JPH09211806A - Developing solution and method for developing silver halide photographic sensitive material with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress silver stain in a developing tank, etc., and to facilitate maintenance without deteriorating photographic characteristics and the stability of a developing soln. when a rapidly processable silver halide photosensitive material is processed by incorporating a specified compd. SOLUTION: This developing soln. contains at least one kind of compd. represented by formula I or II preferably by 0.1-5mmol per 1L of the developing soln. In the formula I, L1 is a divalent group, R1 is amino, ammonio or an alkoxy and M is H or a cation. In the formula II, L3 is a combining group, M is H or a cation and each of X1 and X2 is a group substitutable on a triazine ring. The developing soln. may contain a developing agent, an alkali agent, a pH buffer, preservatives and a chelating agent. The developing agent preferably includes dihydroxybenzene or an ascorbic acid deriv.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing method used for processing a silver halide photographic material (hereinafter, also referred to as a "photosensitive material"). More specifically, in the processing of black-and-white photographic light-sensitive materials for general use, black-and-white photographic light-sensitive materials for printing, and X-ray photographic light-sensitive materials for medical and industrial use, they adhere to the light-sensitive materials, developing tanks, developing racks and rollers of automatic developing machines Or precipitated silver stain (also called silver sludge)
And a method for facilitating the maintenance of daily instruments and machines.

[0002]

2. Description of the Related Art Generally, in the development processing of a silver halide photosensitive material, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used from the viewpoints of speed, simplicity and handling. When using an automatic developing machine, usually, development-fixing-
There is a process of washing and drying. In recent years, there has been an increasing demand for faster development processing. For rapid processing, increasing the activity of the developing solution is one means. For rapid processing of black-and-white photosensitive materials, the activity can be increased by increasing the concentration of the developing agent or the pH of the developing solution, but the deterioration of the developing solution due to air oxidation is remarkable and it is difficult to maintain the activity. In addition, approaches from photosensitive materials have been actively studied for rapid processing. Reducing the film thickness (for example, protective layer) of the photosensitive material is effective for rapid processing.

The use of sulfites to prevent the deterioration of the developer has been known for a long time. However, since a compound having a silver halide dissolving action, such as a sulfite, is added to the developer, the use of a sulfite is difficult. Silver elutes from the photosensitive material as a silver sulfite complex. As the silver complex is reduced in the developing solution, silver gradually adheres and accumulates on the developing tank and the developing roller. This is called silver dirt or silver sludge, which adheres to the photosensitive material to be processed and contaminates the image, so that it is necessary to periodically clean and maintain the equipment. When the amount of sulfite added is increased, the amount of silver sulfite complex eluted increases, and as a result, the degree of silver contamination is further increased, and there is a disadvantage that the advantage of rapid processing cannot be fully utilized.

On the other hand, as a method for reducing the silver contamination, a compound which reduces the amount of silver ions eluted in a developer and / or suppresses the reduction of silver ions to silver as disclosed in JP-A-56-24347. Is known. However, this method has the drawback that the action of suppressing development itself is inevitable and the sensitivity is reduced. Light-sensitive materials that are going to be used with a high sensitivity
As a development processing system, a decrease in sensitivity is a serious drawback. Although reducing the thickness of the photosensitive material (eg, protective layer) is extremely effective for rapid processing, running such a photosensitive material on a self-developing machine increases the amount of silver ions eluted into the developer. Silver contamination will worsen. Various compounds have been disclosed as compounds for reducing silver contamination. Mercaptotriazines are one of them. In Japanese Patent Laid-Open No. 49-5334, a heterocyclic mercapto compound is added to a lith-type developing solution to realize removal of tails from high contrast photographic light-sensitive materials. As a specific example, 2,4,6-trimercapto-1,3,5-triazine is mentioned. In JP-A-59-204037, a heterocyclic mercapto compound is used in combination with a black-and-white developer having a pH of 11.5 or higher for the purpose of preventing silver sludge (silver dirt). As a specific example, 2,4-dimercapto-6-hydroxy-1,3,5-triazine is mentioned. In JP-A-3-53244, mercapto-1,3,5-triazine is used for the purpose of preventing silver sludge in the developing solution. Further, JP-A-3-282457, JP-A-4-11249, JP-A-4-31852, and JP-A-4-29933.
7, the same 4-299338, the same 4-322248, the same 4-
175178, 5-61159, 5-303179.
The publication also discloses that mercapto-1,3,5-triazine is effective. However, these compounds have great adverse effects on photographic properties such as reduction in sensitivity. Further, JP-A-6-230525 also discloses a mercaptotriazine compound, and discloses that when it is processed with a developer containing no alkanolamine, it does not soften and is effective in preventing black spots. However,
It was not disclosed that the mercaptotriazine compound having a specific functional group as in the present invention had an excellent effect, and it could not be expected.

[0005]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is, firstly, when processing a silver halide light-sensitive material capable of rapid processing, first of all, silver stains generated in a developing tank and / or developing racks and rollers. The second, the maintenance of the developing machine and the developing equipment is easy, the third is the reduction of silver stain without affecting the photographic characteristics at all, and the fourth is the stability of the developer. It is to reduce silver dust without damaging it.

[0006]

The above object is achieved by a developer for silver halide photographic light-sensitive material, which contains at least one compound represented by the following general formula (I) or (II). Was done. General formula (I)

[0007]

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In the formula, L ₁ represents a divalent group, and R ₁ represents an amino group, an ammonio group or an alkoxy group. M represents a hydrogen atom or a cation. General formula (II)

[0009]

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L in the formula_ThreeRepresents a linking group, M represents a hydrogen source
Represents a child and a cation. Also, X₁, X _TwoIs the triazine ring
Represents a substitutable group.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (I) will be described in detail below. Examples of the amino group represented by R ₁ in the general formula (I) include unsubstituted amino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, anilino group, o-toluidino group, 2,4 And a xylidino group and the like.

