JPH09319044A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing the silver halide color photographic sensitive material having solved problems on bleach fog and degradation of dye density and suitable for rapid processing by using a peroxide compound as a bleaching agent. SOLUTION: This processing method has a process for processing the photosensitive material in a time of 5-30sec by using the peroxide compound and at least one kind of specified ferric complex salt of aminopolycarboxylic acid. As the peroxide compound, persulfuric acid or its salt is used and a concentration of the peroxide is controlled to 0.02-1.0mol/l and a pH of the bleaching solution is set in 2.5-5.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter, also referred to as "light-sensitive material"), and more specifically, a rapid bleaching property can be obtained, and bleach fog and dye density can be improved. The present invention relates to a treatment method in which the decrease is reduced and the color recovery of the dye is excellent.

[0002]

2. Description of the Related Art A technique of using a peroxide having a good bleaching property and a biodegradability as a bleaching agent is disclosed in US Pat.
5,956, JP-A-6-214365, 7-29.
As described in No. 5174, etc., all of them have a long processing time of about 1 minute, and use a stoppage, a washing tank, etc., which makes it difficult to cope with rapid processing.

[0003]

[Problems to be Solved by the Invention] In recent years, due to the increase in the number of minilab stores, there is an ever-increasing demand for faster processing. Further, from the viewpoint of environmental protection, it is desired to render the photographic processing waste liquid harmless. From these points, it has been studied to use a peroxide as a bleaching agent. However, since the peroxide has a very strong oxidizing power, a bleaching fog in which an unexposed portion is colored is likely to occur. Bleached fog is a color that is colored on a white background, especially in color paper, and greatly reduces the commercial value as a photograph.

There is also a problem that the oxidative power decomposes the dye formed in the color developing process to lower the color density.

Further, the bleaching property is often insufficient when the peroxide alone is used. As described in JP-A-54-147039,
It is necessary to add a mercapto compound to the tank before the bleaching tank. This mercapto compound generally has an odor, which is a serious problem from the viewpoint of the working environment of the automatic processor.

The present invention has been made in view of the above circumstances, and an object thereof is to use a peroxide as a bleaching agent,
It is an object of the present invention to provide a processing method of a silver halide color photographic light-sensitive material which solves the problems of bleaching fog and decrease in dye concentration and is suitable for rapid processing.

[0007]

The above object of the present invention is at least one selected from peroxides and ferric complex salts of the compounds represented by the general formulas (K-1) to (K-4). A method of processing a silver halide color photographic light-sensitive material, which comprises a step of processing for 5 to 30 seconds using a bleaching solution containing A bleaching solution, the peroxide is persulfuric acid or a salt thereof, and the bleaching solution has a pH of 2.5 to 5.
0, and the processing step using the bleaching solution is performed immediately after the completion of the color development step.

Hereinafter, the present invention will be described in detail.

In the present invention, a peroxide is used as the bleaching agent, and at least one selected from the ferric complex salts of the compounds represented by the general formulas (K-1) to (K-4) is used in combination. ~
It is characterized by processing in a short time within a range of 30 seconds.

The peroxide used in the present invention includes persulfuric acid or its salt, percarbonic acid or its salt, hydrogen peroxide or its salt, perboric acid or its salt, perhalogenic acid or its salt, peracetic acid or its salt. , Perbenzoic acid or a salt thereof, and the like, of which persulfuric acid or a salt thereof, percarbonic acid or a salt thereof, perhalogenic acid or a salt thereof are preferable, and persulfuric acid or a salt thereof is particularly preferable. These peroxides may be used alone or in combination.

These peroxides are used in a concentration of 0.02 mol / liter or more, more preferably 0.04 mol / liter or more, 1.0 mol / liter or less, further 0.5 mol / liter or less, It is preferable from the viewpoint of processability and reduction of bleaching fog.

Next, specific examples of the compounds represented by the general formulas (K-1) to (K-4) will be shown, but the invention is not limited thereto.

[0013]

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[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

[Chemical 12]

[0021]

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[0022]

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[0023]

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From the viewpoint of adjusting the pH, the above compound is N
It may be a salt of a, K, NH ₄ , Li or the like, and may be used alone or in combination of two or more kinds. Further, the above compound may contain water of crystallization. The preferred compound is K-
1-25, K-1-26, K-2-1, K-3-2, K
-3-16 and K-4-1 are mentioned.

The ferric complex salt of the above compound is used in an amount of at least 0.10 mol per liter of the tank solution of the bleaching solution,
The content is preferably in the range of 0.10 to 0.5 mol, more preferably 0.10 to 0.25 mol / liter.

The bleaching solution of the present invention contains p containing various salts.
The H buffer may be used alone or in combination of two or more. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Further, compounds known to be added to ordinary bleaching solutions such as alkylamines and polyethylene oxides can be appropriately added.

