JPH09211804A - Developing solution for silver halide photographic sensitive material and processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress silver stain in a developing soln. contg. a carbonate and a sulfite at a high concn. each and excellent in preservability without affecting photographic performance by incorporating a developing agent and a specified compd. and specifying the concn. of the carbonate. SOLUTION: This developing soln. contains a developing agent, 0.3-1.5mol/l carbonate and a compd. represented by formula I or II. In the formula I, Z<1> is a group of nonmetallic atoms required to form a 5- or 6-membered hetero ring contg. 1 or >=3 N atoms in combination with C and N, etc., Z<1> has R<1> and (SX<2> )n as substituents, R<1> is H, halogen, a substituent bonding to the ring through C, O, N, etc., each of X<1> and X<2> is H or a cation and (n) is 0, 1 or 2. In the formula II, Z<2> is a group of nonmetallic atoms required to form a 5- or 6-membered hetero ring in combination with N's and has R<1> as a substituent, R<1> and X<2> have the same meanings as R<1> and X<1> in the formula I, respectively, and (n) is 1, 2 or 3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a developing solution and a processing method used for processing a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material or a light-sensitive material). More specifically, in the development processing of general-purpose black-and-white photographic light-sensitive materials, printing black-and-white photographic light-sensitive materials, medical and X-ray black-and-white photographic light-sensitive materials, silver that adheres to or deposits on photosensitive materials, developing tanks of automatic processors, and rollers. It relates to a method of reducing dirt (also called silver sludge) and facilitating daily maintenance of equipment and machinery.

[0002]

2. Description of the Related Art Generally, in the development processing of photosensitive materials,
From the viewpoints of speed, simplicity, and handling, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used.
In recent years, the demand for low replenishment and speeding up of development processing has been increasing, but to meet these demands,
One means is to increase the activity of the developer. In the processing of black-and-white photosensitive materials, the activity can be increased by increasing the concentration of the developing agent, but the deterioration due to air oxidation is remarkable.
Also, thinning the film thickness of the photosensitive material (for example, the protective layer) is effective for rapid processing.

[0003] By the way, the use of a sulfite to prevent the deterioration of a developer has been known for a long time. However, since it has a dissolving action of silver halide, silver is eluted from the photosensitive material as a silver sulfite complex into the developer. Would. The silver complex is reduced in the developing solution and gradually adheres to and accumulates on the developing tank or roller. This is referred to as silver stain or silver sludge, which adheres to the photographic material to be processed, thereby contaminating the image or contaminating the self-developing machine itself. Therefore, it is necessary to periodically clean and maintain the equipment.

As a method for reducing these silver stains, as described in JP-A-56-24347,
There is known a method of adding a compound that reduces the amount of silver ions eluted in a developer and / or suppresses the reduction of silver ions to silver. In addition to this, JP-A-59-20
4037, JP-A-4-362942, and JP-A-7-29516.
The mercaptohydroxypyrimidine described in 6 and the like is disclosed as a silver stain inhibitor. However, these compounds also have an effect of suppressing development itself and are accompanied by a decrease in sensitivity and Dmax, so that they cannot be used in a large amount and a sufficient silver stain preventing effect cannot be obtained.

Usually, the developing solution is deteriorated by air oxidation,
At this time, since the amount of sulfite also decreases, the elution amount of silver halide in the fatigue solution is smaller than that in the initial developing solution (so-called fresh solution). Although the antifouling agent was insufficient, some effects could be obtained. However, the concentration of the developing agent is increased to maintain the activity of the developing solution, and at the same time, a large amount of sulfite is used in combination to prevent the deterioration thereof, whereby the silver halide is easily eluted from the photosensitive material. In addition, increase the concentration of carbonate to improve the homeostasis
Although it is effective to increase the buffer capacity, the sulfite concentration during running is maintained at a high concentration because the decrease in the activity of the developing solution is small and the reduction due to the air oxidation of sulfite is also small. The elution amount of silver does not decrease. In such a system, a large amount of a silver stain preventing agent is required to prevent silver stains, but when a large amount of the known silver stain preventing agent as described above is used, development is strongly suppressed and fogging becomes high. Can't solve the problem because.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a developer having a high carbonate and sulfite concentration and an excellent preservative property, without affecting the photographic properties at all, in a developing machine and a photographic material. The purpose is to reduce the silver stain that contaminates.

[0007]

[Means for Solving the Problems]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned objects are as follows [1] to [4]
It was achieved by the method of. [1] A silver halide photograph containing at least a developing agent, 0.3 to 1.5 mol / liter of a carbonate, and at least one compound represented by the following general formula (1) or (2). Developer for photosensitive materials.

[0009]

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In the formula, Z ¹ is a nonmetallic atomic group or at least 1 necessary for forming a 5- or 6-membered heterocycle having a total nitrogen number of 1 or 3 in combination with C and N to form a ring.
Represents a non-metal atomic group necessary for forming a 5- or 6-membered hetero ring together with a hetero atom containing one O and / or S, and C and N, Z ¹ represents R ¹ and ( SX ² ) _n . R ¹ represents a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, which is a substituent bonded to the ring. X ¹ and X ² are hydrogen atoms or cations, and n is 0, 1 or 2. Two types of radicals obtained by removing one arbitrary hydrogen atom from Z ¹ may combine to form a bis type structure.

[0011]

Embedded image In the formula, Z ² represents a nonmetallic atomic group necessary for forming a 5-membered or 6-membered heterocycle together with N, and Z ² has R ¹ as a substituent. R ^1, X ² is R ^1, X in the general formula (1)
^In agreement with ² , n is 1, 2 or 3. Two kinds of radicals obtained by removing one arbitrary hydrogen atom from Z ² may combine to form a bis type structure.

[2] The developer according to the above [1], wherein the content of the compound represented by the general formula (1) or (2) is 0.01 to 10 mmol / liter. [3] The developer according to the above [1] or [2], which further contains an auxiliary developing agent. [4] A method for processing a silver halide photographic light-sensitive material, which comprises processing the exposed silver halide photographic light-sensitive material with the developer described in [1], [2] or [3].

Next, the general formula (1) will be described in detail. In the formula, Z ¹ is a non-metal atomic group or at least one O and / or O necessary for forming a 5-membered or 6-membered heterocycle having a total number of nitrogen atoms of 1 or 3 or more together with C and N to form a ring. Alternatively, it represents a non-metal atomic group necessary for forming a 5- or 6-membered heterocyclic ring together with a hetero atom containing S and C and N, and Z ¹ is R ¹ and (SX ² ) _n as a substituent. Have. R ¹ represents a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, which is a substituent bonded to the ring.
Further, it may be condensed with a hydrocarbon ring or a heterocycle, and examples thereof include oxazole, thiazole, triazole, thiadiazole, oxadiazole, indazole, benzoxazole, benzothiazole, pyrazolotriazole and pyrrolotriazole. 5
As a nitrogen-containing aromatic heterocycle of a member, preferably triazole, thiadiazole, oxadiazole, benzoxazole, benzothiazole, pyrazolotriazole, pyrrolotriazole, more preferably triazole, thiadiazole, oxadiazole, most preferably It is a triazole.

The 6-membered nitrogen-containing aromatic heterocyclic ring formed by Z ¹ , N and C is a monocyclic ring or a ring condensed with a carbon ring or a heterocyclic ring, such as pyridine, pyrazine, triazine, quinoline and isoquinoline. Phthalazine, quinoxaline, quinazoline, cynoline, phenanthridine,
Phenanthroline, naphthyridine, pteridine, purine, imidazolopyridine, triazolopyridine, imidazolotriazine, triazolotriazine. The 6-membered nitrogen-containing aromatic heterocycle is preferably pyrazine, triazine, phthalazine, quinoxaline, quinazoline, naphthyridine, buteridine, purine, imidazolopyridine, triazolopyridine, imidazolotriazine, triazolotriazine, and more preferably , Triazine, buteridine, purine, imidazolotriazine and triazolotriazine, most preferably triazine and purine.

R ¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. As the group bonded by the carbon atom of R ¹ , an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group,
A cyano group and a heterocyclic group, which are bonded by an oxygen atom, are a hydroxy group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, and sulfonyloxy group are bonded to each other by a nitrogen atom, such as acylamino group, amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, and sulfamoyl group. The amino group, the alkoxycarbonylamino group, the aryloxycarbonylamino group, the sulfonamide group, the imide group, and the heterocyclic group, which are bound by a sulfur atom, include an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, and an alkoxysulfonyl group. Group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group, and a sulfinyl group. These may be further substituted with the groups mentioned as R ¹ . R ¹ may be plural, and if possible, two R ¹ may combine to form a ring.

The R ¹ will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, t-butyl, benzyl and cyclopentyl. The alkenyl group has 2 to 10 carbon atoms, for example vinyl, 1-
Examples include propenyl, 1-hexenyl and styryl.
The alkynyl group has 2 to 10 carbon atoms and includes, for example, ethynyl, 1-butynyl and phenylethynyl. The aryl group is an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 8 carbon atoms, for example, carbamoyl, N-ethylcarbamoyl,
It is N-phenylcarbamoyl. The alkoxycarbonyl group has 2 to 8 carbon atoms, such as methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 12 carbon atoms,
For example, phenoxycarbonyl. The acyl group has 1 to 8 carbon atoms, such as acetyl and benzoyl. The heterocyclic group linked by a carbon atom on the ring is a 5- or 6-membered saturated or unsaturated heterocycle having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, The number of hetero atoms constituting the ring and the number of elements may be one or plural, and examples thereof include 2-furyl, 2-thienyl, 2-pyridyl, and 2-imidazolyl.