The ammonium group represented by R ₁ in the general formula (I) is, for example, a trimethylammonium group, a triethylammonium group, a diethylmethylammonium group, a tri-n-butylammonium group, and the like. The counter anion that neutralizes is an inorganic anion (eg, halogen ion (eg, chloride ion, bromide ion), etc.), an organic anion (eg, acetate ion, CH ₃ OSO ₃ ⁻ ion).

In the general formula (I), the alkoxy group represented by R ₁ is a methoxy group, an ethoxy group, an isopropyl group, an n-butoxy group, a cyclohexyloxy group,
A methoxyethoxy group etc. are mentioned.

In the general formula (I), examples of the cation represented by M include alkali metal ions such as lithium ion, sodium ion, potassium ion and cesium ion, and ammonium ions such as ammonium ion and tetramethylammonium ion. Etc.

The divalent group represented by L ₁ in the general formula (I) has 1 to 10 carbon atoms (preferably 1 carbon atom).
~ 6) alkylene group (for example, methylene group, ethylene group, propylene group), -N (R ₁₀ ) -L _2- , (wherein R ₁₀ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms) the _{represented), - O-L 2 -} , - S-L 2 -, - C (O) -
_{L 2 -, - SO 2 -L} 2 -, - C (O) O-L 2 -, a methylenedioxy group, such as ureylene groups, and these composite base.

Here, L ₂ is a divalent group and has 1 carbon atom.
It is an alkylene group (for example, a methylene group, an ethylene group, a propylene group) of 10 (preferably 1 to 6).

Further, in the general formula (I), each group represented by R ₁ and L ₁ may be substituted. Examples of the substituent include the following.

Halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, Cyclohexyl group), alkenyl group (eg, allyl group, 2-butenyl group, 3-pentenyl group), alkynyl group (eg, propargyl group, 3-pentynyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl Group (for example, phenyl group, naphthyl group, 4-methylphenyl group), heterocyclic group (for example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group), alkoxy group (for example, methoxy group, ethoxy group, Butoxy group), aryloxy group (eg, phenoxy group, 2-
Naphthyloxy group), amino group (for example, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group), ureido group (for example, unsubstituted ureido group, N-methylureido group, N-phenylureido group), Urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group), sulfonyl group (eg, mesyl group, tosyl group), sulfinyl group (eg, methylsulfinyl group, phenylsulfinyl group), alkyloxycarbonyl group (eg, methoxy group) Carbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (eg, phenoxycarbonyl group), acyl group (eg,
Acetyl group, benzoyl group, formyl group, pivaloyl group), acyloxy group (for example, acetoxy group, benzoyloxy group), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide group), alkylthio group (for example, methylthio). Group, ethylthio group), arylthio group (for example, phenylthio group), cyano group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (for example, trimethylammonio group), phosphonio group, silyl group (for example, trimethylsilyl group, Triethylsilyl group, t-
Butyldimethylsilyl group, t-butyldiphenylsilyl group) and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

Next, the general formula (II) will be described in detail. As the linking group represented by L ₃ in the general formula (II), an alkylene group (eg, methylene group, ethylene group, propylene group), an arylene group (eg, o-phenylene group, p-phenylene group), a simple bond, -N (R ₁₁ )
-, (Wherein R ₁₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, etc.), -O-, -S
-, - SS -, - C (O) -, - SO -, - SO 2 -,
-OC (O) O-, -SC (O) S-, a methylenedioxy group, a ureylene group, etc., and these composite groups are mentioned.

Examples of the group capable of substituting the triazine ring represented by X ₁ and X ₂ in the general formula (II) include the substituents of R ₁ and L ₁ in the general formula (I), and further, acylamino Group (for example, acetylamino group, benzoylamino group), sulfonylamino group (for example, methylsulfonylamino group, phenylsulfonylamino group), sulfamoyl group (for example, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group), carbamoyl group (for example, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group,
N-phenylcarbamoyl group), a sulfo group, a carboxy group, a hydroxy group and the like.

The cation represented by M in the general formula (II) has the same meaning as the cation represented by M in the general formula (I).

In the general formula (I), preferably, the divalent group represented by L ₁ is an alkylene group, —N (R ₁₀ ) -L _{2
-, - O-L 2 -} , - C (O) -L 2 - it is and are those wherein R ₁ is an amino group, an ammonio group. M represents a hydrogen atom or a cation.

More preferably in the general formula (I),
The divalent group represented by L ₁ is an alkylene group, —N (R ₁₀ ).
-L ₂ - is and are those wherein R ₁ is an amino group, an ammonio group. M represents a hydrogen atom or a cation.

Most preferably in the general formula (I), L
Divalent groups represented by _1, an alkylene group, -N (R ₁₀₎ -
L ₂ — and R ₁ is an amino group. M represents a hydrogen atom or a cation.

In the general formula (II), L in the formula is preferable.
₃ is an alkylene group, -N (R ₁₁ )-, -O-, -S-
And M represents a hydrogen atom or a cation.

More preferably, in the general formula (II), L ₃ represents —N (R ₁₁ ) —, (wherein R ₁₁ represents a hydrogen atom or an aliphatic hydrocarbon group) and —O—. , M represents a hydrogen atom or a cation.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0028]

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[0029]

[Chemical 6]

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The compounds represented by the general formulas (I) and (II) are known in the following literature, E. M. Smolin, L .; It can be synthesized according to the method described in Lapoport, s-Triazine and Derivatives (The Chemistry of Heterocyclic Compounds Series, published by Intersunence Publishers).

In the present invention, the general formula (I) or (II)
The amount of the compound represented by the formula (1) added to the developer is arbitrary, but generally 0.01 mmol to 1 liter of the developer.
It is in the range of 10 mmol, preferably 0.1 mmol to 5 mmol.

The developer of the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used.
The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes and an ascorbic acid derivative.

