured using blue light from an optical densitometer (PDA-65 manufactured by Konishiroku Photo Industry Co., Ltd.), and the results are shown in Table 1. Furthermore, the color paper sample was stored in a constant temperature and humidity chamber at 80°C and 75% RH for 7 days to accelerate storage over time, and the yellow stain in the unexposed area after storage was measured using blue light from an optical densitometer. Also shown in Table-1.

【table】

[Table] As is clear from Table 1, Comparative Examples No. 1 to No.
When using the metal salt No. 6 alone, a compound that releases hydrogen ions after treatment alone, and a combination of a metal salt outside the present invention and a compound that releases hydrogen ions after treatment, the yellow stain due to storage over time decreases, but
It has little effect on edge contamination and cannot be put to practical use. On the other hand, in the combination of metal salts of the present invention No. 7 to No. 12 and compounds that release hydrogen ions after treatment, the combination of the compounds of the present invention has a synergistic effect on yellow staining over time. It can be seen that the generation of yellow stain is suppressed to a low level, and that the combined use of the compound of the present invention has a higher preventive effect on edge staining than could be expected from the effect alone, which is extremely preferable. Furthermore, by comparing No. 7 and No. 9 and No. 8 and No. 11, it was found that among the compounds that release hydrogen ions after the treatment of the present invention, ammonium compounds are preferable. No. 1 among metal salts.
It can be seen that the effects of the present invention are very effective for magnesium salts and zinc salts of No. 11 and No. 12. In the above Example-1, a similar experiment was conducted using nickel chloride, stannic chloride, manganese sulfate, ceric sulfate, and zirconium sulfate in place of aluminum sulfate in No. 9. 10, similar favorable results were obtained. Three tanks each of the stabilizers No. 1 to No. 12 were left in one Erlenmeyer flask at room temperature for two weeks, but no precipitate was observed in each. Example 2 PH after adding magnesium sulfate and aqueous ammonia as additive compounds in No. 11 of Example-1
The adjustment was changed with KOH and H ₂ SO ₄ , and the color paper was developed in the same manner as in Example 1, and the emulsion film surface PH, edge contamination, and yellow stain over time were measured. The results are shown in Table 2. It was shown to.

[Table] As is clear from Table 2, when the water-soluble metal salt of the present invention is used in combination with a compound that releases hydrogen ions after treatment, the yellow stain in particular
The lower the PH is, the more preferable it is to suppress the edge staining. However, for edge staining, it is preferable that the emulsion film surface PH is in the range of 3 to 8, more preferably in the range of 3.2 to 6.8, and especially in the range of 3.7 to 8.
It can be seen that the range of 6.0 is extremely preferable. Example 3 Stabilizers Nos. 13 to 24 were obtained according to the stabilizer formulation shown in Table 3, and each was dissolved in 1 part of water (containing orthophenylphenol as an anti-bacterial agent).
The mixture was stored in an Erlenmeyer flask at room temperature and observed for precipitation once a week for 6 weeks, and the results are shown in Table 4. In addition, 20% of the bleach-fix solution after the continuous treatment of Example-1 was added to the stabilizers No. 13 to 24 prepared in the same manner.
ml was added, stored at 40°C, and the number of days until silver sulfide was generated was observed, and the results are shown in Table 4.

【table】

【table】

[Table] As is clear from Table 4, precipitation and gelation do not occur with the exemplary chelating agent [81] in Stabilizer No. 13 and water-soluble bismuth salt, whereas in No. 14, which uses ammonia in combination, In No. 15, precipitation and gelation occurred. Further, in No. 16 and No. 17 in which a chelating agent other than the exemplified chelating agent [81] was used, no precipitation or gelation occurred. However, precipitation and gelation were suppressed in Nos. 18 to 24, which used a combination of precipitation prevention methods, and precipitation and gelation were further suppressed in Nos. 21, No. 22, and No. 24, which used two or more prevention methods in combination. Furthermore, it can be seen that the combined use of a suspending agent has a great effect on the generation of silver sulfide, and is therefore very preferable. Example-1 for stabilizer No. 20 to 24
When experiments were conducted in the same manner as above, the effects of the present invention were comparable to those of Example-1 No. 11 and No. 12, which was extremely preferable. Example 4 Continuous treatment was carried out in the same manner as in Example-1 using the stable solution formulation of Example-1 except that the exemplary chelating agent [81] was removed, and after the continuous treatment, samples were collected from stability tanks 1 to 3, respectively. , per ammonia water (25%
Based on the addition of 4.0 g of aqueous solution) and 0.6 g of magnesium sulfate, example chelating agents (5), (7), (19), (31), (4
4), (88), (93), and (98) were added, the color paper was developed in the same manner as in Example-1, and the emulsion film surface PH, edge contamination, and yellow stain were measured. Similar to No. 11 in Example-1, extremely effective results were obtained.

Claims (1)

[Claims] 1. In a processing method in which a silver halide color photographic light-sensitive material is processed with a processing liquid having a fixing ability, and then subsequently processed with a stabilizing liquid without substantially undergoing a water washing step, a thiosulfate salt is added to the processing liquid having a fixing ability. is contained in the stabilizing solution 1, and a part of the thiosulfate is carried into the stabilizing solution.
Per Ba, Mg, Ca, Al, Zn, Ni, Bi, Sn,
A water-soluble metal salt selected from the metal group consisting of Mn, Ce, and Zr is added in an amount of 1 x 10 ^-4 to 1 x 10 ^-1 mol, and a compound capable of releasing hydrogen ions after treatment is added.
0.002 to 1.0 mol is added, and there are two or more stabilizing liquid tanks, and the compound capable of releasing hydrogen ions is added in a molar ratio of 2 to 1.0 mol to thiosulfate in the stabilizing liquid in the final stabilizing liquid tank. A method for processing a silver halide color photographic material, characterized in that silver halide is added 1×10 ⁴ times.