JPH10268482A - Photographic processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photographic processing method for the silver halide photographic sensitive material restrained from occurrence of residual dye stains even in the case of rapid processing with low replenishing and superior in silver color tone and sensitivity and aftercolor by executing development and fixation processing in the presence of specified compound. SOLUTION: The development processing is carried out in the presence of the compound represented by formula I and reductones and the fixation processing is operated in the presence of a compound or its salt, and in formulae I and II, each of Y and Z is an N atom or a CR2 group; R2 is an H atom or the like; R1 is one or more sulfo or carboxy or hydroxy groups or the like; M is an H or alkali metal atom or the like; each of R3 -R5 is an alkylene group and each may have an ether bond and R3 and R5 , and R4 and R5 may combine with each other to form a ring; each of A and B, independently, an H atom or an alkyl or carboxy group or the like and each may combine with each other to form a ring; and (n) is an integer of 0-10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic processing method for a silver halide photographic light-sensitive material, and more particularly, to a halogenation method which has excellent residual color and silver tone even in rapid low replenishment processing, and excellent sensitivity and fixability (residual silver). The present invention relates to a photographic processing method for a silver photographic material.

[0002]

2. Description of the Related Art In recent years, in photographic processing of silver halide photographic light-sensitive materials, there has been a demand for a processing agent which achieves a low replenishment with a small amount of processing waste liquid in order to reduce an environmental load and does not contain hydroquinone which is an environmental pollutant. ing. Also, in medical practice, rapid processing is required.

[0003] However, rapid replenishment leads to deterioration of residual color and silver tone. In addition, when the replenishment is rapidly reduced, the sensitivity is reduced. As a means for achieving high sensitivity, a method using an emulsion grain having an increased iodide content in a silver halide emulsion has been conventionally disclosed, but the problem is that the fixability deteriorates when the iodine content is increased. was there.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photographic processing of a silver halide photographic light-sensitive material which is excellent in residual color and silver tone and excellent in sensitivity and fixability (residual silver) even in rapid low replenishment processing. It is to provide a method.

[0005]

The above objects of the present invention have been attained by the following constitutions.

(1). In a photographic processing method in which a silver halide photographic light-sensitive material provided with a hydrophilic colloid layer including at least one silver halide emulsion layer on a support is subjected to photographic processing including development processing and fixing processing, the development processing is described below. The fixing treatment is performed in the presence of a compound represented by the general formula (1) and reductones or a derivative thereof, and the fixing treatment is performed in the presence of a compound represented by the following general formula (2) or a salt thereof. A photographic processing method for a silver halide photographic material.

[0007]

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[Wherein, Y and Z represent N or CR ₂ , and R ₂ represents a hydrogen atom, or a substituted or unsubstituted alkyl or aryl group, respectively. R ₁ represents at least one sulfo group, a carboxy group, a hydroxy group or a salt thereof, or an alkyl group substituted with a —B (OH) ₂ group, and the same applies when there are two or more such substituents. Or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. ]

[0009]

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[Wherein R ₃ , R ₄ and R ₅ represent an alkylene group. These alkylene groups may have an ether bond. R ₃ and R ₅ or R ₄ and R ₅ may form a ring. A and B may be the same or different, and include a hydrogen atom, an alkyl group, an amino group, an ammonium group,
It represents a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group, and A and B may form a ring. n represents an integer of 0 to 10. (2). The photographic processing method for a silver halide photographic material according to (1), wherein the compound represented by the general formula (1) is contained in the silver halide photographic material.

(3). 2. The photographic processing method of a silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is contained in a developer.

(4). In a photographic processing method in which a silver halide photographic light-sensitive material provided with a hydrophilic colloid layer including at least one silver halide emulsion layer on a support is subjected to photographic processing including development processing and fixing processing, the development processing is preferably performed by a reductone. Alternatively, the fixing treatment is performed in the presence of a compound represented by the general formula (2) in the presence of a derivative containing 50 to 200 mg / l of iodine ion in terms of KI in the presence of a derivative thereof. A photographic processing method for a silver halide photographic material.

(5). In a photographic processing method in which a silver halide photographic light-sensitive material provided with a hydrophilic colloid layer including at least one silver halide emulsion layer on a support is subjected to photographic processing including development processing and fixing processing, the development processing is described below. In the presence of the compound represented by the general formula (1) and reductones or derivatives thereof, iodide ions are converted to 50 to 20 in terms of KI.
Photographic processing of a silver halide photographic light-sensitive material, wherein the processing is carried out with a developing solution containing 0 mg / l and the fixing processing is performed in the presence of a compound represented by the following general formula (2) or a salt thereof. Method.

(6). The photographic processing method for a silver halide photographic light-sensitive material according to any one of (1) to (5), wherein the supply of the development replenisher in the development processing is supplied as a solid processing agent.

(7). (1) to (1), wherein the amount of the developing replenisher in the developing process and the amount of the fixing replenisher in the fixing process are 300 ml / m ² or less, respectively.
A photographic processing method for a silver halide photographic light-sensitive material according to any one of (6) and (6).

That is, this time, a silver halide photographic light-sensitive material is subjected to a developing treatment in the presence of a compound represented by the general formula (1) and a fixing treatment using a processing solution containing the compound represented by the general formula (2). When processed, the residual color and the silver tone were effective. This effect has been found to be significant only when reductones are used as a developing agent.

Further, in this case, when the silver halide photographic light-sensitive material is processed in a system in which KI is added to a developer and a compound represented by the general formula (2) is added to a fixing solution, high sensitivity can be obtained even in rapid processing. It has become possible to provide a photosensitive material having excellent fixability. Particularly, this tendency is remarkable only when the developing agent is a reductone, and it has been found that the residual color is excellent.

Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (1) will be described.

[0020]

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[Wherein, Y and Z represent N or CR ₂ , and R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group, respectively. R ₁ represents at least one sulfo group, a carboxy group, a hydroxy group or a salt thereof, or an alkyl group substituted with a —B (OH) ₂ group, and the same applies when there are two or more such substituents. Or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. In the general formula (1), examples of the alkyl group substituted with at least one sulfo group, carboxy group, hydroxy group or a salt thereof represented by R ₁ , or an alkyl group substituted with a —B (OH) ₂ group include A linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, hexyl group, dodecyl group, isopropyl group, etc.);
Examples thereof include a cycloalkyl group having 1 to 20 carbon atoms (eg, a cyclopropyl group, a cyclohexyl group, and the like).

The alkyl group substituted by at least one sulfo group, carboxy group, hydroxy group or a salt thereof represented by R ₁ or an alkyl group substituted by -B (OH) ₂ group may be further substituted, For example, a halogen atom (eg, F, Cl, Br, etc.), an alkyl group (eg, a methyl group,
An ethyl group), an aryl group (eg, a phenyl group), an alkoxy group (eg, a methoxy group, an ethoxy group), an aryloxy group (eg, a phenoxy group),
A sulfonyl group (eg, a methanesulfonyl group, a p-toluenesulfonyl group, etc.), a carbamoyl group (eg, an unsubstituted carbamoyl group, a diethylcarbamoyl group, etc.), an amide group (eg, an acetamido group, a benzamide group, etc.),
An alkoxycarbonylamino group (such as a methoxycarbonylamino group), an aryloxycarbonylamino group (such as a phenoxycarbonylamino group), an alkoxycarbonyl group (such as a methoxycarbonyl group), an aryloxycarbonyl group (such as a phenoxycarbonyl group), Cyano group, nilot group, amino group (eg, unsubstituted amino group, dimethylamino group, etc.), alkylsulfinyl group (eg, methylsulfinyl group, etc.), arylsulfinyl group (eg, phenylsulfinyl group, etc.), alkylthio group (eg, methylthio group, etc.) ), And an arylthio group (for example, a phenylthio group).

The substituted or unsubstituted alkyl group represented by R ₂ has the same meaning as the alkyl group represented by R ₁ , and the substituted or unsubstituted aryl group has, for example, 6 to 2 carbon atoms.
And an aryl group of 0 (for example, a phenyl group, a naphthyl group, etc.). The same substituents as those for R ₁ can be used as the substituents.

Particularly preferred as R ₁ is a sulfo group,
A methyl group, an ethyl group, and a propyl group substituted with a hydroxy group and a carboxy group, and particularly preferred as R ₂ are a hydrogen atom.

M is a hydrogen atom, an alkali metal atom (eg, a sodium atom, a potassium atom, etc.), a quaternary ammonium group (eg, a trimethylammonium group, a dimethylammonium group, a tributylammonium group, etc.) Represents a group that can be an alkali metal (for example, an acetyl group, a cyanoethyl group, a methanesulfonyl group, and the like).

Further, among the compounds represented by the general formula (1), a compound represented by the following general formula (3) is more preferable.

[0027]

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[In the formula, R ₁ represents at least one sulfo group, carboxy group, hydroxy group or a salt thereof, or an alkyl group substituted with —B (OH) ₂ group;
When two or more substituents are present, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. ] In the general formula (3), R ₁ has the same meaning as R ₁ in general formula (1), M has the same meaning as M in the general formula (1).

Specific examples of the compound represented by formula (1) used in the present invention are shown below, but the present invention is not limited to these compounds.

