JPH10228082A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an improved development processing method which is less changed in photographic performance by subjecting a silver halide photographic sensitive material contg. specific compds. to development processing with a developer consisting of ascorbic acid, etc., as a developing agent and further contg. a specific aminophenol deriv. as a superadditive auxiliary developing agent. SOLUTION: This development processing method consists in subjecting the silver halide photographic sensitive material contg. the hydrazine deriv. selected from formula I, etc., and the compd. expressed by formula II to the development processing with the developer consisting of the ascorbic acid or its deriv. as the developing agent and further contg. the aminophenol deriv. as the superadditive auxiliary developing agent. In the formula I, Ra1 denotes an aliphat. group, etc.; Ga1 denotes a -CO- group, etc.; Ga2 denotes a mere coupler, -O- group, etc.; Ra2 denotes an aliphat. group, etc.,; Aa1 , Aa2 denote hydrogen atoms or acyl groups, etc. In the formula II, R3 denotes a hydrogen atom, alkyl group, etc.; Q denotes a mere coupler, sulfur atom, etc., as a bivalent group; R1 , R2 respectively denote hydrogen atoms, alkyl groups, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a silver halide photographic material. More specifically, the present invention relates to a method for developing 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 has an ultra-high contrast and little change in performance due to processing.

[0002]

2. Description of the Related Art Generally, hydroquinone has been used as a developing agent in a developing solution of a photosensitive material in view of cost and stability of photographic performance in many cases. However, because hydroquinone is allergic,
It was unfavorable in terms of material safety. For these reasons, developers using ascorbic acid as an alternative to hydroquinone are disclosed, for example, in JP-A-6-19069, JP-A-7-1114153, and JP-A-7-175176.

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. The activity of the nucleating agent decreases due to the decrease in the pH of the developer, and the contrast and D
The photographic performance becomes unstable due to a decrease in max. Therefore, it has been difficult to reduce the replenishment amount of the developer using ascorbic acid or a derivative thereof.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an improved developing solution and an improved processing method in an ascorbic acid-based developing solution which does not use hydroquinone, with little change in photographic performance. It is in.

[0005]

An object of the present invention is to provide a silver halide containing a hydrazine derivative selected from the following formulas (1), (2) and (3) and a compound represented by the following formula (X). The photographic light-sensitive material is substantially free of dihydroxybenzenes, uses ascorbic acid and / or a derivative thereof as a developing agent, and further includes an aminophenol derivative represented by the following general formula (M) as a superadditive auxiliary developing agent. The present invention has been attained by a development processing method characterized in that development processing is carried out with a developing solution containing the developer.

[0006]

DETAILED DESCRIPTION OF THE INVENTION First, the hydrazine derivative represented by the general formula (1) will be described. General formula (1)

[0007]

Embedded image

In the formula, R _a1 represents an aliphatic group or an aromatic group, and further has —O— (CH ₂ CH ₂₎ as a part of the substituent.
₂ O) _n- , -O- (CH ₂ CH (CH ₃ ) O) _n -or -O- (CH ₂ CH (OH) CH ₂ O) _n- (where n is an integer of 3 or more) Or a group containing a quaternary ammonium cation as a part of the substituent. G _a1 represents a —CO— group, a —COCO— group,
CS-group, -C (= NG _a2 R _a2 )-group, -SO- group,-
Represents an SO ₂ — group or a —P (O) (G _a2 R _a2 ) — group.
G _a2 is a mere bond, a —O— group, a —S— group or a —N
_{Represents a} (R _a2 ) — group, wherein R _a2 represents an aliphatic group, an aromatic group, or a hydrogen atom, and when a plurality of R _a2 are present in a molecule, they may be the same or different.

One of A _a1 and A _a2 is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group or an arylsulfonyl group. The general formula (1) will be described in more detail. In the general formula (1), the aliphatic group represented by R _a1 is preferably be of 1 to 30 carbon atoms, in particular straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group has a substituent.

In the general formula (1), the aromatic group represented by R _a1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. For example,
Benzene ring, naphthalene ring, pyridine ring, quinoline ring,
There is an isoquinoline ring and the like. Among them, those containing a benzene ring are preferred.

Particularly preferred as R _a1 is an aryl group. The aliphatic group or the aromatic group represented by R _a1 is substituted. Representative examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy Groups, a carbonamido group, a sulfonamido group, a carboxyl group, a phosphoric acid amide group and the like. Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (Preferably having 7 carbon atoms
To 30), an alkoxy group (preferably having 1 to carbon atoms)
30), a substituted amino group (preferably having 1 to 3 carbon atoms)
An amino group substituted with an alkyl group of 0), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having And a phosphoric acid amide group (preferably having 1 to 40 carbon atoms).

R_a1Aliphatic groups, aromatic groups or their
The substituent is -O- (CH_TwoCH_TwoO) _n-, -O- (CH
_TwoCH (CH_Three) O)_n-Or -O- (CH_TwoCH
(OH) CH_TwoO)_nContains-or 4
Contains quaternary ammonium cation. n is 3 or more
It is an integer, preferably an integer of 3 or more and 15 or less. R_a1Is
Preferably, the following general formula [H1], general formula [H2] or
Is represented by the general formula [H3] or the general formula [H4].

[0013]

Embedded image

In the formula, L _a1 and L _a2 represent a —CONR _a7 — group,
NR _a7 CONR _a8 -group, -SO ₂ NR _{a7 -group} or -N
R _a7 SO ₃ NR _a8 — represents a group, which may be the same or different. R _a7 and R _a8 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable. m is 0 or 1.

