JPS5843454A - Processing method for color photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To enable the long-term storage of a replenisher for a bleaching bath contg. metallic complex salt of org. acid and bromate and to provide superior bleaching power by separating the replenisher into a replenisher contg. the metallic complex salt of org. acid and a replenisher contg. the bromate and by mixing them immediately before replenishment. CONSTITUTION:A replenisher A contg. metallic complex salt of org. acid consisting of aminopolycarboxylic acid, org. phosphonic acid or the like and metallic ion such as Fe<+++> and a replenisher B contg. bromate and adjusted to 3-12, especially 4-8pH with NaOH or acetic acid are stored in different storage tanks until they are added to a bleaching bath. A soln. overflowing from a bleaching tank may be recovered and used as the replenisher A as it is or after supplying the insufficient component. Since the amount of bromate in the recovered soln. is small, the influence is slight. The pH of the replenisher B is kept at said value to improve the stability. Thus, the shelf stability of the replenishers is improved, rapid fixing and long-term continuous use of a bleaching bath are enabled, and imperfect recoloring, defective desilvering, etc. are prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material.2 More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material. The present invention provides a method for processing silver halide color photographic materials that maintains good bleaching performance.

Generally, in order to obtain color AM by developing a silver halide color photographic light-sensitive material that has been exposed to light, the developed silver image is bleached with an oxidizing agent (bleaching agent) after the color development process.
Next, a step of desilvering and fixing is performed using a fixing agent.

. Bleaching solutions used in the bleaching process have been known to contain bleaching agents such as metal complex salts of organic acids such as ferric salt monochloride or ethylenecyamine thisilacetate. .

Red blood salt and ferric chloride as bleaching agents are good bleaching agents in that they have high oxidizing power. But Naka! The bleaching solution used as a bleaching agent becomes cyan due to photolysis! - Since it is a serious pollution, we must take measures to make it completely harmless. In addition, the use of ferric chloride bleach and L-chloride has the disadvantage that the PM content is very low and the oxidizing power is very high, so the parts of the processing machine that fills the pipe are corroded and the quality is poor. It has the disadvantage that iron hydroxide precipitates in the emulsion layer and generates new stain in the washing process after the bleaching process.

For this reason, cleaning using an organic chelating agent in the bleaching solution @tab
This does not meet the objectives of rapid processing and labor saving, and also poses problems in terms of pollution control. Compared to ferric chloride and ferric chloride, metal complex salts of organic acids such as ethylenediaminetetraacetate iron complex salts are less toxic and are advantageous in terms of pollution control, so their use as bleaching agents has been recommended in recent years.

However, organometallic complex salts have relatively low oxidizing power and have insufficient bleaching properties, so those using them as bleaching agents are
For example, when a low-sensitivity silver halide color photographic light-sensitive material containing a silver chlorobromide emulsion is subjected to bleach anchoring or bleach-fixing processing, the desired purpose can be achieved in some cases.
However, this was not enough, and silver halide color photographic materials containing silver iodide or silver iodobromide emulsions as main components and color sensitized silver halide color photographic materials, especially silver halide color photographic materials using high silver content emulsions, were developed. In the case of treatment, the bleaching effect is insufficient and the removal is poor, resulting in poor bleaching efficiency and difficulty in achieving the desired purpose. In view of the above-mentioned requirements for pollution prevention, it is desirable to use a complex salt of an organic acid such as iron complex salt of i-ethylenedi7centetraacetate as a whitening agent. Unless this point is solved, the purpose of rapidly processing high-sensitivity silver halide color photographic materials cannot be achieved.

Conventionally, as a means for increasing the bleaching ability of a bleaching solution using an organic acid metal complex salt such as an iron complex salt of ethylene diacetatetraacetate as a bleaching agent, thiourea derivatives such as those described in Japanese Patent Publication No. 4B-8506, especially Addition of bleaching accelerators such as heptalenourea derivatives as described in Japanese Patent No. 1,138,842, and five-membered ring mercapto compounds as described in British Patent No. 1,138,842. A technique of adding hydrogen peroxide as described in JP-A-50-1097311, etc., JP-A-51-65
Publication No. 937: Hemorrhoids! The technique of adding persulfate such as JJ is described in Japanese Patent Publication No. 35-1478, etc.;
Techniques for adding bromate salts, such as those described in Publication No. 2, have become known. However, these techniques do not necessarily produce a satisfactory bleaching promotion effect;
In addition, although it has an excellent bleaching accelerating effect, it lacks stability in the processing solution, so the effective life of the processing solution is short and it cannot withstand long-term storage, which is a disadvantage 8□L
, r, %M.