In the present invention, it is preferable to use an auxiliary developing agent in combination with the above developing agent. The combination is 1-dihydroxybenzenes and ascorbic acid derivatives and 1-
A combination of phenyl-3-pyrazolidones or a combination of dihydroxybenzenes or ascorbic acid derivative and p-aminophenols is preferable. Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferable. Ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and their salts.

As auxiliary developing agents for 1-phenyl-3-pyrazolidone or its derivative, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4 are used. -Hydroxymethyl-3-pyrazolidone and the like. Examples of p-aminophenol-based auxiliary developing agents include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl) glycine. However, among them, N-methyl-p-aminophenol is preferable.

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

As the buffer, carbonate, JP-A-62-1
Boric acid described in 86259, JP-A-60-93433.
Saccharides (eg saccharose), oximes (eg acetoxime), phenols (eg 5-
Sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like are used, preferably carbonate,
Boric acid is used. The amount of buffer, especially carbonate, is
Preferably, it is 0.5 mol / liter or more, particularly 0.5 to
1.5 mol / l.

In the present invention, the pH of the developing starter solution is 9.0 to 12.0, particularly preferably 9.5 to 1.
It is in the range of 0.7. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also in this range. p
As the alkali agent used for setting H, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

When processing 1 square meter of the silver halide photographic light-sensitive material, the replenisher amount of the developer is 390 ml or less, preferably 325 to 30 ml.
The development replenisher may have the same composition as the development start solution, or may have a higher concentration of components consumed in development than the start solution.

Additives (eg, preservatives) usually used in the developing solution (both the development initiating solution and the developing replenishing solution are collectively referred to as the developing solution, hereinafter) when developing the light-sensitive material in the present invention. , A chelating agent). 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. 0.2 for sulfite
It is used in an amount of 0 mol / liter or more, particularly 0.3 mol / liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is preferably 1.2 mol / liter. Particularly preferably, it is 0.35 to 0.7 mol / liter. As a preservative for a dihydroxybenzene-based developing agent, a small amount of an ascorbic acid derivative may be used in combination with sulfite. Here, the ascorbic acid derivative includes ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof. It is preferable to use sodium erythorbate in terms of material cost. The addition amount is 0.03 to molar ratio based on the dihydroxybenzene type developing agent.
The range of 0.12 is preferable, and particularly preferably 0.05 to
It is in the range of 0.10. 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 or its derivatives; mercapto Compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds may be included as antifoggants or black pepper inhibitors. Specifically, 5-nitroindazole,
5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5- Nitrobenztriazole, 4
-[(2-Mercapto-1,3,4-thiadiazole-
Examples thereof include sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of developer.

Further, various organic / inorganic chelating agents can be used in combination in the developer of the present invention. As the inorganic chelating agent, sodium tetrapolyphosphate, sodium hexametaphosphate or the like can be used. On the other hand, as the organic chelating agent, organic carboxylic acid, aminopolycarboxylic acid, organic phosphonic acid, aminophosphonic acid and organic phosphonocarboxylic acid can be mainly used. Examples of the organic carboxylic acids include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, succinic acid, acelineic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. , Itaconic acid, malic acid, citric acid, tartaric acid and the like, but are not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid. Acetic acid,
Triethylenetetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamine tetraacetic acid, and others, JP-A-52-25632, and JP-A-55-67
Nos. 747, 57-102624, and JP-B-53-
Compounds described in, for example, Japanese Patent No. 40900 can be exemplified.

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, and 54.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65955.
No. 55-69556, and the above-mentioned Research Disclosure 18170. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, in addition to the compound of the present invention as a silver stain preventive agent in a developing solution, JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, and JP-A-4-362942 are described. Can be used. JP-A-62-2126 is used as a development unevenness inhibitor.
No. 51, as a solubilizer, JP-A-61-26
The compound described in No. 7759 can be used. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

Ammonium thiosulfate and sodium 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 appropriately changed and is generally 0.7 to about 3.0 mol / liter. The fixing solution in the present invention may contain a water-soluble aluminum salt or a chromium salt which acts as a hardening agent, and is preferably a water-soluble aluminum salt. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, aluminum lactate and the like. These are the aluminum ion concentrations,
It is preferably contained at 0.01 to 0.15 mol / liter. When the fixer is stored as a concentrated solution, it may be a plurality of solutions having a hardener or the like as a separate part, or may be a one-component concentrated solution containing all components.

If desired, the fixing treatment agent may be a preservative (eg, sulfite, bisulfite, etc.), a pH buffer (eg, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, Adipic acid), p
H regulators (eg sodium hydroxide, ammonia,
Sulfuric acid, etc.), compounds having aluminum stabilizing ability and water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid,
Benzoic acid, salicylic acid, tyrone, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives, their salts, sugars, boric acid, etc.), JP-A-62-78
The compound described in No. 551, a surfactant, a wetting agent, a fixing accelerator and the like can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfone oxides, polyethylene-based surfactants, JP-A-57-684.
The amphoteric surfactant described in No. 0 can be mentioned, and a known antifoaming agent can also be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include alkyl- and allyl-substituted thiosulfonic acids and salts thereof, and JP-B-45-35754 and 58-58.
-122535 and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459,
JP-A-64-4739, JP-A-1-4739, JP-A-1
The mercapto compound described in No. 159645 and No. 3-101728, the mesoionic compound described in No. 4-170539, and thiocyanate can be included.

The pH of the fixing solution in the present invention is 4.0 or higher, preferably 4.7 to 5.0.

When the fixing treatment agent of the present invention is a concentrated fixing solution, it is diluted with water to a predetermined concentration when used. In particular, 0.2 part to 3 parts of water is diluted with 1 part of the concentrated fixing liquid.

The replenishing amount of the fixing solution is 500 ml / m ² or less, preferably 390 ml / m ² or less, with respect to the processing amount of the light-sensitive material.