The bleaching solution of the present invention is used in a pH range of 2.5 to 5.0, and more preferably in a pH range of 3.5 to 4.5, from the viewpoint of color recovery and peroxide storage. preferable.

The replenishing amount of the bleaching solution of the present invention is 200 ml / m.
^It is preferably ² or less, more preferably 100 ml / m ² or less.

The bleaching solution of the present invention preferably contains an organic acid compound represented by the following general formula.

Formula A '(-COOM) _{n In the} formula, A'represents an n-valent organic group, n represents an integer of 1 to 6, M represents ammonium, an alkali metal (sodium,
Potassium, lithium, etc.) or a hydrogen atom.

In the general formula [A], n represented by A '
Examples of the valent organic group include an alkylene group (methylene group, ethylene group, trimethylene group, tetramethylene group, etc.), alkenylene group (ethenylene group, etc.), alkynylene group (ethynylene group, etc.), cycloalkylene group (1,4-cyclohexane). Diyl group, etc.), arylene group (o-phenylene group, p-phenylene group, etc.), alkanetriyl group (1,
2,3-propanetriyl group, etc.) and aryletriyl group (1,2,4-benzenetriyl group, etc.).

The n-valent group represented by A'described above includes those having a substituent (hydroxy group, alkyl group, halogen atom, etc.) (1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-group). 1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloroethynylene and the like).

The processing time of the bleaching step of the present invention is in the range of 5 to 30 seconds, but from the viewpoint of bleaching property and reduction of dyes, it is 5 to 5 seconds.
It is preferably in the range of 10 seconds.

Next, preferable specific processing steps of the processing method of the present invention are shown below.

(1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Coloring development → bleaching → fixing → first Stable → Second stability (5) Color development → Bleach → Bleach-fix → Water wash (6) Color development → Bleach → Bleach-fix → Water wash → Stable (7) Color development → Bleach → Bleach-fix → Stable (8) Color development → Bleach ->Bleach-fixing-> 1st stability-> 2nd stability (9) Color development->Bleach-> Bleach fixing->Fixing->Washing-> Stable (10) Color development->Bleach-> Bleach fixing->Fixing-> 1st stability->
Second stability (11) Color development → stop → bleaching → fixing → stable (12) Color development → stop → washing → bleaching → fixing → stable Among these steps, (1) to (10) are preferable, and further ( 3), (4), (7) and (10) are preferable, and (3) and (4) are particularly preferable.

In the present invention, in order to increase the activity of the bleaching solution, air or oxygen may be blown in the treatment bath and the treatment replenisher storage tank, if desired.

In the present invention, the color developing agent used in the color developing step is preferably a p-phenylenediamine compound having a water-soluble group. When the water-soluble group is p
- at least one there that are mentioned on the amino group or benzene nucleus of phenylene diamine compounds, as a specific water-soluble group _{- (CH 2) n -CH 2} OH, - (CH 2)
_{m -NHSO 2 - (CH 2)} n CH 3, - (CH 2) m -O-
_{(CH 2) n -CH 3,} - (CH 2 CH 2 O) n C m H 2m + 1,
(M and n each represent an integer of 0 or more.) -COO
H group, —SO ₃ H group and the like are mentioned as preferable ones.

Examples of specific compounds preferably used in such a color developing agent include the following (C-1) to (C-
18).

[0039]

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[0040]

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[0041]

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Preferred of these compounds are (C
-1), (C-2), (C-3), (C-4), (C-
15), (C-17) and (C-18).

The color developing agent is preferably a hydrochloride salt,
It is used in the form of sulfate, nitrate and p-toluenesulfonate. The amount of the color developing agent is in the range of 2.5 × 10 ^{−3 to} 5.5 × 10 ⁻² mol, preferably 5.0 × 10 ^{−3 to} 2.5 × 10 per liter of the color developing solution. ^-2 mol.

Further, the following general formula [A] is added to the color developing solution.
The inclusion of the organic preservative represented by [B] is preferable for rapid processing and reduction of bluing, and it is also preferable because crystal protrusion on the liquid surface of the color developer tank can be suppressed.

[0045]

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[0046]

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A detailed description of the compound represented by the general formula [A] is given in JP-A-4-67038, and a detailed description of the compound represented by the general formula [B] is given in JP-A-4-21846. It The compound represented by the general formula [A] or [B] is usually used in the form of free amine, hydrochloride, nitrate, oxalate, phosphate, acetate and the like.

The concentration of the compound represented by the general formula [A] or [B] in the color developing solution is usually 0.2 to 50 g / liter, preferably 0.5 to 30 g / liter, more preferably 1 to 15 g. / Liter. Further, the compound represented by the general formula [A] or [B] can be used in combination with the conventionally used hydroxylamine and organic preservative, but it is preferable to use no hydroxylamine for development. It is preferable from the viewpoint of sex.