Further, the processing solution added to keep the activity of the processing solution in the processing tank constant is hereinafter referred to as a replenisher. ), there is a trend toward lower replenishment from economical and pollution standpoints, and for this reason, the replenisher has a much higher concentration than the treated bulbs in the treatment tank, and it is becoming increasingly difficult to store the replenisher for a long period of time. For this reason, long-term storage stability of the replenisher can be said to be an essential photographic performance. Furthermore, in recent years, rapid processing has been desired, and therefore, an improvement in bleaching speed is required. However, the bleaching solution using a mixture of bromate and electrometal ##- has sufficient bleaching effect and bleaching speed, but the positive quality is rather poor, and it is difficult to use. In particular, the high concentration □ replenisher has extremely low q stability.

□Therefore, our first goal is to develop a silver halide color photographic sensitizer using a replenisher that has sufficient bleaching performance without defective color restoration or desilvering, and has excellent long-term shelf life. The second object of the present invention, which provides a method for processing materials, is that it has low toxicity and prevents pollution! 1
lls: The purpose of this paper is to provide method t-1, a processing method for silver halide color photographic materials that are compatible with JB continuous processing and have excellent bleaching speed. As a result, when processing a silver halide color photographic light-sensitive material with a bleaching solution containing an organic acid metal complex salt and a bromate, a replenisher containing an organic acid metal complex salt and a bromine salt-containing replenisher are used. It has been discovered that the above-mentioned object can be achieved by using a structure consisting of (II) and (II) separated from each other.

The organometallic complex salt according to one aspect of the invention has the function of oxidizing the group silver produced by development and converting it into silver halide, and at the same time coloring the uncolored part of the color former, and its structure is organic. Phosphonic acid, 7 minoboricarvone l! It is made by coordinating metal ions such as iron, cobalt, steel, etc. with an organic acid such as oxalic acid or citric acid.・The most commonly used metal salts of such organic acids are Preferred organic acids include, for example, 7-minobolycarboxylic acids represented by the following general formula CI] or (II).

General formula CI) HOOO-M, -Z-A, -00011 General formula (II
) [In each of the above general formulas, 'A1. A Hiroshi, Mu @ @ A4
g, and 4 are each substituted or < is an unsubstituted hydrocarbon group, 2 is a hydrocarbon group, an oxygen atom, a sulfur atom, or >
N-mu1. (M1 is a substituted or unsubstituted hydrocarbon group or lower fatty acid carboxylic acid). 〕′
"t'L'1f174/'9*"-→・,・,,II
427''''1 salt, ammonium salt or □water-soluble amine salt may be used. Said general formula CI) or (II
) or other 7
Typical examples of cenoboricarboxylic acids include the following.

' Ethylene di7enteF diethylene triacetate Ethylene diamine pentaacetate (/-oxyethyl) -M
, M i N/propylenediamine triacetatetetraacetic acid di)lilotriacetic acid cycloheon! Methyliminodiacetic acid, methyliminodiacetic acid, vinegar, hydroxyiminodiacetic acid ° □ Shetyldaricin ethyl ether in Zidro '-, 1 ethyl acetate, ethyl acetate, disodium salt, ethylene thiamine, thiothioacetate, ethyl ammonium salt, ethylene cyamine, ethyl acetate, diethylene triamine, pentaacetic acid, pentasodium salt, ethylene Diamine-M-(β-oxyethyl-N,N':
N'-F sodium acetate salt propylene diamine sodium tetraacetate disintegrated nitrilotriacetic acid sodium salt cyclohexanediamine decilacetic acid sodium salt Also preferably used ``Representative examples of organic phosphonic acids include the following.'' 0 Ethylene cyano tecilyl methylene phosphonic acid nitria a) Rimethylene phosphonic acid 1,3-diaminopropanol M, M, M', M'-
Tetramethylenephosphonic acid The metal ion of these organometallic complex salts according to the present invention is preferably $12 iron ion, in which case the amount of the complex salt is 1 mol or 1 mol of o or oo per 1 j of bleaching solution,
Preferably from 0.01 mol to 0.01 mol. ! It is S mole.

The bromine salts used in the present invention are full metal salts or ammonium salts, such as potassium bromate, bromate salts, etc.
Lithium bromate, ammonium bromate, lithium bromate, etc.The usage amount per 1j of bleaching solution is 0.
2 to 501, preferably LO to 2DI. This is So, less than 2tt/1, enough, 26
Bleaching effect, benefits, and benefits 2. ≠Flaws, and if the amount exceeds K)III, budding sudenes will occur and it cannot be used.