[0030]

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The addition amount of the compound of the formula (1) of the present invention is preferably 5 mg to 500 mg / l in a developing solution,
More preferably, it is 10 to 200 mg / l. When it is contained in a silver halide photographic light-sensitive material, it may be located anywhere in the hydrophilic colloid layer, but is preferably a silver halide photographic emulsion layer or a protective layer. The addition amount in the photographic material is preferably from 1 to 100 mg / m ^2. If the amount is less than this, the effect of the present invention is not obtained.

Hereinafter, the reductones or derivatives thereof in the present invention will be described.

The reductones or derivatives thereof in the present invention include enediol type, enaminol type, enediamine type, thiol enol type and enamine thiol type. In particular, compounds represented by the following general formula (A) are preferable.

[0034]

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[In the general formula (A), R ₁₁ and R ₁₂ represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, and an alkylthio group, respectively. X is a ring-forming atomic group, preferably composed of a carbon atom, an oxygen atom, or a nitrogen atom;
Two vinyl carbon atoms and carbonyl carbon atoms substituted by R ₁₁ and R ₁₂ together form a 5- to 6-membered ring. More specifically, R ₁₁ and R ₁₂ each independently represent a hydroxyl group, an amino group (an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-butyl group,
Includes those having a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (Such as a methoxycarbonylamino group), a mercapto group,
Represents an alkylthio group (eg, methylthio group, ethylthio group). Preferred examples of R ₁₁ and R ₁₂ include a hydroxyl group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. X is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and forms a 5- to 6-membered ring together with two vinyl carbon atoms and a carbonyl carbon atom substituted by R ₁₁ and R ₁₂ .
Specific examples of the X, -O -, - C ( R 13) (R 14) -,
_{-C (R 15) =, -} C (= O) -, - N (R 16) -, -
N = is combined. Where R ₁₃ , R ₁₄ ,
R ₁₅ and R ₁₆ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxyl group, a carboxyl group, a sulfo group may be mentioned as a substituent), a carbon atom having 6 to 15 carbon atoms. Represents an optionally substituted aryl group (substituents include an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group and a sulfo group), a hydroxyl group and a carboxyl group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. As an example of a preferred 5- to 6-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
A uracil ring can be mentioned.

Specific examples of the compound represented by formula (A) used in the present invention are shown below, but the present invention is not limited to these.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The compound represented by formula (A) of the present invention may be an acid or a salt. Particularly preferred compounds are L-ascorbic acid, erythorbic acid and salts thereof. The amount of addition is preferably from 0.005 mol to 1.0 mol, particularly preferably from 0.020 mol to 0.50 mol, per liter of the developer.
0 mol.

In the present invention, the reductone may be contained in the silver halide light-sensitive material, but is preferably contained in a developer.

Hereinafter, the compound represented by formula (2) or a salt thereof according to the present invention will be described.

[0045]

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[Wherein R ₃ , R ₄ and R ₅ represent an alkylene group. These alkylene groups may have an ether bond. R ₃ and R ₅ or R ₄ and R ₅ may form a ring. A and B may be the same or different, and include a hydrogen atom, an alkyl group, an amino group, an ammonium group,
It represents a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group, and A and B may form a ring. n represents an integer of 0 to 10. In the general formula (2), the alkylene group represented by R ₃ , R ₄ and R ₅ preferably has 1 to 10 carbon atoms,
6 is particularly preferred. For _{example, -CH 2 CH 2 -, -} (CH
_{2) 3 -, - (CH} 2) 4 -, - (CH 2) 2 -O- (C
_{H 2) 2 -, - CH} 2 -CH (OH) -CH 2 - and the like.

In a hydrogen atom, an alkyl group, an amino group, an ammonio group, a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group represented by A and B, in addition to the hydrogen atom, a group having 1 to 1 carbon atoms 10 alkyl groups (here, the alkyl groups include those having a substituent; for example, a methyl group, an ethyl group, etc.), and amino groups (here, the amino groups include those having a substituent. For example, a dimethylamino group, a diethylamino group , -N (CH ₂ CH ₂ C
_{N) 2, -N (CH 2} -CH (OH) -CH 2 OH) 2, -
NH ₂ , a morpholino group, etc.), an ammonio group (here, an ammonio group includes a group having a substituent, for example, a trimethylammonio group), and an aminocarbonyl group (here, an aminocarbonyl group includes a group having a substituent). For example, a dimethylaminocarbonyl group or the like, or an aminosulfonyl group (here, the aminosulfonyl group includes a group having a substituent, for example, a dimethylaminosulfonyl group) is preferable. Among them, a hydrogen atom, an amino group and an ammonium group are preferred.

N represents an integer of 0 to 10, preferably an integer of 1 to 4.

As a salt of the compound represented by the general formula (2), the compound represented by the general formula (2) may take the form of a salt of an inorganic or organic acid. Preferred examples are hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid,
Examples thereof include hydroiodic acid, perchloric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

Hereinafter, specific examples of the compound represented by the general formula (2) or a salt thereof are shown, but the present invention is not limited to these compounds.

[0051]

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[0052]

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[0053]

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The compound represented by the general formula (2) or a salt thereof can be synthesized by a very general method, for example, French Patent 1,108,788, US Pat.
No. 3,776, No. 2,912,329, No. 3,02
No. 1,215, British Patent 950,089, The Journal of the Organic Chemistry, No. 26
Vol., 1991-1995 (1961), edited by The Chemical Society of Japan, Organic Experimental Chemistry, Vol. 14, Synthesis and Reaction of Organic Compounds (I), pp. 1713-1726, Maruzen (1978), and the like. It can be synthesized by referring to the method.

In the present invention, the compound represented by formula (2) or a salt thereof may be added to the fixing replenisher or may be added only at the start.

In the present invention, the amount of the compound represented by the general formula (2) or a salt thereof added to the fixing solution is 5 × 10 ^−5.
10 ^-1 mol / L, and 10 ^{-3 to} 5 × 10 ^-2 mol / L
Is preferred. Below this amount, the effect of the present invention cannot be expected, and even if added above this amount, the effect remains unchanged.

The development processing method of the present invention basically comprises the steps of developing, fixing, washing and drying the exposed silver halide light-sensitive material.

In the present invention, a 3-pyrazolidone (eg, 1-phenyl-3) is used as a secondary developing agent in the developer.
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-
Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1 -Phenyl-3-pyrazolidone, etc.), 3-aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazolin, 1- (p-methylaminophenyl) -3
-Aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.) and phenylenediamines (eg, 4-amino-N, N-diethylaniline, 3-methyl-4-amino) -N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and the like can be added.

Further, even when aminophenols are used as an auxiliary developing agent, a high contrast image can be obtained. Aminophenol developing agents include 4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
Examples thereof include 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, and hydrochlorides and sulfates of these compounds.

An amine compound can be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferred. Further, it is necessary to use sodium chloride, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium borate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

It is preferable to use a carbonate also in a developer using the reductone of the present invention. The concentration of the buffer is 0.3 mol / L or more, and 0.5 to 1.5.
Mol / L is preferred.

As development accelerators, for example, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, ionic compounds, Mesoionic compounds, imidazoles and the like can be added as needed.

As the antifoggant, an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Nitrogen-containing hetero groups such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine Ring compounds.

Further, if necessary, methyl cellosolve,
Methanol, acetone, dimethylformamide, cyclodextrin compound, and other JP-B-47-33378
And the compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

In the present invention, the developing solution includes Japanese Patent Application No.
It is preferable to use a chelating agent or a biodegradable chelating agent described in 86232, page 20.

Next, the fixing solution used in the present invention will be described.

The fixing solution according to the present invention is preferably prepared by preparing a solid processing agent and dissolving it. The fixing agent preferably contains a thiosulfate. The thiosulfate is specifically used as a salt of lithium, potassium, sodium, or ammonium. Preferably, a fixing solution having a high fixing speed can be obtained by using ammonium thiosulfate and sodium thiosulfate.

In addition, iodide salts and thiocyanates can also be used as fixing agents. The fixing solution used in the present invention contains a sulfite. As sulfites,
Solid lithium, potassium, sodium, ammonium salts and the like are used.

The fixing solution used in the present invention may contain a water-soluble chromium salt or a water-soluble aluminum salt.
Examples of the water-soluble chromium salt include chrome alum and the like.
Examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride.

The fixing solution used in the present invention contains acetate ions. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution.However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Sodium salts and ammonium salts are preferred.

Further, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof may be contained.

Examples of these salts (for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium bitartrate) Potassium, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate,
Preferred examples include lithium, potassium, sodium, and ammonium salts represented by ammonium succinate and the like.

In the present invention, iodine ions are added to the developing solution and the developing replenisher, and the amount thereof is 5 in KI conversion.
0 mg to 200 mg / l, preferably 50 to 150 mg
/ L. When the development time is set to the processing time and the replenishing amount of the present invention at a concentration of 50 mg / l or less, sufficient sensitivity cannot be obtained.
Further, if added in a large amount, the fixability and the residual color deteriorate.