Further, the fixing solution can be recycled and used by a known fixing solution recycling method such as electrolytic silver recovery. As such a reproducing device, for example, Recla made by Fuji Hunt
im R-60 and the like.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has 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. . Four steps of a stabilization step may be used instead of the washing step.

The developing solution and the fixing solution in the present invention may be solid, and the solid agent has a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, crushed product, rod). it can. These solid agents may be coated with a water-soluble coating agent in order to separate the ingredients that contact each other and react with each other. Known coating agents can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and vinyl compounds are preferable. In addition, the following may be used.

Gelatin, pectin, polyacrylic acid, polyvinyl alcohol, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid, gum xanthate,
Arabic gum, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene ethyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. The polyoxyethylene alkylphenol ether or the water-soluble binder described in Japanese Patent Application No. 2-203165 can be used alone or in combination of two or more. These can also be used as a granulation aid.

The solid processing agent in the present invention may be composed of a plurality of layers, for example, JP-A-61-259.
921, JP-A-4-15641 and JP-A-4-16841.
No. 4, No. 4-32837, No. 4-78848, No. 5-
The method described in No. 93991 can be used.

The bulk density of the solid processing agent is 0.5 to 6.0 g / from the viewpoint of its solubility and the effect of the object of the present invention.
cm ³ is preferable, and 1.0 to 5.0 g / cm ³ is particularly preferable.

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, JP-A-61-259921 and JP-A-4-25921 are available.
The methods described in 16841 and 4-78848 can be used. Further, as a method of solidification and tableting, there are disclosed in JP-A-4-85533 and JP-A-4-85534.
No. 4-85535, No. 5-134362, No. 5-1
No. 97090, No. 5-204098, No. 5-2243.
No. 61, No. 6-138604, No. 6-138605 and the like can be used.

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 differ 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 Considering the durability against the breakage of the granulated product due to vibration during transportation, the spherical equivalent particle size is 0.5 to 5 in the case of the granular form.
It is preferably about 0 mm, preferably about 1 to 15 mm, and the shape thereof is cylindrical, spherical, cubic, rectangular parallelepiped, etc., and more preferably spherical or cylindrical.

Similarly, in the case of briquettes and tablets, a diameter of about 2 mm to 5 cm is preferable although it depends on the desired characteristics. When it is desired to improve the solubility, a flat plate having a reduced thickness, a flat plate having a further reduced central portion thickness, and a hollow donut type are also useful. On the contrary, the diameter may be further increased for the purpose of slow dissolution, and can be adjusted arbitrarily.

The surface condition (smoothness, porosity, etc.) may be changed to control the solubility.

It is also possible to take a plurality of shapes in order to give different solubilities to a plurality of granules and to adjust the solubilities of materials having different solubilities. Further, it may be a multi-layer granulated product having different compositions on the surface and inside. As a packaging material for the solid processing agent, a material having low oxygen and water permeability is preferable.

As the method for dissolving and replenishing the treating agent of the present invention, 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 stocking a finished liquid are used. , A method of replenishing from the stock section, a method of adding a processing agent to the circulation system of an automatic developing machine to dissolve and replenish it, and an automatic processing machine with a built-in dissolving tank in which the processing agent is added and dissolved according to the processing of the photosensitive material. There are ways,
Any other known method can be used.

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment can be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide photosensitive material. In other words, not only water saving processing becomes possible,
It is possible to eliminate the need for piping for installing the automatic processing machine. When washing with a small amount of water, JP-A-63-18350, 6
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in 2-287252 and the like. In addition, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. As a method for reducing the replenishing amount of the washing water, a multi-stage countercurrent method (for example, two-stage, three-stage, or the like) has been known for a long time. If this multi-stage countercurrent system is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 235
As described in JP-A-133, it can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and as an example, there is JP-A-2-201357.
Baths containing the compounds described in JP-A Nos. 2-132435 and 1-125553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, metal compounds such as ammonium compounds, Bi, and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines, and surfactants may be used in this stabilizing bath. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferred to use. In the development processing of the present invention, the development and fixing time is 40 seconds or less, preferably 6 seconds to 35 seconds, and the temperature of each solution is preferably 25 ° C to 50 ° C.
0 ° C to 40 ° C is more preferred. More preferably, the temperature and time for washing or stabilizing bath are 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, development, fixing and water washing (or stabilization)
The photographic material thus obtained may be squeezed out of washing water, that is, dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as a silver halide, a conventional 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 grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. Even if the particles are formed as
Further, the particles may be 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 preferable example is {10
It is a cube having a 0} plane as a crystal surface. US Pat. Nos. 4,183,756 and 4,225,666,
JP-A-55-26589, JP-B-55-42737, etc., The Journal of Photographic Science (J. Photogr. Sci.), 21-39 (1973).
According to the method described in the literature such as octahedron, tetrahedron,
It is also possible to prepare particles having a dodecahedron shape and use them. 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 monodispersed silver halide grains in the monodispersed emulsion, the weight of silver halide contained within a grain size range of ± 10% around the average grain size γ is 60% of the weight of all silver halide grains.
% Is preferable. 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, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is 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 halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, 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 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. 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 Chimie et Physique Photograph by P. Glafkides.
ique (published by Paul Montel, 1967), by GFDufin
Photographic Emulsion Chemistry (The Focal Press
, 1966), by VLZelikman et al Makig 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.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 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, spherical, or
Research Disclosure 22534 (January 1983)
Any of the tabular silver halide grains having a high aspect ratio described in 1) can be used.

In order to make the particle size uniform,
British Patent No. 1,535,016, Japanese Patent Publication No. Sho 48-368
No. 90, No. 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. 4,24.
2,445, the method of changing the concentration of the aqueous solution as described in JP-A-55-158124,
It is preferred that the growth be performed quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion, and the coefficient of variation is preferably 20% or less, particularly preferably 15% or less.
The average grain size of the grains in the monodispersed silver halide emulsion is 0.5 μm or less, particularly preferably 0.1 μm to
It is 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 amount of the sulfur sensitizer to be added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but is preferably 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.
No.4, No.2,278,947, No.2,410,689
No. 2, ibid. 2,728,668, ibid. 3,501,313
No. 3,656,955.
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. Furthermore, Moisar, Klein Gelationc. Proc. Symp. 2nd, 30
The method of combining polyvinylpyrrolidone and thiosulfate as reported by 1-309 (1970) et al. 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 unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compound represented by (IX).