In addition, in the present invention, the bromine salt is free from organometallic complex salt.
When adding an intermediate rate agent represented by the following general formula [phase], the above general formula (I), or the above general formula (III) to the replenishment f(B), which has a It is particularly preferred because it does not decompose clay and does not generate hydroxides due to calcium or magnesium.

General formula [phase] B-PG, M.

[In the above general formula, M is a hydrogen atom, sodium, potassium'
Indicates alkali metals such as aluminum, lithium, etc. or ammonium. B It shows carboxylic acid, phosphonic acid, hydroxyl group; sulfonic acid 1 Substituent such as amino group □Carbohydrate 1 to 6 fulkyl group 'o) General formula (I) added to replenisher -) Among the compounds of LGID, it is particularly preferable because it has excellent effects such as converting bromate into a benzene.Specific examples of the compounds used are as follows. F
Roxyethyliminodiacetate (diethylene) liamine sodium pentaacetate Nitritetraacetic acid sodium salt 2-phosphonobutane-1,2,4-)licarboxylic acid ethylenecyamine thisilamethylene phosphonic acid 1,3-diaminopropanol-Hōmachi i ,w'-Tesilaacetic acid ethylenecyamine thisilium acetate Nasylium salt Further, at pH 3f = Jq, the bromate salt is not stable, so the bromate is not stable.
11111.11゜pH'''3゜NL, 12F) Range-1''1. ．． 1
When used in the range of 14 to 8, favorable effects are obtained.

The bleaching solution used in the present invention contains the metal anchor ring of the above-mentioned gold-added organic acid as a bleaching agent, and may also contain one kind of additive.゛Do ~ Re-hengenizing agents such as potassium bromide, sodium bromide, sulfurium chloride, ammonium chloride A1 ammonium bromide, etc. Alternatively, it is possible to contain two or more types.

Also, the pH of borates, borates-acetates, carbonates, phosphates, etc.
Things known to be added to ordinary bleaching solutions such as buffering agents, 7-senocarboxylic acids or their bases, fulkylaminol, substituted fluorinated thiols, and lyethylene oxides can be added as appropriate.・Furthermore, the bleaching solution according to the present invention is II! 3.0 to 9
, used in the Oe range, special &-PM4. Oye L
'7. o 61) 1""t L , <,, C&゛6
R! .

For use in the present invention. The liquid is bromate and organometallic complex.
- A replenisher that is substantially free of salt may be used, and other additives may coexist in either part.

In addition, in the bleaching method of the present invention, the liquid tube containing over 7El can be recovered from the processing tank during replenishment and used repeatedly as part of the replenisher. At this time, bromine salts and organic acid metal complex salts coexist in the overflow liquid, but the presence of bromate can be ignored because the bromate in the overflow liquid decreases greatly over time. It is common to simply use the organic acid as a replenisher containing metal complex gold.

At this time, all or part of the overflow liquid may be used as a replenishment liquid, or all or part of the recovered overflow liquid may be supplemented with missing components and water before being refilled. You may also serve it.

A variety of devices may be used in the method of pumping the replenisher of the present invention. For example, a conduit is used to transfer alkaline to a bleaching tank.
At least two replenishment tanks are installed, one replenishment tank containing a replenishment solution containing a bromate ring tube and the other replenishment tank containing a replenishment solution containing an organic acid metal complex salt (4). There is a method of adding the replenisher to the bleaching tank separately when refilling the tube, a method of mixing the replenishing solution (4) and the replenishing solution -) on the way to the bleaching tank, and then adding it to the bleaching tank,
The replenishment tank containing the replenisher -) and the replenishment tank containing the replenisher wI are connected in series through a conduit II! A possible method is to first add the replenisher (#LiL) to the replenisher (4) and then add it to the tm white processing tank. In any case, in the type immediately before replenishing the processing tank, it is desirable to separate the replenisher solution (2) and the replenisher solution (φ) as much as possible.

In the processing method for the heat-generating color photographic material of the present invention, a combination of known processing steps can be used as the processing steps, and the following steps include, but are not limited to: isn't it.