The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and includes, for example, methoxy, 2-
Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 12 carbon atoms and includes, for example, phenoxy, p-methoxyphenoxy, m- (3
-Hydroxypropionamido) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the kinds of elements may be one or more, for example, 1-phenyltetrazolyl-5
-Oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy. The acyloxy group has 1 to 1 carbon atoms.
10, preferably those having 1 to 6 carbon atoms, such as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. Carbamoyloxy group has 1 to 1 carbon atoms
10, preferably 1 to 6 carbon atoms, such as N, N
-Dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy. The sulfonyloxy group has a carbon number of 1 to 8, and examples thereof include methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 10 carbon atoms,
It preferably has 1 to 6 carbon atoms, such as acetylamino and benzoylamino. The alkylamino group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylamino, N- (2-hydroxyethyl) amino and N- (3-dimethylaminopropyl).
It is Amino. Arylamino group has 6 to 1 carbon atoms
Those of 0 are, for example, anilino and N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino. The ureido group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
10 to 10, preferably 0 to 5 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 12 carbon atoms, such as phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 10 carbon atoms, preferably 1 carbon atom.
To 6, for example, methanesulfonamide and p-toluenesulfonamide. The imide group has 4 carbon atoms
And N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocyclic ring composed of a nitrogen atom and at least one of a carbon atom, an oxygen atom or a sulfur atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 10 carbon atoms,
Preferably, it has 1 to 5 carbon atoms, such as methylthio,
It is 2-carboxyethylthio. The arylthio group has 6 to 12 carbon atoms, for example, phenylthio, 2
-Carboxyphenylthio. The heterocyclic thio group is a 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and which constitutes a ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms
It has 0, preferably 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. The alkoxysulfonyl group has 1 to 1 carbon atoms
It preferably has 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxysulfonyl. The aryloxysulfonyl group has 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

R ¹ is preferably hydrogen atom, alkyl group, aryl group, carbamoyl group, acyl group, cyano group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, sulfone. Amido group, alkylthio group, arylthio group, sulfamoyl group, sulfonyl group, more preferably hydrogen atom, alkyl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, alkylthio group, most preferably A hydrogen atom, an alkyl group, an alkoxy group, an amino group, and an alkylthio group.

X ¹ and X ² are hydrogen atoms or cations. Examples of the cation include sodium, potassium, lithium, calcium, ammonium, tetrabutylammonium and triethylammonium. X ¹
And X ² is preferably a hydrogen atom, sodium, potassium or ammonium. n is preferably 1 or 2.

Next, the general formula (2) will be described in detail. In the formula, Z ² represents a nonmetallic atomic group necessary for forming a 5-membered or 6-membered heterocycle together with N, and Z ² has R ¹ as a substituent. R ^1, X ² is R ^1, X ² and consent of the general formula (1), n is 1, 2 or 3. Further, it may be condensed with a hydrocarbon ring or a heterocycle as in the general formula (1), and examples thereof include pyrazole, pyrazoline, pyrazolidine, pyridazine, benzopyrazole and benzopyridazine.

From the general formula (1) or (2), two radicals free of any one hydrogen atom are combined to form a bis type structure, preferably the following general formula (3) or (4). It is shown by.

[0027]

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[0028]

[Chemical 6]

Where Z³¹, Z³²And Z⁴¹, Z⁴²Is it
Z of each formula (1)¹, Z in equation (2) ^TwoTo 1 hydrogen atom
Represents a broken-off group, X³¹, X³²And X⁴¹, X⁴²Is it
Each X¹Or X^TwoIs synonymous with Also, l in the equation (4),
m is the same as n in the formula (2). L^Three, L^FourIs a bivalent chain
Bonding group (alkylene group, alkenylene group, alkynylene
Groups, arylene groups, divalent heterocyclic groups and
O-, -S-, -NH-, -CO-, -SO_Two− Etc.
Grouped by themselves or by a group consisting of combinations)
You. These preferred ones are also the same as those in formula (1) or (2).
The same.

Examples of the alkylene group of L ³ and L ⁴ include ethylene, trimethylene, pentamethylene, propylene, 2-butene-1,4-yl and 2-butyne-1,4.
-Yl and p-xylylene. The alkenylene group is, for example, ethene-1,2-yl. The alkynylene group is ethyn-1,2-yl. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl.
L ^3, the alkylene group as L ^4, -NH (alkylene) NH- group, -O (alkylene) O- group, -S (alkylene) S- group, -NH (alkylene) CONH (alkylene) NH- group, A -NH (alkylene) O (alkylene) NH- group is preferable, and -NH (alkylene) NH-.
The group and the -O (alkylene) O- group are more preferable.

Among the compounds of the present invention represented by the general formula (1), those represented by the following general formulas (5) to (9) are preferable.

[0032]

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In the formula, R ⁵¹ and X ⁵¹ have the same meanings as R ¹ and X ^{1 in} formula (1), respectively. R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an optionally substituted amino group, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an alkyl group, a hydroxy group, An optionally substituted amino group and a mercapto group are preferred, and a hydrogen atom, an alkyl group and a mercapto group are most preferred. R ⁵² is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, or an optionally substituted amino group. R ⁵² is preferably a hydrogen atom, an alkyl group, a hydroxy group,
It is an optionally substituted amino group, more preferably a hydrogen atom or an alkyl group.

[0034]

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In the formula, R ⁶¹ , R ⁶² and X ⁶¹ have the same meanings as R ⁵¹ , R ⁵² and X ^{51 of the} general formula (5), respectively, and the preferred ranges are also the same.

[0036]

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In the formula, R ⁷¹ and X ⁷¹ have the same meanings as R ⁵¹ and X ^{51 in} formula (5), respectively. R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an optionally substituted amino group, a mercapto group or an alkylthio group, more preferably an alkyl group or an optionally substituted group. An amino group, a mercapto group and an alkylthio group are preferred, and a mercapto group and an alkylthio group are most preferred.

[0038]

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In the formula, R ⁸¹ , R ⁸² and X ⁸¹ have the same meanings as R ⁵¹ , R ⁵² and X ^{51 in} formula (5), respectively. R ⁸¹
Preferably a hydrogen atom, an alkyl group, an aryl group,
A heterocyclic group, a hydroxy group, an alkoxy group, an optionally substituted amino group, a mercapto group, an alkylthio group, more preferably a hydroxy group, an alkoxy group,
An amino group which may be substituted, a mercapto group and an alkylthio group are preferred, and a hydroxy group, an amino group which may be substituted and a mercapto group are most preferred. R ⁸¹ is preferably a mercapto group.

[0040]

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In the formula, R ⁹¹ , R ⁹² and R ⁹³ have the same meanings as R ⁵¹ and R ^{52 in} the general formula (5), and the preferred ranges are also the same. However, at least one of them is a mercapto group. More preferably, R ⁹³ is a mercapto group.

Of the general formulas (5) to (9), the general formulas (5) and (7) to (9) are more preferable, and the general formulas (5) and (8) are the most preferable. Next, specific examples of the compound represented by the general formula (1) or (2) in the present invention will be shown, but the invention is not limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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The compounds represented by the general formulas (1) and (2) of the present invention are described in the following patents and the patents / documents cited therein. That is, JP-A-4-301
837, 5-611159, 6-230525, 58-169147, 62-569959, U.S. Pat. No. 3,212,892, 3-53244, 3-282.
457, 5-61159, 5-303179, 4
-362942, Japanese Patent Publication No. 46-11630, JP-A-6-
175302, 6-258783 and the like.

When the compounds represented by the general formulas (1) and (2) of the present invention are added to the developing solution, it is preferably in the range of 0.01 to 10 mmol per liter of the developing solution,
A range of 0.1 to 5 mmol is particularly preferred.

The processing agents and processing methods such as the developing solution and the fixing solution in the present invention are described below, but needless to say, the present invention is not limited to the following description and specific examples.

Any known method can be used for the developing treatment of the present invention, and a known developing treatment solution can be used. There is no particular limitation on the developing agent used in the developing solution used in the present invention (hereinafter, both the developing starting solution and the developing replenishing solution are collectively referred to as a developing solution), but dihydroxybenzenes, ascorbic acid derivatives, hydroquinone It is preferable to contain a monosulfonic acid salt, which may be used alone or in combination, and is used in combination with an auxiliary developing agent. As the auxiliary developing agent, 1-phenyl-3-pyrazolidones and p-aminophenols are preferable. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferable from the viewpoint of material cost.

