JPH11133558A - Developing solution for sliver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ascorbic acid type developing solution reduced in change of photographic performance improved by incorporating a specified aminophenol derivative and 3-pyrazolidones having hydrophilic groups as auxiliary developing agents. SOLUTION: This developing solution does not contain substantially any of hydroxybenzenes but contained the ascorbic acid and/or its derivatives and further, as the auxiliary developing agents exhibiting superadditivity, the 3- pyrazolidones having hydrophilic groups and the aminophenol derivative represented by the formula in which each of R1 -R4 is, independently, an H atom or a substituent; and each of R5 and R6 is, independently, alkyl or aryl or aralkyl or heterocyclic group. It is preferred that the pyrazolidones are 1-aryl-4,4-disubstituted-3-pyraxolidones having hydrophilic groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer for a silver halide photographic light-sensitive material. More specifically, the present invention relates to a developer and a developing method for a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material or a light-sensitive material) which is used in the field of photoengraving and which has ultra-high contrast and little change in performance due to processing. It is.

[0002]

2. Description of the Related Art In general, in developing processing of a photosensitive material, in many cases, as a developing solution, bydroquinone has been used as a developing agent in view of cost and stability of photographic performance. However, because hydroquinone is allergic,
It was unfavorable in terms of material safety. For these reasons, developers using ascorbic acid as a substitute for hydroquinone are disclosed in, for example, JP-A-6-19069, JP-A-7-114153, and JP-A-7-175.
176 publication.

On the other hand, photographic processing waste liquid cannot be discharged to the sewer as it is, and it is necessary to collect the waste liquid and incinerate it. For this reason, it has been desired to reduce the replenishment amount when processing using an automatic developing machine. However, if the replenishment amount of the developer is reduced, there is a problem that the stability of photographic performance is impaired. Further, a developing solution using ascorbic acid or a derivative thereof is susceptible to air oxidation, and when oxidized, generates an acid to lower the pH of the developing solution. Developer pH
Due to the decrease, the activity of the nucleating agent is reduced, causing a decrease in contrast and Dmax, resulting in unstable photographic performance.
Therefore, it has been difficult to reduce the replenishment amount of the developer using ascorbic acid or a derivative thereof.

Further, use of 3-pyrazolidones having a hydrophilic group as an auxiliary developing agent has been disclosed in
20121. However, there was a disadvantage that the development speed was reduced by the introduction of the hydrophilic group.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved ascorbic acid-based developer and an improved development processing method with little change in photographic performance.

[0006]

According to the present invention, the following objects of the present invention are attained by providing the following developer and processing method for a silver halide photographic material. (1) It does not substantially contain dihydroxybenzenes,
An aminophenol derivative represented by the following general formula (A) as an auxiliary developing agent which contains ascorbic acid and / or a derivative thereof as a developing agent and exhibits superadditivity, and 3-pyrazolidone having a hydrophilic group And a developer for a silver halide photographic light-sensitive material.

[0007]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each represents a hydrogen atom or a substituent, and R ₅ and R ₆ are the same or different and each represents an alkyl group, an aryl group , An aralkyl group or a heterocyclic group.) (2) 3-pyrazolidones having a hydrophilic group
The developer according to the above (1), which is an aryl-4,4-disubstituted-3-pyrazolidone. (3) The developer according to the above (1) or (2), further comprising a silver stain inhibitor represented by the following general formula (G).

[0009]

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(Wherein D and E are the same or different and each is a group represented by -CH =, a group represented by -CR ₀ =,
Or a nitrogen atom, wherein R ₀ represents a substituent, and L ₁ , L ₂ and L ₃ are the same or different and are each a hydrogen atom, a halogen atom, or a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom; Represents a substituent bonded to the ring at any one of an atom and a phosphorus atom. However, at least one of L ₁ , L ₂ , L ₃ and R ₀ represents one SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group). Incidentally, any nitrogen atom of the E and D, when the other is a group represented a group represented by or -CR ₀ = at -CH = is, E
Is a nitrogen atom, and L ₂ and L ₃ are not hydroxyl groups. )

(4) The bicarbonate concentration in the developer is 0.1
Mol / l or more, the total concentration of bicarbonate and carbonate is 0.5 mol / l or more, and the pH is 9.0 to 9.0 mol / l.
The developer according to any one of the above (1) to (3), wherein the developer is 10.5. (5) A developing method comprising treating a silver halide photographic light-sensitive material containing a hydrazine derivative with the developer for a silver halide photographic light-sensitive material according to any one of the above (1) to (4). .

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a developing agent used in the present invention will be described. As the developing agent of the ascorbic acid derivative used in the present invention, a compound represented by the following general formula (1) is preferable. General formula (1)

[0013]

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(Wherein R ₁ and R ₂ are the same or different and each is a hydroxyl group, an amino group, an acylamino group,
Alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group,
Or X represents an alkylthio group, X contains at least one atom selected from a carbon atom, an oxygen atom, and a nitrogen atom, and is formed by two vinyl and carbonyl carbons substituted by R ₁ and R ₂ together with a carbonyl carbon. Represents a divalent organic group forming a 5- to 6-membered ring. )

Hereinafter, the general formula (1) will be described in detail. In the formula, R ₁ and R ₂ are each independently a hydroxyl group, an amino group (an alkyl group having 1 to 10 carbon atoms as a substituent, for example, a methyl group, an ethyl group, an n-butyl group,
Includes those having a hydroxyethyl group or the like as a substituent. ), Acylamino group, (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group,
(Methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio group, ethylthio group Etc.). Among the above groups, preferred groups include a hydroxyl group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

[0016] X includes at least one atom selected from a carbon atom, an oxygen atom and a nitrogen atom, and R ₁
And it represents a divalent organic group R ₂ forms a 5- or 6-membered ring in cooperation with the two vinyl carbons and the carbonyl carbon is substituted. X is, for example _{-O -, - C (R 3} ) (R 4) -, - C (R 5)
=, - C (= O) -, - N (R 6) -, - N =, it can be constructed by combining. Where R ₃ , R ₄ ,
R ₅ and R _{6 each} represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxyl group,
A carboxyl group and a sulfo group) and an optionally substituted aryl group having 6 to 15 carbon atoms (an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group and a sulfo group can be mentioned as substituents) , A hydroxyl group and a carboxyl group. Furthermore, the above 5-6
The membered ring may be a saturated or unsaturated condensed ring.
Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Preferred examples of the 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring and a uracil ring.