In addition to the above, the color developing solution may contain the following developing solution components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate,
Potassium metaborate, trisodium phosphate, tripotassium phosphate, borax and the like can be used alone or in combination within a range where precipitation does not occur and a pH stabilizing effect is maintained. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

The color developer preferably contains a fluorescent whitening agent. The fluorescent whitening agent not only improves the white background performance of the unexposed areas of the light-sensitive material, but also provides good results in preventing crystal precipitation.

The fluorescent whitening agent is preferably a triazinyl stilbene type compound, and particularly preferably a compound represented by the following general formula [F].

[0053]

[Chemical 21]

Detailed description of the compound represented by formula [F] is described in JP-A-4-76038. Further, the triazinyl stilbene-based whitening agent can be synthesized by the usual method described in, for example, “Fluorescent Whitening Agent” (published in August 1976), page 8 edited by Chemical Industry Association. The compound F- exemplified in the above-mentioned publication is preferable as the optical brightener.
4, F-24, F-34, F-35, F-36, F-3
7, F-41. The triazinyl stilbene whitening agent is preferably used in an amount of 0.2 to 10 g, and more preferably 0.4 to 5 g, per liter of the color developing solution.

Further, it is preferable to add a chelating agent represented by the following general formula [L] to the color developing solution.

[0056]

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A detailed description of the compound represented by formula [L] is also given in JP-A-4-76038.

The pH of the color developing solution is preferably 9.5 or more and 13.0 or less, and more preferably 9.8 or more and 12.5 or less. The replenishing amount of the color developing solution is preferably 600 ml / m ² or less, more preferably 20 to 100 ml / m ^2.
It is.

The fixing agent used in the fixing solution is a compound which reacts with silver halide to form a water-soluble complex salt, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate and thiocyanate. Examples thereof include thiocyanates such as sodium acid salt and ammonium thiocyanate, thioureas, thioethers, mesoions, and alkylthiosulfonates.

In addition to these fixing agents, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
A single pH buffer or two or more pH buffers composed of various salts such as sodium acetate and ammonium hydroxide can be contained. Further, pH buffers such as borate, oxalate, acetate, carbonate, phosphate, etc., and those known to be added to ordinary fixing solutions and bleach-fixing solutions such as alkylamines and polyethylene oxides are appropriately added. be able to.

The fixing agent was added in an amount of 0.
It is used in an amount of 1 mol or more, preferably in the range of 0.6 to 4 mol, particularly preferably in the range of 0.9 to 3.0 mol, particularly preferably in the range of 1.1 to 2.0 mol.

The pH of the fixing solution is preferably in the range of 4-8.

The fixing solution preferably contains a sulfite and a sulfite-releasing compound, and examples of the compound include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite and meta. Examples include sodium bisulfite and ammonium metabisulfite. Furthermore, the compound represented by the following general formula [M-1] or [M-2] is also included.

[0064]

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In the formula, R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁸ is an optionally substituted alkyl group having 1 to 5 carbon atoms, M ′ is an alkali metal atom, and R ¹⁹ and R ²⁰ are A hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, n
₁₀ represents an integer of 0 to 4.

Specific examples of the compound represented by the above general formula are shown below, but the invention is not limited thereto.

M-1 Formaldehyde Sodium Bisulfite M-2 Acetaldehyde Sodium Bisulfite M-3 Propionaldehyde Sodium Bisulfite M-4 Butylaldehyde Sodium Bisulfite M-5 Succinic Aldehyde Sodium Bisulfite M-6 Glutaraldehyde Bisulfite Sodium M-7 β-Methylglutaraldehyde bis sodium bisulfite M-8 Maleic acid dialdehyde bis sodium bisulfite These sulfites and sulphite-releasing compounds are at least 0.1 mol of sulfurous acid per liter of fixer or bleach-fixer. Preferably 0.12 to 0.5
The range of 5 mol / liter is preferable, and 0.15 to 0.5
A range of 0 mol / liter is particularly preferred. The range of 0.20 to 0.40 mol / liter is particularly preferable.
However, the number of moles of these sulfites and sulfite-releasing compounds is shown as a value converted to sulfite.

It may also contain an alkylsulfinic acid compound.

In carrying out the method of the present invention, silver may be recovered from the processing solution having fixing ability by various methods, and the silver recovery method may be any method as long as silver can be recovered from the processing solution having fixing ability. Any of them may be used, for example, an electrolysis method (see French Patent 2,299,667), a precipitation method (JP-A-52-73037, and German Patents 2,331,22).
No. 0), an ion exchange method (JP-A-51-17114).
No. 2, German Patent No. 2,548,237) and the metal substitution method (see British Patent No. 1,353,805) can be effectively used.

The processing solution having the fixing ability after the recovery of silver is returned to the original processing tank having the fixing ability, but an antioxidant such as sulfite can be added before returning.

In the present invention, it is preferable to carry out the stabilizing treatment without substantially washing with water subsequent to the bleach-fixing treatment or the fixing treatment.