The auxiliary developing agent used in the present invention is 1
-Phenyl-3-pyrazolidone or its derivative 1-
Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Examples include dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-as a p-aminophenol-based auxiliary developing agent used in the present invention
There are aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene type developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l. It is preferable to use 0.5 to 0.5 mol / l and the latter in an amount of 0.06 mol / l or less, preferably 0.03 to 0.003 mol / l.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / liter to 0.5 mol / liter, and preferably 0.05 mol / liter to 0.5 mol / liter.
0.3 mol / l is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or less.
It is preferable to use 0.5 mol / l, 1-phenyl-3-pyrazolidones or p-aminophenols in an amount of 0.005 mol / l to 0.2 mol / l.

The developer used for processing the light-sensitive material in the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffer, preservative, chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of buffering agent, especially carbonate, used is 0.3 to 1.5 mol / l, particularly preferably 0.5 to 1.5 mol / l.

Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is more than 0.2 mol / l, especially 0.3
It is used in an amount of at least mol / l, but if it is added in too large an amount, it causes silver contamination in the developing solution.
Desirably, it is mol / liter. Particularly preferably,
It is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite.
Of these, sodium erythorbate is preferably used from the viewpoint of the cost of the raw material. The addition amount is 0.03 to 0.12 in terms of molar ratio with respect to the dihydroxybenzene type developing agent.
Is preferable, and particularly preferably 0.05 to 0.10.
Range. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide,
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3-
(5-Mercaptotetrazol-1-yl) benzenesulfonate sodium salt, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A No. 62-212651 may be added as a physical development unevenness preventing agent. In addition, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound is used as an antifoggant or a black spot (blackpe).
pper) inhibitor may be included. Specifically, 5
-Nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzo Imidazole, 5-nitrobenzotriazole, 4- (2-mercapto-1,
3,4-thiadiazol-2-yl) thio) butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5
-Methylbenzotriazole, 2-mercaptobenzotriazole, etc. can be mentioned. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, in the developer of the present invention, various organic compounds,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, asheric acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, Maleic acid, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of aminopolycarboxylic acids include:
Aspartic acid diacetic acid, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine monohydroxyethyl triacetic acid, ethylenediamine tetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropane tetraacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine Hexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, etc. JP-A-52-25632, 55-67747, 57-10
2624, and the compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene compounds described in US Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication No. 2,227,369.
Diphosphonic Acid and Research Disclosure No. 181
Vol., Item 18170 (May 1979 issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid.
Disclosure 18170, JP-A-57-2085
54, 54-61125, 55-29883, 5
6-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, 54-112127, 55-4024 and 55-40.
25, 55-126241, 55-65955, 55-69556 and the above-mentioned Research Disclosure 18170.

These organic and / or inorganic chelating agents are not limited to those mentioned above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁴ mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol, per liter of the developing solution.

The compounds of the present invention may be used alone as a silver stain preventing agent, and for example, JP-A-56-2434.
7, JP-B-56-46585, JP-B-62-2849,
In addition to the compounds described in JP-A-4-362942, polyoxyalkylphosphonates described in US Pat. No. 5457011 may be used in combination. The addition amount of the silver stain preventing agent is preferably 0.05 to 10 mmol, and more preferably 0.1 to 5 mmol, per 1 L of the developing solution.

Further, as a dissolution aid, JP-A-61-267
The compound described in 759 can be used. Further, if necessary, a color toning agent, a surfactant, a defoaming agent, a hardener and the like may be contained.

The preferred pH of the developer is 9.0 to 12.0.
And particularly preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

The replenishing amount of the developing solution is 390 ml or less per 1 m ² of the light-sensitive material, preferably 325 to 30 ml, and most preferably 180 to 50 ml. The development replenisher has the same composition and //
Alternatively, it may have a concentration, or may have a composition and / or concentration different from that of the starting solution.

Ammonium thiosulfate, sodium thiosulfate, and ammonium ammonium thiosulfate can be used as the fixing agent of the fixing processing agent in the present invention. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt which acts as a hardening agent, and the water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as the aluminum ion concentration in the used liquid.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

Preservatives (for example, sulfite, bisulfite, metabisulfite, etc., 0.0
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), a compound having an aluminum stabilizing ability or a water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cis line, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars,
0.001 mol / liter to 0.5 mol / boric acid
Liter, preferably 0.005 mol / l to 0.
3 mol / l).

In addition, the compounds described in JP-A-62-78551, pH adjusting agents (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
The amphoteric surfactants described above can be used, and known antifoaming agents can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-B-58-122535, and JP-B-58-1.
22536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.
739, ibid. 1-159645 and ibid. 3-101728.
And the mesoionic compound and thiocyanate described in 4-1-170539.

The fixing solution used in the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0.

The replenishing amount of the fixing solution is 500 ml or less, preferably 390 ml or less, and more preferably 320 to 80 ml per 1 m ² of the light-sensitive material. The replenishing solution may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration as the starting solution.

The fixing solution can be regenerated and used by a known fixing solution regenerating method such as recovery of electrolytic silver. As the reproducing device, for example, Reclaim R-6 manufactured by Fuji Hunt Co., Ltd.
There is 0 etc.

When the developing and fixing processing agents used in the present invention are stored in a liquid form, for example, JP-A-61-731.
47, it is preferable to store in a packaging material having low oxygen permeability. Furthermore, when these liquids are supplied as a concentrated liquid, they are diluted with water to a predetermined concentration at the time of use, and are diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated liquid.

Even when the developing treatment agent and the fixing treatment agent in the present invention are solid, the same results as the liquid agent can be obtained, but the solid treatment agent will be described below.

As the solid processing agent in the present invention, known forms (powder, granule, granule, lump, tablet, compactor, briquette, plate, crushed product, rod, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or coating film to separate components that react with each other upon contact,
A plurality of layers may be formed to separate the components that react with each other, or these may be used in combination.

As the coating, known materials can be used, such as polyvinylpyrrolidone, polyethylene glycol,
Polystyrene sulfonic acid and vinyl compounds are preferred. In addition, gelatin, pectin, polyacrylic acid,
Polyvinyl alcohol, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, alginic acid, chitanic acid gum, gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, poly Polyoxyethylene alkyl ethers such as oxyethylene stearyl ether and polyoxyethylene ethyl ether; polyoxyethylene alkyl phenol ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; and water-soluble binders described in Japanese Patent Application No. 2-203165. Can be used alone or in combination of two or more. That. These can also be used as granulation aids.

In the case of forming a plurality of layers, the components which do not react even when contacted may be sandwiched between the components which react with each other and processed into tablets, briquettes or the like. It may be packaged in the same layer structure. Examples of these methods include, for example, JP-A-61-25992.
1, JP-A-4-15641, JP-A-4-16841, and JP-A-4-15641
32837, 4-78848, 5-93991 and the like.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferable, and particularly, the tablet is 1.0 to 5.0 g / c.
m ³ is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, as a packaging method, Japanese Patent Application Laid-Open Nos. 61-259921 and 4-1
6841 and 4-78848 can be used. As a method of solidification, JP-A No. 4-8
5533, 4-85534, 4-85535, 5
-134362, 5-197070, 5-2040
98, 5-224361, 6-138604, 6
138605, Japanese Patent Application No. 7-89123, and the like.

More specifically, rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method, stirring granulation method, spray drying method, melt coagulation method, briquetting method, roller compaction method. The Ting method or the like can be used.

The particle size and shape of the granulated product suitable for the present invention vary depending on the desired characteristics, but generally, the solubility desired for the photographic processing agent and the amount of residual powder in the waste packaging material after preparation or transportation are required. Considering the durability against breakage of the granulated product due to vibration at the time, in the case of granules, the sphere-converted particle size is 0.5 to 5
It is about 0 mm, preferably about 1 to 15 mm, and the shape thereof is cylindrical, spherical, cubic, rectangular parallelepiped, etc., more preferably spherical or cylindrical. The roller-compacted product may be crushed and further sieved to a diameter of about 2 mm to 1 cm. Similarly, in the case of briquettes and tablets, the particle size and shape are different depending on the desired properties, but a diameter of about 2 mm to 5 cm is preferable, and the shape is cylindrical, spherical, cubic, rectangular parallelepiped, etc., more preferably spherical or cylindrical. Is. When it is desired to improve the solubility, a plate-shaped material having a reduced thickness, a material having a further reduced central portion thickness, and a hollow donut shape are also useful. Conversely, the diameter and thickness may be further increased for the purpose of slowly dissolving, and can be arbitrarily adjusted.
Further, the surface state (smooth, porous, etc.) may be changed in order to control the solubility. Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid processing agent is preferably a material having low oxygen and water permeability, and the packaging material may have a known shape such as a bag, a cylinder or a box. Also,
JP-A-6-242585, 6-242588, 6-
247432, 6-247448, and Japanese Patent Application No. 5-306.
64, JP-A-7-5664, and 7-5666 to 7-5.
The foldable shape as disclosed in 669 is also preferable in order to reduce the storage space of the waste packaging material. These packaging materials may be provided with a screw cap, a pull-top, an aluminum seal at the processing agent outlet, or the packaging material may be heat-sealed, but other known packaging materials may be used and are not limited to these. I don't. In addition, recycling or waste of the waste packaging material is preferable for environmental protection.