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 the silver halide grain. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the compounds described in Vol. 2 (1987) can be used. In particular, the compounds represented by the general formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 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 particularly suitable as a reversal light-sensitive material is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 to 10 is contained. 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, it is desirable that the silver halide emulsion used for the reversal light-sensitive material of the present invention contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
r, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenoate ligand Cyanate, tellurocyanate, acid and aquo ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salts, sodium salts, potassium salts, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

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 ] ^-3 15 [Re (NO) Cl ₅ ] ^-1 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 range of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain. , Especially 6.5 × 10 ^{−7 to} 2.0 ×
The addition amount range of 10 ⁻⁶ mol is preferable.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). 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, A) For an argon laser light source,
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
18, JP-A-62-284343, JP-A-2-10.
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formula (IIIa) and general formula (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Volume 176 17643 (December 1978)
(Published monthly), page 23, IV, J.

[0090]

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[0091]

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For the helium-neon light source, in addition to the above, the sensitizing dye represented by formula (I) of JP-A-6-75322 is particularly preferable. Specific examples are shown below.

[0093]

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[0094]

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The following dyes are particularly preferably used for the LED light source and the infrared semiconductor laser.

[0096]

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[0097]

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The following dyes are preferably used for the infrared semiconductor laser light source.

[0099]

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[0100]

[Chemical 21]

[0101]

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The sensitizing dye of the general formula (IV) described in JP-A-7-36139 is preferably used for a white light source for photographing with a camera. Specific compound examples are shown below.

[0103]

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[0104]

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[0105]

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[0106]

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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.

A preferred grain form of the tabular silver halide emulsion is an aspect ratio of 4 or more and less than 20, 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 knack (Cu
Gnac) and Château "Evolution of the Morphology of Silver Bromide Crystals during Physical Aging (Evolution of the Morphology of Silver Promise Crystals Dualing Physical Raising)" Science・ Industrial photography, 3
3, No.2 (1962), pp. 121-125, Duffin, "Photographic emulsion chemistry"
Focal Press, New York, 1
966, p. 66 to p. 72, APH Tribelli (Tribv
lli), WF Smith Photographic Journal, 80, 285 (19)
40) and the like, but JP-A-58-127,9
21, JP-A-58-113,927, JP-A-58-
It can be easily prepared by referring to the method described in No. 113,928. In addition, pBr 1.3 or less, relatively pBr
The seed crystal is formed by forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere having the same value, and growing the seed crystal while simultaneously adding silver and a 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 using a silver salt for growing the grains.
And the rate of addition of the halide can be controlled. In the present invention, a tetrazolium compound, a hydrazine compound and a nucleation accelerator may be added.

Examples of the hydrazine derivative used in the present invention include Japanese Patent Application No. 7-287335 (corresponding EP67051).
The compounds of general formula (I) described in 6A) are used. Specifically, compounds represented by I-1 to I-53 described in the same specification are used. The addition amount, addition layer, addition method, etc. are also in accordance with the description in the above publication.

The following hydrazine derivatives are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. A compound represented by the general formula (I) described in JP-B-6-93082, specifically, pages 8 to 1 of the publication
Compounds 1 to 38 on page 8. JP-A-6-23049
A compound represented by the general formula (4), the general formula (5) or the general formula (6) described in No. 7;
Compounds 4-1 to 4-10 described on page 26, compounds 5-1 to 5-42 described on pages 28 to 36, and 39
6-1 to 6-7. Compounds represented by the general formula (1) and the general formula (2) described in JP-A-6-289520, specifically, from page 5 of the same publication.
Compounds 1-1) to 1-17) and 2-
1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by 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-102 described on pages 10 to 27 of the publication. Compounds represented by formula (H) and formula (Ha) described in JP-A-7-104426, specifically compound H described on pages 8 to 15 of the same;
-1-H-44. Compounds represented by the general formulas (1), (A), (B), and (C) described in Japanese Patent Application No. 7-191007, specifically, compounds N-1 to N- described in the publication. Thirty
And D-1 to D-55.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of a 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 capable of releasing an inhibitor during development described in JP-A-62-30243 may be incorporated for the purpose of stabilizing or preventing black spots.

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

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.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material prepared by using the present invention may be coated with 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, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl 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, and in the case of a direct medical X-ray sensitive material, it is disclosed in JP-A-58-58. 127921, 59-90841, 5
As described in JP-A Nos. 8-111934 and 61-201235, those having at least one silver halide emulsion layer on both sides of a support are preferred.
The photographic material of the present invention may further include, if necessary, an intermediate layer,
It can have a filter layer, an antihalation layer and the like.

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. Preferably, the suitability for rapid processing does not exceed 5 g / m ² . Further, in order to obtain a constant image density and a constant contrast, 0.5 g / m ² or more is preferable.

Gelatin is used as the binder of the light-sensitive material used in the present invention. 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 for 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 and other polymers, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used. 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
Polyacrylamide as described in No. 58, or alternatively, polyvinyl alcohol, a hydrophilic polymer such as polyvinylpyrrolidone can be effectively used,
Sugars 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 10,000 or less. The amount of the effluent in the processing is preferably 10% or more and 50% or less of the total weight of the coated organic substance other than the silver halide grains, and is preferably 15% or less.
% Or more and preferably 30% or less. 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 the case of a light-sensitive material in which the emulsion layer has a multilayer structure, when the total coating amount of the organic substance is the same,
It is preferable that the emulsion layer is contained in a larger amount, which is closer to the surface protective layer.

In the present invention, as a matting agent, a polyacetic agent as described in US Pat. Nos. 2,992,101, 2,701,245, 4,142,894 and 4,396,706 is used. A homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, and fine particles of an inorganic compound such as silica, titanium dioxide, and strontium barium sulfate can be used. 1.0 to 10μ as particle size
m, particularly preferably 2 to 5 μm.

The silver halide photographic light-sensitive material of the present invention has a purpose of absorbing light in a specific wavelength range, that is, halation and irradiation, and a spectral composition of light to be incident on a photographic emulsion layer provided with a filter layer. The photographic emulsion layer or other layers may be dyed with a dye for the purpose of suppression. 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 Patent 584,609, and 1,117,42.
9, No. 26-7777 and 39-22069
No. 54-38129, JP-A-48-85130.
No. 49-99620, No. 49-114420,
49-129537, PB Report 74175,
Photographic Abstract (Photo.Absrt.)
128 ('21) and the like. In particular, it is preferable to use these dyes in a bright room reversal light-sensitive material. In addition, Japanese Patent Application No. 5-244717, 23-30
Solid fine particle dispersions of the dyes listed on the page 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 mordante an anionic dye into 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 a 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-59-166,940, US Pat. No. 3,958,9
95, JP-A-55-142339, JP-A-54-1.
26,027, JP-A-54-155,835, JP-A-53-30328, and JP-A-54-92274; U.S. Pat. No. 2,54.
8,564, 3,148,061, 3,75
Polyvinylpyridinium salt described in US Pat. No. 6,814; Water-soluble quaternary ammonium salt polymer described in US Pat. No. 3,709,690; Water-insoluble quaternary ammonium salt polymer described in US Pat. No. 3,898,088 And so on. 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, for example, 55350 or WO88 / 04794 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 corresponding to the density of an image at the time of development in a hydrophilic colloid layer such as a photographic emulsion layer. Good. Specific examples thereof are U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, U.S. Pat. No. 4,377,6.
34, U.S. Pat. No. 4,332,878, JP-A-49
-129,536, JP-A-54-67,419, JP-A-56-153,336, JP-A-56-153,3
42, JP-A-59-278,853 and 59-90.
No. 435, No. 59-90436, No. 59-13880.
Examples thereof include compounds described in No. 8 and the like.

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.
No. 34, No. 61-228443, No. 62-25745
And the records of JP-B-62-55642 can be referred to. Particularly preferred among these compounds is ascorbic acid as the low molecular weight compound,
The polymer compound is a water-dispersible latex of a copolymer comprising an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene.

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), Sections VII-D and 187
17 (November 1979).

In addition, various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following parts can be preferably used. Item 1) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. 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; Compounds described in JP-A-1-179939. 2) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Spectral sensitizing dyes described in column 20, line 20 and JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and JP-A-5-11389. 3) Surfactant 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 line 4 Line 18 in the lower right column of the page. 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 JP-A 1-237538. Thiosulfinic acid compounds described in the official bulletin. 5) Polymer latex: JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, 15th line. 8) Hardener From page 5, right upper column, line 5 to line 17, JP-A-2-103536. 9) Dyes Dyes in the lower right column, lines 1 to 18 of page 17, JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound A compound represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A No. 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in JP-A-5-25729. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 14) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12, lower left column, and EP452772A.

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The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.

Developer Formulation (1) (per liter of used liquid) KOH (100%) 35.0 g diethylenetriamine / pentaacetic acid 2.0 g potassium carbonate 40.0 g sodium metabisulfite 40.0 g potassium bromide 3.0 g diethylene glycol 20.0 g hydroquinone 25.0 g 5-methylbenzotriazole 0.08 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2- Thioxo-4- (1H) -quinazolinone 0.04 g Sodium 2-mercaptobenzimidazole-5-sulfonate 0.15 g Sodium erythorbate 3.0 g Compounds shown in Table 1 Described in Table 1 pH 10.5

Development Formulation (2) (per liter of working solution) KOH (100%) 40.0 g Diethylenetriamine / pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Diethylene glycol 5 0.0 g hydroquinone 40.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.50 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.30 g 3- ( 5-Mercaptotetrazol-1-yl) Sodium benzenesulfonate 0.10 g Sodium erythorbate 6.0 g Compounds shown in Table 1 Described in Table 1 pH 10.5

Fixing liquid formulation (per 1 liter of working liquid) Ammonium thiosulfate 119.7 g Ethylenediaminetetraacetic acid · 2Na · dihydrate 0.03 g Sodium thiosulfate / 5-hydrate 10.9 g Sodium sulfite 25.0 g Sodium hydroxide (100 %) 12.4 g glacial acetic acid 29.1 g tartaric acid 2.9 g sodium gluconate 1.7 g aluminum sulfate 8.4 g pH 4.8

Photosensitive materials (1) to (4) used in the examples below.
The following shows the production method.

Manufacturing Method of Light-Sensitive Material (1) A method for manufacturing Emulsion-A will be described. While stirring 2nd and 3rd liquids in the following 1st liquid kept at 38 ° C and pH 4.5, 2 at the same time
Added over 4 minutes to form 0.18 μm particles. Then, add the following 4 liquid and 5 liquid over 8 minutes,
Grain formation was completed by adding 0.15 g of potassium iodide. 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, added sodium thiosulfate 4 mg, N, N-dimethylselenourea 2 mg, chloroauric acid 10 mg, sodium benzenethiosulfonate 4 mg and sodium benzenethiosulfinate 1 mg, and optimum sensitivity at 55 ° C. Chemically sensitized so that Further, 50 mg of 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was used as a stabilizer, and phenoxyethanol was used as a preservative in an amount of 10 mg.
It was added so as to be 0 ppm, and finally silver iodochlorobromide cubic particles having an average particle size of 0.20 μm and containing 80 mol% of silver chloride were obtained. (Variation coefficient 9%)

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

<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 dispersion of 30 wt% of polyethyl acrylate with respect to gelatin was added to an aqueous gelatin solution and coated so as to have a gelatin content of 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 (b), 4 × 10 ⁻⁴
Mol of the triazine compound represented by (c), 2 × 10 ⁻³
Mol of 5-chloro-8-hydroxyquinoline, nucleating agent (H-1) (hydrazine derivative) 7.0 × 10 ⁻⁵ mol,
4.2 × 10 ⁻⁴ mol of the nucleation accelerator (AC-1), 9 × 10 ⁻³ mol of sodium p-dodecylbenzenesulfonate and 3 × 10 ⁻² mol of hydroquinone were added. Further, a dispersion of polyethyl acrylate is 200 mg / m ² , a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5:
7) 200 mg / m ^2, the compound of colloidal silica having an average particle size of 0.02μm 200mg / m ^2, as a further hardening agent (d) is added 200 mg / m ^2. The amount of silver coated on them 3.
It was applied so as to be 5 g / m ² . The pH of the finished liquid is 5.
It was 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 40 having an average particle size of about 3.5 μm
mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , silicone oil 20 mg / m ^2, and fluorine surfactant 5 mg / m ² represented by the compound (f) as a coating aid and dodecylbenzene. sodium sulfonate 100 mg / m ² and the compound (g) 20mg / m ² was coated.

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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, average particle size 0.20 μm) 200 mg / m ² 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

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[Back protective layer] Gelatin 0.8 mg / m ² polymethylene methacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

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

Preparation of Photosensitive Material (2) Emulsion B The same preparation as in Emulsion A was carried out except that 2 mg of sodium thiosulfate was added per mol of silver and no selenium sensitizer was 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.

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The swelling ratio on the side having the emulsion layer was determined according to Sensitive Material (1).
Was the same as

Preparation of Photosensitive Material (3) Emulsion C 3 per mol of silver chloride and silver kept at 40 ° C.
× 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 1 mol of silver by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds to half the amount of silver in the final grains. Is added at the same time, and the particles of the core are 0.12
μm was prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 6.0 × 10 ⁻⁶ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes, and chloride having an average particle size of 0.15 μm was added. Silver cubic particles were prepared (coefficient of variation 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 at 60 mg each per 1 mol of silver, and then pH is adjusted to 5.
7, pAg = 7.5, and per mol of silver,
4 × 10 ^-5 mol of chloroauric acid, 4 × 10 ^-5 mol of compound-
After Z is added, 1 × 10 ^-5 mol of sodium thiosulfate and 1 × 10 ^-5 mol of potassium selenocyanide are added, and 6
After heating for 60 minutes at 0 ° C. and chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer was added.
Tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver (as final particles, pH = 5.7, pAg = 7.
5, Ru = 4.0 × 10 ⁻⁶ mol / Ag mol).

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 Nucleation accelerator (AC-2) 3.6 × 10 ⁻³ mol / mol Ag N-oleyl-N-methyltaurine sodium salt 10 mg / m ² compound-B 10 mg / m ² compound-C 10 mg / m ² compound-D 10 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 760 mg / m ² compound-E ( Hardener) 105 mg / m ² Sodium polystyrene sulfonate 57 mg / m ² Nucleating agent (H-2) 1.2 × 10 ^-3 mol / mol Ag

The following compounds were added to the (PC) gelatin aqueous solution, and the gelatin coating amount was 0.6 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.6 g / m ² p-sodium dodecylbenzene sulfonate 10 mg / m ² sodium polystyrene sulfonate 6 mg / m ² compound-A 1 mg / m ² compound-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 2700ppm) 0.45g / m ² Amorphous silica matting agent 40mg / m ² (Average particle size 3.5μ, Pore diameter 25Å, Surface area 700m ² / g) Amorphous silica matting agent 10mg / 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 p-sodium dodecylbenzenesulfonate 30 mg / m ² compound- A 1 mg / m ² Liquid paraffin 40 mg / m ² Solid disperse dye-G ₁ 30 mg / m ² 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 Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² p-sodium dodecylbenzenesulfonate 13 mg / m ² dihexyl-α- Sulfosuccinate sodium 12 mg / m ² Polystyrene sodium 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 Compound -H 140 mg / m ² Compound -I 140 mg / m ² Compound -J 30 mg / m ² compound-K 40 mg / m ² p-sodium dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-L 5 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine Potassium 5 mg / m ² Sodium sulfate 150 mg / m ² Sodium acetate 40 mg / m ² Compound-E (hardener) 105 mg / m ²

(Support, Undercoat Layer) The first and second undercoat layers having the following compositions were coated on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm). <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g 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 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. The dry film thickness was 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-N 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g 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 was 0.1 μm. A sample was prepared in this way. The swelling ratio on the side having the emulsion layer was 100.

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Manufacturing Method of Photosensitive Material (4) Emulsion D 250 cc of an aqueous solution of silver nitrate in which 64 g of silver nitrate was dissolved, and K ₂ Rh (H corresponding to 1 × 10 ⁻⁷ mol per mol of silver in the whole emulsion)
250 cc of an aqueous solution of halogen salt in which 20 g of potassium bromide containing ₂ O) Cl ₅ and K ₃ IrCl ₆ corresponding to 2 × 10 ⁻⁷ mol and 14 g of sodium chloride are dissolved is added to sodium chloride (0.3
%) And 1,3-dimethyl-2-imidazolithione (0.
002%) and citric acid (0.05%) in a 2% aqueous gelatin solution with stirring at 38 ° C. for 12 minutes by the double jet method to give an average particle size of 0.16 μm.
Nucleation was carried out by obtaining silver chlorobromide grains having 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 added.
The particles were added by the double jet method over 20 minutes 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 the compound represented by the following structural formula (h) and 8 mg of chloroauric acid were added per mol of silver. , 60
Chemical sensitization was performed by heating at 70 ° C. for 70 minutes. Then, 4-hydroxy-6-methyl-1,3,3a, 7 as a stabilizer
-After adding 150 mg of tetrazaindene and 100 mg of proxel as a preservative, 400 mg of the dye represented by the following structural formula (i) was added, and the temperature was lowered after 10 minutes. The obtained grains were cubic silver iodochlorobromide grains having an average grain size of 0.22 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10
%)