The amount of replenisher for development and fixing in development and fixing is preferably 300 ml / m ² or less, and 80 to ² ml.
It is more preferably 50 ml / m ² or less. When the replenishment amount is large, the effect of the present invention is small, and when the replenishment amount is too small, the release ratio of the compound of the general formula (1) or the general formula (2) becomes too large with respect to the replenishment amount, and the effect is sufficient. Can not be demonstrated.

In the present invention, the total processing time is 15 minutes for Dry To Dry after development, fixing, washing and drying steps.
To 120 seconds, and particularly preferably 15 to 40 seconds.

The processing temperature of the developer is 25 to 50 ° C.
Preferably it is 30-40 degreeC. The development time is 5 to 25 seconds, and more preferably 5 to 15 seconds.

The processing temperature of the fixing solution is 25 to 50 ° C.
Preferably it is 30-40 degreeC. The fixing time is 5 to 25 seconds, more preferably 5 to 15 seconds.

Is as follows.

As for the silver halide photographic light-sensitive material, any known and publicly available materials can be used as long as the constitutional requirements of the present invention are satisfied.

The crystal habit of the crystal may be cubic, tetradecahedral, octahedral, and arbitrarily mixed intermediate (111) and (100) planes.

The crystal structure of silver halide may have different silver halide compositions on the inside and outside.

The silver halide emulsion preferably used in the present invention is tabular grains having an average aspect ratio of more than 1. The advantage of such tabular grains is that they can improve spectral sensitization efficiency, improve graininess and sharpness of an image, and the like.
U.S. Pat. Nos. 4,439,520 and 4,433,048
Nos. 4,414,310 and 4,434,226
JP-A-58-113927 and JP-A-58-12792.
No. 1, 63-138342, 63-284272
And JP-A-63-305343, and emulsions can be prepared by the methods described in these publications. In particular, Japanese Patent Application No. 6-138568 (pages 1 to 3), JP-A-59-177535 (pages 2 to 5),
No. 42146 (pages 14 to 15) are preferably used.

Further preferred silver halide emulsions used in the present invention are silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide and silver chloride of less than 3 mol% of silver iodide. Preferred is silver chlorobromide or silver chloride having a silver chloride content of 50 mol% or more. The emulsion described above is a surface latent image type in which a latent image is formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain,
Any type of emulsion that forms a latent image on the surface and inside may be used. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a washing method such as a noodle washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086,
Alternatively, a method using G3, G8, etc., as an aggregating polymer agent described in JP-A-63-158644 is a particularly preferred desalting method. As the method of chemical ripening of the emulsion used in the light-sensitive material of the present invention, sensitization by a chalcogen compound such as selenium sensitization such as gold sensitization, reduction sensitization and sulfur sensitization, or a combination thereof is preferably used.

The silver halide emulsion of the present invention can be spectrally sensitized. Examples of the spectral sensitizing dye used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, and hemioxonol dye.

For example, oxacarbocyanine, benzimidazolocarbocyanine, benzimidazolooxacarbocyanine and the like as described in JP-A-5-113609 can be mentioned. Further, dyes having a sensitizing effect in the blue light region described in JP-A-6-332102 are also preferably used. These spectral sensitizing dyes can be used alone or in combination.

The spectral sensitizing dye is preferably added as a solution dissolved in an organic solvent such as methanol. The addition amount of the spectral sensitizing dye is not uniform depending on the type of the dye and the emulsion conditions, but the amount added is 10 mol / mol of silver halide.
It is preferably from 900 to 900 mg, particularly preferably from 60 to 400 mg. The spectral sensitizing dye is preferably added before the completion of the chemical ripening step, and may be added in several portions before the completion of the chemical ripening. More preferably, after the growth step of the silver halide grains and before the completion of the chemical ripening step, particularly preferably before the start of the chemical ripening.

In the present invention, in order to stop the chemical sensitization (chemical ripening), it is preferable to use a chemical ripening terminator in consideration of the stability of the emulsion. Examples of the chemical ripening terminator include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene) and the like. These may be used alone or in combination of a plurality of compounds.

In the emulsion of the light-sensitive material used in the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Examples thereof include a hydrazine compound and a tetrazolium salt.

As the support used in the present invention, for example, RD-17643, page 28 and RD-308119
On page 1009 of the publication.

As a suitable support, a plastic film or the like may be used. The surface of the support may be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

An emulsion layer may be present on both sides of the support,
Only one side may be used. In the case of both sides, both sides may have the same performance or different performances.

Next, the solidification (solidification) of the photographic processing agent will be described.

To solidify the photographic processing agent, a concentrated solution, a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily molded photographic processing agent. Any means can be adopted, such as forming a coating layer by spraying a liquid (Japanese Patent Laid-Open Nos. 4-29136 and 4-8).
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

The granulation method for tablet formation is to use a known method such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a pre-ketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, for example, an alkali agent, a reducing agent, a preservative and the like are separated and granulated for each component.

The method for producing a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808 and the like.
It can be produced by the method described in JP-A-2-10942, JP-A-2-109043, JP-A-3-39735 and JP-A-3-39939. Furthermore, powder processing agents, for example,
JP-A-54-133332, British Patent 725,892
No. 729,862 and German Patent 3,733,8.
No. 61 or the like.

[0098] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0g
/ Cm ³ in terms of the strength of the resulting solid,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

The solid processing agent used in the present invention falls within the scope of the present invention in that only one part of a certain processing agent is solidified, but it is preferable that all the components of the processing agent be solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the processing tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

When the developer is solidified, all of the alkali agent, reducing agent, etc., are converted into solid processing agents, and in the case of tablets, at least three agents can be used, that is, one agent can be used. When divided into solid processing agents, it is preferable that these tablets and granules are packaged in the same manner.

The package of the solid processing agent used in the present invention can be implemented using the following materials.

As synthetic resin materials, polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched, unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, acrylonitrile butadiene copolymer, epoxy-phosphate resin (JP-A-63-63037)
Or the polymer described in JP-A-57-32952). Or it may be pulp.

These are preferably made of a single material. When used as a film, the films are laminated and adhered, but may be used as a coating layer or a single layer.

Further, it is more preferable to use various gas barrier films, for example, using aluminum foil or aluminum vapor-deposited synthetic resin between the above-mentioned synthetic resin films.

The oxygen permeability of these packaging materials is 50 ml in order to preserve the solid processing agent and prevent the generation of stain.
/ M ² 24 hr.atm or less (20 ° C., 65% RH
), More preferably 30 ml / m ² 24 hr · atm
The following is preferred.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
μm, more preferably 50 to 1000 μm.

The above synthetic resin film may be a one-layer (polymer) resin film or two or more laminated (polymer) films.
It may be a resin film.

Examples of the one-layer polymer resin film satisfying the conditions of the present invention include (1) polyethylene terephthalate (PET) having a thickness of 0.1 mm or more, and (2) 0.3 mm thickness.
The above-mentioned acrylonitrile-butadiene copolymer, (3) a rubber hydrochloride having a thickness of 0.1 mm or more, and the like, among which polyethylene terephthalate is also excellent in alkali resistance and acid resistance, can be suitably used in the present invention.

Next, examples of the laminated polymer resin film satisfying the conditions of the present invention include (4) PET / polyvinyl alcohol / ethylene copolymer (EVAL) / polyester (PE), and (5) stretched polypropylene ( (6) Unstretched polypropylene (CPP) /
Eval / PE, (7) Nylon (N) / aluminum foil (Al) / PE, (8) PET / Al / PE, (9)
Cellophane / PE / Al / PE, (10) Al / paper / P
E, (11) PET / PE / Al / PE, (12) N /
PE / Al / PE, (13) paper / PE / Al / PE,
(14) PET / Al / PET / polypropylene (P
P), (15) PET / Al / PET / high density polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene (LDPE), (17) Eval / P
P, (18) PET / Al / PP, (19) paper / Al /
PE, (20) PE / PVDC coated nylon / PE /
Ethyl vinyl acetate / polyethylene condensate (EV
A), (21) PE / PVDC coated N / PE, (2
2) EVA / PE / aluminized nylon / PE / EV
A, (23) Aluminum evaporated nylon / N / PE / EVA,
(24) OPP / PVDC coated N / PE, (25) P
E / PVDC coated N / PE, (26) OPP / EVAL / LDPE, (27) OPP / EVAL / CPP,
(28) PET / EVAL / LDPE, (29) ON
(Stretched nylon) / EVAL / LDPE, (30) CN
(Unstretched nylon) / EVAL / LDPE, among which the above (20 to (30)) are preferably used.

As a more specific configuration of the packaging material, if the side in contact with the treatment agent is the inner surface, the PE / PE
Main paperboard / PE / Al / epoxy-phosphate resin layer / polyester resin layer / PE PE / K-nylon / PE or adhesive / Al / PE /
Paperboard / PE, PE / vinlon / PE or adhesive / Al
/ PE / paperboard / PE, PE / vinylidene chloride / PE or adhesive / Al / PE / paperboard / PE, PE / polyester / PE or adhesive / Al / PE / paperboard / PE, polypropylene / K-nylon / polypropylene / Al / polypropylene / paperboard / polypropylene.

As a method for moisture-proof packaging tablets and granules,
There are 4-sided seals, 3-sided seals, sticks (pillow packaging, gusset packaging), PTP, and cartridges.