The method of dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and known methods can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in Japanese Patent Application No. 7-235499. Dissolve in
Method of replenishing from stock section, JP-A-5-11945
No. 4, 6-19102, and No. 7-261357, a method of adding a processing agent to the circulation system of an automatic developing machine to dissolve and replenish it, and processing a photosensitive material with an automatic developing machine having a dissolution tank. Depending on the method, a treatment agent may be added and dissolved, and any other known method may be used. In addition, the processing agent may be supplied by opening it when it is obtained, or by automatically opening it by a dissolving device or an automatic processor having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferable from the viewpoint of working environment. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting, a method of pushing off, and
102, 6-95331, and the like.

The light-sensitive material which has been developed and fixed is then washed or stabilized (hereinafter, referred to as washing including stabilizing treatment unless otherwise specified. That.). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. These replenishing amounts are generally 1 m ² of photosensitive material.
The amount is about 17 liters to about 8 liters, but it is also possible to replenish with a replenishing amount of less than or equal to the amount. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method for reducing the replenishment amount of water washing, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time, and the replenishment amount of water washing is 200 to ⁵ per 1 m ² of the light-sensitive material.
0 ml is preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, a means for preventing scales may be added to the washing step by the method of the present invention. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. Further, it may be preliminarily rinsed with water and replenished with it, and it is also preferable to carry out different scale control means at regular intervals in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example,
-Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, Japanese Patent Application Laid-Open Nos.
7, 4-16280, 4-18980 and the like.

In addition, a known water-soluble surfactant or defoaming agent may be added to prevent unevenness of water bubbles and stain transfer. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

A part or all of the overflow liquid from the water washing step can be mixed and used in a processing liquid having a fixing ability, as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. If necessary, the stabilizing bath may contain an ammonium compound, a metal compound such as Bi or Al, a fluorescent whitening agent, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a deterrent, an alkanolamine or a surfactant. Agents can also be added.

Additives such as antifungal agents and stabilizers to be added to the washing and stabilizing baths may be solid agents like the above-mentioned developing and fixing processing agents.

Waste liquids of the developer, fixing solution, washing water and stabilizing solution used in the present invention are preferably incinerated. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5439560 or the like before disposing.

When the replenishment amount of the processing liquid is reduced, it is preferable to reduce the opening area of the processing bath to prevent the evaporation of the liquid and the air oxidation. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. further,
A rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, dry to d
ry is preferably 25 to 160 seconds, and the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds.
5 to 50C is preferable, and 30 to 40C is preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is about 40 to about 100 ° C
The drying time can be changed as appropriate depending on the surrounding conditions. Any known drying method can be used and there is no particular limitation.
4, 5-2256, and 5-289294, heat roller drying, far-infrared drying, and the like, and a plurality of methods may be used in combination.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as a silver halide, a usual halogenated silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide or the like. Any silver halide emulsion may be used, and preferably, a negative silver halide emulsion containing 60 mol% or more of silver chloride or a positive silver halide emulsion of 6 mol.
Silver chlorobromide, silver bromide, and silver iodobromide containing 0 mol% or more of silver bromide. The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method. The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or a core / shell grain having a different silver halide composition between the inside and the surface layer of the grain,
The particles may be such that the latent image is mainly formed on the surface, or the particles are mainly formed inside the particles. Further, it may be particles whose surface is previously covered. The silver halide grains according to the present invention may have any shape. One preferred example is (1
It is a cube having a (00) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, and the like,
The Journal of Photographic Science (J. Photogr. Sci.), 21-39 (1
973), etc., and the octahedron, 1
Particles having a tetrahedral shape, a dodecahedron shape, or the like can be formed and used. Further, particles having a twin plane may be used. As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed. In the present invention, a monodisperse emulsion is preferred. As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained in the grain size range of ± 10% around the average grain size γ is 60% or more of the total weight of silver halide grains. Some are preferred. The halogen composition of the silver halide emulsion used in the present invention is not particularly limited. In order to achieve the object of the present invention more effectively, silver chloride, silver chlorobromide and silver chloroiodobromide having a silver chloride content of 50 mol% or more are preferred. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, a light-sensitive material suitable for high-illuminance exposure such as scanner exposure and a light-sensitive material for line drawing are
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound,
Alternatively, rhodium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachlororhodium (III) complex salt and hexabromorhodium (II
Examples thereof include I) complex salts, hexaaminerhodium (III) complex salts, and trisalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or alkali halides (eg KCl, NaCl, KB
r, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^-8 per mol of silver in the silver halide emulsion.
To 5 × 10 ^-6 mol, preferably 5 × 10 ^-8 to 1 × 10 ^-6
Is a mole. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is described in P. Glafkides
Author, Chimieet Physique Photo
graphique (published by Paul Montel, 1
967); F. Dufin, Photogra
phicEmulsion Chemistry (Th
e Focal Press, 1966), V.E.
L. By Zelikman et al, Making
and Coating Photographic
Emulsion (published by The Focal Press,
1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions.

The grain shape of the silver halide used in the present invention is not particularly limited, and it may be cubic, octahedral or spherical.
Research Disclosure 22534
Any of tabular silver halide grains having a high aspect ratio described in (January 1983) can be used.

In order to make the particle size uniform,
British Patent No. 1,535,016, Japanese Patent Publication No. 48-3689
0, 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
5, it is preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-55-158124 to grow the growth rapidly within a range not exceeding the critical saturation.
The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 20%.
It is particularly preferably 15% or less. The average grain size of grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.1 μm to 0.4 μm.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination,
For example, a sulfur sensitization method and a gold sensitization method, a sulfur sensitization method, a selenium sensitization method and a gold sensitization method, a sulfur sensitization method, a tellurium sensitization method, and a gold sensitization method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The addition amount of the sulfur sensitizer changes under various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the sulfur sensitizer, various sulfur compounds, such as thiosulfates, thioureas, thiazoles and rhodanins, can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat. No. 1,574,94.
4, Same 2,278,947, Same 2,410,689, Same 2,728,668, Same 3,501,313, Same 3,6
56,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Further Noise
r, Klein Gelation. Proc. Sy
mp. 2nd. The method using a combination of polyvinylpyrrolidone and thiosulfate as reported by No. 301-309 (1970) also gives good results.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-A-43-13489, JP-A-4-109240 and JP-A-4-324855 can be used. In particular, JP-A-4-3248
It is preferable to use the compounds represented by the general formulas (VIII) and (IX) in 55.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in 313284. Specifically, US Patent Nos. 1,623,499 and 3,3
20,069, 3,772,031, UK Patent No. 2
35, 211, first 1,121,496, first 1,29
No. 5,462, No. 1,396,696, and Canadian Patent No. 8
00,958, JP-A-4-204640 and 4-271.
341, 4-333043, 5-303157, and Journal of Chemical Society Chemical Communication (J. Chem. Soc. Che.
m. Commun. ) 635 (1980), ibid
1102 (1979), ibid 645 (197)
9), Journal of Chemical Society
Parkin Transaction (J. Chem. Soc.
Perkin. Trans. ) 1,191 (198
0), S. Edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Companies (The Chemistry)
of Organic Serenium and T
elluniumCompounds), Vol 1
(1986) and Vol 2 (1987). In particular, JP-A-5-313284
The compounds represented by the general formulas (II) (III) (IV) are preferred.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention according to the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

In the present invention, a silver halide emulsion which is particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

Further, the silver halide emulsion used in the light-returning light-sensitive material of the present invention preferably contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
f, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, seleno Cyanate ligands, tellurocyanate ligands, acid ligands and core ligands. When the core ligand is present, it preferably occupies one or two of the ligands.

Specifically, it contains a rhodium atom.
For the preparation of particles, use a metal salt of any shape such as a simple salt or complex salt.
It can be added at times. As rhodium salt, monosalt
Rhodium chloride, rhodium dichloride, rhodium trichloride, hexa
Examples include ammonium chlororhodate, but preferred
Very water soluble trivalent rhodium halogen complex compound
Hexachlororhodium (III) acid or its salt
Ammonium salt, sodium salt, potassium salt, etc.)
You. The amount of these water-soluble rhodium salts added is silver halide.
1.0 x 10 per mole ^-6Mol ~ 1.0 × 10^-3Mole
Used in the range. Preferably 1.0 × 10^-FiveMole
~ 1.0 × 10^-3Mol, particularly preferably 5.0 × 10^-Five
Mol ~ 5.0 x 10 ^-FourIs a mole.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl ₄ ] ^-1 10 [Ru (NO) CN ₅ ] ^-2 11 [Ru (NO) Br ₅ ] ^-2 12 [Rh (NS) Cl ₅ ] ^-2 13 [Os (NO)] Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-2 15 [Re (NO) Cl ₅ ] ^-2 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ]. ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The spectral sensitizing dye used in the present invention is not particularly limited. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but it is used in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grain. , Especially 6.5 × 10 ^{-7 to} 2.0
An addition amount range of × 10 ^-6 mol is preferred.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCROSURE It.
em 17643 IV-A (December 1978 p.
23), Item 1831 X (ibid., P. 437, August 1978), US-4425425, 442542.
6 or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, as for A) an argon laser light source, JP-A-60-1
62247, JP-A-2-48653, US Pat. No. 2,16
1,331, West German Patent 936,071, JP-A-5-11
389, simple merocyanines, B) helium
Japanese Patent Application Laid-Open No. 50-6242 discloses a neon laser light source
5, trinuclear cyanine dyes shown in Nos. 54-18726 and 59-102229, C) LED light source and red semiconductor laser, Japanese Patent Publication No. 48-42172, No. 51.
JP-A-62-284 to -9609 and 55-39818.
343, thiocarbocyanines described in JP-A-2-105135, and D) tricarbocyanines described in JP-A-59-191032 and JP-A-60-80841 for infrared semiconductor laser light sources, Kaisho 59-192
242, the general formula (IIIa) of JP-A-3-67242,
Dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIb) are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Research on useful sensitizing dyes, combinations of dyes showing supersensitization and substances showing supersensitization
Disclosure 176 Volume 17643 (1978 1
February issue), page 23, section IV-J.