Specific examples of the compound represented by the general formula (1) are shown below.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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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;
No. 237443. Methods for synthesizing these ascorbic acids are also well known, and are described, for example, in Tsukio Nomura and Hirohisa Omura, "Reducton Chemistry" (Uchida Lao Tsuruhoshinsha 1969). 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.

As the aminophenol derivative of the auxiliary developing agent having super additivity used in the present invention, p-aminophenols represented by the following formula (A) are preferred. General formula (A)

[0025]

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(In the general formula (A), R ₁ , R ₂ , R ₃ , R
₄ is the same or different and each represents a hydrogen atom or a substituent. R ₅ and R ₆ are 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 are the same or different and each represent 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 hydroxyl 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 salts), and a sulfo group (including salts).
These are an alkyl group, an alkenyl group, an alkynyl group,
Aryl group, halogen atom, cyano group, nitro group, hydroxyl group, alkoxy group, alkylthio group, amino group, alkylamino group, ammonio group, carbonamide group, sulfonamide group, sulfamoylamino group, ureido group, carbamoyl group , A sulfamoyl group, a carboxyl group (including a salt), a sulfo group (including a salt), or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom.

More preferred examples of the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ are shown below. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl,
Examples include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-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 are the same or different and each represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group. The details 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, a morpholine ring Can be mentioned. 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 benzene ring to be formed may be, for example, indole, indoline, dihydroquinoline, tetrahydroquinoline, 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)

[0033]

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(Wherein, R ₁₁ and R ₂₂ are the same or different and each represents a hydrogen atom or a substituent. R ₅₅ and R ₆₆ are
The same or different, each represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. )

R ₁₁ , R ₂₂ and R ₅₅ in the general formula (B)
For R ₆₆ described for the preferred combinations below. R ₁₁ and R ₂₂ represent a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group,
Preferred is a combination of a carbonamide group, a sulfonamide group, a sulfamoylamino group, or a ureido group, wherein R ₅₅ and R ₆₆ are alkyl groups. Here, the alkyl group, the alkoxy group, and the alkylamino group include those substituted with another substituent. In this combination, R ₅₅ and R ₆₆ are more preferably an unsubstituted alkyl group or an alkyl group substituted with a hydrophilic group. Here, as the hydrophilic group, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group, an ammonium group, a carbonamide group, a sulfonamide group, a sulfamoylamino group, a ureido group, a carbamoyl group, a sulfamoyl group, a carboxyl group ( And sulfo groups (including salts).

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 hydroxyl 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 hydroxyl 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 by a hydroxyl group or an alkoxy group.

Examples of the specific compounds represented by the general formula (A) of the present invention include the compounds listed in the following Tables 1 to 9, but are not limited thereto. 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 general formula (A) include hydrochloric acid, hydrobromic acid, sulfuric acid, p-toluenesulfonic acid,
Methanesulfonic acid, naphthalene-1,5-disulfonic acid and the like can be mentioned, and a salt of sulfuric acid or naphthalene-1,5-disulfonic acid is preferable.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[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.

Next, the 3-pyrazolidones having a hydrophilic group used in the present invention will be described. The 3-pyrazolidones having a hydrophilic group used in the present invention include the following hydrophilic groups: carboxy group, sulfo group, hydroxyl group, sulfonamide group, sulfamoyl group, amino group, ammonium group, sulfino group, 3-pyrazolidone having a phosphono group, and in addition to these hydrophilic groups,
It may have an optional substituent. Among them, preferred 3-pyrazolidones in the present invention are 1-aryl-3-pyrazolidones having a hydrophilic group, and are represented by the following general formula (P). General formula (P)

[0051]

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In the general formula (P), R ₁ , R ₂ , R ₃ ,
And R ₄ are the same or different and are each a hydrogen atom or
(A) represents m- (L) nB- (So1) p, and R ₅ represents a substituted or unsubstituted aryl group. Where A and B
Are the same or different and each represents an alkylene group or an arylene group, and L is the following divalent group: —O—, —S
_{-, - NR 6 -, -} OC (O) -, - C (O) O -, -
OC (O) O-, -C (O)-, -OC (O) NR
_{7 -, - NR 8 C (} O) -, - C (O) NR 9 -, - NR 1
_{0 S0 2 -, - S0 2} NR 11 -, - NR 12 S0 2 NR 13 - represents, So1, the following hydrophilic groups, i.e., -CO ₂ H, -
_{SO 3 H, -OH, -NHSO 2} R 14, -SO 2 NH
_{R 15, -NR 16 R 17,} -N + (R 18) 3, -SO 2 H, -
Represents PO (OH) ₂ , and m, n, and p represent integers from 0 to 3. Note that R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ are
Represents a hydrogen atom, an aliphatic hydrocarbon group, or an aryl group. Further, at least one of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ has a Sol group. R ₁ , R ₂ ,
R ₃ , R ₄ and R ₅ may be bonded to each other to form a ring.

The compound of the formula (P) will be described in more detail. In formula (P), A, alkylene group represented by of B, preferably has 1 to 10 carbon atoms, e.g., methylene, _{ethylene, -CH 2 CH (CH 3)} -, -
(CH ₂ ) ₃ —, — (CH ₂ ) ₄ — and the like, and the arylene group preferably has 6 to 12 carbon atoms, for example, an O-phenylene group, a p-phenylene group, an m-phenylene group, and the like. Is mentioned. R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ ,
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , and R
_{As the} aliphatic hydrocarbon group represented by ₁₈ , C 1 to C 1
0 alkyl group (for example, methyl, ethyl, n-propyl, topropyl, t-butyl, sec-butyl, n-octyl, cyclopropyl, cyclopentyl), carbon number 1
Alkenyl groups such as vinyl, allyl, 2-
Butenyl, 3-pentenyl), an arginyl group having 1 to 10 carbon atoms (eg, propargyl, 3-pentynyl), an aralkyl group having 1 to 10 carbon atoms (eg, benzyl, phenethyl), and R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
As the aryl group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ , an aryl group having 6 to 14 carbon atoms (eg, phenyl, naphthyl, 4-methylphenyl) Is mentioned.

