JPH11119384A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To restrain occurrence of precipitate due to a hardener without using a boric acid for a fixing solution containing the hardener, by processing the photosensitive material with a developer containing a specified compound and a fixing agent containing a specified compound. SOLUTION: The photosensitive material is processed by using the developer containing a compound represented by the formula and the fixing solution containing substantially no boric acid but a compound having a calcium chelate- stabilizing coefficient of 0.8-5.0. In the formula, each of R1 and R2 is an optionally substituted alkyl or amino or alkoxy or alkylthio group and may combine with each other to form a ring; (k) is 0 or 1; when k=1, X is a -CO- or -CSgroup; and each of M1 and M2 is H or an alkali metal atom. The compound having a calcium-chelate stabilizing coefficient of 0.8-5.0 can be embodied by oxalic acid, maleic acid, citraconic acid, itaconic acid, glycine, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic material using a fixing solution containing a hardener.

[0002]

2. Description of the Related Art Conventionally, an acidic fixing solution containing a hardener has been used as a fixing solution for processing a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) for printing plate making. Aluminum compounds are mainly used as hardeners, but boric acid compounds are sometimes used to prevent precipitation of this hardly soluble aluminum salt, since aluminum salts are unstable and tend to precipitate. Many.

On the other hand, in recent years, it has been required to reduce the replenishment amount of the fixing solution from the viewpoint of the environment. However, when development and fixing are performed at a low replenishment amount, precipitation presumably of a hardly soluble aluminum salt is likely to occur. Become.

[0004] Nevertheless, there has been a demand for removing boric acid from the treating agent due to the demand for reducing the environmental load.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to use a hardener without using a boric acid compound in a hardener containing the hardener. The purpose is to suppress the occurrence of precipitation.

[0006]

An object of the present invention is to provide a developer containing the compound represented by the above general formula (A), and a method for stabilizing a chelate with calcium which is substantially free of boric acid. A processing method for a silver halide photographic material, wherein the processing is performed using a fixing agent containing a compound having a constant of 0.8 to 5.0.

That is, the present inventors have made the fixing agent contain a compound having a chelate stabilization constant of 0.8 to 5.0 with calcium, and the developer contains the compound represented by the general formula (A). The present inventors have found that the formation of precipitates can be suppressed by performing the process, and have led to the present invention.

Hereinafter, the present invention will be described.

In the present invention, the chelate stabilization constant with calcium is a logarithm of a formation constant in which one chelating agent is bound to one calcium ion, and is measured at 20 ° C. and an ionic strength of 0.2. Shall be done. Specific examples of the compound of the present invention having a chelate stabilization constant of 0.8 to 5.0 with calcium (hereinafter, also referred to as the compound of the present invention) include oxalic acid, maleic acid, citraconic acid, itaconic acid, and glycine. , Citric acid, gluconic acid, glyceric acid,
Examples include glucoheptanoic acid, glycolic acid, malic acid, tartaric acid and salts thereof.

In the present invention, the stabilization constant of the compound capable of chelating with calcium ions is preferably 0.9 to 3.0, more preferably 1.0 to 2.5. , Gluconic acid, glucoheptanoic acid and their derivatives and salts can be preferably used.

The compound of the present invention is used at a concentration of about 0.005 to 0.2 mol / l, preferably 0.005 to 0.1 mol / l, and may be used alone or in combination of two or more. Good.

The compound represented by the general formula (A) includes
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is preferred.

[0013]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄
Represents R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the general formula (A) and the general formula [Aa] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group or an unsubstituted amino group. An amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Preferred examples of the group which can be substituted include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or [Aa] according to the present invention are shown below.
It is not limited to these.

[0017]

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[0018]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

The developer and the fixing agent according to the present invention comprise powder,
The treatment may be performed in any form such as a paste, granules, tablets, a concentrated solution, and a used solution, but granules, tablets, and a concentrated solution are preferred. When used as a starting solution, they are used by adjusting them by dissolving them in water or the like. When it is used as a replenisher, it is used by mixing and dissolving it with water in advance, or by directly putting it into an automatic developing machine.

In the developer, sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite, and metabisulfite are used as preservatives.
Sulfite is 0.25 mol / l or more, especially 0.4 mol / l
1 or more is preferably used.

An alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Is preferred. As the pH buffer, a carbonate is preferable, and the amount of the carbonate added is 0.5 to 1 l.
~ 2.5 mol is preferred, more preferably 0.75-
The range is 1.5 moles. If necessary, dissolution aids (polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (nonionic surfactants including polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoaming Agents, antifoggants (halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (ethylenediaminetetraacetic acid or its alkali) Metal salts, nitrilotriacetates, polyphosphates, etc.),
A development accelerator (a compound described in U.S. Pat. No. 2,304,025, Japanese Patent Publication No. 47-45541, etc.), a hardening agent (glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent Can be added. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5.
More preferably, the pH is 8.5 or more and 10.4 or less.

Other commonly used fixing solutions can be used as the fixing solution according to the present invention. pH is usually 3.8 ~
5.8, thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate;
In addition to thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixing solution according to the present invention preferably contains a thiosulfate. Examples of the thiosulfate include lithium, potassium, sodium, and ammonium salts, and are preferably sodium or ammonium salts. The addition amount of thiosulfate is 0.1 to 5 mol, preferably 0.5 to 2.0 mol, more preferably 0.7 to 1 mol per liter of the fixing solution.
〜1.8 mol, most preferably 0.8-1.5 mol.

The concentration of ammonium ions in the fixing solution according to the present invention is preferably 0.1 mol or less per liter of the fixing solution, and particularly preferably in the range of 0 to 0.05 mol. Sodium thiosulfate may be used instead of ammonium thiosulfate as the fixing agent, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

The fixing solution according to the present invention contains, in addition to a water-soluble aluminum salt acting as a hardening agent such as aluminum chloride, aluminum sulfate and potassium alum, an aldehyde compound (glutaraldehyde or a sulfurous acid adduct of glutaraldehyde). Etc. can also be added. If desired, preservatives (sulfites, bisulfites, etc.), pH buffers (acetic acid,
Compounds such as citric acid), a pH adjuster (such as sulfuric acid), and a chelating agent capable of softening water.

The acetate ion concentration in the fixing solution is preferably less than 0.33 mol / l. As with any compound that dissociates acetate ions in the fixing solution, acetic acid or lithium, potassium, sodium, ammonium salts of acetic acid and the like are preferable, and sodium salts and ammonium salts are particularly preferable. The acetate ion concentration is more preferably 0.22 mol or less, particularly preferably 0.13 mol or less, per liter of the fixing solution, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

After exposure, the photosensitive material for printing plate making is generally processed in a process of development, fixing, washing or stabilization using an automatic developing machine, and the processing method of the present invention is performed using such an automatic developing machine. Is what you do.

In this case, in order to reduce the amount of waste liquid, processing is carried out while replenishing a fixed amount in proportion to the area of the photosensitive material in the developing step and the fixing step. The development replenishment amount is preferably 300 ml or less, more preferably 30 to ² per m ² of the photosensitive material.
It is 50 ml. Fixing replenishing amount The replenishing amount is preferably 30 to 400 ml, more preferably 60 to 400 ml per m ² of the light-sensitive material.
３５０350 ml. The replenishing amount referred to here is the replenishing amount of the liquid when replenishing the same liquid as the mother liquor in the tank, and the total amount of the concentrated liquid and water when replenishing the concentrated liquid with a solution diluted with water, This is the total volume of the solid processing agent and the volume of water when the processing agent is replenished with a solution dissolved in water, and the total volume of the solid processing agent and the volume of water when the solid processing agent and water are separately replenished. Quantity.

Particularly, the replenishment amount of the development is 1 / m ^{2 of the} light-sensitive material.
In the case of 20 ml or less, the developing replenisher is preferably a liquid or a solid processing agent different from the developing mother liquor in the developing tank of the automatic developing machine, and the amount of the mercapto group-containing silver sludge inhibitor contained in the developing replenisher is Is preferably larger than the amount contained in the developing mother liquor, and the general formula (A) contained in the developing replenisher is
Is 1.2 times the amount contained in the developing mother liquor.
Preferably, the amount is twice to four times. In particular, when the replenishing amount of the fixing is 150 ml or less per m ^{2 of the} photosensitive material, the replenishing solution is preferably a liquid or a solid processing agent different from the fixing mother liquor in the tank of the automatic developing machine, and is included in the replenishing solution. The amount of thiosulfate is preferably larger than the amount contained in the fixing mother liquor.