Stabilizers used for the stabilizing treatment include the general formula [CH-I] described in JP-A-3-243948.
It is preferable to contain a chelating agent represented by [CH-III]. The amount of the chelating agent used is preferably 0.01 to 100 g per liter of the stabilizing solution, more preferably 0.1.
It is in the range of 05 to 50 g, particularly preferably 0.1 to 2
The range is 0 g.

The stabilizing solution preferably contains a metal salt in combination with the chelating agent. Examples of such metal salts are Ba, Ca, Ce, Co, In, La, Mn, Ni,
There are metal salts of Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr, and inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelates. It can be supplied as an agent.

To the stabilizing solution, organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloric acid, sulfate salts, etc.) are added. can do.

Known antifungal agents can be used alone or in combination.

Further, in the processing of the present invention, silver may be recovered from the stabilizing solution by a known method.

Further, the stabilizing solution is subjected to ion exchange treatment, electrodialysis treatment (see JP-A-61-28949) and reverse osmosis treatment (JP-A-60-240153 and JP-A-62-25415).
No. 1). It is also preferable to use water which has been previously deionized from water used for the stabilizing solution. That is, the antifungal property of the stabilizer, the stability of the stabilizer, and the image storability are improved. As a means of the deionization treatment, any method may be used as long as the Ca and Mg ions of the washing water after the treatment are reduced to 5 ppm or less. For example, treatment with an ion exchange resin or a reverse osmosis membrane may be used alone or in combination. preferable. The ion exchange resin and the reverse osmosis membrane are described in detail in JP-A-87-1984 and JP-A-89-20511.

No washing treatment is required after the stabilizing treatment, but rinsing, surface washing and the like can be optionally performed by washing with a small amount of water within an extremely short time.

The pH of the stabilizing solution is preferably in the range of 5.5 to 10.0. The pH adjusting agent that can be contained in the stabilizing solution may be any of generally known alkali agents or acid agents.

The stabilizing tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, and particularly preferably 2 to 3 tanks in a counter current system (supplied to the post-bath. It is preferable to adopt a method of overflowing from the previous bath).

Examples of the light-sensitive material processed by the processing method of the present invention include silver halide photographic light-sensitive materials containing silver chloride, silver chlorobromide, silver bromide and silver iodobromide emulsions, and these are magnetic materials. It may have a recording layer.

[0082]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 FIG. 1 is a schematic configuration diagram of a main part of an automatic developing machine (hereinafter, also referred to as “developing machine”) used in this example. The processing tank of this automatic processor had the structure shown in FIG. In the automatic developing machine of FIG. 1, the photosensitive material P is exposed and then conveyed by a plurality of pairs of feed rollers and first processed in a color development processing tank CD. After that, the bleaching treatment tank BL, the fixing treatment tank Fix, and the stabilization tank STB are sequentially conveyed by the roller conveying means and processed. The photosensitive material P which has been subjected to each of these processes is dried in the drying section and discharged outside the machine.

The structure of the treatment tank of FIG. 2 is shown below.

In the photosensitive material processing tank 1Y, the lower side of the processing tank tank having a shape along the transfer path is defined, and the lower member 13Y also serves as a transfer guide for the silver halide photographic photosensitive material. On the transport path between the upper member 12Y, which defines the shape of the upper side of the processing tank along the transport path and also serves as a transport guide for the silver halide photographic light-sensitive material, and the lower member 13Y and the upper member 12Y. It has transport rollers 16Y, 17Y, 18Y for driving the silver halide photographic light-sensitive material and transporting the silver halide photographic light-sensitive material. Then, only the insertion port 14Y and the discharge port 15Y of the transport path defined between the lower member 13Y and the upper member 12Y are
It is the gas-liquid interface of the processing liquid in the processing tank 1Y. Further, although not shown, the transition guide 28 provided in close contact with the upper member 13Y on the downstream side of the discharge path 15Y in the transport path.
Crossing roller pair 30 which is a facing roller that conveys the silver halide photographic light-sensitive material along Y and the crossing guide 28Y.
Y is provided.

On the side of the photosensitive material processing tank 1Y, the processing tank 1 is provided.
It has an auxiliary tank 2Y provided separately from Y. Then, a circulation pipe 21Y is formed from the processing tank 1Y to the lower part of the auxiliary tank 2Y so that the processing liquid can flow.

The rod-shaped heater 26Y penetrates the upper wall of the auxiliary tank 2Y and is immersed in the processing liquid in the auxiliary tank 2Y. The heater 26Y is connected to a processing liquid circulation path and a processing tank 1 based on a temperature detected by a thermometer (not shown) provided in the auxiliary tank 2Y.
The processing solution in Y is heated, in other words, the processing solution in the processing tank 1Y is heated to a temperature range suitable for processing (for example, 20 ° C.).
To 55 ° C.).