Regarding the argon light source, Japanese Patent Application No. 7-37
S1-1 to S1-13 described in 811 can be preferably used.

For the helium-neon light source, the sensitizing dye represented by formula (I) described in JP-A-6-75322, page 7, column 11, line 42 to page 8 is particularly preferable. Specifically, the compounds I-1 to I-35 in the same specification are preferable. In addition to these, all of those described in the general formula (I) of JP-A-6-75322 and I-1 to I-34 of the general formula (I) of Japanese Patent Application No. 6-103272 are preferably used.

Regarding the LED light source and the infrared semiconductor laser, S3 to S3 described in Japanese Patent Application No. 7-37811.
A dye of -8 is particularly preferably used.

In addition to the infrared semiconductor laser light source, S4-1 to S4-9 described in Japanese Patent Application No. 7-37811.
Are preferably used.

The sensitizing dyes of the general formula (IV) described in JP-A-6-313937 are preferable for a white light source for photographing with a camera, and specifically, IV-1 to IV- of the specification.
20 is preferably used. In addition, JP-A-4-19
General formulas (III) and (IV) described in 647 are preferable, and specifically, III-1 to III-20 in the same specification.
And IV-1 to IV-11 are preferably used.

In the case of an X-ray sensitive material, it is preferable to use a tabular silver halide emulsion. In this case, silver bromide or silver iodobromide is preferred.
-5 mol% is preferred, and a highly sensitive one is obtained, and it is suitable for rapid processing.

The tabular silver halide emulsion preferably has an aspect ratio of 4 or more and less than 20 and more preferably 5 or more and less than 10. Furthermore, the particle thickness is 0.3μ
The following is preferable, and 0.2 μ or less is particularly preferable. Here, the aspect ratio of the tabular silver halide emulsion is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain. . The tabular grains are preferably 80% by weight of all grains in the tabular silver halide emulsion, more preferably 90% by weight.
Preferably, it is present in an amount of at least% by weight. By using a tabular silver halide emulsion, the photographic stability during running processing according to the present invention can be further enhanced. Also, since the amount of coated silver can be reduced,
Especially, the load of the fixing process and the drying process is reduced, and the rapid processing is possible also from this point.

The tabular silver halide emulsion is a knuck (C
”, and Chateau (Chatau)“ Progress in the morphology of silver bromide crystals during physical ripening (Evolution of the Morphology of Silver Bromide Crystals Dualing Physical Livening) ” Science & Industry Photography, Vol. 33, No. 2 (1962), pp. 1
21-125, Duffin, "Photographic Emulsion Chemistry (Photog)
radical emulation chemistr
y) ”Focal Press
s), New York, 1966, p. 66 to p. 7
2, A. P. H. Tribvlli, W.C.
F. Smith Photographic Journal,
Volume 80, page 285 (1940) and the like, but JP-A-58-127,921 and JP-A-58-113,9.
No. 27, JP-A-58-113, 928 and the like can be easily prepared. Further, in an atmosphere having a relatively pBr value of pBr 1.3 or less, the weight of tabular grains is 4
It can be obtained by forming a seed crystal of 0% or more and growing the seed crystal while simultaneously adding a silver and halogen solution while maintaining the same pBr value. It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth. In the present invention, a tetrazolium compound, a hydrazine compound and a nucleation accelerator may be added.

As the hydrazine derivative used in the present invention, compounds of the general formula (I) described in Japanese Patent Application No. 6-47961 are used. Specifically, I-described in the specification is used.
The compounds represented by 1 to I-53 are used.

The following hydrazine derivatives are also preferably used. The compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically the compounds described on pages 3 and 4 of the publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication; Compounds represented by the general formula (4), the general formula (5) and the general formula (6) described in JP-A-6-230497, specifically, Compound 4-1 described on pages 25 and 26 of the same publication. -Compound 4-10, Compounds 5-1 to 5-42 described on pages 28 to 36, and Compound 6-1 to Compound 6-7 described on pages 39 and 40. JP-A-6-28
9520 are compounds represented by the general formula (1) and the general formula (2), specifically, compounds 1-1) to 1-17) and 2-1 described on pages 5 to 7 of the publication. ). JP 6
The compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in -313936, specifically, the compounds described on pages 6 to 19 of the same publication; The compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically the compounds described on pages 3 to 5 of the same. Compounds represented by the general formula (I) described in JP-A-7-5610, specifically compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-1 described on pages 10 to 27 of the publication.
02. Compounds represented by formula (H) and formula (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the publication. The general formulas (1), (A) described in Japanese Patent Application No. 7-191007,
Compounds represented by (B) and (C), specifically the compounds N-1 to N-30 and D-1 to D-5 described in the publication.
5.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro. Benzotriazoles and the like; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added. Among these, benzotriazole (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole) are preferred. Further, these compounds may be contained in the treatment liquid. Further, a compound described in JP-A-62-30243, which releases an inhibitor during development, can be incorporated for the purpose of stabilizing or preventing black spots.

Further, a technique of incorporating a polymer latex in a silver halide emulsion layer or a backing layer to improve dimensional stability can also be used. These techniques are disclosed in, for example, Japanese Examined Patent Publication Nos. 39-4272, 39-17702 and 43
-13482 and the like. For the purpose of dimensional stability, a dispersion of a water-insoluble or sparingly soluble synthetic polymer may be included. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. be able to.

The emulsion layer of the photographic light-sensitive material of the present invention may contain a polymer such as an alkyl acrylate latex, an emulsion, or a plasticizer such as a polyol such as trimethylolpropane in order to improve pressure characteristics.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may be a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfinates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amino oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings.

The silver halide photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer on a support. 127921, 59-90841, 58-
As described in JP-A-111934 and 61-201235, those having at least one silver halide emulsion layer on each side of the support are preferred. The photographic material of the present invention may further have an intermediate layer, a filter layer, an antihalation layer, and the like, if necessary.

The silver amount of the light-sensitive material used in the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 1 g / m ^{2 to} 4 g / m ² (on one side). Is. It is preferable that the suitability for rapid processing does not exceed 5 g / m ² . Further, 0.5 g / m ² or more is preferable in order to obtain constant image density and contrast.

Gelatin is used as the binder of the light-sensitive material used in the present invention, and gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or co-polymers. A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as coalesced can also be used in combination.

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, cellulose, sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

It is particularly preferable for the X-ray sensitive material to contain an organic substance which flows out in the development processing step in the emulsion layer or in the hydrophilic colloid layer. When the substance to be washed away is gelatin, a gelatin species which is not involved in the crosslinking reaction of gelatin by the hardener is preferable, for example, acetylated gelatin or phthalated gelatin, and a material having a small molecular weight is preferable. On the other hand, as a polymer substance other than gelatin, US Pat. No. 3,271,1
58, or hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be effectively used, and saccharides such as dextran, saccharose and pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less,
More preferably, it is 10,000 or less. The amount of effluent in the process is 1 of the total weight of the applied organic substances other than silver halide grains.
0% or more and 50% or less is effective, and preferably 15% or more and 30% or less disappears. The layer containing the organic substance flowing out in the treatment of the present invention may be either an emulsion layer or a surface protective layer.However, when the total amount of the organic substance applied is the same, the layer containing the organic substance is more effective than the layer containing only the emulsion layer. It is preferable that the compound is contained in the emulsion layer, and it is more preferable that the compound is contained only in the surface protective layer. In a light-sensitive material having a multi-layered emulsion layer, when the total coating amount of the organic substance is the same, it is preferable that the emulsion layer is contained more in the emulsion layer closer to the surface protective layer.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 4,142,89 are used.
4, homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid, organic compounds such as starch,
Fine particles of an inorganic compound such as silica, titanium dioxide, or strontium barium sulfate can be used. The particle size is preferably 1.0 to 10 μm, and particularly preferably 2 to 5 μm.