A four-sided seal, a three-sided seal, and a stick (pillow, gusset) package are different in form, and the above-mentioned materials are used. However, when used in the peel-open method, a sealant is laminated to make the film open to peel-open.

The peel-open system generally includes a cohesive failure system, an interfacial peeling system and an interlayer peeling system.

The cohesive failure method is a method in which an adhesive (heat seal lacquer) called hot melt is used as a sealant, and peels off when the sealant is opened due to internal cohesive failure of the sealant layer.

The surface-active peeling method is a method of peeling at the interface between the films, and the sealing film (sealant) and the adherend are not completely fused and can be peeled off with an appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, polyester, or the like depending on the material of the adherend can be selected.

Further, the interlayer peeling method uses a multilayer co-extruded film such as a laminate film to peel off the sealant between layers of the laminate film.

In the peel open system using the film of the present invention, an interlayer peeling system or an interface peeling system is preferable.

Further, since such a sealant is thin,
Normally, other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, and aluminum are laminated and used. Consider moisture proofness, environmental compatibility, and matching with the contents. Polyethylene, polypropylene, polyester, eval and the like are preferred. In consideration of printability, the outermost surface is preferably made of unstretched polypropylene, polyester, paper or the like.

Examples of the sealant film include CMPS film manufactured by Tocelo, Diflan PP-100, PS-300 manufactured by Dainippon Ink and LTS film manufactured by Toppan Printing, Sunseal FR and Sunseal M manufactured by San-A Chemical Co., Ltd.
S, etc., and as types already laminated with polyester, Diclan C-1600T, C-16
02T.

PTP is a packaging form in which a solid processing agent is placed in a sheet of PVC, CPP, or the like, which is formed as a type of blister packaging, and heat-sealed with an aluminum sealing material.

Environmentally friendly PVC is not used as a forming material. Recently, A-PET or highly moisture-proof PP (for example, TA
S-1130, TAS-2230, TAS-3230:
Taisei Kako Co., Ltd.) is preferably used.

When the treating agent is packaged or bound or coated with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methylcellulose-based, polyethylene oxide-based, starch-based, polyvinylpyrrolidone-based, Hydroxypropyl cellulose type,
Film or binder consisting of pullulan, dextran or gum arabic, polyvinyl acetate, hydroxyethylcellulose, carboxyethylcellulose, carboxymethylhydroxyethylcellulose sodium salt, poly (alkyl) oxazoline or polyethylene glycol base Agents are preferably used, and among these, polyvinyl alcohol-based and pullulan-based ones are more preferably used from the viewpoint of the effect of coating or binding.

Preferred polyvinyl alcohols are very good film-forming materials and have good strength and flexibility under most conditions. Commercially available polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but preferably have a molecular weight of about 10,000 to about 100,000. The degree of hydrolysis is the rate at which the acetate group of polyvinyl alcohol is replaced with a hydroxyl group. For film applications, the range of hydrolysis is usually from about 70% to 100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.

The method for producing these water-soluble films is described, for example, in JP-A-2-124945 and JP-A-61-9934.
No. 8, No. 60-158245, JP-A-2-86638.
JP-A-57-117867, JP-A-2-7565
No. 0, JP-A-59-226018 and JP-A-63-2187.
It is manufactured by a method as described in JP-A Nos. 41 and 54-13565 and the like.

Further, as these water-soluble films, those commercially available under the names of Sorblon (manufactured by Aicello Chemical Co., Ltd.), Hicelon (manufactured by Nichigo Film Co., Ltd.) and Pullulan (manufactured by Hayashibara) can be used. Also, Chris Craft Industries (Chris Craft I)
ndustries) Inc. The 7-000 series polyvinyl alcohol films available from MONO-SOL, Inc., dissolve at a water temperature of about 34 ° F. to about 200 ° F., are harmless, exhibit high chemical resistance, and are particularly preferred. Used.

The thickness of the water-soluble film is preferably from 10 to 120 μm in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film, and the precipitation of crystals in an automatic developing machine. Is particularly preferred, and especially those having a size of 20 to 60 μm are preferably used.

Further, the water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

Further, the tensile strength of the water-soluble film is 0.3.
5 × 106~50 × 106kg / m ² are preferred, especially 1 × one hundred and six to twenty-five preferably × 106 kg / m ^2, more especially is 1.5 × 106~10 × 106kg / m ² preferred. These tensile strengths are measured by a method described in JIS Z-1521.

The photographic processing agent packaged or bound or coated with a water-soluble film or binder can be used during storage, transportation, and handling to prevent atmospheric humidity such as high humidity, rain and fog, and the like. It is preferable that the moisture-proof packaging material has a film thickness of 10 to 1 in order to prevent damage from sudden contact with water due to splashing or wet hands.
A film having a thickness of 50 μm is preferable, and the moisture-proof packaging material is polyethylene terephthalate, polyethylene, a polyolefin film such as polypropylene, kraft paper, wax paper, moisture-resistant cellophane which can have a moisture-proof effect with polyethylene,
It is preferably at least one selected from glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and metal foils such as aluminum and metallized polymer films, and composites using these. It may be a material.

In the practice of the present invention, it is preferable to use a degradable plastic, particularly a biodegradable or photodegradable plastic, as the moisture-proof packaging material.

Examples of the biodegradable plastic include those composed of natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, and blending of biodegradable natural polymers with plastics. ,
Examples include those in which a group that is excited by ultraviolet light and is linked to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability can be used favorably. Specific examples of these are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microbial polymers such as PHB-PHV (3-hydroxybutyrate and 3-hydroxyvale). Of “Bio”) as a component
pol ", microbial-produced cellulose, etc. Synthetic polymers with good biodegradability Polyvinyl alcohol, polycaprolactone, etc., or their copolymers or mixtures Compounding of biodegradable natural polymers into plastics As natural polymers with good biodegradability , Starch and cellulose, which have shape-disintegrating properties in addition to plastics.

Examples of the photodegradability include introduction of a carbonyl group for photodisintegration, and an ultraviolet absorber may be added for accelerating the disintegration.

Such degradable plastics are described in "Science and Industry", Vol. 64, No. 10, 478-484.
Page (1990), "Functional Materials", July 1990, No.2
Those generally described on pages 3-34 and the like can be used.
In addition, Biopol (manufactured by ICI),
Eco (manufactured by Union Carbide),
Ecolite (Eco Plasti)
c), Ecostar (St. La)
Commercially available degradable plastics such as wrench starch (product of Wrench Starch) and Knuckle P (product of Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hr or less.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63-975.
No. 22, No. 1-85732, etc., but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powder, it is disclosed in Japanese Utility Model Application Laid-Open No. 62-81964.
No. 63-84151, Japanese Unexamined Patent Publication No. 1-292375, etc.
Although there is a known method using a screw or a screw described in JP-A-63-195345 or the like, the method is not limited thereto.

However, in a preferred method, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened according to the processing amount of the photosensitive material. There is a way to take it out. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials, and the package is separated in two directions or the package is separated. A part is opened to make it ready for removal. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall. Since a predetermined amount of the solid processing agent is stored in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off, the moisture proof is guaranteed unless opened.

As an embodiment, a configuration is conceivable in which a package made of at least two packaging materials is adhered or adhered to each other so as to be able to separate the periphery of the solid processing agent so as to sandwich the solid processing agent. . By pulling each packaging material sandwiching the solid processing agent in different directions, the contact surfaces adhered or adhered are separated, and the solid processing agent can be taken out.

As another embodiment, a configuration is conceivable in which at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or to the opening side package. It is considered that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting information on the processing amount. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. In addition, when the processing agent is packaged and opening is required, a driving unit for separating or opening based on the obtained supply start signal operates, and a driving unit for separating or opening based on the supply stop signal is provided. Can be controlled to stop.

It is preferable that the supply means of the solid processing agent has a control means for supplying a fixed amount of the solid processing agent according to the processing amount information of the photosensitive material. That is, in the automatic processor of the present invention, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance. The processing amount information of the silver halide photographic light-sensitive material refers to the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, the processing amount of the processed silver halide photographic light-sensitive material, or the silver halide photographic material being processed. This is a value proportional to the processing amount of the photosensitive material, and indicates indirectly or directly the amount of reduction in the processing agent in the processing solution. The detection may be performed at any timing before or after the photosensitive material is carried into the processing solution, or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution, a change in the concentration, pH, and specific gravity may be used. Also, the amount of the treatment liquid that has come out after drying may be used.

The place where the solid processing agent of the present invention is charged may be in a processing tank, but is preferably in communication with a processing section for processing a photosensitive material, and a processing liquid flows between the processing section and the processing section. And a structure in which there is a constant processing solution circulation amount with the processing unit and the dissolved components move to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

Generally, the temperature of an automatic developing machine is controlled by an electric heater to control the temperature of the processing solution. As a general method, a heat exchange unit is provided in an auxiliary tank connected to the processing tank, a heater is installed, and a pump is arranged in this replenishment tank so that the liquid is sent from the processing tank at a constant circulation amount and the temperature is constant. I have.

Usually, a filter is disposed for the purpose of removing crystal foreign substances that are mixed in the processing solution or generated by crystallization, and play a role of removing the foreign substances.