The plate-shaped filter 22Y is used for the auxiliary tank 2
Y and a circulation pipe 29Y to the processing liquid storage tank 4Y
The auxiliary tank 2Y is provided so as to be replaceable, and has a function of removing insolubles, for example, precipitates and the like in the processing liquid. The circulation pipe 29Y communicates with the lower part of the auxiliary tank 2Y and the upper part of the processing liquid storage tank 4Y. The lower part of the processing liquid storage tank 4Y is connected to the suction side of a circulation pump 24Y (circulation means) via a circulation pipe 23Y provided through the lower wall of the processing liquid storage tank 4Y.

The circulation system is the auxiliary tank 2Y / circulation pipe 2
The processing tank 1Y includes the processing liquid circulation path formed by 9Y, the processing liquid storage tank 4Y, the circulation pipe 23Y, the circulation pump 24Y, and the circulation pipe 25Y. The other end of the circulation pipe 25Y communicating with the discharge side of the circulation pump 24Y penetrates the lower wall of the processing tank 1Y, and is connected to a nozzle 27Y that uniformly discharges the processing liquid in the width direction toward the transport path of the processing tank 1Y. Communicating. With such a configuration, when the circulation pump 24Y is operated, the processing liquid is sucked from the auxiliary tank 2Y, discharged to the processing tank 1Y, and again circulated into the auxiliary tank 2Y.

The bleaching time was adjusted as shown in the table by replacing the upper and lower members of the bleaching tank with the automatic processor of FIG.
Color paper manufactured by Konica Color QA Paper Type A6 was processed under the following processing conditions.

(Treatment Step) (Treatment Time) (Treatment Temperature) Color development 25 seconds 39.5 ° C. Bleach Described in table 38.0 ° C. fixation 10 seconds 38.0 ° C. stability 60 seconds 38.0 ° C. Dry 30 seconds 80.0 ° C. (color developer composition) bis (sulfoethyl) hydroxylamine disodium 2.0 g sodium p-toluenesulfonate 20.0 g optical brightener F 1.0 g potassium carbonate 30.0 g diethylenetriamine pentaacetic acid 5 sodium 2.0 g Color developing agent C-1 7.5 g Potassium chloride 4.0 g Water is added to make 1 liter, and the pH is adjusted to 10.0 with sulfuric acid or potassium hydroxide.

[0092]

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(Bleaching liquid composition) Compound shown in the table 1 g Ammonium salt of ferric complex salt of the compound 0.13 mol Peroxide shown in the table 0.05 mol Succinic acid 20 g Ammonium bromide 100 g Water was added. 1 liter, pH 4 with sulfuric acid or aqueous ammonia (25%). Adjust to 0.

(Fixing Solution Composition) Sodium sulfite 10 g Ammonium thiosulfate 80 g Ethylenediaminetetraacetic acid 2 g Water was added to make 1 liter, and pH was adjusted to 6 with sulfuric acid or aqueous ammonia (25%). Adjust to 0.

(Stabilizing Solution) 1-Hydroxyethylidene-1,1-diphosphonic acid (60% solution) 5 g Ethylenediaminetetraacetic acid 1 g Sodium sulfite 0.5 g Water was added to make 1 liter, and sulfuric acid or ammonia water (25%) PH of 7. Adjust to 0.

The photographic material after processing was evaluated for bleaching property and the maximum color density (Dmax (M)) at 550 nm was measured.

<< Evaluation of Bleachability >> 10 of the photographic material after processing
The maximum reflection density (Dmax) and the minimum reflection density (Dmin) of 00 nm were measured using an infrared densitometer, and evaluated by the values obtained by the following formula.

Bleachability = Dmax-Dmin The results are shown in Tables 1 and 2.

[0099]

[Table 1]

[0100]

[Table 2]

Thus, by using a bleaching solution in which a peroxide and a ferric complex salt of the compound of the present invention are used in combination, it is possible to obtain good bleaching properties and a concentration of a coloring dye by adjusting the processing time. It is understood that the effect is remarkably exhibited by the sulfuric acid compound.

Example 2 The bleaching step was carried out for 10 seconds, the amount of ammonium persulfate shown in Table 3 was used as the peroxide, and 0.13 mol / liter of the ammonium salt of the ferric complex salt of compound K-1-25 was used. The bleaching property was evaluated and the minimum density (Dmin (Y)) at 440 nm of the unexposed area was measured in the same manner as in Example 1 except that the above was used. The results are shown in Table 3.

[0103]

[Table 3]

From this, it is understood that bleaching fog can be suppressed and good bleaching properties can be obtained by setting the addition amount of ammonium persulfate in the range of 0.02 to 1.0 mol / liter.

Example 3 In Example 2, the concentration of ammonium persulfate was adjusted to 0.0.
The bleaching property and the recoloring property were evaluated in the same manner as in Example 2 except that the amount of the bleaching solution was changed to 5 mol / liter and the pH of the bleaching solution was changed as shown in Table 4.