The silver halide photographic light-sensitive material of the present invention has a spectral composition of light for the purpose of absorbing light in a specific wavelength range, that is, for halation and irradiation, and for providing a filter layer to make light incident on the photographic emulsion layer. The photographic emulsion layer or other layers may be colored with a dye for the purpose of controlling the temperature. In a double-sided film such as a direct medical x-ray film, a layer for crossover cut may be provided below the emulsion layer. Such dyes include oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus, hemioxonol dyes, azo dyes, azomethine dyes, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, cyanine dyes, etc. Is mentioned. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in German Patent 616,00.
7, British Patents 584,609, 1,117,429,
Japanese Patent Publications 26-7777, 39-22069, 54-
38129, JP-A-48-85130, and JP-A-49-996.
20, the same 49-114420, the same 49-129537,
PB Report 74175, Photographic Abstract (Photo.Abstr.) 128 ('2
1) and the like. In particular, it is preferable to use these dyes in a bright room reversal light-sensitive material.
Further, solid fine particle dispersions of dyes described in Japanese Patent Application No. 5-244717, pages 23 to 30 may be used. In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

When using these dyes, it is an effective technique to mord an anionic dye in a specific layer in a light-sensitive material using a polymer having a cation site. In this case, it is preferable to use a dye which irreversibly decolorizes during the development-fixing-washing step. The layer in which the dye is mordanted by using a polymer having a cation site may be the emulsion layer, the surface protective layer may be on the side opposite to the emulsion layer and the support, but preferably between the emulsion layer and the support. For the purpose of crossover cutting of medical X-ray double-sided films, it is ideal to mordant into the undercoat layer.

As a coating aid for the undercoat layer, a polyethylene oxide nonionic surfactant can be preferably used in combination with the polymer having a cation site. As the polymer providing the cation site, an anion conversion polymer is preferable. Various known quaternary ammonium salt (or phosphonium salt) polymers can be used as the anion conversion polymer. Quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers in the publications listed below. JP-A-59-166940, U.S. Pat. No. 3,958,99
5, JP-A-55-142339, JP-A-54-126,
027, JP-A-54-155835, JP-A-53-3
0328, water-dispersed latex described in JP-A-54-92274; polyvinylpyridinium salts described in U.S. Pat. Nos. 2,548,564, 3,148,061, 3,756,814; U.S. Pat. , 709, 69
Water-soluble quaternary ammonium salt polymer described in US Pat. No. 3,898,088; and the like. Further, a monomer having at least two (preferably 2 to 4) ethylenically unsaturated groups is copolymerized because it moves from the desired layer to another layer or into the processing solution and does not have a photographically unfavorable effect. It is particularly preferable to use a crosslinked aqueous polymer latex.

As a method for immobilizing a dye, JP-A-55-1 is used.
The solid dispersion method described in 55350, WO88 / 04794 or the like is also effective.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl) -Hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, etc.), etc. Can be used alone or in combination.

The photographic light-sensitive material of the present invention contains a hydroquinone derivative (so-called DIR-hydroquinone) which releases a development inhibitor in a photographic emulsion layer or other hydrophilic colloid layer corresponding to the density of an image at the time of development. May be. Specific examples thereof are U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, U.S. Pat. No. 4,377,63.
4, U.S. Pat. No. 4,332,878, JP-A-46-12
9,536, JP-A-54-67,419, JP-A-56-
153, 336, JP-A-56-153, 342, JP-A-59-278, 853, 59-90435, 59-.
The compounds described in 90436, 59-138808 and the like can be mentioned.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid,
A polymer or copolymer having an acid monomer such as maleic acid or phthalic acid as a repeating unit can be given. These compounds are disclosed in JP-A-61-2238.
34, 61-228437, 62-25745, and 62-55642. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and a high molecular compound composed of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

The silver halide emulsion thus produced is applied to a support such as a cellulose acetate film or a polyethylene terephthalate film by a dip method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method or the like and dried. It

The present invention can also be applied to a color light-sensitive material. In this case, various color couplers can be used. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17
643 (December 1978) Item VII-D and 18
717 (November 1979).

In addition, the various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following sections can be preferably used. Item This section 1) Nucleation accelerator A compound represented by formula (I), (II), (III), (IV), (V) or (VI) described in JP-A-6-82943. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound examples II-1 to II-22, The compound described in Kaihei 1-179939. 2) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to right lower column, line 4; JP-A 2-103536, page 16, lower right column, line 3 to page 17, lower left column The 20th line, and further, the spectral sensitizing dyes described in JP-A Nos. 1-112235, 2-124560, 3-79928 and 5-11389, and Japanese Patent Application No. 3-411064. 3) Surfactants JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, lower right column 18th line. 4) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and further JP-A-1-237538. The thiosulfinic acid compound described. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 of the same. 9) Dyes The dyes described in JP-A-2-103536, page 17, lower right column, lines 1 to 18 and solid dyes described in JP-A 2-294638 and 5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and Japanese Patent Application Laid-Open No. 1-118832. 12) Redox compound A compound represented by formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), a general formula (R in page 3 to page 20 of JP-A-3-174143). -1), (R-2), (R-3), Compound Examples 1 to 75, further compounds described in 5-257239 and 4-278939. 13) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 14) Dihydroxybenes Compounds described in JP-A-3-39948, page 11, upper left column to first zen, page 2, lower left column, and EP452772A.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

The composition of the developing solution (1) per 1 L of the used solution is shown below. Potassium hydroxide 28.0 g Diethylenetriamine / pentaacetic acid 2.0 g Potassium carbonate 75.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4 -Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g Compound shown in Table 1 Amount shown in Table 1 Sodium erythorbate 3.0 g Diethylene glycol 20.0 g pH 10.5

The composition of the developer (2) is shown below. Sodium hydroxide (beads) 99.5% 6.5 g Potassium sulfite (bulk powder) 63.0 g Sodium sulfite (bulk powder) 46.0 g Potassium carbonate 80.0 g Hydroquinone (briquette) 40.0 g To form briquettes Diethylenetriamine / pentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g Compounds shown in Table-1. Amount indicated 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g sodium erythorbate 6.0 g potassium bromide 6.6 g This is dissolved in water to 1 L. pH 10.65

Here, in the raw material form, the bulk powder was used as a general industrial product, and the beads of the alkali metal salt were commercial products. If the raw material is briquette, it is pressed and compressed using a briquetting machine to give an irregular length of 4 to 6
A rugby ball type shape having a size of about mm was prepared, crushed and used. For minor components, each component was blended before briquetting. 10 L of the above treatment agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, a dissolution and replenishment device having an automatic opening mechanism disclosed in Japanese Patent Application Nos. 7-235499 and 7-235498 was used.

The formulation for 1 L of the fixing solution (1) is shown below. Ammonium thiosulfate 120 g Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.03 g Sodium thiosulfate / 5-hydrate 11.0 g Sodium metasulfite 19.0 g Sodium hydroxide 12.4 g Acetic acid (100%) 30.0 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g pH 4.8

The composition of the fixing agent (2) is shown below. Agent A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (bulk powder) 19.0 g Sodium metabisulfite (bulk powder) 18.0 g Anhydrous sodium acetate (bulk powder) 42.0 g B Agent (Liquid) Ethylenediamine / tetraacetic acid / 2Na / 2-hydrate 0.03 g Anhydrous citric acid 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 mL. The A agent and the B agent were dissolved in water to make 1 L. pH 4.8

Ammonium thiosulfate (compact) was obtained by compressing flakes prepared by the spray drying method with a roller compactor and crushing them into chips of irregular shape of about 4 to 6 mm, and blending them with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. A 10 L portion of each of the agents A and B was filled in a foldable container made of high-density polyethylene, and the outlet of the agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. Japanese Patent Application Laid-Open No. 7-2
The dissolution replenishing device having an automatic opening mechanism disclosed in 35499, Japanese Patent Application No. 7-235498 was used.

Photosensitive materials (1) to (1) used in Examples are described below.
The production method of (4) will be described. Manufacturing method of the light-sensitive material (1) The method of manufacturing the emulsion-A will be described. The following solutions 2 and 3 were added to the following solution 1 kept at 38 ° C. and pH 4.5 at the same time for 24 minutes while stirring to form particles of 0.18 μm. Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and 0.15 g of potassium iodide was added to complete the particle formation. After that, it was washed with water by the flocculation method according to a conventional method, and after adding gelatin, the pH was adjusted to 5.2 and pAg.
Adjusted to 7.5, 4 mg of sodium thiosulfate and N, N-
Dimethylselenourea (2 mg), chloroauric acid (10 mg), sodium benzenethiosulfonate (4 mg) and sodium benzenethiosulfinate (1 mg) were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity. Furthermore, as a stabilizer,
2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene 50 mg, phenoxyethanol as a preservative were added so as to be 100 ppm, and finally the average particle size containing silver chloride 80 mol% was 0.20 μm. To obtain silver iodochlorobromide cubic grains. (Variation coefficient 9%)

<Part 1> Water 1.0 liter Gelatin 20 g Sodium chloride 2 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium benzenethiosulfonate 3 mg <Part 2> Water 600 ml Silver nitrate 150 g < Liquid 3> Water 600 ml Sodium chloride 45 g Potassium bromide 21 g Potassium hexachloroiridium (III) acid (0.001% aqueous solution) 15 ml Ammonium hexabromorhodium (III) acid (0.001% aqueous solution) 1.5 ml < 4 solution> water 200 ml silver nitrate 50 g <5 solution> water 200 ml sodium chloride 15 g potassium bromide 7 g K ₄ Fe (CN) ₆ 30 mg

<Preparation of silver halide photographic light-sensitive material> A layer structure of a UL layer, an EM layer, a PC layer and an OC layer is formed in this order from the support side on a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride. Was applied to prepare a sample. The preparation method and coating amount of each layer are shown below.