The most preferable method is to put a solid processing agent into a place where the temperature is controlled, such as a place communicating with the processing section, such as the auxiliary tank. This is because the insoluble components of the input processing agent are blocked from the processing unit by the filter unit, so that the solid content can be prevented from flowing into the processing unit and adhering to the photosensitive material, etc., and the solubility of the solid processing agent is very high. It will be good.

In the case where a processing agent charging section is provided together with the processing section in the processing tank, it is preferable to devise a shield or the like so that the insoluble portion does not directly contact the film or the like.

As the materials of the filter and the filtration device, those used in general automatic developing machines can be used in the present invention, and the special structure and material do not influence the effects of the present invention.

The number of cycles of the treatment liquid circulated by the circulation means in the present invention is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and more preferably 1.0 to 2.0 times / min.
2.0 times / min is preferable. As a result, the dissolution of the solid processing agent is promoted, and it is possible to prevent the formation of a cluster of a high-concentration liquid, to prevent the occurrence of uneven density of the processed photosensitive material, and to prevent the occurrence of insufficiently processed photosensitive material. Can be prevented. Here, the number of circulations indicates the flow rate of the circulated liquid, and the time when the liquid amount corresponding to the total liquid amount in the processing tank flows is defined as one time.

The solid treating agent used in the present invention is added to the treatment tank separately from the replenishing water, and the replenishing water is supplied from a refilling tank.

The fungicide means of the water refill tank in this case will be described. If the exchange rate in the rehydration tank is reduced and the residence time of the water is prolonged, scales are generated, and after two to three weeks, the water rots and a bad odor is generated. Also, if the generated scale is replenished as it is, it adheres to the surface of the photographic material or the solid processing agent.
In the case of a fixing tank, there is a serious problem that fixing failure occurs and the commercial value is significantly reduced. Therefore, it is necessary to perform regular cleaning to remove the scale, which is very troublesome. Therefore, the water supply tank used in the present invention has antifungal means. This antifungal means can be achieved by at least one means selected from the following group.

(Group) 1) Chelating agent adding means 2) Fungicide adding means 3) Deionizing treatment means 4) Ultraviolet irradiation means 5) Magnetic treatment means 6) Ultrasonic treatment means 7) Electrolytic sterilization means 8) Silver ions Release means 9) Air foaming means 10) Active oxygen release means 11) Means by contact with porous material Means for adding harmless other fungi to prevent harmful bacteria from multiplying These means will be specifically described. . As the chelating agent and the bactericide used as the fungicide in the present invention, known chelating agents and bactericides can be arbitrarily used.

Examples of the chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 2-hydroxy-4-sulfophenol, 2-hydroxy-3 , 5-disulfophenol is preferred, and bactericides are preferably phenolic compounds, thiazole compounds and benzotriazole compounds. Specifically, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazoline-
Preferred compounds include 3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, sodium o-phenylphenol, and benztriazole.
If these compounds are packaged together, they are preferably in the form of tablets, and if they are divided and weighed in advance, they are preferably individually packaged in an amount to be charged at one time. Means for adding these may be manually added by the dispenser, but preferably a solid processing agent supply device is installed,
It is preferable from the viewpoint of maintenance-free that the addition is performed by this, and more preferably the addition is automatically performed when the water supplement tank has a detector and water is replenished to a certain amount in the tank.

The means for modifying water with an ion exchange resin can be implemented based on the means described in JP-A-61-131632.

As the ion exchange resin, various publicly known cation exchange resins (strongly acidic cation exchange resin, weakly acidic cation exchange resin) described in, for example, Technical Publication No. 90-473.
And various anion exchange resins (strongly basic anion exchange resins)
And these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H-type cation exchange resin and a weakly basic OH-type anion exchange resin. It may be placed in a water refill tank or the water may be improved elsewhere.

Preferred ion exchange resins for strong acid include DIAION SK1B SK102, SE104, S104
K106, SK110, SK112 and SK116 (Mitsubishi Kasei Co., Ltd.). Preferred OH-type strong basic anion exchange resins are DIAION PA406 and PA40.
8, PA412, PA416 and PA418 (Mitsubishi Kasei Co., Ltd.).

The means for irradiating ultraviolet rays is disclosed in JP-A-60-2
No. 63939 can be implemented. As the ultraviolet irradiation device, a device manufactured by Kindai Bio Research Laboratories (head office Kobe City) is preferably used in a small size. The means for applying a magnetic field according to the present invention can be implemented by the means described in JP-A-60-263939. The means for applying ultrasonic waves can be implemented by the means described in JP-A-60-263940. Means for applying electrolysis is disclosed in
It can be carried out by the means described in Japanese Patent No. 22468.
Further, the means for releasing silver ions include a means for putting silver foil or a silver plate in a water replenishing tank, a means for coating the inner wall with silver, and a means for putting a silver ion releasing compound.

On the other hand, the air foaming means may be a very simple means for blowing air bubbles into the water refill tank, and is appropriately selected according to the size of the water refill tank. Means for preventing the generation of scales and fungicides are 1), 2), 3), 7) and 8), and more preferably 1), 3) and 8), in terms of compactness and economy. ) Is selected.

The silver ion releasing compound of the means 8) includes silver chloride, silver bromide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver acetate, silver oxalate, silver behenate, silver maleate and the like. Organic acid silver and the like are mentioned as specific examples.

These silver compounds include those having a SiO ₂ —Na ₂ O-based glass body having a network structure as a chemical structure as a base structural component, a SiO ₄ tetrahedron having a methane type structure and an Al ₄
In the present invention, a zeolite having a three-dimensional skeleton structure in which O ₄ tetrahedra share one oxygen atom with each other and containing the silver compound is preferably used in the present invention.

These silver compounds and zeolite bodies and glass bodies containing the compounds can be obtained as commercial products. For example, Bio-Sure SG (Kinki Pipe Giken Co., Ltd.), Opogens (Switzerland)
Tablets) and Zeomic (Zemic) manufactured by Sinanen Zeomic Co., Ltd.
omic) and the like.

Further, the silver compound and the zeolite or glass containing the compound can be used in various shapes. For example, it can be in the form of a powder, a sphere, a pellet, a sensation or a filter, or it can be used by being entangled with fibers of cotton, wool, polyester or the like. Specific examples of these include Saniter 30 (manufactured by Kuraray Co., Ltd.).

Among these, a filter-like or spherical one is one of the preferable embodiments in the present invention.

Further, it is a preferable embodiment of the present invention that the silver compound or the zeolite or glass containing the compound is used in a water-permeable container such as a plastic case or a tea bag. . In addition, a clinker 205 manufactured by Nippon Research Institute Co., Ltd. or a lacquering by Pacific Chemical Co., Ltd. can be preferably used. On the other hand, the solid processing agent used in the present invention contains at least one kind of saccharide and / or compounds represented by the following general formulas (B) and (C). The content of the saccharide in the solid processing agent is preferably 0.5% or more and less than 30% of the total weight, particularly preferably 3% or more and less than 20%.

The saccharides referred to in the present invention refer to monosaccharides, polysaccharides in which a plurality of these are glycosidically bonded to each other, and degradation products thereof.

The monosaccharides include single polyhydroxy aldehydes, polyhydroxy ketones and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives and thio derivatives. Many saccharides are represented by the general formula CnH ₂ nOn, and the present invention includes monosaccharides, including compounds derived from the saccharide skeleton represented by the general formula. Preferred among these monosaccharides are sugar alcohols in which the aldehyde group and ketone group of the sugar are reduced to primary and secondary alcohol groups, respectively.

Polysaccharides include celluloses, starches,
Glycogens and the like are included, celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various degradation products from hydrolysis to maltose. Contains certain dextrin sugars. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Those preferably used as these polysaccharides are celluloses and dextrins, more preferably dextrins.

Preferred compounds as monosaccharides include: • Erythrit (trade name, Mitsubishi Kasei Shokuhin Erythritol) • D-Sorbit • L-Sorbit • D-Mannit • L-Mannit • D-Igit • L-Igit • D -Talit-L-Talit-Zursit-Allozursit.

Preferred compounds as specific examples of polysaccharides and saccharide degradation products are shown below.

Α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxypropyl-γ-cyclodextrin, maltodextrin.

The dextrin used in the present invention may have any weight average molecular weight.
~ 1000.

[0172] Saccharides exist widely and naturally, and commercially available products are easily available. Also, various derivatives can be easily synthesized by performing reduction, oxidation, dehydration, or the like.

As a commercial product, starch decomposed products include Pine Flow, Paindex series, Foodtex, Max 100, Glister P, TK-16, MPD, H-PDX, H-PDX, manufactured by Matsutani Chemical Industry Co., Ltd. And Oil Q series manufactured by NOF Corporation.

Next, the compound represented by formula (B) in the present invention will be specifically described.

Formula (B) HO- (A ₁ -O) l _1- (A ₂ -O) l _2- (A ₃ -O)
l in ₃ -H _{formula, A 1, A 2, A} 3 is substituted independently represent an unsubstituted straight-chain or branched alkylene group, which may optionally be the same or different.