A, B, and R ₆ , R ₇ , R ₈ ,
R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R
Each of the groups ₁₇ and R ₁₈ may have a substituent, and examples of the substituent include the following. That is, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (eg, methyl, ethyl, i-propyl, t-butyl, n-octyl, cyclopropyl, cyclohexyl), an alkenyl group (eg, allyl) , 2-butenyl,
3-pentenyl), alkynyl group (e.g., propargyl, 3-pentynyl), aralkyl group (e.g., benzyl, phenethyl), aryl group (e.g., phenyl, naphthyl, 4-methylphenyl), heterocyclic group (e.g., pyridyl, Furyl, imidazolyl, piperidyl, morpholino), alkoxy group (e.g., methoxy, ethoxy, butoxy), aryloxy group (e.g., phenoxy, 2-naphthyloxy), amino group (e.g., unsubstituted amino, dimethylamino, ethylamino, Anilino), a ureido group (e.g., unsubstituted ureido, N-methylureide, N-phenylureido), a urethane group (e.g., methoxycarbonylamino, phenoxycarbonylamino), a sulfonyl group (e.g., mesyl, tosyl), a sulfinyl group ( For example, methylsulfinyl, phenyl Rufiniru) alkyl Oki dicarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an acyl group (e.g., acetyl, benzoyl, formyl, pivaloyl),
Acyloxy group (e.g., acetoxy, benzoyloxy), alkylthio group (e.g., methylthio, ethylthio), arylthio group (e.g., phenylthio), cyano group, mercapto group, carboxyl group, phosphono group, nitro group, sulfino group, ammonium group ( For example, a trimethylammonio group), a silyl group (eg, trimethylsilyl) and the like. These groups may be further substituted, and when there are two or more substituents, they may be the same or different.

[0055] More preferably used in the present invention,
The compound represented by the general formula (P) is 1-aryl-4,4
A di-substituted-3-pyrazolidone compound, and in the general formula (P), R ₁ and R ₂ are (A) m- (L) n-B-
(So1) p, and R ₃ and R ₄ are a hydrogen atom or (A)
m- (L) nB- (So1) p, wherein R ₅ is a substituted or unsubstituted aryl group. The compound represented by the general formula (P), which is more preferably used, is a compound represented by the general formula (P) wherein R ₁ and R ₂ are (A) m- (L) nB-
(So1) p, and R ₃ and R ₄ are a hydrogen atom or (A)
m- (L) n-B- ( So1) is p, R ₅ is a substituted or unsubstituted aryl group, So1 group is -CO ₂ H, -
SO ₃ H, -OH.

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

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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In the developing solution of the present invention, the ascorbic acid-based developing agent is used in an amount of 0.01 to 0.1 per liter of the developing solution.
It is used in an amount corresponding to 5 mol, preferably 0.05 to 0.3 mol. The amount of each of the aminophenol derivative and the 3-pyrazolidone having a hydrophilic group, which are auxiliary developing agents, is 0.005 to 1 liter per developer.
Preferably, it is used in an amount corresponding to 0.2 mol.

The developer of the present invention contains, for the purpose of pH adjustment,
Preference is given to adding carbonates and / or bicarbonates. As the carbonate, sodium carbonate and potassium carbonate are preferable. As the hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate are preferable. Carbonate is the developer 1
It is used in an amount corresponding to 0.5 mol or less, particularly 0.1 to 0.5 mol per liter, and the bicarbonate is used in an amount corresponding to 0.1 to 1.5 mol per liter of the developing solution. preferable. To the developer of the present invention, a carbonate and / or bicarbonate is added in the above-mentioned amount to adjust the pH to 9.0 to 10.3.
Adjustment within the range of 5 is preferable in terms of stability of photographic performance in processing running.

The developing solution of the present invention contains, in addition to the above-mentioned ascorbic acid-based developing agent, auxiliary developing agent, carbonate and bicarbonate, additives which are usually used in developing solutions for silver halide photographic light-sensitive materials. can do. 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.

The preservatives include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. 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 compound, an indazole compound, a benzotriazole compound, and a benzimidazole compound are added to an antifoggant or black pot (pepper).
fog) may be included as an 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-
Sodium ((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-
Examples thereof include thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Various kinds of organic and inorganic chelating agents can be used alone or in combination in the 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, acyelinic acid,
Sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

Examples of the aminopolycarboxylic acid include, 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 other JP-A Nos. 52-25632 and 55- Compounds described in JP-A-67747, JP-A-57-102624, and JP-B-53-40900 can be exemplified.

Examples of the organic phosphonic acid include, for example, US Pat. Nos. 3,214,454 and 3,974,591 and West German Patent Publication.
2227369 Hydroxyalkylidene- described in the specification and the like
Diphosphonic acid or Research Disclosure No. 181
Vol., Item 18170 (May 1979). Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition, Research Disclosure 18170, JP-A-57-208554, and JP-A-57-208554. -61125
And the compounds described in JP-A-55-29883 and JP-A-56-97347.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726, 53-42730, and 54-12.
No. 1127, No. 55-4024, No. 55-4025, No. 55
Compounds described in JP-A-126241, JP-A-55-65955, JP-A-55-65956 and the aforementioned Research Disclosure 18170 can be exemplified.

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, a compound represented by the following general formula (G) is preferably used as a silver stain preventive in a developer or a solid developer. General formula (G)

[0074]

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(In the general formula (G), D and E are the same or different and each represents a group represented by -CH =, a group represented by -CR ₀ =, or a nitrogen atom, wherein R ₀ is ,
L ₁ , L ₂ and L ₃ are the same or different and each represents a hydrogen atom, a halogen atom, or any one of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Represents a substituent to be bonded. However, L ₁ , L ₂ ,
At least one of L ₃ and R ₀ represents one SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group). One of E and D is a nitrogen atom, and the other is -CH
When = is a group or a group represented by -CR ₀ = indicated in, E is a nitrogen atom, moreover L ₂ and L ₃ are not a hydroxyl group. )

Next, the compound represented by formula (G) will be described in detail. Specific examples of the substituent represented by L ₁ , L ₂ , L ₃ and the substituent represented by R ₀ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), Alkyl groups (including aralkyl groups, cycloalkyl groups, active methine groups, etc.), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, heterocyclic groups containing quaternized nitrogen atoms (eg, pyridinio groups), acyl Group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, Hydroxy group, alkoxy group (repeating ethyleneoxy or propyleneoxy unit) Repeating groups), aryloxy groups, heterocyclic oxy groups, acyloxy groups, (alkoxy or aryloxy) carbonyloxy groups, carbamoyloxy groups, sulfonyloxy groups, amino groups, (alkyl, aryl or heterocyclic) amino Group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoyl An amino group, a semicarbazide group, a thiosemicarbazide group, a hydrazino group, a quaternary ammonium group, an oxamoylamino group, an (alkyl or aryl) sulfonyluureido group, an acylureido group,
Acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or heterocycle) thio group,
(Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, including phosphoric acid amide or phosphate ester structure Groups, and the like. These substituents may be further substituted with the above substituents. When E is a nitrogen atom and D is a group represented by -CH = or -CR ₀ =, L ₂ and L _2
3 is not a hydroxy group.

The substituents represented by L ₁ , L ₂ and L ₃ and the substituents represented by R ₀ are more preferably a substituent having ₀ to 15 carbon atoms, such as a chloro atom, an alkyl group or an aryl group. Group, heterocyclic group, acyl group, alkoxycarbonyl group, carbamoyl group, carboxy group or salt thereof, cyano group, alkoxy group, aryloxy group, acyloxy group, amino group, (alkyl, aryl or hetero ring)
Amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl ,
Aryl or heterocyclic) thio group, sulfo group or salt thereof, and sulfamoyl group, more preferably alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, carboxy group or salt thereof, alkoxy group , Aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido Group, thioureido group, sulfamoylamino group, mercapto group, (alkyl, aryl or heterocycle) thio group, sulfo group or a salt thereof, and most preferably amino group, alkyl group, aryl group, alkoxy group, aryl Oxy group, alkylamino group, arylamino group, alkyl Thio, a Aruruchio group, a mercapto group, a carboxy group or a salt thereof, a sulfo group or a salt thereof. In the general formula (G), L ₁ , L ₂ , L ₃ and R ₀ may combine with each other to form a condensed ring in which a hydrocarbon ring, a hetero ring or an aromatic ring is condensed.

In the general formula (G), M represents an alkali metal atom, a hydrogen atom, or an ammonium group. Here specifically the alkali metal atom, Na, and a K, Li, Mg, Ca, etc., -S ^- present as a counter cation. M is preferably a hydrogen atom, an ammonium group,
Na ⁺ or K ⁺ , particularly preferably a hydrogen atom. Among the compounds of the general formula (G), the following general formula (G
Compounds represented by A) and (GB) are preferred.

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Next, the general formula (GA) will be described in detail. R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, or an arbitrary substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, which is represented by L _{1 in the} general formula (G). , L ₂ and L ₃ are the same as defined above, and the preferred range is also the same. However, R ₁ and R ₃ do not represent a hydroxy group. R _{1 to} R ₄ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group.

In the general formula (GA), at least one of R _{1 to} R ₄ is a —SM group, and more preferably, R _{1 to} R ₄
At least two are -SM groups. When at least two of R _{1 to} R ₄ are a —SM group, preferably R ₄ and R ₁ ,
Or R ₄ and R ₃ is an -SM group.

In the present invention, among the compounds represented by the general formula (GA), the following general formulas (GA-1) to (GA-
The compound represented by 3) is particularly preferred.

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In the general formula (GA-1), R ₁₀ represents a mercapto group, a hydrogen atom, or an arbitrary substituent, and X represents a water-soluble group or a substituent substituted with a water-soluble group. In Formula (GA-2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₂₀ represents a hydrogen atom or an arbitrary substituent. In Formula (GA-3), Y ₂ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₃₀ represents a hydrogen atom or an arbitrary substituent. However, R ₁₀ and Y ₁ do not represent a hydroxy group.

Next, the general formulas (GA-1) to (GA-
The compound represented by 3) will be described in detail. In General Formula (GA-1), R ₁₀ represents a mercapto group, a hydrogen atom, or an arbitrary substituent. Here, the optional substituents are the same as those described for R _{1 to} R _{4 in} the general formula (GA). R ₁₀ is preferably a mercapto group, a hydrogen atom, or a group selected from the following substituents having 0 to 15 carbon atoms. That is, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Acylamino group, sulfonamide group, alkylthio group,
An arylthio group, an alkylamino group, an arylamino group and the like can be mentioned. In the general formula (GA-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group is a sulfonic acid or a carboxylic acid and a salt thereof, a salt such as an ammonio group, or a group containing a dissociable group which can be partially or completely dissociated by an alkaline developer. Include a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group, a sulfonamide group, an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, Or a substituent containing these groups. In the present invention, the active methine group refers to a methyl group substituted with two electron-withdrawing groups, and specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy And groups such as carbonylmethyl. General formula (GA-
The substituent represented by X in 1) is the above-mentioned water-soluble group or a substituent substituted with the above-mentioned water-soluble group, and the substituent is a substituent having 0 to 15 carbon atoms, Group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, (alkyl, aryl or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group,
Imide group, sulfamoylamino group, (alkyl, aryl or hetero ring) thio group, (alkyl, aryl)
Examples thereof include a sulfonyl group, a sulfamoyl group, and an amino group, preferably an alkyl group having 1 to 10 carbon atoms (particularly, a methyl group substituted with an amino group), an aryl group, an aryloxy group, an amino group, (alkyl, aryl, Or a heterocycle) amino group or an (alkyl, aryl or heterocycle) thio group.

Among the compounds represented by the general formula (GA-1), more preferred compounds are those represented by the following general formula (GA-1-a)
It is a compound represented by these.

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In the formula, R ₁₁ has the same meaning as R _{10 in} formula (GA-1), and the preferred range is also the same. R ₁₂ and R ₁₃ may be the same or different and each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. However,
At least one of R ₁₂ and R ₁₃ has at least one water-soluble group. Here, the water-soluble group includes a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group, a sulfonamide group, an acylsulfamoyl group, and a sulfonylsulfamoyl group. Group, active methine group, or a substituent containing these groups, preferably a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group,
And groups such as amino groups. R ₁₂ and R ₁₃ are preferably an alkyl group or an aryl group. When R ₁₂ and R ₁₃ are an alkyl group, the alkyl group is preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. As the substituent, a water-soluble group, particularly a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, or an amino group is preferable. When R ₁₂ and R ₁₃ are an aryl group, the aryl group has from 6 to 6 carbon atoms.
Preferred are 10 substituted or unsubstituted phenyl groups, which are water-soluble groups, particularly sulfo groups (or salts thereof), carboxy groups (or salts thereof), hydroxy groups,
Or an amino group is preferred. When R ₁₂ and R ₁₃ represent an alkyl group or an aryl group, they may combine with each other to form a cyclic structure. Further, a saturated hetero ring may be formed by a cyclic structure.

In formula (GA-2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group, and has the same meaning as X in formula (GA-1). In the general formula (GA-2), the water-soluble group represented by Y ₁ or a substituent substituted by a water-soluble group is more preferably an active methine group,
Or the following groups substituted with a water-soluble group, namely, an amino group,
An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl group, and an aryl group. More preferably, Y ₁ is an active methine group or an amino group substituted with a water-soluble group (alkyl, aryl, or heterocycle), wherein the water-soluble group is a hydroxy group, a carboxy group or a salt thereof, or a sulfo group. Groups or salts thereof are particularly preferred. Particularly preferred as Y ₁ is a (alkyl, aryl, or heterocyclic) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ₀₁ )
(R ₀₂ ). Here, R ₀₁ and R ₀₂ are groups having the same meanings as R ₁₂ and R _{13 in} formula (GA-1-a), respectively, and the preferred ranges are also the same.

In the general formula (GA-2), R ₂₀ represents a hydrogen atom or an arbitrary substituent, and the optional substituent is the same as those described for R _{1 to} R _{4 in} the general formula (GA). The same is given. R ₂₀ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms. That is, examples include a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a hydroxylamino group. Most preferably, R ₂₀ is a hydrogen atom.

In formula (GA-3), Y ₂ represents a water-soluble group or a substituent substituted with a water-soluble group, and R ₃₀ represents a hydrogen atom or an arbitrary substituent. General formula (GA
-3), Y ₂ and R ₃₀ are each represented by the general formula (GA-
Y ₁ of 2), an R ₂₀ group having the same meaning as in formula (GA-2), the preferred range thereof is also the same.

Next, the general formula (GB) will be described in detail. R _{5 to} R ₇ in the general formula (GB) have the same meanings as R _{1 to} R _{4 in} the general formula (GA), and their preferred ranges are also the same. Among the compounds represented by the general formula (GB), the compound represented by the general formula (GB-1) is particularly preferable.

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[0094]

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In the general formula (GB-1), R ₅₀ has the same meaning as R _{5 to} R _{7 in} the general formula (B), and more preferably X or R in the general formulas (GA-1) to (GA-3). A hydrophilic group as defined for Y ₁ and Y ₂ or a group substituted with a hydrophilic group. Further, among the compounds of the general formula (GB-1), the compound represented by the general formula (GB-1-a) is most preferred.

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In the general formula (GB-1-a), R ₅₁ and R
₅₂ is a group having the same meaning as R ₁₂ and R _{13 in} formula (GA-1-a), and the preferred range is also the same.

The following are specific examples of the compound represented by formula (G) of the present invention, but needless to say, the present invention is not limited thereto.

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[0101]

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[0102]

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The amount of the compound represented by the general formula (G) is 0.01 to 10 mmol, preferably 0.1 to 1 mmol per 1 L of the working solution.
５5 mmol.

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, the description of JP-A-5-45805, column 2, line 48 to column 3, line 13 can be referred to.

In the case of forming a plurality of layers, components that do not react even if they come into contact with each other may be sandwiched between components that react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921,
These are disclosed in JP-A-6841, JP-A-4-78848, and JP-A-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 the 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-4-16
No. 841, No. 4-32837, No. 4-78848, No. 5-9
No. 3991, JP-A-4-85533, JP-A-4-85534,
No. 4-85535, No. 5-134362, No. 5-197070, No. 5-04098, No. 5-224361, No. 6-138604
JP-A-6-138605 and JP-A-8-286329 can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt coagulation, briquetting, roller A compacting 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 (smooth, porous, etc.) or partly 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 for 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, or a box. Also, JP-A-6-2425
No. 85 to No. 6-242588, No. 6-247432,
No. 6-247448, No. 7-5664, No. 7-5666 or No. 7-5669. Is preferred for 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. As these methods, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, dissolving with a dissolving device having a dissolving portion and a portion for storing a completed solution,
How to replenish from the stock department, JP-A-5-119454,
No. 6-19102, No. 7-261357 A method of introducing and dissolving and replenishing a processing agent into a circulating system of an automatic developing machine as described in JP-A-7-261357, a photosensitive material in an automatic developing machine with a built-in dissolution tank. There is a method of adding and dissolving the treating agent in accordance with the above treatment, but any other known method can be used. The treatment agent may be charged manually, or may be automatically opened and supplied automatically by a dissolving device or an automatic developing machine having an opening mechanism. The latter is preferred from the viewpoint of working environment. Specifically, a method of piercing the outlet, a peeling method, a cutting method, a pushing method, and a method disclosed in JP-A-6-19102,
-95331, 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 when a solid fixing agent and a fixing solution are prepared using the same.

The replenishing amount of the developing solution is 300 ml or less, preferably 30 to 250 ml, per 1 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 than 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 preferred. 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, or the like) 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 contained. . Examples of the surfactant include an anionic surfactant such as a sulfated sulfone oxide.
Examples include polyethylene surfactants and amphoteric surfactants described in JP-A-57-6840, and known antifoaming agents can also be used. As the wetting agent, alkanolamine,
Examples include alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681,
-35754, 58-122535, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Patent 4,216,459, JP-A-64-4739 JP, JP-A 1-44739, Id.
And mercapto compounds described in JP-A-159645 and JP-A-3-110728, mesoionic compounds described in JP-A-4-170539, and thiocyanate.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0. The pH of the fixer is increased by mixing with the developer due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for the hardened fixer, and 7.0 or less, preferably 6.7 or less for the 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 fixer can be recycled by a known fixer 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 agent, it is preferable to store it in a packaging material having 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 liquid. 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. Also, various oxidizing agents (eg, 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 or three-stage) 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 liquid is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. Known means can be used as the scale preventive means, and is not particularly limited, but a method of adding a sunscreen (a so-called scale preventive agent), a method of energizing, a method of irradiating ultraviolet rays or infrared rays or far infrared rays, 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 according to the processing of the photosensitive material, may be performed at regular intervals irrespective of the state of use, 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 oxide (for example,
2-mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination. As a method of energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16
280 and 4-18980 can be used.

In addition, a known water-soluble surfactant or defoaming 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 with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (for example, 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 performed to obtain a biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use silver-compatible polymers or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos.
A bath containing a compound described in JP-A Nos. 2435, 1-102553 and 46-44446 may be used as the final bath of the photosensitive material. If necessary, this stabilizing bath also contains ammonium compounds, metal compounds such as Bi and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, deterrents, alkanolamines and surfactants. Agents can also be added.

Additives such as deterrents and stabilizing agents to be added to the water washing and stabilizing baths can 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 as described in, for example.

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 evaporation of the liquid and oxidation of the air. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,554,971 and the like, and in this specification, it is simply referred to as a roller transport type automatic developing machine. This automatic machine develops, fixes,
The method comprises four steps of washing and drying, and the method of the present invention does not exclude other steps (for example, a stopping 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-4-15534, JP-A-5-256256, and JP-A-5-289294 are disclosed. Such methods include heat roller drying and drying with far infrared rays, and a plurality of methods may be used in combination.

In the present invention, the term "substantially free of dihydroxybenzenes" means that substantially no dihydroxybenzenes are contained, or the term "substantially free of dihydroxybenzenes" means that no dihydroxybenzenes are contained at all or to such an extent that no allergic action or developing effect is exhibited. Say,
In the present invention, those not containing at all are preferable.

Next, a 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)

[0134]

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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,

[0136]

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A represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group; A ₁ and A ₂ are each a hydrogen atom, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group; Or an unsubstituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as radical as defined 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 a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. is there. 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, a benzene ring,
There are 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, and among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aliphatic group or aromatic group for 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, hydroxyl 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 A group having a quaternary ammonium structure, an alkyl or arylthio group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carboxyl group, a sulfo group, an acyl group, an alkoxy or aryloxycarbonyl group, a carbamoyl group, An amoyl group, a halogen atom, a cyano group, a phosphoric amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, 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), phosphorus An acid amide group (preferably having 1 to 30 carbon atoms);

In 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 aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or a sum of the Hammett's substituent constants).
A phenylsulfonyl group substituted so as to be -0.5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a Hammett substituent such that the sum of the substituent constants becomes -0.5 or more). A benzoyl group, or a straight-chain, 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 carboxyl group, a sulfonic acid; Groups))).
A ₁ and A ₂ are most preferably hydrogen atoms.

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 formula (I) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from. As a polymer,
For example, those described in JP-A-1-100530 can be mentioned.

R ₁ or R _{2 in} the formula (I) may have a group in which a group for enhancing the adsorption to the surface of the silver halide grain is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,45, such as alkylthio, arylthio, thiourea, heterocyclic thioamide, mercapto heterocyclic, and triazole groups.
9,347, JP-A-59-195233, JP-A-59-200231, and JP-A-59-20104.
No. 5, No. 59-201046, No. 59-20
Nos. 1047, 59-201048, 59
JP-201049-A, JP-A-61-170733, JP-A-61-270744, JP-A-62-948, JP-A-63-234244, and 63-234424
No. 5, JP-A-63-234246.

In the present invention, preferred hydrazine derivatives are those wherein R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureide 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.

More 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)

[0149]

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In the formula, 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 a hydrogen atom of an anionic group or hydrazine. Represents a nonionic group forming an internal hydrogen bond. General formula (3)

[0151]

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[0152] In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, Y ²
Represents an anionic group or a nonionic group which forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. General formula (4)

[0153]

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In the formula, X ³ represents a group that can be substituted on 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 an anion. Represents a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. m ³ is an integer from 0 to 4, and n ³ is 1 or 2. When n ³ is 1, R ³ 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 plural, for example, 2-furyl, 2-thienyl, 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 hydroxyl 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 preferable,
Sulfonamide groups and ureido groups are more preferred. When possible, these groups may be linked to each other to form a ring.

[0158] 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 -, - SO 2 - is the concatenation alone or in composed of a combination groups such as. L ¹ and L ² may be substituted with the groups described as substituents for R ¹ .
Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-buten-1,4-yl,
2-butyn-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 preferably an alkylene group, an alkenylene group, an alkynylene group, or an arylene group, and more preferably an alkylene group. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L The ² alkylene group, an arylene group, -NH- alkylene -, - O-alkylene -, - NH- arylene - are preferred, -NH- alkylene -, - O-alkylene - is more preferable.

The electron-withdrawing group of L ¹ includes 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.

Examples of the group capable of substituting on the benzene ring of X ³ and preferable ones include those described as the substituent 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 imino silver 5
And a 6-membered nitrogen-containing heterocycle (eg, benzotriazole). 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)

[0166]

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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)

[0168]

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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)

[0170]

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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.

[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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The hydrazine derivatives used in the present invention include, 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, No. 4,269,929, No. 4,2
Nos. 76,364, 4,278,748, 4,385,108, 4,459,3
Nos. 47, 4,478, 928, 4,
560,638, 4,686,167 and 4,912,016, 4,988,6
No. 04, No. 4,994, 365, No. 5,
041,355, 5,104,769, UK Patent No. 2,011,391B, European Patent Nos. 217,310, 301,799, 356. No. 898, JP-A-60-1797
No. 34, No. 61-170733, No. 61-2
Nos. 70744, 62-178246, 6
Nos. 2-270948 and 63-29751,
JP-A-63-32538, JP-A-63-104047, JP-A-63-121838, JP-A-63-12933.
No. 7, No. 63-223744, No. 63-23
Nos. 4244 and 63-234245 and 63
-234246, 63-294552,
JP-A-63-306438, JP-A-64-10233, JP-A-1-90439, JP-A-1-100530
Gazette, JP-A-1-105941 and JP-A-1-10594
No. 3, No. 1-276128, No. 1-2807
Nos. 47, 1-283548 and 1-283
No. 549, No. 1-285940, No. 2-25
No. 41, 2-77057, and 2-1395
No. 38, 2-196234 and 2-196
No. 235, No. 2-198440, No. 2-19
No. 8441, No. 2-198442, and No. 2-2200
No. 42, No. 2-219553, No. 2-221
954, JP-A-2-285342, JP-A-2-28
No. 5343, No. 2-289843, No. 2-3
JP-A Nos. 02750, 2-304550 and 3-
Nos. 37642, 3-54549 and 3-1
No. 25134, No. 3-184039, No. 3-
No. 240036, No. 3-240037, No. 3
JP-A-259240, JP-A-3-280038, JP-A-3-282536, JP-A-4-51143, JP-A-4-56842, JP-A-4-84134 and JP-A-2
JP-A-230233, JP-A-4-96053, JP-A-4-96053
Nos. 216544, 5-45761, 5
Nos. 455762 and 5-45763, 5-
No. 45765, No. 5-45765, No. 6-2
Those described in JP 89524 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, more preferably 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. In addition, by an already well-known emulsification dispersion method, dissolution is performed 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 emulsified and dispersed. 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 such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole 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 coating amount of gelatin as a binder is such that the total hydrophilic colloid layer on the side having the silver halide emulsion layer has a gelatin amount of 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. The total amount of gelatin in the hydrophilic colloid layer and the entire hydrophilic colloid layer on the opposite side is 6 g.
/ M ² or less, and 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 JP-A-3-131842. Syndiotactic polystyrene, polyethylene coated paper, etc. are used.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention. For example, those described in the corresponding places shown below can be preferably used. Item 1) The silver halide emulsion and the lower right column, page 20, page 20 of JP-A-2-97937, from its production method to the line 14 of the lower left column, page 21 of JP-A-2-97937 and JP-A-2-12236. 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 9, 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 on 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, furthermore, JP-A-1-237538 Thiosulfinic acid compounds described in the gazette. 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 US Pat. No. 4,956,257 and JP-A-1-18832. 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 From page 15, upper left column, line 15 to upper right column, line 6 of JP-A-2-103536. 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 and a fluorinated surfactant described in US Pat. No. 4,999,276.