<< Evaluation of Recoloring Property >> The concentration D ₁ of 660 nm of the treated whole surface exposed sample was measured, and this sample was further immersed in an aqueous solution of ethylenediaminetetraammonium iron acetate (30 g / liter, pH 7.0, 30 ° C.). After soaking for a minute, D
In and again measuring the 660nm density D ₂ equal portions and _one of the measurement was evaluated by [Delta] D = D ₂ -D _1.

The results are shown in Table 4.

[0108]

[Table 4]

From Table 4, the pH of the bleaching solution is 2.5 to 5.0.
It is understood that good bleaching property and color recovery property can be obtained by adjusting to the range.

Example 4 Preparation of magnetic recording medium << Preparation of support >> 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were mixed with 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst. After the addition, a transesterification reaction was carried out according to a conventional method.
To the obtained product, 0.05 parts by weight of antimony trioxide,
0.03 parts by weight of trimethyl phosphate was added.
Then gradually raise the temperature and reduce the pressure to 290 ° C, 0.05 mm
Polymerization was performed under the conditions of Hg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

This was vacuum-dried at 150 ° C. for 8 hours, then melt-extruded in layers from a T-die at 300 ° C., adhered to a cooling drum at 50 ° C. while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. in a total transverse stretching ratio of 3. It was stretched so as to be three times. Then 10
Heat treated at 0 ° C for 2 seconds, and further heat-fixed zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while performing a 5% relaxation treatment in the lateral direction to obtain a polyethylene naphthalate film having a thickness of 85 μm.

Wrap this around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to form a support.

12 W / m ² / min on both sides of this support
Of the undercoating coating solution B-1
To a dry film thickness of 0.4 μm and then apply 1
A 2 W / m ² / min corona discharge treatment was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment of 12 W / m ² / min, the undercoat coating solution B-3 was applied to give a dry film thickness of 0.
2 μm, and 12 W / m ² / m
An in-corona discharge treatment was performed, and a coating solution B-4 was applied so as to have a dry film thickness of 0.2 μm.

Each layer was dried at 90 ° C. for 10 seconds after coating, and after four layers were coated, heat treatment was performed at 110 ° C. for 2 minutes, followed by cooling treatment at 50 ° C. for 30 seconds.

<Undercoating Coating Liquid B-1> Copolymer latex liquid of butyl acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxyethyl acrylate 25% by weight (solid content 30% ) 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Undercoating liquid B-2> Hydroxylation of styrene-maleic anhydride copolymer Aqueous sodium solution (solid content 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size 3 μ) 0.2 g Finish with water 1000 ml <Coating liquid B-3> Butyl Acrylate 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight and 2-hydroxy acrylate 25 % By weight of copolymer latex liquid (solid content 30%) 50 g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (ethylene urea) 1.1 g Finish with water 1000 ml

[0118]

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<Coating Liquid B-4> 60 mol% of dimethyl terephthalate as dicarboxylic acid component, 30 mol% of dimethyl isophthalate, 10 mol% of sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol as glycol component, 50 mol% of diethylene glycol was copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

Water dispersion of tin oxide-antimony oxide composite fine particles (average particle size 0.2 μ) (solid content 40% by weight) 109 g Water dispersion A 67 g Finish with water 1000 ml << Coating of magnetic recording layer >> Undercoat layer U- of the treated support
On the layer coated with the coating liquid, the coating liquid for the magnetic recording layer having the following composition was dried at a dry film thickness of 0.1 using a precision extrusion coater.
The coating was applied so as to have a thickness of 8 μm, and at the same time as drying, the magnetic substance was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

[Composition and Preparation of Magnetic Recording Layer Coating Solution M-1] Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Specific surface area 40 m ² / g, Hc = 750 Oe) 10 parts by weight Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 3 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132, Japan) Polyurethane Co., Ltd. 15 parts by weight Stearic acid 2 parts by weight Cyclohexanone 920 parts by weight Acetone 920 parts by weight After thoroughly mixing and dispersing the above, a polyisocyanate of Coronate-3041 (manufactured by Nippon Polyurethane Co., Ltd., solid) 50% by weight), and then sufficiently stirred and mixed to obtain a magnetic paint M-1.

<< Coating of Lubricant Layer >> A lubricant coating solution (wax solution below) dispersed in a water / methanol mixed solution so as to contain 0.1% of carnauba wax on the magnetic recording layer was prepared. The coating amount was 15 mg / m ² . The raw material after the wax application was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of Wax Liquid) Polyoxyethylene lauryl ether 4 was added to 100 parts by weight of water heated to 90 ° C.
After mixing with 40 parts by weight of carnauba wax separately melted at 90 ° C., the mixture was sufficiently stirred using a high-speed stirring homogenizer to prepare a carnauba wax dispersion (WAX1). .

Next, 995 parts by weight of water, 900 parts by weight of methanol and 10 parts of propylene glycol monomethyl ether.
0 parts by weight, and 5 parts by weight of WAX1 was added thereto.
The mixture was stirred to prepare a wax liquid.