■ Color development - constant bleaching, one wash, one stable Φ Color development - bleaching - small amount of constant washing, one washing, one stable ■ Color development - constant bleaching, one washing, one washing, one stable ■ Color development - one small amount of bleach Wash with constant water - Wash with water - Stable 0 Color development wing image - Stop - Bleach 1 Small amount of water Wash with constant color - Preliminary wash - Wash with water - Stable■ Color development - Supplementary color bleach - Small amount of water wash with constant wear - Wash with water 1 Wash with water - Stable 0 Stability (2) Color development - Stop - Bleaching - Constant fixing - Preparation - Washing - Stability Among the above steps, one in which a pre-washing step is provided next to the fixing step is preferably used in the present invention. The reason for this is that polluting components that adhere to silver halide photographic light-sensitive materials during the washing process are extremely reduced, and soluble silver salts dissolved in the fixing solution are less likely to be lost to the washing process. This is because favorable results can be obtained socially, environmentally, and economically, such as by increasing collection efficiency. Further, it is preferable that the number of processing steps is small in terms of rapid processing, and therefore, among the above steps, steps (1) and (2) are particularly preferably used in the present invention.

Hurricane applicable to the present invention 4. -Color photographic light-sensitive materials are manufactured using an internal development method in which the coloring agent is contained in the halogenated photographic material (for example, Hyogoku Patent No. 2, 37).
No. 6.679, the specification of No. 2,801,171, etc.).

In addition, external methods in which a coloring agent is included in the aqueous solution (e.g., U.S. Pat. No. 2,252,718, $2,5
No. 92°243, No. 2,590470, etc.). As the heavy color former, any of those commonly known in the art can be used. For example, as a cyan color former, an indoaniline dye based on 7)-al or phenol structure is formed by coupling one, and as a magenta color former, an active methylene dye is used as a magenta color former.
-5-pyrazoline ring having a ring group.

The skeleton structure and yellow coloring include benzoylacetonilide having an active methylene chain;
Biparyl ace) Ayulide 1 Allerua 7) Ani□Ride structure 'rnt*N'tsra with or without a substituent at the coupling position such as 'V%V'.

, · and ayo'>e*colorant atrtt, so-called 2-equivalent turnip)- and 4-equivalent coupler if f'L. □v
*11: l'%is, T ah. □、6゜・Silver germide emulsion and L; ゛ is silver chloride, silver bromide, silver iodide, filled silver emulsion,
Any silver halide such as silver chloroiodide, silver iodobromide, and silver chloroiodobromide may be used. Especially silver iodobromide,
In the case of silver chloroiodobromide, the effects of the present invention are fully exhibited. Furthermore, as protective colloids for silver halide, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.

The present invention can be used regardless of the processing deviation of all silver halide color photographic materials such as color negative film, color pane, color reversal film, and color negative film. It is most effective when used in the processing of silver halide color photographic light-sensitive materials using high silver content emulsions when the total silver content is (9) da per ood or more, and especially when the total silver content is 40 da or more per ood. It is advantageous to use it in processing certain silver halide color photographic materials.

Next, according to the example, is □ the invention? This is an example, but the embodiments of the present invention are not limited thereto.

Example 1 An antihalation layer and a gelatin layer were provided on a syriacetate film base, and thereon a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive halogen layer. The silver oxide emulsion layer was coated to give a total silver content of '96 parts per 100 parts. At this time, the blue-sensitive silver halide emulsion layer contains α-(4-diphenophenol)-α-vivalluz as a yellow coupler.
1-(2
,4,6-)rikvsayenyl)-3-((α-(2
, 4-di1-7acetamido]benzamide)-5-pyrazoline and 1-(2,4,
6-) Red sensitivity using -3-([α-(λ4-di-tert-phenoxy)7cetamido]pensamide)-4-(4-methodiphenylazo)-6-pyrazolone In the silver halide emulsion layer, 1. -Hydroxy-N-(α, -(2,4-t-
Amylphenoxy)butyl)-2-su7amide was used, and conventional additives such as sensitized colored threads, hardeners, and spreading agents were added to each emulsion layer. The silver halide color negative light-sensitive material thus obtained was used as a sample.

After photographing this sample using a Konica '11B-1 camera (manufactured by Konishiroku Photo Industry Co., Ltd.), it was continuously processed using an automatic processor according to the following steps. The automatic developing machine used was a modified automatic film developing machine type H4-728 manufactured by Noritsu Koki Co., Ltd.

Processing process II (38°C) Number of tanks Processing time The composition of the alternating color developing solution ρ is as follows.

[Potassium-acid 301] The composition of the color development replenishment solution used is as follows.

The composition of the fixer used was as follows.

The composition of the fixing replenisher used was as follows: O--ammonium osulfate 220I The composition of the stabilizer used was as follows.

The #M composition of the used replenishment solution is as follows.