From the demand for shortening the developing time, it is preferable that the total processing time from the insertion of the leading end of the photosensitive material into the automatic developing machine to the exit from the drying zone is 10 to 80 seconds. The total processing time as referred to herein includes the total processing time required for processing the photosensitive material, and specifically includes the processing time required for processing, such as development, fixing, bleaching, washing, stabilizing processing, and drying. This is the time including all the time, that is, the time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time is 15 to 44 seconds. In order to stably process a large amount of photosensitive material of 10 m ² or more, the developing time is preferably 18 seconds or less and 2 seconds or more.

In the present invention, an automatic developing machine having the method and mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column (2) Washing water regeneration purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638 388
(2) Lower left column of page 391 (5) Lower left column of page (4) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) Lower right column to page 501 (7) Lower right column and JP-A-2-1080
No. 51, page 588 (2), lower left column to page 589 (3), lower left column (7) Method for recovering silver of fixing waste liquid: JP-A-6-27623, page (4), "0012" to page (7), "0071".

In the present invention, after the fixing process, it is washed and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, the film pH is adjusted (the film surface after treatment is p
Inorganic and organic acids and salts thereof, or alkali agents and salts thereof (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, hydroxide) Sodium, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid,
Malic acid, acetic acid, etc. used in combination, aldehydes (formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphates, etc.), anti-biotic agents (Phenol, 4-chlorophenol,
Cresol, o-phenylphenol, chlorophene,
Dichlorophen, formaldehyde, p-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzoisothiazolin-3-one, dodecyl-benzyl-methylammonium-chloride, N-
(Fluorodichloromethylthio) phthalimide, 2,
4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, 2-mercapto-5 -Sodium sulfonate-benzimidazole, 1-phenyl-5
-Mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-
Triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form. When replenished in a solid state, the above-described method for producing and using the solid processing agent can be used.

[0035]

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

Example 1 The following experiment was carried out using a return film REL for RST express system manufactured by Konica Corporation.

(Preparation of developer) Pure water 500 g Diethylenetriaminepentaacetic acid 4 g Sodium metabisulfite 10 g Potassium bromide 2.5 g Potassium carbonate 55.2 g Compound represented by formula (A) described in Table 1 8-mercaptoadenine 0.075 g 5-methylbenzotriazole 0.55 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone (dimesone S) 2.65 g 1-phenyl-5-mercaptotetrazole 0.04 g potassium hydroxide 7. After dissolving 4 g, make up to 1 liter with pure water.

(Preparation of Fixing Solution) Ammonium thiosulfate 140 g Pure water 130 g Sodium sulfite 25 g Compound of the present invention listed in Table 1 Sodium acetate trihydrate 32.27 g Acetic acid (90%) 16.27 g Aluminum sulfate 27% aqueous solution 33 g dissolved Thereafter, the solution was adjusted to 1 liter with pure water and adjusted to pH 4.70.

(Processing conditions) Automatic developing machine G manufactured by Konica Corporation
X-680 was used under the following conditions.

Temperature (° C.) Time (second) Replenishment amount (ml / one sheet) Developing 35 15 50 Fixing 35 10 100 Washing Normal temperature 8 Drying 50 10 (Processing) Daizen where 20% of the area was exposed under the above conditions The photosensitive material having a size of 500 sheets was processed per day and ran for 10 days.

(Evaluation of Precipitation Condition in Fixing Solution Tank) After the completion of running, the processed film, the fixing solution tank and the transport rack in the fixing solution tank were observed, and the deposition condition was evaluated. Rank 3 indicates a level that is not problematic for practical use although rank 3 shows slight precipitation on the tank and rack. Racks 2 and 1 have deposits deposited on the bottom of the tank and deposits adhered to the processed film. It was evaluated on a five-point scale as a level that does not withstand use.

The results are shown in Table 1.

[0043]

[Table 1]

[0044]

According to the present invention, it is possible to suppress the occurrence of precipitation caused by the hardener even without using a boric acid compound in the fixing solution.

Claims (1)

[Claims] 1. A developer containing a compound represented by the following general formula (A), and a chelate stabilization constant with calcium that is substantially free of boric acid and 0.8 to 5.0. A method for processing a silver halide photographic material, wherein the processing is performed using a fixing agent containing a compound. Embedded image Wherein R ₁ and R ₂ are each a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group,
R ₁ and R ₂ may combine with each other to form a ring. k is 0
Or 1 and when k = 1, X is -CO- or -CS-
Represents M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ]