JPH10246936A - Method for preparing developing solution, solid developer, and method for forming high-contrast image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing solution small in deterioration of photographic performance in the case of using an ascorbic acid type developing agent without hydroquinone compounds, and to provide a solid developing agent. SOLUTION: This developing solution contains substantially no dihydroxybenzene derivative developing agent but ascorbic acid and an auxiliary developing agent exhibiting superadditivity to this ascorbic acid type developing agent, and having a pH of 9.0-10.5 by adding as a pH buffer a <=0.5mol/l carbonate salt and a 0.1-1.5mol/l hydrogen carbonate salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
A method for stably producing a developer containing a relatively large amount of a buffer agent having a buffering ability for a range of 0.5 and containing ascorbic acids as a developing agent, a solid developer, and a developer prepared by the production method And a method for forming a high-contrast image using a developer prepared by dissolving the solid developer in a predetermined amount of water.

[0002]

2. Description of the Related Art Generally, a dihydroxybenzene developing agent (for example, hydroquinone) has been used as a developing solution in a developing process of a silver halide photographic light-sensitive material. However, it has been pointed out that hydroquinone may induce allergies, and the use of ascorbic acid and its derivatives as developing agents as hydroquinone substitutes has been studied (ascorbic acid and its derivatives are hereinafter referred to as ascorbic acid). Acid developing agents). Some attempts have been made to use a developing solution containing an ascorbic acid-based developing agent as a developing solution for a silver halide photographic light-sensitive material containing a hydrazine derivative and forming a high contrast image.

[0003] Among them, US Pat. No. 5,236,816 discloses an ascorbic acid developing agent, an auxiliary developing agent having superadditivity to the ascorbic acid developing agent, and 0.1.
A developer having a pH of 9.5 to 11.5 containing at least 5 mol / l, preferably at least 0.8 mol / l of carbonate (sodium carbonate and / or potassium carbonate) is described. Although the upper limit of the pH value of this developer is defined as 11.5, the pH of the developer that can withstand actual use is appropriately 9.0 to 10.5. However, if a carbonate is added in an amount exceeding 0.5 mol / liter when preparing such a developer, the pH of the developer rises to 11 or more. Lowering the pH of the developer to a pH range that can withstand the actual use can be easily achieved by adding an acid. However, when an acid is added, carbon dioxide is generated, and the degree of the generation varies depending on operating conditions such as addition speed and stirring conditions and environmental conditions such as atmospheric pressure and air temperature. Has proven to be extremely difficult to produce.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ascorbic acid-based developing agent having a pH range of 9.0 to 10.5. An object of the present invention is to stably produce a developing solution containing an auxiliary developing agent exhibiting superadditivity and a buffer agent effective at 0.5 mol / liter or more in the above-mentioned pH range. Still another object of the present invention is to provide a p of 9.0 to 10.5.
H range, an ascorbic acid-based developing agent, an auxiliary developing agent exhibiting superadditivity to the ascorbic acid-based developing agent, and a buffer agent effective in the above pH range.
An object of the present invention is to provide a solid developer capable of stably and easily adjusting a developer containing 5 mol / liter or more. Another object of the present invention is to form a high-contrast image by processing a silver halide photographic light-sensitive material containing a hydrazine derivative using these developing solutions.

[0005]

The above object has been attained by the present invention described below. (1) pH 9.0 to 10.5 containing substantially no dihydroxybenzene-based developing agent and containing an ascorbic acid-based developing agent and an auxiliary developing agent showing superadditivity to the ascorbic acid-based developing agent A developing method comprising the steps of: adding 0.5 mol / l or less of a carbonate as a pH buffer agent and 0.1 to 1.5 mol / l of a bicarbonate as a pH buffering agent. Liquid production method. (2) A developer produced by the above production method. (3) At least an ascorbic acid-based developing agent, an auxiliary developing agent having superadditivity to the ascorbic acid-based developing agent, a carbonate equivalent to 0.5 mol or less per liter of the developing solution, and 1 liter of the developing solution 0.1-1.5 per
Solid developer containing bicarbonate equivalent to mole. (4) After exposing the silver halide photographic light-sensitive material containing a hydrazine derivative, using a developing solution prepared by dissolving the developing solution of (2) or the solid developer of (3) in a predetermined amount of water. A method for forming a high-contrast image, characterized by processing. (5) The method for forming a high contrast image as described in (4) above, wherein the development time is 30 seconds or less, and the total processing time from development to drying is 90 seconds or less. (6) The replenishment amount of the developer is 3 per square meter of the photosensitive material.
The method for forming a high-contrast image according to the above (4) or (5), wherein the amount is not more than 00 ml.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As a developing agent of an ascorbic acid derivative used in the present invention, a compound represented by the following general formula (1) is preferable. General formula (1)

[0007]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group, and X represents a carbon atom or X is composed of an oxygen atom or a nitrogen atom, and X forms a 5- to 6-membered ring in cooperation with two vinyl carbons and carbonyl carbons substituted by R ₁ and R ₂ . Hereinafter, the general formula (7) will be described in detail. In the formula, R ₁ and R ₂ each represent a hydroxy group or an amino group (substituents having an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group or the like as a substituent) ), An acylamino group, an (acetylamino group, a benzoylamino group, etc.),
Alkylsulfonylamino group, (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto group, alkylthio group ( Methylthio group, ethylthio group, etc.). R ₁ , R
Preferred examples of ₂ include a hydroxy group, an amino group,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group. X is composed of a carbon atom, an oxygen atom, or a nitrogen atom, and is a group represented by X together with two vinyl and carbonyl carbons substituted by R ₁ and R _2.
Constitutes a 5- to 6-membered ring. As specific examples of X, -O-,
_{-C (R 3) (R 4} ) -, - C (R 5) =, - C (= O) -, - N
(R ₆ )-and -N =. However, R ₃ , R ₄ , R ₅ , and R ₆ are a hydrogen atom and have 1 to 10 carbon atoms.
An optionally substituted alkyl group (a hydroxyl group, a carboxy group, a sulfo group can be mentioned as a substituent) and an optionally substituted aryl group having 6 to 15 carbon atoms (an alkyl group, a halogen atom, A hydroxy group, a carboxy group and a sulfo group), a hydroxy group and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. This 5
Examples of the 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring. Specific compound examples are shown below.

[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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The ascorbic acids used in the present invention include an endiol type (Endiol), an enaminol type (Enaminol),
Endiamin type, Thiol enol type (Thiol
-Enol) and the enamine-thiol form (Enamin-Thiol) are commonly known as compounds. Examples of these compounds are described in U.S. Pat. No. 2,688,549, JP-A-62-237.
443, etc. Methods for synthesizing these ascorbic acids are also well known. For example, Tsuguo Nomura and Hirohisa Omura, "Reducton Chemistry" (Uchida Lao Tsuruhoshinsha 19
69)). The ascorbic acids used in the present invention can be used in the form of an alkali metal salt such as a lithium salt, a sodium salt and a potassium salt.

The auxiliary developing agent having superadditivity to the ascorbic acid-based developing agent used in the present invention includes 1
Examples of -phenyl-3-pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-
3-pyrazolidone, 1-p-tolyl-4-methyl-4-
And hydroxymethyl-3-pyrazolidone. Among them, a compound represented by the following general formula (A) is preferable. General formula (A)

[0016]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or a substituent. R
₅ , R ₆ may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group.

The p-aminophenol represented by the general formula (A) will be described in detail. Wherein R ₁ , R ₂ , R ₃
And R ₄ may be the same or different and each represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a mercapto group, a hydroxy group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyloxy group. Group, amino group, alkylamino group, carbonamido group, sulfonamido group,
Examples include a sulfamoylamino group, a ureido group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carboxyl group (including a salt), and a sulfo group (including a salt).
These are an alkyl group, an alkenyl group, an alkynyl group,
Aryl group, halogen atom, cyano group, nitro group, hydroxy group, alkoxy group, alkylthio group, amino group,
Alkylamino group, ammonium group, carbonamide group,
Formed of a sulfonamide group, a sulfamoylamino group, a ureido group, a carbamoyl group, a sulfamoyl group, a carboxyl group (including a salt), a sulfo group (including a salt), or other oxygen, nitrogen, sulfur, or carbon atom May be substituted with a substituent.

Examples of the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ are shown in more detail below. The alkyl group has 1 to 1 carbon atoms.
0 linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, benzyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2, Examples thereof include 3-dihydroxypropyl, 2-methoxyethyl and the like.

The aryl group is an aryl group having 6 to 10 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl. The aralkyl group has 7 to 7 carbon atoms.
And 10 aralkyl groups such as benzyl.
The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and the type of the hetero element constituting the ring is one. However, there may be more than one such as 2-furyl, 2-pyrrolyl, 2-imidazolyl, 1-pyrazolyl, 2-pyridyl, 2-pyrimidyl, 2-thienyl and the like. Examples of the halogen atom include a fluorine atom and a chlorine atom. The alkoxy group has 1 to 10 carbon atoms,
Preferably an alkoxy group having 1 to 6 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, 2-hydroxyethoxy, 3-hydroxypropoxy, 2-methoxyethoxy, hydroxyethoxyethoxy, 2,3
-Dihydroxypropoxy, 2-hydroxypropoxy, 2-methanesulfonylethoxy and the like. The aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and examples thereof include phenoxy, p-carboxyphenoxy, and o-sulfophenoxy. The alkylthio group is an alkylthio group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methylthio and ethylthio. The arylthio group is an arylthio group having 6 to 10 carbon atoms, such as phenylthio and 4-methoxyphenylthio. The acyloxy group is an acyloxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as acetoxy and propanoyloxy.

The alkylamino group has 1 to 1 carbon atoms.
0, preferably an alkylamino group having 1 to 6 carbon atoms, such as methylamino, diethylamino and 2-hydroxyethylamino. The carbonamido group is a carbonamido group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as acetamido and propionamido.
The sulfonamide group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and is, for example, methanesulfonamide. The sulfamoylamino group is a sulfamoylamino group having 0 to 10 carbon atoms, preferably 0 to 6 carbon atoms, such as methylsulfamoylamino and dimethylsulfamoylamino. The ureido group is a ureido group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureide, and N, N-dimethylureide. The acyl group has 1 to 1 carbon atoms.
An acyl group having 0, preferably 1 to 6 carbon atoms, such as acetyl and benzoyl. The oxycarbonyl group is an oxycarbonyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. The carbamoyl group has 1 to 1 carbon atoms.
0, preferably a carbamoyl group having 1 to 6 carbon atoms such as carbamoyl, N, N-dimethylcarbamoyl, N
-Ethylcarbamoyl. The sulfonyl group is a sulfonyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and ethanesulfonyl. The sulfinyl group is a sulfinyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfinyl. The sulfamoyl group has 0 to 0 carbon atoms.
10, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl and dimethylsulfamoyl.

R ₅ and R ₆ may be the same or different,
Each represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group. The details thereof are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . However, when R ₅ and R ₆ are an alkyl group, they may be linked to form a 5- to 6-membered ring together with a nitrogen atom. In this case, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring are exemplified. I can do it. When at least one of R ₅ and R ₆ is an alkyl group and at least one of R ₃ and R ₄ is an alkyl group or an alkoxy group, these are linked to form a condensed heterocyclic ring together with a nitrogen atom and a benzene ring. The 5- or 6-membered ring condensed with the formed benzene ring may be, for example, indole, indoline, dihydroquinoline, tetrahydroquinoline, or benzoxazine. The compound represented by the general formula (A) may be a dimer to form a bis-type structure.

Among the compounds represented by the general formula (A),
Compounds represented by the following general formula (B) are preferred. General formula (B)

[0024]

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In the formula, R ₁₁ and R ₂₂ may be the same or different and each represents a hydrogen atom or a substituent. R ₅₅ , R ₆₆
May be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group.

In the general formula (B), R ₁₁ , R ₂₂ and R ₅₅ , R
_{66 is} described below regarding preferred combinations thereof. R ₁₁ and R ₂₂ are a hydrogen atom, an alkyl group, a hydroxy group, an alkoxy group, an amino group, an alkylamino group, a carbonamido group, a sulfonamido group, a sulfamoylamino group, a ureido group, and R ₅₅ and R ₆₆ are Combinations that are alkyl groups are preferred. Here, the alkyl group, the alkoxy group, and the alkylamino group include those substituted with another substituent. In this combination, R ₅₅ , R
₆₆ is more preferably an unsubstituted alkyl group or an alkyl group substituted with a water-soluble group. Here, the water-soluble group includes a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an ammonio group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, a ureido group, a carbamoyl group, a sulfamoyl group, a carboxyl group ( And a sulfo group (including a salt).

More preferably, in the formula (B), R ₁₁ is a hydrogen atom, and R ₂₂ is an alkyl group, an alkoxy group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, a ureido group. Yes, R
₅₅ and R ₆₆ are compounds wherein the alkyl group is an alkyl group. Here, an alkyl group, an alkoxy group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, and a ureido group are a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an ammonium group, a carbonamide group, and a sulfonamide group. Or those substituted by a ureido group.

As still more preferred compounds, in the general formula (B), R ₁₁ is a hydrogen atom, R ₂₂ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
A carbonamide group having 1 to 3 carbon atoms, a sulfonamide group having 1 to 3 carbon atoms, a ureido group having 1 to 3 carbon atoms,
A compound in which R ₅₅ and R ₆₆ are an unsubstituted alkyl group having 1 to 3 carbon atoms. Wherein the alkyl group, alkoxy group represented by R ₂₂ includes those substituted hydroxy group, an alkoxy group, a carbonamido group, the sulfonamido group.

As the most preferred compound, in the general formula (B), R ₁₁ is a hydrogen atom, and R ₂₂ is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 3 carbon atoms. A sulfonamide group having 1 to 3 carbon atoms, a ureido group having 1 to 3 carbon atoms, and R ₅₅ ,
A compound in which R ₆₆ is a methyl group. Here, the alkyl group and the alkoxy group represented by R ₂₂ include those substituted with a hydroxy group or an alkoxy group.

Examples of the specific compounds of the present invention include, but are not limited to, the following compounds.
Since the compound represented by the general formula (A) may be unstable as a free aniline, it is generally produced and stored as a salt with an inorganic acid or an organic acid, and is added with a free amine only after being added to the treatment solution. Preferably. Examples of the inorganic and organic acids that form the salt of the compound of the formula (A) include hydrochloric acid, hydrobromic acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid. Is preferably a salt of sulfuric acid or naphthalene-1,5-disulfonic acid.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

The compound represented by the general formula (A) is, for example,
Photographic Science and Engineering, 10, 306 (196
According to a general synthesis method such as 6), Japanese Patent Application No. 8-70
No. 908, the compound can be easily synthesized.

The ascorbic acid-based developing agent is used in an amount of 0.01 to 0.5 mol, preferably 0.0 to 0.5 mol per liter of the developing solution.
It is used in an amount corresponding to 5 to 0.3 mol. The auxiliary developing agent is preferably used in an amount corresponding to 0.005 to 0.2 mol per liter of the developing solution.

The carbonate used in the present invention is preferably sodium carbonate or potassium carbonate. As the hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are preferable. In the present invention, carbonate is used in an amount of 0.1 per liter of the developer.
It is used in an amount corresponding to 5 mol or less (preferably 0.1 to 0.5 mol), and hydrogen carbonate is added in an amount of 0.1 to 1 liter of the developer.
It is used in an amount corresponding to 1 to 1.5 mol.

The process for producing a developer according to the present invention is characterized in that it comprises a step of adding the above-mentioned amounts of carbonate and bicarbonate to water. The target pH range of the developer of the present invention is 9.0 to 1
0.5, and the pH buffer agent is preferably present in an amount of 0.6 mol / liter or more. When adjusting only such a developing solution, adding only carbonate as a pH buffer agent causes the above-described problem, but the present invention sets the amount of carbonate to 0.5 mol or less per liter of developing solution,
By adding a bicarbonate having a pH buffer action equivalent to that of a carbonate in combination or alone, it is possible to stably produce a developer having a certain performance.

In the developing solution or solid developer of the present invention, in addition to the above-mentioned ascorbic acid-based developing agent, auxiliary developing agent, carbonate and bicarbonate, it is usually used for a developing solution of a silver halide photographic light-sensitive material. Additives can be included.
Such additives include alkaline agents (sodium hydroxide, potassium hydroxide), pH buffering agents other than carbonates or bicarbonates (eg, boric acid, tertiary phosphates, sugars, oximes, etc.), preservatives And chelating agents.

Examples of the preservative include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. If the sulfite is added in an excessively large amount, it causes silver staining in the developing solution. Therefore, it is preferably used in an amount corresponding to 0.01 to 0.2 mol per liter of the developing solution.

Other additives include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide, and alkanolamines such as diethanolamine and triethanolamine. , A development accelerator such as imidazole or a derivative thereof, a heterocyclic mercapto compound (eg, sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.),
The compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, and a benzimidazole-based compound may be contained as an antifoggant or a black fog (pepper fog) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl
-5-nitrobenzimidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,3,4-thiadiazole-
Sodium 2-yl) thio) butanesulfonate, 5-amino
Examples thereof include -1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these additives is usually 0.01 to 1 liter per developer.
It is 10 mmol, more preferably 0.1 to 2 mmol.

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

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others JP-A-52-25632, 55-67747, 57-1
02624 and the compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in US Pat. Nos. 3,214,454 and 3,794,591 and German Patent Publication 2,227,369, and Research Disclosure, Vol. 181, Item 18170 (1979).
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid,
Amino trimethylene phosphonic acid and the like, and the other Research Disclosure 18170, JP-A-57-
Compounds described in 208554, 54-61125, 55-29883, 56-97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, 54-121127, and 55-4
024, 55-4025, 55-126241, 55-65955, 55-6595
6 and the compounds described in Research Disclosure 18170 described above.

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

Further, as a silver stain preventing agent in a developing solution or a solid developer, for example, JP-A-56-24347, JP-B-56-4
6585, JP-B-62-2849, JP-A-4-362942, and triazines having at least one mercapto group (for example, JP-B-6-23830, JP-B5-55059, JP-A-3-282457,
Compounds described in JP-A-7-175178 and JP-A-8-6215), pyrimidines having one or more mercapto groups (for example, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-
Dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine and the like, pyridine having one or more mercapto groups (for example, 2-mercaptopyridine, 2,6-dimer Mercaptopyridine,
3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-248587, etc., and pyrazines having at least one mercapto group (for example, 2-mercaptopyrazine, 2,6-dimer Mercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc.), pyridazine having one or more mercapto groups (for example, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,
5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), the compounds described in JP-A-7-175177, the polyoxyalkyl phosphonates described in US Pat. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol per liter of the developer.
0.1-5 mmol is more preferred. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid.
Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The pH of the developer is from 9.0 to 10.5.
If the pH cannot be adjusted with only the carbonates and bicarbonates described above, the pH is adjusted to this range with another alkaline agent (sodium hydroxide, potassium hydroxide, etc.).

The present invention also includes a solid developer containing the above essential components and other additives. The form of the solid developer in the present invention may be any of powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste and the like. These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating assistants can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 48, line 48 to column 3
Line 13 can be helpful.

When a plurality of layers are formed, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described, for example, in JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

The bulk density of the solid developer is 0.5 to 6.0 g / cm
³ are preferred, particularly tablets preferably 1.0 to 5.0 g / cm ^3, the granules is preferably 0.5 to 1.5 g / cm ^3.

As a method for producing the solid developer in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-328
37, 4-78848, 5-93991, JP-A-4-85533, 4-8553
4, 4-85535, 5-134362, 5-97070, 5-04098,
5-224361, 6-138604, 6-138605, Japanese Patent Application 7-89123
Etc. can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid developer in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut. Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material of the solid developer is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, a box, or the like. Also, JP-A-6-2425
85 to 6-242588, 6-247432, 6-247448, Japanese Patent Application 5-30
664, JP-A-7-5664, JP-A-7-5666 to JP-A-7-5669, and a foldable shape are also preferable to reduce the storage space of the waste packaging material. For these packaging materials, a screw cap, a pull-top, or an aluminum seal may be attached to the developer outlet, or the packaging material may be heat-sealed, but other known materials may be used. do not do. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid developer is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and Japanese Patent Application No. 7-2354.
A method of dissolving with a dissolving apparatus having a dissolving part and a part for storing a finished liquid as described in 99, and replenishing from the stock part, JP-A-5-119454, JP-A-6-19102, JP-A-7-26135
Method of charging and dissolving and replenishing the processing agent into the circulating system of the automatic developing machine as described in 7, and adding and dissolving the processing agent according to the processing of the photosensitive material in the automatic developing machine having a built-in melting tank. Although there are methods and the like, any other known methods can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred from an environmental point of view.
Specifically, a method of breaking through the outlet, a peeling method, a cutting method, a pushing method, and JP-A-6-19102, 6-953
31 and the like. The above-described form of the solid developer, the production method, the packaging material, the dissolution replenishment method, and the like can be referred to also when a solid fixing agent and a fixing solution are prepared using the solid fixing agent.

The replenishing amount of the developing solution is 300 ml or less, preferably 30 to 250 ml, per m ² of the light-sensitive material. The development replenisher may have the same composition and / or concentration as the development start solution, or may have a different composition and / or concentration from the start solution.

After completion of the development, the silver halide photographic light-sensitive material is subjected to a fixing treatment, a washing or stabilizing treatment, and dried. As a fixing agent for the fixing solution, ammonium thiosulfate, sodium thiosulfate, and sodium ammonium thiosulfate can be used. The amount of the fixing agent to be used can be varied as appropriate, but is generally from about 0.7 to about 3.0 mol / l.

The fixing solution may contain a water-soluble aluminum salt or a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are preferably contained at 0.01 to 0.15 mol / l as the aluminum ion concentration in the working solution. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

The fixing solution may contain a preservative (for example, a sulfite, a bisulfite, a metabisulfite, etc.) in an amount of 0.015 mol / L or more, preferably 0.02 mol / L to 0.3%.
Mol / l), pH buffer (eg, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc.) in an amount of 0.1 mol / l to 1
Mol / l, preferably 0.2 mol / l to 0.7 mol / l), compounds having an aluminum stabilizing ability or a water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, Citric acid, oxalic acid, maleic acid, glycolic acid,
Benzoic acid, salicylic acid, tyrone, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars, boric acid, etc. 0.001 mol /
Liter to 0.5 mol / liter, preferably 0.005 mol / liter
Liter to 0.3 mole / liter).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be included. Examples of the surfactant include an anionic surfactant such as a sulfated sulfone oxide, a polyethylene-based surfactant, and an amphoteric surfactant described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754 and 58-12253.
5, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.No. 4,216,459, JP-A-64-4739, JP-A-1-4739, and 1-159
645 and the mercapto compound described in 3-101728, 4-1
70539, which may comprise a thiocyanate.

The pH of the fixing solution in the present invention is 4.0 or more, preferably 4.5 to 6.0. The pH of the fixer is increased by mixing with a developer due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.7 or less for a non-hardened fixer.

The replenishment rate of the fixing solution is 50 per m ² of the photosensitive material.
0 ml or less, preferably 390 ml or less, more preferably 320 to 60 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid, it is preferable to store it in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated liquid so as to have a predetermined concentration.

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

As a method of reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount of washing is preferably 200 to 50 ml per 1 m ² of the photosensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, means for preventing water scale may be applied to the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, 4-189
The method described in 80 or the like can be used.

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

A part or all of the overflow solution from the washing step can be mixed and used with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Volume (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining, or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-132435,
A bath containing a compound described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains an ammonium compound, a metal compound such as Bi or Al, a fluorescent whitening agent, various chelating agents, a membrane pH regulator,
Hardening agents, fungicides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths may be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water, and stabilizing solution used in the present invention is incinerated. In addition, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, US5439560
It is also possible to dispose after concentrating or liquefying or solidifying with a concentrating device such as described in US Pat.

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

In the development processing of the present invention, 25 to 25 dry to dry
To 90 seconds, and the development and fixing times are each 30 seconds or less, preferably 6 to 20 seconds. The temperature of each liquid is preferably 25 to 50 ° C, and more preferably 30 to 40 ° C. The temperature and time of water washing are preferably 0 to 50 ° C. and 40 seconds or less. The developed, fixed and washed photosensitive material may be dried by squeezing washing water, that is, passing through a squeeze roller. Drying is about 40 to about 100
C., and the drying time varies depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.Hot air drying and JP-A Nos. 4-15534 and 5
Heat roller drying and far infrared drying as disclosed in JP-A-2256 and 5-289294, and a plurality of methods may be used in combination.

In the present invention, the term "substantially free of dihydroxybenzenes" means "substantially free of dihydroxybenzenes" means that they are not contained at all or contained to such an extent that allergic action or developing effect is not exhibited. Say,
In the present invention, those not containing at all are preferable.

Next, the photosensitive material containing hydrazine will be described. The hydrazine derivative contained in the light-sensitive material of the present invention is represented by the following general formula (I). General formula (I)

[0084]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. G ₁ represents a —CO— group,
A —SO ₂ — group, a —SO— group,

[0086]

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A represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group; A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or Or an unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (I),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aliphatic group or the aromatic group represented by R ₁ may be substituted. Representative examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring, and a pyridinium. Group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, hydrazide structure Group having a quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulf Moyl group, halogen atom, cyano group, phosphoric acid amide group, diacylamino group, imide group, group having acylurea structure, group containing selenium atom or tellurium atom, group having tertiary sulfonium structure or quaternary sulfonium structure, etc. Examples of the preferred substituent include a straight-chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms in the alkyl moiety). A) an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms). Having), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid And an amide group (preferably having 1 to 30 carbon atoms).

In the formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. It contains a ring. At least one nitrogen as an unsaturated heterocyclic group,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic one, and the amino group is an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms, or an aryl group. Amino groups are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ .

Among the groups represented by R ₂ , when G ₁ is a —CO— group, a hydrogen atom, an alkyl group (for example, methyl, trifluoromethyl, 3-hydroxypropyl, 3 A methanesulfonamidopropyl group, a phenylsulfonylmethyl group, an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.). When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group),
An aryl group (eg, a phenyl group) or a substituted amino group (eg, a dimethylamino group) is preferable. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferred. G of the general formula (I)
Is preferably a -CO- group or a -COCO- group,
The O- group is most preferred. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. For example, Japanese Patent Application Laid-Open No. 63-2
No. 9751 and the like.

A ₁ and A _{2 each} represent a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a Hammett having a sum of substituent constants of-
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferred examples include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may have a group in which a group which enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
Groups described in JP-A-3-234246.

Preferred hydrazine derivatives in the present invention are those wherein R ₁ is a ballast group via a sulfonamide group, an acylamino group or an ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure or an alkylthio group. A phenyl group having a group
Is a —CO— group, and R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (an electron-withdrawing group or a hydroxymethyl group at the 2-position is preferable as the substituent). It should be noted that any combination of the above-mentioned options of R ₁ and R ₂ is possible and preferable.

In the present invention, a hydrazine derivative characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine near the hydrazine group is particularly preferably used.

Specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means an atom selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom between a nitrogen atom and an anionic group near the anionic group of hydrazine.
It means that a binding chain formed by the individual is interposed. More preferably, a bond chain formed by 2 to 5 atoms selected from at least one of a carbon atom and a nitrogen atom is present as the vicinity, and a bond chain formed by 2 to 3 carbon atoms is more preferable. It is the case of intervening. The nonionic group that forms an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and has at least an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred hydrazine derivatives used in the present invention are those represented by the following general formulas (2) to (4). General formula (2)

[0099]

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(Wherein, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, L ¹ represents a divalent linking group having an electron withdrawing group, and Y ¹ represents an anionic group or a hydrogen atom of hydrazine. Represents a nonionic group that forms an intramolecular hydrogen bond.) General formula (3)

[0101]

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(Wherein R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group,
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (4)

[0103]

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(Wherein X ³ represents a group capable of substituting for a benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents Represents an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine, wherein m ³ is an integer of 0 to 4 and n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The hydrazine derivatives of the general formulas (2) to (4) will be described in more detail. The alkyl group of R ¹ and R ² has 1 to 16 carbon atoms, preferably 1 to 1 carbon atom.
2 linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl,
-Methylbenzyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl It is. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the kind of element may be one or more, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

R ¹ and R ² are preferably an aryl group,
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (for example, phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent. Examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl or aryl substituted amino group,
Amide group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphoramide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferred, and a sulfonamide group and a ureido group are more preferred. When possible, these groups may be linked to each other to form a ring.

[0108] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Linear, branched or cyclic alkoxy group such as methoxy, isopropoxy and benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom.
And ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. n ³ =
In the case of 2, R ³ is preferably an amino group or an alkoxy group.

As the electron-withdrawing group possessed by R ³ , those having a Hammett σ _m value of 0.2 or more, preferably 0.3
As described above, for example, a halogen atom (fluorine, chlorine, bromine), a cyano group, a sulfonyl group (methanesulfonyl, benzenesulfonyl), a sulfinyl group (methanesulfinyl), an acyl group (acetyl, benzoyl), an oxycarbonyl group (methoxycarbonyl) ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl, and ethoxycarbonylmethyl.

L ¹ and L ² each represent a divalent linking group, and include an alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group and those represented by —O—, —S—,
-NH -, - CO -, - it is the concatenation in made from one or a combination of such groups - SO _2. L ¹ and L ² are R
^It may be substituted with the group described as ¹ substituent. Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-buten-1,4-yl,
-Butin-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
Alkenylene, alkynylene and arylene groups are preferred, and alkylene groups are more preferred. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² represents an alkylene group, an arylene group, -NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

Examples of the electron-withdrawing group possessed by L ¹ include R ³
Examples of the electron-withdrawing group included in are described.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

The group which can be substituted on the benzene ring of X ³ and preferable ones include those described as the substituents of R ^{1 in the} general formula (1). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion-resistant group used in photographic couplers or may have a group promoting adsorption to silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (eg, thiourethane,
Thioureido, thioamide), mercaptos (for example, 5
-Mercaptotetrazole, 3-mercapto-1,2,2
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole, alkyl mercapto,
Aryl mercapto) and 5- or 6-membered nitrogen-containing heterocyclic ring forming imino silver (eg benzotriazole)
It is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (2) to (4), the radicals of each of the two compounds from which the hydrogen atoms have been removed may be bonded to each other to form a bis-type. In the general formulas (2) to (4), the general formulas (2) and (3) are preferable, and the general formula (2) is more preferable. Further, in the general formulas (2) to (4), the following general formulas (5) to (7) are more preferable, and the general formula (5) is most preferable. General formula (5)

[0116]

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(Wherein R ⁴ , X ⁴ and m ⁴ have the same meanings as R ³ , X ³ and m ^{3 in} formula (4), respectively, and L ⁴ , Y ⁴
Has the same meaning as L ¹ and Y ^{1 in} the general formula (2). ) General formula (5)

[0118]

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(Wherein R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in} formula (4), respectively, and L ⁵ , Y ⁵
Has the same meaning as L ² and Y ^{2 in} the general formula (3). ) General formula (7)

[0120]

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(Wherein, R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ , n ³ , Y in the general formula (4)
Synonymous with ³ . )

The following are specific examples of the hydrazine derivative used in the present invention, but the present invention is not limited to these.

[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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As the hydrazine derivative used in the present invention, in addition to the above, RESEARCHDISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 356, 898, JP-A-60-1797.
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 2-2541
No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442
Nos. 2-220042, 2-221953, 2-221954, 2-285342, and 2-2
No. 85343, No. 2-289843, No. 2-3027
No. 50, No. 2-304550, No. 3-37642,
3-54549, 3-125134, 3-1
No. 84039, No. 3-240036, No. 3-2400
No. 37, No. 3-259240, No. 3-280038
Nos. 3-282536, 4-51143, and 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
5-45761, 5-45762, 5-45
No. 763, No. 5-45764, No. 5-45765,
Those described in Japanese Patent Application No. 5-94925 can be used.

In the present invention, the hydrazine derivative is preferably added in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, particularly 1 × 1 ^-6 mol, per mol of silver halide.
The range of 0 ^-5 mol to 2 × 10 ^-2 mol is a preferable addition amount.

The hydrazine derivative of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve. It can be used by dissolving it in, for example. Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. Further, as described in JP-A-2-948, it can be used by being contained in polymer fine particles.

Gelatin is used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, but other hydrophilic colloids may be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be. 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. In the present invention, the coated amount of gelatin as a binder is such that the amount of gelatin in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less and the total hydrophilic colloid layer on the side having the silver halide emulsion layer is not more than 3 g / m ^2. total gelatin sex colloid layer and all hydrophilic colloid layers on the opposite surface is at 6 g / m ² or less, preferably 2.0 to 6.0 g / m ^2.

Examples of the support for the light-sensitive material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate described in JP-A-07-28188, and syndite described in JP-A-3-131842. For example, tactic polystyrene or polyethylene coated paper is used.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the corresponding places shown below can be preferably used. Item 1) Silver halide emulsion and page 12, lower right column, line 12 in JP-A-2-97937, page 14 and lower left column, line 14 in JP-A-2-97937, and from JP-A-2-2236. From page 19, upper right column, line 19 to page 8, lower left column, line 12, JP-A-4-330430 and JP-A-5-11389. 2) Spectral sensitizing dyes JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; JP-A-2-39042, page 7, lower right column, line 8, Page 13, lower right column, 5th line. JP-A-2-12236, page 8, lower left column, line 13 to lower right column, JP-A-2-103536, page 16 lower right column, line 3 to page 17, lower left column, line 20 And JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, JP-A-5-11389, and JP-A-4-330434. 3) Nucleation accelerator 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.

4) Surfactant: From page 7, upper right column, line 7 to lower right column, line 7 of JP-A-2-12236. 5) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1, and JP-A-2-55349, page 8, lower right column, line 13 From the eye, page 11, line 8 in the upper left column. 6) 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. 7) Polyhydroxyl JP-A-2-55349, page 11, upper left column, page 9 or benzenes, right lower column, line 17; 8) Slip agent, plasticizer From page 6, upper right column, line 6 to page 19, upper right column, line 15 of JP-A-2-103536. 9) Hardener JP-A-2-103536, page 18, line 5 to line 17, upper right column.

10) Dyes JP-A-2-103536, page 17, lower right column, line 1 to line 18, JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 And solid dyes described in JP-A-2-294638 and JP-A-5-11382. 11) Tetrazolium compound JP-A-2-39143, page 4, lower left column, line 8 to page 6, lower left column, line 6, JP-A-3-123346, page 3, upper right column, line 19 to page 5 Line 20 in the upper left column. 12) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 13) Redox compound The compound represented by formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50), and the compound represented by the general formula (3) of JP-A-3-174143, pp. 3 to 20: (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 14) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 15) Colloidal silica A compound described in paragraph [0005] of JP-A-4-214551. 16) Matting agent JP-A-2-103536, page 19, upper left column, line 15 to upper right column, line 6. JP-A-3-109542, page 2, lower left column, line 8 to page 3, upper right column, line 4. JP-A-4-127142, page 3, upper right column, line 7 to page 5, lower right column, line 4. JP-A-6-118542, paragraph numbers (0005) to (0026). 17) Antistatic A conductive compound described in U.S. Pat. No. 4,999,276 and a fluorinated surfactant.

[0148]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 Production was performed using the following two formulations (A) and (B) while changing the temperature during mixing and the stirring conditions. The developer formula is a formula value per liter, and the experiment was performed on a 500 liter scale. Formula (A) is at the level of the present invention, and (B) is a comparative example.

(A) (B) Sodium sulfite 10 g 10 g Potassium hydrogen carbonate 0.4 mol-potassium carbonate 0.15 mol 0.55 mol Sodium carbonate monohydrate 0.25 mol 0.25 mol Sodium erythorbate monohydrate 45 g 45 g Diethylene triamine pentaacetic acid 2 g 2 g Potassium bromide 2g 2g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5g 1.5g trimercaptotriazine 0.1g 0.1g 4-dimethylamino-2- (3-hydroxypropoxy) phenol 1.0g 1.0g Was dissolved in water to make 1 liter. Further, H ₂ SO ₄ or NaO is used so that the pH becomes 9.6.
Adjusted with H.

The prescription (A) can be used even before the pH adjustment.
Approximately 9.6, but prescription (B) exceeded 11.0
Large amount of H for adjusting pH_TwoSO_FourCost. H_Two
SO _FourWhen adding, a large amount of carbon dioxide gas was generated. pH
Was adjusted to the target value of 9.6, and stirring was continued for another hour.
Dissolution and mixing were complete. After this, measure the pH again.
became. The measurement of the carbonate ion concentration was also performed. Carbonated
The ON prescription value is 0.8 mol / l.

The temperature and the number of rotations for stirring during the preparation of the solution were determined under the following five conditions. 1 2 3 4 5 Temperature 25 ° C 25 ° C 25 ° C 35 ° C 35 ° C Stirring 200 rpm 400 rpm 600 rpm 200 rpm 400 rpm

The pH at the preparation and the carbonate ion concentration (total of the carbonate ion concentration and the hydrogen carbonate ion concentration) measured by ion chromatography are shown below.

Formulation A A A A A A B B B B Preparation Condition 1 2 3 4 4 5 1 2 3 4 5 pH 9.60 9.61 9.60 9.61 9.60 9.50 9.52 9.55 9.51 9.53 Carbonate Concentration 0.79 0.80 0.80 0.79 0.80 0.71 0.74 0.74 0.72 0.75 degrees (mol / liter)

From the above results, the level of the present invention (A1 to A5)
It can be seen that pH fluctuation is small and the carbonate ion concentration is stable.

Example 2 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] An aqueous solution of silver nitrate, potassium bromide, sodium chloride and K corresponding to 3.5 × 10 ^-7 mol per mol of silver.
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ^-7 mol
A halogen salt aqueous solution containing (H ₂ O) Cl ₅ , sodium chloride, and a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinthione were added by stirring by a double jet method to give an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per 1 mol of silver, and 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver.
H6.0, adjusted to pAg7.5, 2 mg per mole of silver
Of sodium thiosulfate and 4 mg of chloroauric acid
Chemical sensitization was carried out at 0 ° C. to obtain the optimum sensitivity. Then, 4-hydroxy-6-methyl-1,3,3, as a stabilizer
150 mg of a, 7-tetrazaindene was added, and 100 mg of compound (a) was further added as a preservative. The obtained particles were silver chlorobromide cubic particles each having an average particle size of 0.25 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

[0157]

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Preparation of Coated Sample On a polyethylene terephthalate film support having an undercoat of a moisture-proof layer containing vinylidene chloride, a UL layer, an EM layer, a P
The sample was applied so as to have a layer structure of a C layer and an OC layer to prepare a sample. The preparation method and application amount of each layer are shown below.

(UL layer) Gelatin was coated so as to be 0.5 g / m ² .

[0160] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ⁻⁴ mol of mercapto compound represented by the following (b) per mol of silver, 4 × 10 ⁻⁴ mol of mercapto compound represented by (c), and 4 × 10 ⁻⁴ mol of (d) Triazine compound, 2 × 10 ^-3 mol of 5-chloro-8-hydroxyquinoline, 5 × 10 ^-4 mol of the following compound (e), and 4 × 10 ^-4 mol of the following compound (A) as a nucleation promoting agent Was added. Further, 100 mg of hydroquinone and sodium salt of N-oleyl-N-methyltaurine were added so as to be applied at 30 mg / m ² . Next, the hydrazine derivative shown in Compound Example I-55 was 0.8 × 10 ⁻⁵ mol / m ² , the polymer latex shown in (f) was 200 mg / m ² , and the average particle size was 0.1 mg / m ² .
200 μm / m ^{2 of} 0.2 μm colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.)
2-bis (vinylsulfonylacetamido) ethane is converted to 2
00 mg / m ² was added. The pH of the solution was 5.6 using acetic acid.
5 was prepared. They were coated so that the coated silver amount was 2.5 g / m ² and the gelatin was 0.8 g / m ² .

[0161]

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(PC layer) The following surfactant (g) was added to an aqueous gelatin solution at 5 mg / m ² , and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² so as to be applied.
Gelatin was coated to 0.5 g / m ² .

(OC layer) An amorphous SiO ₂ matting agent 40 having a gelatin of 0.5 g / m ² and an average particle size of about 3.5 μm.
mg / m ² , 0.1 g / m ^{2 of} colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.), 100 mg of polyacrylamide
/ M ² and the sliding agent (h) 20 mg / m ² and coating the fluorine surfactant 5 mg / m ² of sodium dodecylbenzenesulfonate 100 mg / m ² of the following structural formula (i) as an auxiliary agent was applied.

[0164]

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Next, the following conductive layer and back layer were simultaneously coated on the opposite side of the support. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 250 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 100 {compound- (a) 7} sodium dodecylbenzenesulfonate Salt 20〃Dihexyl-α-sulfosuccinate sodium salt 20〃Polystyrene sulfonate sodium salt 20〃 <Back layer> Gelatin (Ca ⁺⁺ content 30 ppm) 2.6 g / m ² Dye Dye [a], Dye [b], Dye [c] mixture Dye [a] 70 mg / m ² Dye [b] 70 〃 Dye [c] 90 〃 sodium dodecylbenzenesulfonate 80 〃 dibenzyl-α-sulfosuccinate sodium salt 20 １，２ 1,2- Bis (vinylsulfonylacetamide) ethane 110 ナ ト リ ウ ム sodium acetate 40 40 lithium perfluorooctanesulfonate 5 微粒子 fine particles of polymethyl methacrylate (average particle size 4.5 μm) 30 〃

[0166]

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After the obtained sample was stored for 1 week in an atmosphere of 25 ° C. and 55% RH, the following running stability was evaluated. The results are shown in Table-10.

[0168]

[Table 10]

As is clear from Table 10, the level of the present invention is extremely high in photographic characteristics and excellent in running stability. (1) Evaluation of running stability The sample was passed through an interference filter having a peak at 480 nm.
Exposure was performed with a xenon flash light having an emission time of 10 ^-5 sec through a step wedge, and the drive gear was changed to a high-speed drive using an FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd. using a developer having the following composition. After developing at 35 ° C. for 15 seconds, fixing, washing and drying were performed. The running conditions were as follows: the photosensitive material described above was 20 m ² per day.
5 days continuous processing at 80% blackening rate
The performance of the fresh liquid and the fatigue liquid after running was evaluated. The sensitivity was determined from the exposure amount giving fog + density = 1.5 in the characteristic curve. As an index (gamma) indicating the contrast of an image, a point between fog + density 0.3 and a point fog + density 3.0 on the characteristic curve is connected by a straight line, and the slope of the straight line is expressed as a gamma value. That is, gamma = (3.0
−0.3) / [log (exposure to give a density of 3.0) −
(Exposure amount giving a density of 0.3)], indicating that the greater the gamma value, the harder the photographic characteristics. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more.

The composition of the developer per liter of working solution is shown below. Developer Potassium hydrogen carbonate (addition amount described in Table 10) Potassium carbonate monohydrate (addition amount described in Table 10) Diethylenetriamine.pentaacetic acid 4 g Sodium sulfite 5 g (0.04 mol) Potassium bromide 2 g 5-methylbenzotriazole 0. 08 g Sodium erythorbate monohydrate 45 g Compound A-24 shown in Table 2 2.5 g Trimercaptotriazine 0.03 g The pH was adjusted to 9.7. The replenishment rate was 120 ml / m ² .

The fixing solution used had the following formulation. (Formulation of fixing solution) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g Water To 3 liters and adjust to pH = 4.85 with sulfuric acid or sodium hydroxide. The replenishment rate was 160 ml / m ² .

Example 3 A conductive layer of Example 2 and a back layer having the following composition were simultaneously coated on one side of the same support as in Example 2. <Back Layer> Gelatin (Ca ⁺⁺ content 3000ppm) 2.0 g / m ² Compound - 3 mg / m ² Compound - 40 〃 compound - 40 〃 compound - 155 〃 compound - 150 〃 sodium dodecylbenzenesulfonate 7 〃 dihexyl - α-Sulfosuccinate sodium 30 １，２ 1,2-bis (vinylsulfonylacetamide) ethane 140 ナ ト リ ウ ム Sodium sulfate 180 化合物 Compound-5 微粒子 Fine particles of polymethyl methacrylate (average particle size 4.7 μm) 10 微粒子

[0173]

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[0174]

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Next, the first and second emulsion layers and the lower and upper protective layers having the following compositions were simultaneously coated on the opposite side of the support. <Emulsion layer first layer> 4-hydroxy-6 kept at 40 ° C
In an aqueous gelatin solution containing methyl-1,3,3a, 7-tetrazaindene (5 × 10 ⁻³ mol per mol of silver), an aqueous solution of silver nitrate and 2 × 10 ⁻⁵ mol of (NH ₄ ) per mol of silver were used. ₂ Rh
A sodium chloride aqueous solution containing (H ₂ O) Cl ₅ was simultaneously added in 7 minutes, and the potential during that time was controlled at 95 mV, thereby preparing 0.12 μm of core particles. afterwards,
1.2 × 10 ⁻⁴ mol of (N) per mol of silver nitrate aqueous solution and silver
H ₄ ) ₂ Rh (H ₂ O) Cl ₅ containing sodium chloride aqueous solution
Silver chloride cubic grains having an average grain size of 0.15 μm were prepared by adding for 4 minutes and controlling the potential during the addition to 95 mV. The hydrazine derivative I
-37 at 0.5 × 10 ⁻⁵ mol / m ² , 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene is added to 30
mg / m ² , each of the following compounds-and-was 40 mg / m ² , 1
0 mg / m ² , 1,1-bis (vinylsulfonyl) methane as a hardening agent, 1 g of gelatin on the side having an emulsion layer
55 g / g, 1.6 g / m ^{2 of} silver and 0.6 g of gelatin.
g / m ² .

[0176]

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<Emulsion Layer Second Layer>
Cyclopentane-4-hydroxy-1,3,3a, 7-
An aqueous silver nitrate solution and 4 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per mol of silver were added to an aqueous gelatin solution containing tetrazaindene (5 × 10 ⁻³ mol per mol of silver). Sodium chloride aqueous solution at the same time in three and a half minutes.
By controlling to mV, the particle of the core part 0.0
8 μm was prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per mol of silver were simultaneously added over 7 minutes, and the potential between them was controlled at 95 mV. Thus, silver chloride cubic grains having an average grain size of 0.10 μm were prepared. An emulsion layer similar to the first layer of the above-mentioned emulsion layer was coated except that this emulsion was used, so that a silver amount of 1.0 g / m ² gelatin was 0.4 g / m ² .

<Lower Layer of Protective Layer> Gelatin 0.60 g / m ² Polymer Latex Compound Example P-4 0.50 {1-hydroxy-2-benzaldoxime 15 mg / m ² Compound-80} Compound- (10) 10} <Protection Upper layer> Gelatin 0.40 g / m ² Amorphous matting agent (SiO ₂ , average particle size 4.4 μm) 30 mg / m ² Liquid paraffin (gelatin dispersion) 50 ° N-perfluorooctanesulfonyl-N-propyl glycine potadium 5 ナ ト リ ウ ム Sodium dodecylbenzenesulfonate 10 〃 * Solid disperse dye A 80 〃 * Solid disperse dye B 40 〃 * Preparation method of fine particle dispersion of solid disperse dyes A and B The preparation method in the present invention is described in JP-A-63-197943. According to the method of No. That is, water (434 ml) and
Triton X-200R surfactant (TX-200R)
(53 g) (sold by Rohm & Haas) and a 6.7% solution were placed in a 1.5 liter screw cap bottle. 20 g of dye and zirconium oxide (ZrO ₂ ) beads (8
00 ml) (2 mm diameter) was added, the bottle was tightly closed, placed in a mill and the contents were ground for 4 days. The contents were dissolved in a 12.5% aqueous gelatin solution (160
g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove the ZrO ₂ beads. Although the average particle size was about 0.3 μm in this state, coarse particles were still contained. Therefore, the particles were classified by centrifugation to reduce the maximum particle size to 1 μm or less.

[0179]

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Using the obtained sample, crushing running was performed in the same manner as in Example 2, and running stability was evaluated in the same manner as in Example 2. However, the photographic performance was evaluated as follows. <Evaluation of photographic performance> The sample was used as a photo room printer FPA-800FX manufactured by Fuji Photo Film Co., Ltd.
Exposure was performed through an optical wedge (using a Fresnel lens), and the developer was Compound A-2 of the developer used in Example 2.
Using the same amount of A-26 shown in Table 3 in place of 4, using the same fixing solution as in Example 1, using an automatic developing machine AP-560 (manufactured by Fuji Photo Film Co., Ltd.) at 35 ° C. 2
The processing was performed under the developing condition of 0 second. The results are shown in Table-11.

[0181]

[Table 11]

As is clear from Table 11, the level of the present invention is excellent in running stability as in Example 2.

Example 4 The emulsion of Example 2 was replaced with the following emulsion B, and the sensitizing dye for the EM layer was replaced with the following compound (S-3), and 2.1 × 10 ^-4 per mol of silver. A sample was prepared in the same manner as in Example 1 except that moles were added. [Emulsion B] Performed except that 1 mg of a selenium sensitizer of the following structural formula per mole of silver, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid were added and chemically sensitized at 60 ° C. to obtain an optimum sensitivity. The preparation was carried out in the same manner as in Emulsion A of Example 2.

[0184]

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The sample thus obtained was evaluated in the same manner as in Example 2. However, the evaluation of the photographic performance was based on the emission time of 10 ⁻⁶ , instead of the interference filter having a peak at 633 nm.
Exposure was performed with xenon flash light for sec., and the development treatment was performed using the compounds shown in Table 12 in place of the compound A-24 in the developer formulation of Example 2. Further, potassium hydrogen carbonate in the developing solution was 0.4 mol / l and potassium carbonate was 0.4 mol / l. Table 12 shows the evaluation results.

[0186]

[Table 12]

As is evident from the results in Table 12, p-aminophenols such as monol are more preferable as auxiliary developing agents having superadditivity than phenidone and pyrazolidones because of their high sensitivity, high contrast and running stability. You can see that.

Example 5 The sensitizing dye in the EM layer of Example 4 was replaced with the following compound (S-4), and 5.4 × 10 ^-5 mol per mol of silver was added. Bis- (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt 350 mg / Ag 1 mol, 2,5-dimethyl-3
-Allyl-benzothiazole iodine salt 450 mg / Ag1
A sample was prepared in the same manner as in Example 4, except that the moles were added instead of the moles, and the back layer was changed to the back layer and the back protective layer having the following compositions.

[0189]

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<Back Layer> Gelatin 2.0 g / m ² Compound- (1) 3 mg / m ² Dye-a 35 染料 Dye-b 95 染料 Dye-c 70 〃 Dihexyl-α-sulfosuccinate sodium 25 〃 Dodecylbenzene Sodium sulfonate 35 {acetic acid 10} 1,3-divinylsulfonyl-2-propanol 130 {back protective layer> gelatin 0.8 g / m ² compound- (1) 1 mg / m ² polymethyl methacrylate fine particles (average particle size 3 .4 μm) 35 ナ ト リ ウ ム sodium dihexyl-α-sulfosuccinate 7 ナ ト リ ウ ム sodium dodecylbenzenesulfonate 10 化合物 compound-(2) 2 ナ ト リ ウ ム sodium acetate 30

[0191]

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The sample thus obtained was evaluated in the same manner as in Example 4. However, evaluation of photographic performance is 780 nm
The test was performed in place of an interference filter having a peak at
As a result, as in Example 4, a photosensitive material for a semiconductor laser scanner having extremely high photographic characteristics and excellent running stability could be obtained.

Example 6 <Formulation of Solid Developer> Sodium sulfite (raw powder) 10 g Potassium hydrogen carbonate (raw powder) 42 g Potassium carbonate (raw powder) 19 g Sodium carbonate / water salt (raw powder) 30 g Sodium erythorbate-1 Water salt (briquette) 45 g. Diethylenetriamine / pentaacetic acid 2 g Potassium bromide 2 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g Trimercaptotriazine 0.1 g 4-Dimethylamino-2- (3-hydroxypropoxy) phenol 1.0 g Dissolve in water to make 1 liter. The pH was adjusted to 9.6.

Here, in the form of raw materials, the raw powder was used as it is a general industrial product, and the alkali metal salt beads used were commercial products. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, Japanese Patent Application Nos. 7-235499 and 7-23.
A dissolution replenisher with an automatic opening mechanism, disclosed in US Pat. When the halogenated photosensitive material was processed in the same manner as in Example 1 except that the developing solution thus prepared was used, the same results as in Example 1 were obtained.

[0195]

As described above, according to the present invention, in an ascorbic acid-based developer using no hydroquinone, there is little change in photographic performance, and an improved developer, a solid developer and an improved high contrast image can be formed. A method can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/30 G03C 5/30 5/31 5/31

Claims (6)

[Claims] Claims: 1. A pH of 9.0 to 10 containing substantially no dihydroxybenzene-based developing agent and containing an ascorbic acid-based developing agent and an auxiliary developing agent having superadditivity to the ascorbic acid-based developing agent. 5. The method for producing a developer according to item 5, wherein a step of adding 0.5 mol / l or less of a carbonate and 0.1 to 1.5 mol / l of a bicarbonate as a pH buffer agent is included. Of producing a developing solution. 2. A developer produced by the production method according to claim 1. 3. An at least ascorbic acid-based developing agent, an auxiliary developing agent having superadditivity to the ascorbic acid-based developing agent, a carbonate equivalent to 0.5 mol or less per liter of a developing solution, and a developing solution. 0 per liter.
A solid developer containing 1 to 1.5 mol of bicarbonate. 4. A developer prepared by dissolving the developer according to claim 2 or the solid developer according to claim 3 in a predetermined amount of water after exposing a silver halide photographic material containing a hydrazine derivative. A method for forming a high-contrast image, wherein the method is used for processing. 5. The development time is 30 seconds or less, and the total processing time from development to drying is 90 seconds or less.
The method for forming a high-contrast image described in the above. 6. The method according to claim 4, wherein the replenishing amount of the developing solution is 300 ml or less per square meter of the photosensitive material.
Or the method for forming a high contrast image according to 5.