(UL layer) A 30 wt% dispersion of polyethylene acrylate in gelatin was added to a gelatin aqueous solution, and the gelatin was coated at 0.5 g / m ² .

(EM Layer) The following compound (S-1) as a sensitizing dye was added to the above emulsion A at 2.5 × 10 ⁻⁴ per mol of silver.
3 × 10 ⁻⁴ mol of mercapto compound represented by the following (a), which is added per mol of silver: KBr 3.0 × 1
0 ^-3 mol, of 4-hydroxy-6-methyl-l, 3,3
a, 7-Tetrazaindene 7.0 × 10 ⁻⁴ , 4 × 10 ⁻⁴
Molar mercapto compound represented by the following (b), 4 × 1
0 ^-4 mol of a triazine compound represented by the following (c), 2
X 10 ^-3 mol of 5-chloro-8-hydroxyquinoline,
The following nucleating agent (HZ-1) (hydrazine derivative) 7.0 ×
10 ⁻⁵ mol, the following nucleation accelerator (AC-1) 4.2 × 10
^-4 mol, sodium p-dodecylbenzenesulfonate 9
× 10 ⁻³ mol and 3 × 10 ⁻² mol of hydroquinone were added. In addition, 200m of polyethyl acrylate dispersion
g / m ² , methyl acrylate and 2-acrylamide-
200 mg / m ² of latex copolymer of 2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7) and 200 mg / m of colloidal silica having an average particle diameter of 0.02 μm.
m ² and 200 mg / m of the following (d) as a hardening agent
² was added. They were coated so that the coated silver amount was 3.5 g / m ² . The pH of the finished liquid was 5.7.

(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
The following surfactant (e) was added at 5 mg / m ² and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² so that gelatin was 0.5 g / m ² . .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 4 having an average particle size of about 3.5 μm 4
0 mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 2
0 mg / m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (f) as a coating aid, 100 mg / m ^{2 of} sodium dodecylbenzenesulfonate and 20 mg / m ² of the following structural formula (g) were applied. .

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ² Hardener Hardener (d) 200 mg / m ² SnO ₂ / Sb ( Weight ratio 90/10, 200 mg / m ² average particle size 0.20 μm) Dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ² [Back protective layer] Gelatin 0.8 mg / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p -Sodium dodecylbenzene sulfonate 15 mg / m ² sodium acetate 40 mg / m ²

The swelling ratio ((swelled film thickness / dry film thickness) × 100) on the side having the emulsion layer was 100.

Manufacturing Method of Photosensitive Material (2) Emulsion B 2 mg of sodium thiosulfate added per 1 mol of silver.
Was prepared in the same manner as Emulsion A except that the selenium sensitizer was not used.

The sensitizing dye of the light-sensitive material (1) was converted into S-2 (5 ×
10 ⁻⁴ mol / mol Ag) and S-3 (5 × 10 ⁻⁴ mol / mol Ag), Emulsion B as emulsion for EM layer
A sample was prepared in the same manner as in the light-sensitive material (1) except that was used.

The swelling ratio ((swollen film thickness / dry film thickness) × 100) on the side having the emulsion layer was 100.

Preparation of Photosensitive Material (3) Emulsion C Sodium chloride kept at 40 ° C. and 3 per mol of silver
× 10 ^-5 mol sodium benzenesulfonate, 5 × 1
0 ^-3 mole of 4-hydroxy-6-methyl-l, 3,3
a, 1.5 containing pH = 2.0 containing 7-tetrazaindene
% Gelatin aqueous solution and sodium chloride aqueous solution containing 2.0 × 10 ⁻⁶ mol of K ₂ Ru (NO) Cl ₅ per mol of silver by the double jet method at a potential of 95 mV for 3 minutes 3
Half of the silver amount of the final particles was simultaneously added in 0 seconds to prepare 0.12 μm particles of the core. Then, an aqueous solution of silver nitrate and 6.0 × 10 ⁻⁶ mol of K ₂ Ru (NO) C per mol of silver were added.
A sodium chloride aqueous solution containing ₁₅ was added in the same manner as above for 7 minutes to prepare silver chloride cubic grains having an average grain size of 0.15 μm (variation coefficient: 12%). Then, after washing with water by a flocculation method well known in the art to remove soluble salts, gelatin is added, and compound-A and phenoxyethanol as preservatives are added in amounts of 60 per mol of silver.
After adding mg, the pH was adjusted to 5.7 and pAg = 7.5,
Furthermore, 4 × 10 ^-5 mol of chloroauric acid and 4 per mol of silver
After the addition of × 10 ^-5 mol of compound-Z, 1 × 10 ^-5 mol of sodium thiosulfate and 1 × 10 ^-5 mol of potassium selenocyanide were added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization. After that, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer was added in an amount of 1 × 10 ⁻³ mol per mol of silver (as final particles, pH =
5.7, pAg = 7.5, Ru = 4.0 × 10 ⁻⁶ mol /
Ag mole).

EM, PC and OC were applied in this order on the following support. (EM) The following compounds were added to the above emulsion C, and a silver halide emulsion layer was coated so that the gelatin coating amount was 0.9 g / m ² and the coating silver amount was 2.7 g / m ² . 1-phenyl-5-mercapto-tetrazole 1 mg / m ^{2 following} nucleation accelerator (AC-2) 3.6 × 10 ⁻³ mol / mol Ag N-oleyl-N-methyltaurine sodium salt 10 mg / m ^{2 following} compound -B 10 mg / m ² the following compounds -C 10 mg / m ² the following compound -D 10 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 760mg / m ² Compound-E (hardening agent) 105 mg / m ² Sodium polystyrene sulfonate 57 mg / m ² Nucleating agent (HZ-3) below 1.2 × 10 ⁻³ mol / mol Ag

The following compounds were added to an aqueous solution of gelatin (PC) and coated so that the coating amount of gelatin was 0.6 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.6 g / m ² sodium p-dodecylbenzenesulfonate 10 mg / m ² sodium polystyrene sulfonate 6 mg / m ² compound below-A 1 mg / m ² compound below-F 14 mg / m ² n-Butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 250 mg / m ²

The following compounds were added to the (OC) gelatin aqueous solution and coated so that the coating amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent 40 mg / m ² (average particle diameter 3.5 μ, pore diameter 25 Å, surface area 700 m ² / g) amorphous silica matting agent 10 mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² sodium p-dodecylbenzenesulfonate 30 mg / m ² Compounds below -A 1 mg / m ² Liquid paraffin 40 mg / m ^{2 The following} solid disperse dye-G ₁ 30 mg / m ^{2 The following} solid disperse dye-G ₂ 150 mg / m ² Sodium polystyrene sulfonate 4 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support. <Preparation of coating liquid for conductive layer and coating> The following compounds were added to an aqueous gelatin solution to give a gelatin coating amount of 0.06 g / m ^2.
It applied so that it might become. SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 186 mg / m ₂ gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ₂ p-sodium dodecylbenzenesulfonate 13 mg / m ₂ dihexyl-α- Sodium sulfosuccinate 12 mg / m ₂ Sodium polystyrene sulfonate 10 mg / m ₂ Compound-A 1 mg / m ₂

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 3.4μ) 15mg / m ² the following compound -H 140 mg / m ² the following compounds -I 140 mg / m ² the following compound - J 30 mg / m ^{2 following} compound-K 40 mg / m ² sodium p-dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ^{2 following} compound-L 5 mg / m ² N-perfluorooctanesulfonyl -N- propyl glycine Potassium 5 mg / m ² sodium sulfate 150 mg / m ² sodium acetate 40 mg / m ² the following compound -E (hardener) 105 mg / m ²

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate supports (thickness: 100 μm) were coated with the undercoat layers 1 and 2 having the following compositions on both surfaces. <Undercoat layer 1 layer> The following core-shell type vinylidene chloride copolymer 15 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 µ) 0.05 g The following compound-M 0 .20 g Colloidal silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10% by weight of KOH was added to adjust the pH = 6 to obtain a coating liquid at a drying temperature. The dry film thickness is 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g The following compound-N 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g The following compound-A 3.5 × 10 ^-3 g acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness would be 0.1 μm. A sample was prepared in this way. The swelling ratio ((swelled film thickness / dry film thickness) × 100) on the side having the emulsion layer was 100.

Preparation of Photosensitive Material (4) Emulsion D 250 cc of an aqueous silver nitrate solution in which 64 g of silver nitrate was dissolved, and K ₂ corresponding to 1 × 10 ^-7 mol per 1 mol of silver in the whole emulsion.
Rh (H ₂ O) Cl ₅ and K corresponding to 2 × 10 ⁻⁷ mol
250 cc of an aqueous solution of halogen salt in which 20 g of potassium bromide containing ₃ IrCl ₆ and 14 g of sodium chloride were dissolved was added to sodium chloride (0.3%), 1,3-dimethyl-2-imidazolithione (0.002%) and citric acid. (0.05
%) Containing 2% gelatin aqueous solution with stirring 38
Nucleation was carried out by adding the mixture by the double jet method at 12 ° C. for 12 minutes to obtain silver chlorobromide grains having an average grain size of 0.16 μm and a silver chloride content of 55 mol%. Subsequently, 300 cc of an aqueous solution of silver nitrate in which 106 g of silver nitrate was dissolved and 300 cc of an aqueous solution of halogen salt in which 28 g of potassium bromide and 26 g of sodium chloride were dissolved were used to measure 20 cc by a double jet method.
It was added over a period of time to form particles.

Then, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, and the product was washed with water by a flocculation method according to a conventional method. Then, 40 g of gelatin was added per 1 mol of silver, pH was 5.9, pAg was
After adjusting to 7.5, 3 mg of sodium benzenethiosulfonate, 1 mg of sodium benzenesulfinate, 2 mg of sodium thiosulfate, 2 mg of a compound represented by the following structural formula (h) and 8 mg of chloroauric acid per mol of silver.
Was added and the mixture was heated at 60 ° C. for 70 minutes for chemical sensitization. Thereafter, 4-hydroxy-6-methyl-1,
After adding 150 mg of 3,3a, 7-tetrazaindene and 100 mg of proxel as a preservative, 400 mg of a dye represented by the following structural formula (i) was added, and the temperature was lowered after 10 minutes. The obtained particles have an average particle size of 0.22 μm,
The particles were silver iodochlorobromide cubic grains having a silver chloride content of 60 mol%. (Coefficient of variation 10%)

(Preparation of emulsion layer coating solution) To this emulsion, silver 1
2 x 10 per mole^-FourMolar represented by the following structural formula (j)
Shortwave cyanine dye, 5 × 10^-3Molar potassium bromide,
2 × 10^-FourMol of 1-phenyl-5-mercaptotetra
Sol, 2x10^-FourMolar represented by the following structural formula (k)
Mercapto compound, 3 × 10^-FourMolar structural formula (l)
And a nucleation accelerator (AC-1) represented by
6 × 10^-FourMolar, nucleating agent (Hz-2) 2 × 10 ^-FourMole
Added, and further hydroquinone 100 mg / m^Two, P
-Sodium dodecylbenzenesulfonate 10 mg / m
^Two, Colloidal silica (Snowtex C made by Nissan Chemical)
150 mg / m^Two, Polyethyl acrylate dispersion 5
00 mg / m^Two1,2-bis (vinylsulfonylacetate
Toamide) ethane 80 mg / m^TwoAdd to be applied
An emulsion layer coating solution was prepared. Adjust the pH of the coating solution to 5.6
did.

(Preparation of PC and OC coating solution) In a gelatin solution containing proxel as an antiseptic, the compound represented by (n) was 10 mg / m ² , the compound represented by (o) was 100 mg / m ² , A dispersion of polyethyl acrylate was added so as to be applied at 300 mg / m ² to prepare a PC liquid. Further, in a gelatin solution containing proxel as a preservative, an amorphous SiO 2 having an average particle size of about 3.5μ
₂ Matting agent 50 mg / m ² , colloidal silica (Nissan Chemical's Snowtex C) 100 mg / m ² , liquid paraffin 30 mg / m ² , the following structural formula (p) as a coating aid
5 mg / m ^{2 of} a fluorosurfactant represented by and p-dodecylbenzenesulfonic acid sodium salt 30 mg / m ² were added so as to be applied to prepare an OC solution.

These coating solutions were applied onto a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides, the emulsion layer (silver content 3.0 g / m ² , gelatin 1.5 g / m ² ) as the bottom layer, and PC ( Gelatin 0.5g /
m ² ) and OC (gelatin 0.4 g / m ² ) were applied.
The pH of the emulsion surface of the obtained sample was 5.8.

The back layer was coated according to the following formulation. (Back layer) Gelatin 1.5 g / m ² Surfactant p-dodecylbenzenesulfonic acid sodium salt 30 mg / m ² Gelatin hardening agent 1,2-bis (vinylsulfonylacetamide) ethane 100 mg / m ² Dye The following dye (q) , (R), (s), (t) mixture Dye (q) 50 mg / m ² Dye (r) 100 mg / m ² Dye (s) 30 mg / m ² Dye (t) 50 mg / m ² Proxel 1 mg / m ²

The swelling ratio ((swelled film thickness / dry film thickness) × 100) on the side having the emulsion layer was 150.

The structures of various additives used in the photosensitive materials (1) to (4) of the examples are shown below.

[0180]

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[0181]

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[0182]

[Chemical 21]

[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190] meet the developer and fixer in Example 1 manufactured by Fuji Photo Film Co., Ltd. automatic processor FG-680AG, the company manufactured a contact film RU-100 1 day 100 m ² at 10 days, developing temperature 38 ° C., the fixing temperature After being processed at 37 ° C. for a developing time of 20 seconds, the photosensitive materials (1) to (4) and the output photosensitive material LS-5 manufactured by the same company were used.
Sensitometry was performed on 500 and DU-150WP, a duplication paper sensitive material. The developer (1) is used in combination with the fixer (1) and the developer (2) is used in combination with the fixer (2).
/ M ^2, the developer (2) is 160 mL / m ^2, both the replenishment of fixing solution was 260 mL / m ^2. The following C-1 and C-2 were used as comparative compounds.

[0191]

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The exposure and processing conditions of each light-sensitive material were as follows. Through the sensitive material (1) 633 nm interference filter, through an interference filter having a peak at the exposure sensitive material (2) 488 nm with a xenon flash light of issuing times 10 ^-6 sec through step wedge, issued time 10 through step wedge ^{- Five}
Exposure with xenon flash light for 2 seconds Sensitive material (3) Exposure via step wedge with P-627FM printer manufactured by Dainippon Screen Co., Ltd. Sensitive material (4) Through step wedge 3200 ° K
Exposure with tungsten light LS-5500 Issue time 10 through step wedge through interference filter with peak at 488 nm
-Exposure with ⁴ second xenon flash light DU-150WP Dainippon Screen P-627F
Exposure processing conditions with M printer through step wedge Sensitive materials (1), (2) and (4) were processed by setting the developing temperature to 35 ° C, the fixing temperature to 34 ° C and the developing time to 30 seconds. Other sensitive materials are developing temperature 38 ℃, fixing temperature 37 ℃,
Processing was performed by setting the developing time to 20 seconds. Tables 1 and 2 show the difference between the minimum density (D _min ) and the sensitivity (S _3.0 ) at a density of 3.0 with respect to the blank. The smaller the difference is, the more it has no effect on the photographic properties, which is preferable, and the compound of the present invention has a small effect on the photographic properties, and is excellent because there is no effect on the D _{min of the} dub sensitive material even at a large addition amount. It should be noted that, within D _min difference 0.03, S _{3. 0} Sa ± 0.02
The allowable range is within.

[0193]

[Table 1]

[0194]

[Table 2]

[0195]

[Table 3]

[0196]

[Table 4]

Example 2 In Example 1, the developer was filtered through a 0.45 μm microfilter immediately after the completion of the treatment of RU-100, and the amount of silver in the solution was measured. The results are shown in Tables 1 and 2. The compounds of the present invention all showed excellent silver elution suppressing ability.

Example 3 After the treatment of RU-100 in Example 1, an unexposed contact paper sensitive material KU-150WP (cut into 4 pieces) manufactured by the same company was treated to observe the degree of contamination. The results are shown in Tables 1 and 2. A level of 4 or higher is a level at which there is no practical problem.

[0199]

EFFECT OF THE INVENTION By using the compound of the present invention, it is possible to obtain an excellent effect of preventing silver stain without affecting the photographic property in a developer having a particularly high pH buffering ability and an excellent preservative property. did it.

Claims (4)

[Claims] 1. A halogenated compound containing at least a developing agent, 0.3 to 1.5 mol / liter of a carbonate, and at least one compound represented by the following general formula (1) or (2). Developer for silver photographic materials. General formula (1) In the formula, Z ¹ is a non-metal atomic group or at least one O and / or O necessary for forming a 5-membered or 6-membered heterocycle having a total number of nitrogen atoms of 1 or 3 or more together with C and N to form a ring. Alternatively, it represents a non-metal atomic group necessary for forming a 5- or 6-membered heterocyclic ring together with a hetero atom containing S and C and N, and Z ¹ is R ¹ and (SX ² ) _n as a substituent. Have. R ¹ represents a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, which is a substituent bonded to the ring. X ¹ and X ² are hydrogen atoms or cations, n is 0,
1 or 2. Two types of radicals obtained by removing one arbitrary hydrogen atom from Z ¹ may combine to form a bis type structure. General formula (2) In the formula, Z ² represents a nonmetallic atomic group necessary for forming a 5-membered or 6-membered heterocycle together with N, and Z ² has R ¹ as a substituent. R ^1, X ² is R ^1, X in the general formula (1)
^In agreement with ² , n is 1, 2 or 3. Two kinds of radicals obtained by removing one arbitrary hydrogen atom from Z ² may combine to form a bis type structure. 2. The developer according to claim 1, wherein the content of the compound represented by the general formula (1) or (2) is 0.01 to 10 mmol / liter. 3. The developer according to claim 1, further comprising an auxiliary developing agent. 4. A method of processing a silver halide photographic light-sensitive material, which comprises processing the exposed silver halide photographic light-sensitive material with the developer according to claim 1, 2 or 3.