[0200]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 A developer having the following formulation was prepared. As a comparative compound of the p-aminophenol derivative of the auxiliary developing solution, metol (N-methyl-p-aminophenol.1 / 2) was used.
Sulfate) WO was used. In addition, as a comparative compound of 3-pyrazolidones, dimezone S (1-phenol-4-methyl-4-hydroxymethyl-3-pyrazolidone) was used.

(Developer solution formulation) Sodium sulfite 10 g Potassium hydrogen carbonate 0.4 mol Potassium carbonate 0.15 mol Sodium carbonate monohydrate 0.25 mol Sodium erythorbate monohydrate 45 g Diethylene triamine pentaacetic acid 2 g Potassium bromide 2 g Trimercaptotriazine 0.1 g p-Aminophenol derivative (described in Table 10) 0.01 mol 3-pyrazolidones (described in Table 10) 0.01 mol The above components were dissolved in water to make 1 liter. Also, p
It adjusted with sulfuric acid or sodium hydroxide so that H might be 9.7.

Further, in order to simulate the photographic performance due to processing fatigue, the pH of the above developer was reduced by 0.4 to prepare a solution having a pH of 9.3, and the pH was adjusted to 9.7 and 9.3.
The performance was evaluated with two kinds of liquids.

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 the pH was adjusted to 4.85 with sulfuric acid or sodium hydroxide. The fixing solution used had the above formulation in Examples 1 to 4.

<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, 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. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per mole of silver, followed by chemical sensitization at 60 ° C. for optimum sensitivity.
Thereafter, 4-hydroxy-6-methyl-
150 mg of 1,3,3, a, 7-tetrazaindene was added, and 100 mg of compound (a) was further added as a preservative. Each of the obtained particles has an average particle size of 0.25 μm.
m, silver chlorobromide cubic grains having a silver chloride content of 70 mol%. (Coefficient of variation 10%)

[0206]

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Preparation of Coated Sample A polyethylene terephthalate film support having an undercoat of a moisture-proof layer containing vinylidene chloride was placed on a support from the support side.
Samples were prepared by applying the layers sequentially to form a UL layer, an EM layer, a PC layer, and an OC layer. 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 .

[0209] 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 30 mg / m ^{2 of} N-oleyl-N-methyltaurine sodium salt were added.
Added as applied. Next, the hydrazine derivative shown in Compound Example I-55 was added at 0.8 × 10 ⁻⁵ mol / m ² ,
200 mg / m of the polymer latex represented by (f)
^2, an average particle size of colloidal silica (Nissan Chemical [lines] Ltd. SNOWTEX C) a 200 mg / m ² of 0.02 [mu] m, further 1,2-bis hardener (vinylsulfonyl acetamide) ethane 200 mg / m ² added. The pH of the solution was adjusted to 5.65 using acetic acid. They were coated so that the coated silver amount was 2.5 g / m ² and the gelatin was 0.8 g / m ² .

[0210]

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

(OC layer) An amorphous SiO ₂ matting agent having a gelatin of 0.5 g / m ² and an average particle size of about 3.5 μm 4
0 mg / m ^2, colloidal silica (Nissan Chemical [lines] Ltd. Snowtex C) 0.1g / m ^2, polyacrylamides 100 mg / m ² and a sliding agent (h) 20mg / m ² and the following structural formula as a coating aid ( 5 mg / m ^{2 of the} fluorine surfactant shown in i) and 100 mg / m ² of sodium dodecylbenzenesulfonate were applied.

[0213]

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Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite side of the support. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 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], Mixture of dye [c] Dye [a] 70 mg / m ² Dye [b] 70 〃 Dye [c] 90 〃 sodium dodecylbenzenesulfonate 80 〃 dibenzyl-α-sulfosuccinate sodium salt 20 〃 1,2- Bis (vinylsulfonylacetamide) ethane 110 ナ ト リ ウ ム sodium acetate 40 リ チ ウ ム lithium perfluorooctanesulfonate 5 微粒子 fine particles of polymethyl methacrylate (average particle size 4.5 μm) 30 〃

[0215]

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(Evaluation of Photographic Performance) A sample was exposed to xenon flash light having an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 480 nm, and a Fuji Photo Film ( The drive gear was changed to a high-speed one using an FG-680AG automatic developing machine manufactured by KK-KK, developed at 35 ° C. for 15 seconds, and then fixed, washed with water and dried.

The sensitivity was determined from the exposure amount giving fog + density = 1.5 in the characteristic curve. The index (gamma) indicating the contrast of the image is fog + density 0.3 of the characteristic curve.
And a point of fog + density 3.0 was connected by a straight line, and the slope of this straight line was represented as a gamma value. That is, gamma =
(3.0-0.3) / [log (exposure to give a density of 3.0) -log (exposure to give a density of 0.3)], and the higher the gamma value, the harder the photographic characteristics. Is shown. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more.

The evaluation results are shown in Table 10. From the results shown in Table 10, the level of the combination of the p-aminophenol and the 3-pyrazolidone compound of the present invention is lower than that of the standard developing solution (pH = 9.7) and the low pH solution assuming a decrease in pH due to processing fatigue. (PH = 9.3), it is clear that high sensitivity and high gamma (high contrast) are obtained.