The color development/replenishment liquid is replenished into the color image bath with 15-11 color wings per 100-color negative film, and the fixing replenishment liquid is
97-1111 for the fixing bath
%, and fixer replenisher was added to the IR bath at 111 sl per 1.0 of color negative and film. In addition, the water in the preliminary washing bath is 100 cs of color negative film.
The washing bath was filled with 3 ml of water per 100 ml of color negative film.

In addition, the composition of the bleaching solution used is as follows. - is used to adjust T to νH3,0.

The composition of the replenisher used was as follows.

, this replenisher) is added at a rate of 151kIjll per 100aI of color negative film, and at the same time, the replenisher (
B) was replenished in a separate conduit to 31 bleach baths per color negative film loo di @20m per day in this way. Color negative film was processed and processed continuously for 10 days.
The replenisher (4) was first prepared in advance at 3001, and the replenisher* (!I) was also prepared in advance at 6 oI, and used in this continuous treatment. The treated liquid tube thus prepared after 10 days of continuous treatment was used as the bleaching bath liquid (a) of the present invention.

Furthermore, 300 j of the supplementary liquid (A) and the replenishing liquid (
B) A comparative bleaching bath solution (B) was prepared by processing 601 continuously for 10 days in the same manner as above using a replenisher and 1 ton of ℃ temperature.

The bleaching bath solutions (l&) and (b) prepared in this way are
1cs-7! The color negative film, which had been subjected to white stage exposure using an Ii sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), was subjected to a color development process according to the steps described above. After this color development process was completed, the maximum density of the red photosensitive layer was measured using a PDA-omega type electroconcentration needle (manufactured by Konishiroku Photo Industry Co., Ltd.).

Furthermore, the bleaching bath solution (~
The amount of bromate before and after the continuous treatment in (b) was measured, and the reduction rate (a) was determined.

The results are summarized in Table 1.0 Table 1 (Note 1) i! The large density is the measured value of the maximum density part minus the capri density.

Example 2 The replenisher (B) used in Example 1 was mixed with calcium ion II Op p m and iron (m) ion 5 p, p, y.
a. Comparative sample solution (0) dissolved with water contained;
The above replenisher solution contains 1- and deoxyethylidene-1,1-.
The sample solution (2) of the present invention is obtained by adding 11/l of diphosphonic acid and dissolving it in the same water, and the sample solution of the present invention is obtained by adding 11/l of hydroxyethyliminodiacetic acid to the replenisher solution (-) and dissolving it in the same water. A comparative sample solution (7) was prepared by adding 11/l of trigly sodium phosphate to solution (2) and the above-mentioned replenisher solution and dissolving it in the same water. The results of observing the appearance of this sample solution (0) or self) are shown in Table 2. Table 2 (Note 2) In the table, the number of X indicates the amount of precipitate, and the larger the number, the more precipitate. .

Example 3 Replenisher (9) 11 used in Example 1 was added to 2.3.5.
7. Sample solution prepared using sodium hydroxide or acetic acid according to 11゜11 (()) 72 Ishiku 1)
And so. This sample solution (G) or 6) was heated to 38'C,
It was stored in a beaker for 1 month, and the appearance was observed, and at the same time, the reduction rate of bromate after 1 month was measured.

The results are shown in Table 3.

Table 3 As mentioned above, from Example 1, the anchor ring method according to the present invention takes 2 minutes (
There is no problem even with extremely short bleaching time of seconds.
In the case of using a mixture of salt and bromate, the bromate is severely reduced and a leuco dye is formed, resulting in poor color restoration and cannot be put to practical use. Furthermore, from Example 2, replenishment liquid)
When the chelating agent according to the present invention is added to water, there is no problem even if the water is of very poor quality. However, if no chelating agent is used or a chelating agent other than the present invention is used, It can be seen that hydroxide is generated so much that it cannot be put to practical use. Furthermore, from Example 3, the p of the replenisher (B)
It was found that a range of H in the range of 3 to 9 is good, but in other cases, bromine gas is generated and bromine rIII11 is decomposed to a large extent, making it impossible to put it to practical use.

: Agent Yoshi Kuwa Hara Shu ,・p%− ゛・:j

Claims (1)

[Claims] In a method for processing a silver halide color photographic light-sensitive material in which a silver halide color photographic light-sensitive material is treated with a bleaching solution containing an organic acid metal complex salt and a bromate salt. Silver halide color photographic sensitization characterized by using a bleaching replenisher composed of a solution (A) and a replenisher (B) containing bromate acid and salt separated from each other!・How to process fees.