After forming an undercoat layer on the side opposite to the magnetic recording layer side of the magnetic recording medium, the undercoat coating solutions B-1 and B-2 were applied under the same conditions, and then the composition shown below was used. Sample 101 was provided with a photographic constituent layer. The addition amount is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and the increasing dye (indicated by SD) was shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.044 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) AS-10 .16 OIL-1 0.20 Gelatin 1.40 Third layer (low-sensitivity red color-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-4 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 SD-6 3.0 × 10 ^-6 C-1 0.51 CC-1 0.047 OIL-2 0.45 AS- 2 0.005 Gelatin 1.40 4th layer (medium sensitivity red color-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ⁻⁵ SD-2 1.5 × 10 ⁻⁴ SD− ^{3 3.0 × 10 -4 C-2} 0.22 CC-1 0.028 DI-1 0.002 OIL-2 0.21 AS-3 0.006 Zera Down 0.87 Fifth Layer (high sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.14 SD-1 3.0 × 10 -5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.085 C-3 0.084 CC-1 0.029 DI-1 0.027 OIL-2 0.23 AS-3 0.013 Gelatin 1 .23 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 SD-6 5.0 × 10 ^-4 SD-5 5.0 × 10 ^-4 M-1 0.21 CM-2 0.039 OIL-1 0.25 AS-2 0.003 AS-4 0.063 gelatin 0.98 8th layer (intermediate layer) M-1 0.03 CM-2 0.005 OIL-1 0.16 AS-1 0.11 gelatin 0.80 9th layer (medium speed green color-sensitive layer) Silver iodobromide e 0.87 SD-7 3.0 × 10 ^-4 SD-8 6.0 × 10 ^-5 SD-9 4.0 × 10 ^-5 M-1 0.17 CM-2 0.048 CM-3 0.059 DI-2 0.012 OIL-1 0.29 AS-4 0.05 AS-2 0.005 Gelatin 1.43 10 layers (high sensitivity green color-sensitive layer) Silver iodobromide f 1.19 SD-7 4.0 × 10 ^-4 SD-8 8.0 × 10 ^-5 SD-9 5.0 × 10 ^-5 M -1 0.09 CM-3 0.020 DI-3 0.005 OIL-1 0.11 AS-4 0.026 AS-5 0.014 AS-6 0.006 Gelatin 0.78 11th layer (yellow Filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-7 0.16 Gelatin 1.00 12th layer (low sensitivity blue color Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-10 8.0 × 10 ^-4 SD-11 3.1 × 10 ^-4 Y-1 0.91 DI-40 022 OIL-1 0.37 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-10 4. 4 × 10 ^-4 SD-11 1.5 × 10 ^-4 Y-1 0.48 DI-4 0.019 OIL-1 0.21 AS-2 0.004 Gelatin 1.55 14th layer (first protection) Layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 Gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55 In addition to the above composition, coating aids SU-1 and S -
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 two types of polyvinylpyrrolidone (AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1, H-2 and the preservative Ase-1 were added.

The structure of the compound used in the above sample is shown below.

Table 5 shows the characteristics of the above silver iodobromide.

[0129]

[Table 5]

[0130]

[Chemical formula 26]

[0131]

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[0132]

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[0133]

[Chemical 29]

[0134]

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[0135]

[Chemical 31]

[0136]

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[0137]

[Chemical 33]

[0138]

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The magnetic recording medium thus produced was cut into 1-inch widths and 300-meter lengths, and a test pattern was image-exposed and a magnetic writing head recorded a square wave signal of 6 kHz at a conveying speed of 100 mm / sec. (Model magnetic recording) and wound on a reel. This light-sensitive material was subjected to the same experiment as in Example 1 under the following processing conditions by using the automatic processor shown in FIG.

(Treatment Step) Treatment Step Treatment Time Treatment Temperature Replenishment Amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach Table 6 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml stability 60 seconds 38 ± 5.0 ° C. 830 ml dry 1 minute 55 ± 5.0 ° C. − * Replenishment amount is a value per 1 m ² of the light-sensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution and color developing replenishing solution Developer replenishing solution Replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriamine pentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water was added to make 1 liter, and the color developer was adjusted to pH 10.06 with potassium hydroxide or 20% sulfuric acid, and the replenisher was adjusted to pH 10. Adjust to 18.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700 ml 700 ml Ammonium salt of ferric complex salt of compound shown in Table 6 125 g 175 g Compound shown in Table 6 2 g 2 g Sodium nitrate 40 g 50 g Ammonium bromide 150 g 200 g Amber Acid 40 g 56 g Peroxide shown in Table 6 0.05 mol 0.06 mol Water was added to make 1 liter, and the bleaching solution was adjusted to pH 3 with ammonia water or glacial acetic acid. Adjust the pH of the replenisher to 0 and the replenisher to pH 2.5.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 ml 800 ml Ammonium thiosulfate 200 g 240 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g 3-Mercapto-1,2,4-triazole 0.5 g 0.5 g Ammonia water or ice The fixing solution is adjusted to pH 6.2 with acetic acid and the replenisher is adjusted to pH 6.5, and water is added to make 1 liter.