(Preparation of Coating Solution for Emulsion Layer) To this emulsion, silver 1
2 × 10 ⁻⁴ mol per mol of a short-wave cyanine dye represented by the following structural formula (j), 5 × 10 ⁻³ mol of potassium bromide,
2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 2 × 10 ⁻⁴ mol of the mercapto compound represented by the following structural formula (k), 3 × 10 ⁻⁴ mol of the following structural formula (1)
And a nucleation accelerator (AC-1) represented by
6 × 10 ^-4 mol, nucleating (H-3) were added 2 × 10 ^-4 mol, further, hydroquinone 100 mg / m ^2, sodium p- dodecylbenzenesulfonate 10 mg / m ^2, colloidal silica (Nissan Chemical Snowtex C) 150mg /
m ² , a dispersion of polyethyl acrylate 500 mg / m ² ,
1,2-bis (vinylsulfonylacetamido) ethane was added so as to be coated at 80 mg / m ² to prepare an emulsion layer coating solution. The pH of the coating solution was adjusted to 5.6.

[0170]

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

[0172]

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These coating solutions were applied to a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides, and an emulsion layer (silver content 3.0 g / m ² , gelatin 1.
5 g / m ² ) as the bottom layer, PC (gelatin 0.5 g / m ² ),
OC (gelatin 0.4 g / m ² ) was applied. The pH of the emulsion surface of the obtained sample was 5.8.

The back layer was applied by 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

[0175]

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The swelling ratio on the side having the emulsion layer was 150.

Example 1 250 ml of the developing solution was heated to 38 ° C., 16 sheets of contact film RU-100 (3.6 cm × 12 cm) manufactured by Fuji Photo Film Co., Ltd. were soaked for 20 seconds while stirring with nitrogen bubbling, and then, in the developing solution. Was measured for silver concentration. The results for the developer (1) are shown in Table 1, and the results for the developer (2) are shown in Table 2.
Shown in The compound of the present invention showed an excellent ability to suppress silver elution.

[0178]

[Table 1]

[0179]

[Table 2]

[0180]

[Table 3]

[0181]

[Table 4]

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Example 2 The developing solution and the fixing solution were observed in the automatic developing machine FG-460A manufactured by Fuji Photo Film Co., Ltd., and the light-sensitive materials (1) to (4) and the output light-sensitive material LS-5500 manufactured by the same company, and the dupe paper feeling were detected. Material DU-150WP was subjected to sensitometry. exposure,
The processing conditions were as follows. Light-sensitive material (1) Through a 633 nm interference filter, exposed through a step wedge with xenon flash light with an emission time of 10 ^-6 seconds Light-sensitive material (2) Through an interference filter having a peak at 488 nm, an emission time of 10 ^-5 through a step wedge Exposure with xenon flash light for 2 seconds Sensitive material (3) Exposure through step wedge with Dainippon Screen P-627FM printer Sensitive material (4) Exposure with 3200 ° K tungsten light through step wedge LS-5500 Peak at 488 nm Exposure through a step wedge through an interference filter with xenon flash light with a light emission time of 10 ^-4 seconds DU-150WP Exposure through a step wedge with a P-627FM printer manufactured by Dainippon Screen Co., Ltd. Processing condition Sensitive material (1), (2) and (4) are development temperature 3
The processing was performed at 5 ° C., a fixing temperature of 34 ° C., and a developing time of 30 seconds. Other photosensitive materials were processed by setting a developing temperature of 38 ° C., a fixing temperature of 37 ° C., and a developing time of 20 seconds. Tables 1 and 2 show the difference between the minimum density (Dmin) and the sensitivity (S3.0) at the density of 3.0 with respect to the blank. It is understood that the smaller the difference is, the more the photographically has no effect, and the compound of the present invention has less influence on the photographic property. In particular, even in a large amount of addition, the Dmin of the duplication sensitive material is not affected and is excellent. In addition, Dmin difference within 0.03, S
The practically acceptable range is within 1.5 difference ± 0.02.

Example 3 In Example 2, the unexposed contact film RU-100 manufactured by the same company was treated with 100 m ² per day for 5 days, and then,
Unexposed contact paper sensitive material KU-150W
P (4 pieces) was processed, and the degree of stain attachment was observed. Replenishment of developer (1) 320 ml / m ² , developer (2)
Was 160 ml / m ² and the fixer was 260 ml / m ^{2 in} all cases. The results are shown in Tables 1 and 2. A level of 4 or more is a level at which there is no practical problem.

[0185]

By using the compound of the present invention, an excellent effect of preventing silver stain can be obtained without affecting photographic performance.

Claims (3)

[Claims] 1. A developer for a silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (I) or (II). General formula (I) In the formula, L ₁ represents a divalent group, and R ₁ represents an amino group, an ammonio group or an alkoxy group. M represents a hydrogen atom or a cation. General formula (II) In the formula, L ₃ represents a linking group, and M represents a hydrogen atom or a cation. Further, X ₁ and X ₂ each represent a group capable of substituting on the triazine ring. 2. A method for developing a black-and-white silver halide photographic light-sensitive material, which comprises subjecting the black-and-white silver halide photographic light-sensitive material to image exposure and then treating it with the developer according to claim 1. 3. A black-and-white silver halide photographic light-sensitive material containing a hydrazine derivative is imagewise exposed and then treated with the developer according to claim 1, further containing 0.3 mol / liter or more of sulfite. A method for developing a black and white silver halide photographic light-sensitive material.