Examples of the substituent include a hydroxy group, a carboxy group, a sulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoyl group. Those preferably used are those in which A ₁ , A ₂ and A ₃ are each unsubstituted. Most preferably, A ₁ , A ₂ ,
A ₃ is _{-CH 2 CH 2 -, - CH} (CH 3) -CH 2 - is.

Each of l ₁ , l ₂ and l ₃ is 0 or 0
Represents an integer of 500. Here, l ₁ + l ₂ + l ₃ ≧ 5.

Of these, at least one of l ₁ , l ₂ and l ₃ is preferably 15 or more, and more preferably 20 or more.

In the case where the compound represented by the general formula (B) in the present invention is, for example, a copolymer obtained by mixing two kinds of monomers A and B and copolymerizing them, those having the following sequence are also included. Is done.

-ABBABABABABA-
B-A-A-B-B-B-B-A-A-A-B-A-A-A-
BBAA- -AAAAAABABBBBBB-
A-A-A-A-A- Among these copolymers, particularly preferred compounds are represented by the following general formula (B-1). It is a block polymer of ethylene glycol and propylene glycol (pluronic non-ion).

Formula (B-1) HO— (CH ₂ CH ₂ —O) l ₄ [CH (CH ₃ ) CH ₂ —
O] l ₅ - in _{(CH 2 CH 2 -O) l} 6 -H _{formula, l 4, l 5, l} 6 is l ₁ in the foregoing formula (B),
It is synonymous with l ₂ and l ₃ .

In the compound represented by formula (B-1) in the present invention, the content (% by weight) of ethylene oxide in the total molecular weight is preferably at least 70% by weight, particularly preferably at least 80% by weight. Things.

In the following, formulas (B) and (B-
Specific compounds represented by 1) are shown below.

HO— (CH ₂ —CH ₂ —O) n′-H average molecular weight B-1 300 B-2 600 B-3 1000 B-4 1500 B-5 2000 B-6 3000 B-7 4000 B- 8 6000 B-9 10000 B- 10 15000 B-11 20000 B-12 30000 HO- (CH 2 CH 2 -O) a '- [CH (CH ₃₎ -CH ₂ -O] b' - (CH ₂ CH _2- O) c'-H Content (weight%) of ethylene oxide average molecular weight in total molecules B-1-1 80 8350 B-1-2 80 10800 B-1-350 50600 B-1-470 6500 B-1-5 80 5000 B-1-6 50 3500 B-1-7 70 7850 B-1-8 50 4150 In the above formula, n 'represents an integer of 5 or more, and a', b ',
c 'has the same meaning as l ₁ , l ₂ and l ₃ .

Of the compounds represented by the formulas (B) and (B-1) in the present invention, the most preferred is polyethylene glycol (sometimes referred to as PEG).

In the case of polyethylene glycol,
Those having an average molecular weight in the range of 2,000 to 20,000 are preferred, and those in the range of 3,000 to 15,000 are particularly preferred.

Here, the average molecular weight in the present invention is a molecular weight calculated from a hydroxyl value. The compound represented by formula (B) may be used alone or in combination of two or more.

Formula (C) R-SxOyM wherein R is an aliphatic group, an aromatic group or a heterocyclic group, x is 1 or 2, y is an integer of 2 to 8, and M is a cation. Next, the organic sulfur oxide represented by the general formula (C) will be described.

The solid treating agent according to the present invention contains the organic oxide represented by the general formula (C) in an amount of 0.01% to 3.0% of the total weight. Preferably 0.1% or more;
5% or less, more preferably 0.5% or more and 2.0% or less.

In the general formula (C), examples of the aliphatic group represented by R include an alkyl group, an alkenyl group and an alkynyl group. Examples of the alkyl group include methyl, ethyl, i-propyl, butyl, and t. -Butyl, pentyl,
Each group includes cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like. These alkyl groups further include a halogen atom (for example, chlorine, bromine, fluorine, etc.) and an alkoxy group (for example, methoxy, ethoxy, 1,
1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), an aryloxy group (eg, phenoxy, naphthyloxy), an aryl group (eg, phenyl, naphthyl, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-
Ethylhexylcarbonyl, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl group (for example, vinyl, allyl, etc.), heterocyclic group (for example, 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidine, piperazil,
Pyrimidine, pyrazoline, furyl, etc.), alkynyl group (eg, propargyl), amino group (eg, amino,
(N, N-dimethylamino, anilino), a cyano group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

Examples of the alkenyl group include vinyl and allyl, and examples of the alkynyl group include propargyl.

Examples of the aromatic group represented by R include phenyl and naphthyl. Examples of the heterocyclic group represented by R include a pyridyl group (eg, 2-pyridyl, 3-pyridyl, 4-pyridyl), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a cyenyl group, a pyrrolyl group, a pyrazinyl group, Examples include a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a pipedilinyl group, a pyrazolyl group, and a tetrazolyl group.

The above-mentioned alkenyl group, alkynyl group, aromatic group and heterocyclic group can be substituted by the same groups as the alkyl groups represented by R and the substituents of the alkyl groups.

The group represented by M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (ammonium, tetramethylammonium,
Tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidyl and the like.

The compound represented by the general formula (C) is used when the solid processing agent containing the saccharide of the present invention and / or the compound represented by the general formula (B) is formed into a tablet by compression molding. It was found that lubrication, tablet hardness and friability were drastically improved by doing this. Specific examples of the compound represented by formula (C) are shown below, but the present invention is not limited thereto.

[0196] _{C-1 C 2 H 5 SO} 3 Na C-2 CH 3 (CH 2) 6 SO 3 Na C-3 CH 3 (CH 2) 7 SO 3 Na C-4 CH 3 (CH 2) 5 OSO _{3 Na C-5 CH 3 (} CH 2) 6 OSO 3 Na C-6 CH 3 (CH 2) 7 OSO 3 Na C-7 CH 3 O (CH 2) 2 SO 3 Na

[0197]

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[0198]

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 <Preparation of coated sample><< Preparation of photosensitive material >> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml S-3 (10% aqueous ethanol solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g water 2825 ml D1 1.75N Potassium bromide aqueous solution The following silver potential control amount: 42 ° C, JP-B-58-58288 and 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After stopping the addition of the solution B1 and the solution C1, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then again The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm, (Circle diameter conversion)
Was confirmed to be 0.595 μm by an electron microscope. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

<Preparation of Em-1 and Em-2> Seed emulsion-1
And four kinds of solutions shown below were used to prepare a tabular silver halide emulsion Em-1.

A2 Ossein gelatin 34.03 g S-3 (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3150 ml with water.

B2 1734 g of potassium bromide Make up to 3644 ml with water.

C2 Finish with silver nitrate 2478 g water to 4165 ml.

D2 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05 μm) Equivalent to 0.080 moles * 5.0 weight containing 0.06 moles of potassium iodide To 6.64 liters of a 6% aqueous gelatin solution, 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

In the reaction vessel, the solution A2 was vigorously stirred while being kept at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Thereafter, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and then a part of the solution B2, a portion of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solution B2 and solution C2 to 33
Added over minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rate of the solution B2 and the solution C2 was changed like a function with respect to the time corresponding to the critical growth rate.

Further, the above solution D2 was added in an amount corresponding to 0.15 mol% with respect to the total amount of silver to carry out halogen substitution.

After completion of the addition, the emulsion was cooled to 40 ° C.
1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregated polymer, and the mixture was stirred for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.
After stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 4
9.0 L of distilled water at 0 ° C. was added, the supernatant was drained after stirring and standing, and 11.25 L of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% (by weight) aqueous sodium carbonate solution were added, and the pH was adjusted.
Was adjusted to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.8 at 40 ° C, p
Ag was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average particle size was 1.11 μm and the average thickness was 0.2.
Tabular silver halide grains having a size of 5 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. or,
The average of the twin plane distance is 0.020 μm, and grains having a twin plane distance to thickness ratio of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains are 49 or more. %, 15
These particles accounted for 17%. AgNO ₃ , K
The amount of Br, the amount of potassium iodide, the pH and the pAg were changed, and Em was changed.
Preparation of particles was carried out in the same manner as in Example -1.
Em-2 silver halide emulsions having different gI contents were prepared.

Next, each of the emulsions Em-1 and Em-2 was heated to 60 ° C., and a predetermined amount of the following spectral sensitizing dye was added as a dispersion of solid fine particles. A mixed aqueous solution of ammonium acid, chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,
A predetermined amount of 3,3a, 7-tetrazaindene (TAI) was added.

The above additives and their amounts (AgX1
(Per mole) is shown below.

5,5'-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt 400 mg 5,5'-di- (butoxycarbonyl) -1,1 '-Diethyl-3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride 4.0 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine Selenide 0.2 mg Silver iodide fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg Solid fine particle dispersion of spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-994.
Prepared by a method according to the method described in No. 37. That is, a predetermined amount of the above-mentioned spectral sensitizing dye was added to water whose temperature had been previously adjusted to 27 ° C., and the mixture was stirred at 3,500 rpm for 30 to 120 minutes by high-speed stirring (dissolver).