[0219]

[Table 10]

(Example 2) On one side of the same support as in Example 1, the conductive layer of Example 1 and a back layer having the following composition were simultaneously applied.

<Back Layer> Gelatin (Ca ⁺⁺ content: 3000 ppm) 2.0 g / m ² compound-3 mg / m ² compound-40 compound 40 compound 155 compound Compound 150 sodium dodecylbenzenesulfonate 7 〃 sodium dihexyl-α-sulfosuccinate 30 〃 1,2-bis (vinylsulfonylacetamido) 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 〃

[0222]

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[0223]

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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 is 0.5 × 10 ⁻⁵ mol / m ² , 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene is converted to 3
0 mg / m ² , 40 mg each of the following compounds
/ M ² , 10 mg / m ² , and 1,1-
Bis (vinylsulfonyl) methane was added in an amount of 55 mg / g of gelatin on the side having the emulsion layer, and a silver amount of 1.6 g / m ² ,
Gelatin was applied to 0.6 g / m ² .

[0225]

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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. This except that an emulsion was coated so as to become an emulsion layer the same as the emulsion layer first layer of silver amount 1.0 g / m ² gelatin 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 〃 [* Method for preparing fine particle dispersion of solid disperse dyes A and B] 63-197943. 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 the dye and zirconium oxide (ZrO)
₂ ) Beads (800 ml) (2 mm diameter) were added, the bottle was tightly closed, placed in a mill and the contents were ground for 4 days. The contents were added to a 12.5% aqueous gelatin solution (160 g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture is filtered and Zr
O ₂ beads were removed. In this state, the average particle size is about 0.3 μm, but still contains coarse particles. Therefore, the particles were classified by centrifugation to make the maximum particle size 1 μm or less.

[0228]

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The photographic performance was evaluated in the same manner as in Example 1 using the obtained sample. The developing solution was the same as that used in Example 1 except that the p-aminophenol derivative and 3-pyrazolidones were changed to those shown in Table 11. The same fixing solution as in Example 1 was used. The sample is Fuji Photo Film
Exposure was performed through an optical wedge with a name room printer FPA-800FX (using Fresnel lens) manufactured by Co., Ltd., and processing was performed at 35 ° C. for 20 seconds using an automatic developing machine AP560 manufactured by Fuji Photo Film Co., Ltd. . Table 1 shows the results
It is shown in FIG.

[0230]

[Table 11]

As is clear from the results shown in Table 11, the level of the developing solution of the present invention is high in sensitivity and high in contrast, and the preferable performance is maintained even in a low-activity developing solution having a lowered pH. I understand.

(Example 3) Emulsion A in Example 1 was replaced with Emulsion B shown below, and the sensitizing dye for the EM layer was changed from the following compound (S-
A sample was prepared in the same manner as in Example 1, except that 2.1 × 10 ^-4 mol per mol of silver was added instead of 3). [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 1.

[0233]

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The samples thus obtained were evaluated in the same manner as in Example 1. However, the evaluation of the photographic performance was performed by exposing with a xenon flash light having an emission time of 10 ⁻⁶ sec instead of the interference filter having a peak at 633 nm.
Used in place of those described in 2. Table 12 shows the results.

[0235]

[Table 12]

As is evident from the results shown in Table 12, the level of the developing solution of the present invention is high in sensitivity and high in contrast, and excellent performance is maintained even in a low-activity developing solution having a lowered pH. I understand.

Example 4 The sensitizing dye in the EM layer of Example 3 was replaced with the following compound (S-4), and 5.4 × / mol of silver was used.
10 ^-5 mol was added, and the stabilizer was 4,4'-bis- (4,6
-Dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt 350 mg / Ag1
Mole, 2,5-dimethyl-3-allyl-benzothiazole iodide salt 450 mg / Ag 1 mole, and the back layer was replaced with the back layer and the back protective layer having the following compositions, and the other conditions were the same as in Example 3. Thus, a sample was prepared.

[0238]

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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

[0240]

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The sample thus obtained was evaluated using the same developer as in Example 3. However, the evaluation of the photographic performance was performed in place of an interference filter having a peak at 780 nm. As a result, as in Example 3, low pH
Even with a developing solution, a laser scanner photosensitive material having extremely high sensitivity and high contrast was obtained.

[0242]

As described above, according to the present invention, in an ascorbic acid-based developer not using hydroquinone, a change in photographic performance is small, an improved developer, and an improved method of forming a high contrast image are provided. can do.

Claims (5)

[Claims] 1. An auxiliary developing agent which does not substantially contain dihydroxybenzenes, contains ascorbic acid and / or a derivative thereof as a developing agent, and exhibits superadditivity. A developer for a silver halide photographic light-sensitive material, comprising an aminophenol derivative represented by the formula: and a 3-pyrazolidone having a hydrophilic group. Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and represent a hydrogen atom or a substituent, and R ₅ and R ₆ are the same or different and represent an alkyl group, an aryl group, an aralkyl group Or a heterocyclic group.) 2. The developer according to claim 1, wherein the 3-pyrazolidones are 1-aryl-4,4-disubstituted-3-pyrazolidones having a hydrophilic group. 3. The developing solution according to claim 1, further comprising a silver stain inhibitor represented by the following general formula (G). Embedded image (Wherein D and E are the same or different and -CH =
Represents a group represented by —CR ₀ 、, or a nitrogen atom, wherein R ₀ represents a substituent, and L ₁ and L ₂
And L ₃ are the same or different and represent a hydrogen atom, a halogen atom, or a substituent bonded to the ring at any one of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. However, at least one of L ₁ , L ₂ , L ₃ and R ₀ represents one SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group). Incidentally, any nitrogen atom of the E and D, when the other is a group represented a group represented by or -CR ₀ = by -CH =, E is a nitrogen atom, moreover L ₂ and L ₃ Is not a hydroxyl group. ) 4. The developer has a bicarbonate concentration of 0.1 mol / liter or more and a total concentration of bicarbonate and carbonate of 0.1 mol / liter or more.
5 mol / l or more and pH 9.0 to 1
The developer according to claim 1, wherein the developer is 0.5. 5. A developing method comprising treating a silver halide photographic material containing a hydrazine derivative with the developer for a silver halide photographic material according to claim 1.