Stabilizer and stable replenisher Water 900 ml Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0. After 5 ml of water was added to make 1 liter, pH was adjusted to 8 with ammonia water or 50% sulfuric acid. Adjust to 5.

Magnetically recorded information on the developed photosensitive material was read by a magnetic head at a transport speed of 100 mm / sec, and at the same time, the occurrence of clogging of the magnetic head was evaluated. In addition, the transport speed is 200
The running stability at mm / sec was also investigated.

<< Evaluation of Clogging of Magnetic Head >> A square wave signal was read by the magnetic reading head at the same transport speed, and the point where the output dropped by 2 dB or more from the initial value was taken as the head clog generation point. The generation level of head clogs was evaluated by the length (m). It means that the smaller the value is, that is, the lesser the head clog is generated in the shorter distance, the less preferable.

<< Evaluation of Running Stability >> The operation of running for 0.15 seconds at a conveying speed of 200 mm / second, then stopping for 0.3 seconds and then running again at 200 mm / second was repeated continuously, and jamming occurred. The situation was evaluated.

Good: No jamming occurred. Defect: Occurred at least once every 10 m.

Table 6 shows the results.

[0151]

[Table 6]

[0152]

EFFECTS OF THE INVENTION According to the present invention, good bleaching property and color-reversing property can be obtained without causing bleaching fog problem even when a rapid treatment is carried out using a peroxide as a bleaching agent.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a main part of an automatic developing machine used in an embodiment.

FIG. 2 is a diagram showing a configuration of a processing tank of the automatic processor of FIG.

[Explanation of reference numerals] 1Y processing tank 2Y auxiliary tank 4Y processing liquid storage tank 12Y upper member 13Y lower member 16Y transport roller 24Y circulation pump 25Y circulation pipe 27Y nozzle for discharging processing liquid

Claims (5)

[Claims] 1. A bleaching solution containing a peroxide and at least one selected from ferric complex salts of compounds represented by the following general formulas (K-1) to (K-4) is used. A method of processing a silver halide color photographic light-sensitive material, which comprises a step of processing for 30 seconds. Embedded image [In the formula, A _{1 to} A ₄ are each a hydrogen atom, a hydroxy group,
_{COOZ, -PO 3 (Z 1)} 2, -CH 2 COOZ 2, -C
H ₂ OH or a lower alkyl group which may have a substituent, Z, Z ₁ and Z ₂ are each a hydrogen atom, an ammonium group,
Represents an alkali metal or organic ammonium group, A ₁ ~
At least one of A ₄ is —COOZ, —PO ₃ (Z ₁ ) ₂ ,
It is a -CH ₂ COOZ _2. R ₁ and R ₂ each represent a hydrogen atom or a lower alkyl group which may have a substituent, and adjacent groups may form a ring. k _{1 to} k ₄ and l each represent 1 to 4. These may constitute stereoisomers. [Chemical formula 2] Wherein, A ₁₁ to A ₁₄ are each, -CH ₂ OH, -COOZ ₃
Or —PO ₃ (Z ₄ ) ₂ and each of Z ₃ and Z ₄ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. W is an alkylene group having 2 to 6 carbon atoms or-
_{(B 1 O) m -B 2} - represents, each B ₁ and B ₂ represents an alkylene group having 1 to 5 carbon atoms, m represents 1-8. ] [Chemical 3] [In the formula, A _{21 to} A ₂₄ may be the same or different and each represents a hydrogen atom, a hydroxy group, —COOM ′, or —PO.
₃ (M ₂₁ ) ₂ , —CH ₂ COOM ₂₂ , —CH ₂ OH or a lower alkyl group which may have a substituent. However, A ₂₁ ~
At least one of A ₂₄ is -COOM ', -PO
₃ (M ₂₁ ) ₂ and —CH ₂ COOM ₂₂ . M ₂₁ , M ₂₂ ,
Each M'represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. [Formula 4] [In the formula, R ₁₁ represents a hydrogen atom or a substituent, M ₃₁ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group, and Q is necessary to form a 5- to 7-membered nitrogen-containing heterocycle. And Q may be further condensed with a heterocycle. m ₁₁ represents 0 to a substitutable number in the nitrogen-containing heterocycle, and m ₁₂ represents 0 or 1. ] 2. The concentration of the peroxide is 0.02 to 1.0.
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the bleaching solution is mol / liter. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the peroxide is persulfuric acid or a salt thereof. 4. The method for processing a silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the bleaching solution has a pH of 2.5 to 5.0. 5. The processing of a silver halide color photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein the processing step using the bleaching solution is carried out immediately after the completion of the color developing step. Method.