A dispersion of the selenium sensitizer was prepared as follows. That is, triphenylphosphine selenide 1
20 g was added to 30 kg of ethyl acetate at 50 ° C. and stirred to dissolve completely. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.
Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was 0.3 wt.
% While removing the ethyl acetate while stirring. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Emulsion Layer Coating Solution) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² 1,1-dimethylol-1-bromo-1 -Nitromethane 70 mg / m ² t-butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² sodium ² -mercaptobenzimidazole-5-sulfonate 5 mg / m ² compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Colloidal silica (Rudox AM: DuPont 0.013 μm particle size) 0 .5g / m ² However, as the gelatin by mixing the emulsion 1.5 g / m ²
It was adjusted to become.

(Preparation of Coating Solution for Protective Layer) Gelatin 0.8 g / m ² Polymethyl methacrylate A matting agent (area average particle size 7.0 μm) 50 mg / m ² Hardener (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 36 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Latex (L) 0.2 g / m ² Polyacrylamide (average molecular weight 10,000) 0.2 g / M ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² compound (F-1) 3 mg / m ² compound (F-2) 2 mg / m ² compound (F-3) 1 mg / m ² a compound of general formula (1) (Table 1-3 described) Table 1-3 wherein the amount Incidentally, the amount with the material is one-sided 1 m ² per silver coverage 1.6 g / m as one side component Adjusted to be ² .

(Formation of Crossover Cut Layer) Glycidyl methacrylate 50 wt%, Metriacrylate 1
A copolymer dispersion obtained by diluting a copolymer composed of three types of monomers of 0 wt% and 40 wt% of butyl methacrylate so as to have a concentration of 10 wt% was applied as a subbing liquid to give a 175 μm-thick blue color. on both sides of a polyethylene terephthalate support to prepare a support samples coated with the cross-over cut layer as the coating amount per surface 1 m ² is the following composition.

Solid fine particle dispersion dye (AH) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg Colloidal silica ( (Average particle size 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg The structure of the compound used above is shown below.

[0221]

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[0222]

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[0223]

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(Coating) Using these coating solutions, two slide hopper type coaters were used so that the coating amount was 1.6 g / m ² per side and the gelatin amount was 2.5 g / m ^2. Was applied simultaneously on the above-mentioned support sample at a speed of 120 M / min with the following layer constitution and dried for 2 minutes and 20 seconds to prepare a coated sample (photosensitive material).

Layer Position Layer Type Layer Amount of Gelatin per Side (g / m ² ) Upper Protective Layer 0.8 Intermediate Layer Emulsion Layer 1.5 Lower Layer Filter Layer 0.2 << Preparation of Processing Agent >> Preparation of Developer α (Developer of hydroquinone developing agent) 10 as developer
Preparation of 0 L [Preparation of Granulated Material (A)] Hydroquinone 30 as a developing agent
00 g, 1-phenyl-3-pyrazolidone 400 g, N
-Acetyl-D, L-penicillamine 10 g, boric acid 10
00g, glutaraldehyde sodium bisulfite 500
g are each ground in a commercially available bantam mill to an average of 10 μm. This fine powder has sodium sulfite 700
g, 10 g of 5-nitrobenzotriazole, 1.5 g of 1-phenyl-5-mercaptotetrazole, and a binder sorbitol so that the total amount of the granulated product (A) becomes 6000 g, and the mixture is mixed in a mill for 30 minutes to be commercially available. After granulating by adding 30 ml of water at room temperature for about 5 minutes in a stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to obtain a water content of the granulated product. Is almost completely removed.

[Preparation of solid developer (A)] The granulated product (A) thus obtained and 150 g of sodium 1-hexanesulfonate were mixed in a room conditioned at 25 ° C and 40% RH or less. After uniformly mixing for 10 minutes using a mixer, the resulting mixture was mixed with Kikusui Seisakusho Co., Ltd. Tough Presto Collect 15
27HU modified tableting machine reduces filling amount per tablet to 1
The tablet was compressed to 0 g and subjected to compression tableting to prepare a hydroquinone-based developer in a cylindrical shape having a diameter of 30 mm.

[Preparation of Granulated Material (B)] Potassium carbonate 11
000 g and 2,000 g of sodium bicarbonate are each ground in a commercially available bantam mill to an average of 10 μm.
Each of fines LiOH · H ₂ O 250g, DTP
A · 5H 250 g, 1-phenyl-5-mercaptotetrazole 5 g, sodium sulfite 4000 g, and a binder mannitol were added so that the total amount of the granulated product (B) was 19000 g, and the mixture was mixed in a mill for 30 minutes and commercially available stirring was performed. After granulating in a granulator at room temperature for about 15 minutes by adding 30 ml of water, the granulated product is dried at 40 ° C. for 2 minutes in a fluidized drier.
After drying for a time, the water content of the granules is almost completely removed.

[Preparation of solid developer (B)] The granules (B) thus obtained and 300 g of sodium 1-hexanesulfonate were mixed in a room conditioned at 25 ° C and 40% RH or less. After uniformly mixing for 10 minutes using a mixer, the resulting mixture was mixed with Kikusui Seisakusho Co., Ltd. Tough Presto Collect 15
27HU modified tableting machine reduces filling amount per tablet to 1
The tablet was compressed to 0 g and subjected to compression tableting to prepare an alkali-developed tablet.

Preparation of Developing Tablet β (Developing agent of developing agent containing reductones of the present invention) Preparation of 100 L as developer [Preparation of granulated product (A ')] 300 g of 1-phenyl-3-pyrazolidone, N -Acetyl-D, L-penicillamine 1
0 g, glutaraldehyde sodium bisulfite 500 g
Are ground in a commercially available bantam mill to an average of 10 μm. Sodium metabisulfite 1
500 g, sodium erythorbate (reductone compound of the present invention) 5000 g (the amount shown in Tables 1 to 3), sodium metabisulfite 1500 g, binder sorbitol, and the total amount of granulated product (A ') is 9000 g. After mixing in a mill for 30 minutes and granulating in a commercial stirred granulator at room temperature for about 10 minutes by adding 30 ml of water. After drying at 2 ° C. for 2 hours, the water content of the granules is almost completely removed.

[Preparation of solid tablet (A ')] To the granulated product (A') thus obtained, 150 g of sodium 1-hexanesulfonate was added, and the mixture was conditioned at 25 ° C and 40% RH or less. After uniformly mixing in a room for 10 minutes using a mixer, the obtained mixture was compressed and compressed into tablets at a filling amount of 10 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. An anthropologic developing tablet was prepared.

[Preparation of Granulated Material (B ')] Potassium carbonate 9
000 g and 100 g of sodium bicarbonate are each pulverized in a commercially available bandamill to an average of 10 μm. DTPA. 5Na 250g, the following structural formula (Z)
(I.e., 1- (p-sulfophenyl) -5-mercaptotetrazole) 40 g of the compound of the formula (1) of the present invention
The compounds represented by the formulas described in Tables 1-3 are represented by the amounts shown in Tables 1-3, KI 7 g, sorbitol 700 g, methyl-β
200 g of cyclodextrin and mannitol as binder are mixed in a mill for 30 minutes so that the total amount of the granulated product (B ') is 14000 g, and the mixture is mixed in a commercially available stirring granulator at room temperature for about 15 minutes at 30 ml. After granulating by adding water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the moisture of the granulated material.

[0232]

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[Preparation of solid tablet (B ')] To the granulated product (B') thus obtained, 300 g of sodium 1-hexanesulfonate was added, and the mixture was conditioned at 25 ° C and 40% RH or less. After uniformly mixing in a room for 10 minutes using a mixer, the obtained mixture was subjected to compression tableting with a tableting machine obtained by modifying a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho at a filling amount of 10 g per tablet to obtain a tablet. Developed tablets were prepared.

By the following operation, a solid fixing agent having a fixing solution amount of 100 L was prepared.

[Granulated product (C)] Ammonium thiosulfate /
Sodium thiosulfate (90/10 weight ratio) 15000g
Is ground in a commercial bantam mill to an average of 10 μm. 500 g of sodium sulfite, Na ₂
750 g of S ₂ O _{5 and} 1300 g of a binder pine flow are added, and the amount of water added is 50 ml, and the mixture is stirred and granulated. The granulated product is dried at 40 ° C. with a fluidized bed drier to remove water almost completely.

[Granulated product (D)] 400 g of boric acid, 1600 g of aluminum sulfate octahydrate, 1200 g of succinic acid, tartaric acid 3
50 g of the compound of the general formula (2) of the present invention (the amount corresponding to the amount shown in Tables 1 to 3) was averaged to 10 μm in a commercially available bantam mill.
Crush until it becomes Add the binder mannitol 3 to this fine powder
00g, 200g of PEG # 4000 and total amount is 430
Sorbitol is added so that the amount becomes 0 g, and water is added to 30 ml to carry out stirring granulation, and the granulated product is dried at 40 ° C. with a fluidized bed drier to completely remove water.

[Preparation of solid tablet (C)] 1400 g of β-alanine, 4000 g of sodium acetate and 150 g of sodium 1-octanesulfonate were added to the granulated product (C) thus obtained at 25 ° C. 40% RH
After uniformly mixing for 10 minutes using a mixer in a humidified room below, the obtained mixture was adjusted to a filling amount of 10 g per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Perform compression tableting, diameter 30
mm cylindrical fixing tablets were prepared.

[Preparation of solid tablet (D)] Sodium metabisulfite 750 was added to the granulated product (D) thus obtained.
g and 250 g of sodium 1-hexanesulfonate were added and uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less, and the resulting mixture was tough pressed by Kikusui Seisakusho Co., Ltd. Compression tableting was performed with a tableting machine modified from Collect 1527HU with a filling amount of 10 g per tablet to produce a cylindrical fixing tablet having a diameter of 30 mm.

<< Processing Method >> The automatic processing machine was a modified SRX-701 (manufactured by Konica Corporation). The development temperature is 35 ° C,
The fixing temperature is 35 ° C., the drying temperature is 55 ° C., and the processing time is 30
Seconds and replenishment rates were treated as shown in Tables 1, 2 and 3.

The developing solution in the developing tank at the start was a developing tablet α using hydroquinone.
13.5 L of each of the solid tablets (B) and 19 solid tablets (B) were dissolved in water to make a 1 L finish. Note that p
H was adjusted to 10.55 with KOH and acetic acid. 13.5 L of the developing solution thus adjusted was applied to an automatic developing machine SRX-701.
, And the following starter was added to make a start solution, and the processing was started by filling the developing tank. Starter addition amount is 30
ml / l. The pH after addition of the starter was adjusted to 10.4.

Developed tablets β were prepared by dissolving 9 solid tablets (A ′) and 14 solid tablets (B ′) with water to give a 1 L finish at 13.5 L in this ratio. The pH was adjusted to 10.10 with KOH and acetic acid. 13.5 L of the developing solution thus adjusted was put into an automatic developing machine SRX-701, and a starter similar to that for the developing tablet α was added thereto to form a starting solution, and the developing tank was filled to obtain a processing solution. The starter addition amount was 30 ml / l. The pH after the addition of the starter was adjusted to 9.90.

As the fixing agent, 23 solid tablets (C) and 5 solid tablets (D) were finished with water to make 1 L, and 13.5 L of this ratio was prepared. 12. Fixer prepared
5 L was placed in an automatic developing machine SRX-701, and the fixing tank was filled to obtain a processing solution. The pH at the start of the fixer
Was adjusted to 4.70.

Starter formulation KBr 5.5 g HO (CH ₂ ) ₂ S (CH ₂ ) S (CH) ₂ OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g Sodium metabisulfite Amount: Water finish 35 ml In SRX-701, a built-in chemical mixer was modified for solid processing agents for both development and fixing. That is, the charging section was modified so that the solid processing agent could be charged into the built-in chemical mixer.

For both development and fixing, a 5 L tablet was dropped into the inlet of each solid agent, and at the same time, warm water (25 to 30 ° C.) was poured and the solution was adjusted to 5.0 L while stirring and dissolving. This was used as a developing and fixing replenisher, and the prepared replenisher was supplied to a developing tank and a fixing tank.

The photosensitive material prepared above was subjected to uniform exposure over the entire surface so that the optical density after the development processing was 1.0, and the replenishment amounts of the photosensitive material, the developing solution, the fixing solution, and the developing and fixing amounts were as shown in Tables 1 to 3. 3
Running was performed as described. During running per photosensitive material 1 m ^2, developing and fixing both Table 1,
The replenishment amount was set as described in a few items. Running is 1
100 sheets per day were processed and continued for 30 days.

<< Evaluation of Sensitometry >> The obtained film was coated with a fluorescent intensifying screen SRO-250 (manufactured by Konica Corporation).
Tube voltage 90KVp, current 20mA, time 0.0
X-ray irradiation was performed under the conditions of 5 seconds, and a sensitometric curve was created by a distance method to determine the sensitivity. The value of sensitivity was determined as the reciprocal of the X-ray dose required to obtain fog +1.0.
Tables 2 and 3 show the sensitivities 30 days after the running treatment, which were obtained by this method. However, Table 2, No. The relative sensitivity is expressed assuming that the sensitivity of one sample is 100.

<< Evaluation of Remaining Color >> The obtained sample was 30.5 c
It was cut to a size of mx 25.4 cm and developed by the above processing method without exposure. Table 1 shows the levels after 30 days.
The results are shown in Figs. The degree of residual color was visually evaluated according to the following criteria.

1 Unacceptable level of residual color 2 Remaining color 3 Slight residual color but practically acceptable 4 Almost no residual color << Evaluation of Silver Tone >> Fluorescent intensifying screen SRO
-250 (manufactured by Konica Corporation), tube voltage 90KV
X-ray irradiation was performed using a phantom as a subject under the conditions of p, current 20 mA, and time 0.05 seconds. This was processed during the run. The film treated with the treatment liquid after 30 days was visually evaluated.

1 Obviously yellowish 2 Color tone slightly yellowish and impossible level 3 Color tone slightly yellowish 4 Color tone is warm black tone 5 Color tone is black tone 3 ~ 5 is the OK level.

<< Evaluation of Residual Silver >> Residual silver was evaluated by the blue optical density of silver sulfide formed by residual silver ions and sodium sulfide. Specifically, the following method was used. 0.2 ml of aqueous sodium sulfide solution (0.5N) was dropped on the unexposed photosensitive material, and after 3 minutes, blotted with blotting paper.
Dry for 0 minutes. After drying, the blue density of the portion where the sodium sulfide is dropped and the portion where the drop is not dropped are measured with PDA65 (manufactured by Konica Corporation).
And the difference was evaluated as residual silver. The smaller the value, the better the fixability.

Tables 1, 2 and 3 show the above results.

[0252]

[Table 1]

As apparent from Table 1, claims 1, 2, and
According to the inventions of 3, 6, and 7, a photosensitive material having excellent residual color and silver tone can be provided. It can be seen that this is particularly remarkable when development processing is performed using a solution containing reductones in the developer.

[0254]

[Table 2]

As is apparent from Table 2, claims 4, 6
According to the invention of No. 7, it can be seen that the processing stability with time is excellent, and in particular, when the development processing is carried out with a solution containing reductones in the developing solution, there is an effect on the residual color.

[0256]

[Table 3]

As apparent from Table 3, claims 5, 6
It can be seen that the invention of No. 7 is excellent in stability over time, residual color and silver tone.

[0258]

According to the present invention, a photographic processing method for a silver halide photographic light-sensitive material which is excellent in residual color and silver tone even in rapid low replenishment processing and excellent in sensitivity and fixability (residual silver) can be provided. .

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/31 G03C 5/31 5/38 5/38 5/395 5/395

Claims (7)

[Claims] A photographic processing method for developing and fixing a silver halide photographic light-sensitive material provided with at least one hydrophilic colloid layer including at least one silver halide emulsion layer on a support, comprising: The developing treatment is performed in the presence of a compound represented by the following general formula (1) and a reductone or a derivative thereof, and the fixing treatment is performed by the following general formula (2)
A photographic processing method for a silver halide photographic light-sensitive material, wherein the processing is carried out in the presence of a compound represented by the formula: or a salt thereof. Embedded image [In the formula, Y and Z represent N or CR ₂ , and R ₂ represents a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group, respectively. R ₁ is at least one sulfo group,
A carboxy group, a hydroxy group or a salt thereof, or-
Represents an alkyl group substituted by a B (OH) ₂ group, and when there are two or more such substituents, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. [Chemical formula 2] [Wherein R ₃ , R ₄ and R ₅ represent an alkylene group.
These alkylene groups may have an ether bond. R ₃ and R ₅ or R ₄ and R ₅ may form a ring. A and B may be the same or different and represent a hydrogen atom, an alkyl group, an amino group, an ammonio group, a hydroxy group, a carboxy group, a sulfo group, an aminocarbonyl group or an aminosulfonyl group; It may be formed. n represents an integer of 0 to 10. ] 2. The photographic processing method for a silver halide photographic material according to claim 1, wherein the compound represented by the general formula (1) is contained in the silver halide photographic material. 3. The photographic processing method of a silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is contained in a developer. 4. A photographic processing method in which a silver halide photographic light-sensitive material provided with a hydrophilic colloid layer including at least one silver halide emulsion layer on a support is subjected to photographic processing including development processing and fixing processing. The development is carried out in the presence of a reductone or a derivative thereof by converting iodine ions to a KI conversion of 5%.
A photographic processing method for a silver halide photographic light-sensitive material, wherein the processing is performed with a developing solution containing 0 to 200 mg / l, and the fixing processing is performed in the presence of the compound represented by the general formula (2). . 5. A photographic processing method for developing and fixing a silver halide photographic material having a hydrophilic colloid layer comprising at least one silver halide emulsion layer provided on a support, comprising: The developing treatment is carried out in the presence of the compound represented by the general formula (1) and a reductone or a derivative thereof by converting iodine ions to 50 to 200 m in terms of KI.
photographic processing of a silver halide photographic light-sensitive material, wherein the processing is carried out with a developing solution containing g / l and the fixing processing is performed in the presence of the compound represented by the general formula (2) or a salt thereof. Method. 6. The photographic processing method for a silver halide photographic light-sensitive material according to claim 1, wherein the supply of the developing replenisher in the developing processing is supplied as a solid processing agent. 7. The developing replenisher in the developing process and the fixing replenisher in the fixing process each have an amount of 300.
photographic processing method of a silver halide photographic material of any one of claims 1 to 6, characterized in that ml / m ² or less.