R_a3, R_a4, R_a5Is a divalent aliphatic group or
An aromatic group, preferably an alkylene group or an arylene
Or a group thereof and a -O- group, -CO- group, -S- group,-
SO- group, -SO_Two-Group, -NR_a9-Group (R_a9Is the general formula
R of (1), (2), (3) _a7Synonymous with)
This is a divalent group created by More preferred
Is R_a3Is an alkylene group having 1 to 10 carbon atoms or
And -S- group, -SO- group, -SO_Two-Combining groups
Is a divalent group formed by_a4, R_a5Has 6 to 2 carbon atoms
0 is an arylene group. Especially R_a5Is preferably a phenylene group
Good.

R _a3 , R _a4 and R _a5 may be substituted, and preferred substituents include those listed as substituents for R _a1 . In the general formulas [H1] and [H2], Z ₁ represents an atom group necessary for forming a nitrogen-containing aromatic ring. Z ₁ and pyridine ring Preferable examples of the nitrogen-containing heteroaromatic ring formed by the nitrogen atom, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, a pyrazole ring, pyrrole ring, oxazole ring, thiazole ring, and their benzo In addition to condensed rings, pteridine rings, naphthyridine rings and the like can be mentioned.

[0017] Formula [H1], [H2], X in [H3] ^- case of forming a counter anion or intramolecular salt represents a counter anion moiety. General formula [H2], [H
In 3] and [H4], R _a6 represents an aliphatic group or an aromatic group. Preferably, R _a6 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

The three R _a6 in the general formula [H3] may be the same or different, and may combine with each other to form a ring. Z ₁ and R _a6 may be substituted, and preferred substituents include those listed as substituents for R _a1 . L in the general formula [H4]
_a3 is -CH ₂ CH _{2 O-group, -CH 2 CH (CH 3)} O
—, Or —CH ₂ CH (OH) CH ₂ O—, wherein n is as defined in the general formula [H1].

In general formula (1), G _a1 represents —CO
- group, -SO ₂ - groups are preferred, -CO- group is most preferred. A _a1 and A _a2 are preferably hydrogen atoms.

In the general formula (1), the aliphatic group represented by R _a2 preferably has 1 to 30 carbon atoms, and particularly is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. . This alkyl group has a substituent. In the general formula (1), the aromatic group represented by R _a2 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group. For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring and the like. Among them, those containing a benzene ring are preferred. R _a2
Is particularly preferably an aryl group. In formula (1), the alkyl group represented by _Ra2 is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, including a benzene ring thing). As the substituent of R _a2 , R
_Examples of the substituent of _a1 include those mentioned above.

When G _a1 is a —CO— group, of the groups represented by R _a2 , preferred are a hydrogen atom and an alkyl group (for example, a methyl group, a methoxymethyl group, a phenoxymethyl group, a trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (for example, o-
A hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, a 2-hydroxymethylphenyl group), and particularly hydrogen. Atoms are preferred.

R _a2 may be substituted, and as the substituent, the substituents listed for R _a1 can be applied. or,
R _a2 disrupts the portion of G _a1 -R _a2 from the remainder molecule, -G
_a1 -R _a2 part of atoms may be such as to rise to cyclization reaction to form a cyclic structure containing, include those described in, for example, JP 63-29751 as examples .

R _a1 or R _{a2 in} the general formula (1) 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, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Further, as a polymer, for example, JP-A-1-1005
No. 30.

R _a1 or R _{a2 in} the general formula (1) may have a group in which a group that enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorptive group include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups such as U.S. Pat.
No. 4,459,347, JP-A-59-195,233.
Nos. 59-200, 231 and 59-201, 04
No. 5, 59-201, 046, 59-201, 0
No. 47, 59-201, 048, 59-201,
Nos. 049, 61-170, 733, 61-27
Nos. 0,744, 62-948, 63-234,2
No. 44, No. 63-234, No. 245, No. 63-234,
No. 246.

The compounds of the general formula (1) of the present invention are described, for example, in JP-A-61-213,847 and JP-A-62-260,153.
No. 4,684,604, Japanese Patent Application No. 63-8 / 1988.
No. 03, U.S. Pat. Nos. 3,379,529 and 3,62.
0,746, 4,377,634, 4,33
2,878, JP-A-49-129,536 and 56
153,336, 56-153,342, U.S. Pat. Nos. 4,988,604 and 4,994,365.

The compounds represented by the general formula (1) used in the present invention are listed below, but the present invention is not limited thereto.

[0027]

Embedded image

[0028]

Embedded image

Next, the compound represented by formula (2) will be described in more detail. General formula (2)

[0030]

Embedded image

R _b1 represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G _b1 is -CO-
Group, -SO ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or -P (O) (R
_b3) - represents a group, R _b2 is a substituted alkyl group in which the carbon atom substituted by G _b1 is substituted with at least one electron withdrawing group. R _b3 represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group.

Next, the compound represented by formula (2) will be described in more detail. In the general formula (2), R
_The aliphatic group represented by _b1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. R _b1
The aromatic group represented by is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group.

As the heterocyclic ring for R _b1 , N, O, or S
A 3- to 10-membered saturated or unsaturated hetero ring containing at least one atom, which may be a single ring or may form a condensed ring with another aromatic or hetero ring . The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, and a benzothiazolyl group. Are preferred.

Preferred as R _b1 are an aromatic group, a nitrogen-containing heterocyclic ring and a group represented by formula (b). General formula (b)

[0035]

Embedded image

(Where X is_FiveIs an aromatic group or a nitrogen-containing complex
A ring group;_b ¹~ R_b ^FourAre hydrogen and halogen
X represents an alkyl atom or an alkyl group;_FiveAnd R_b ¹
~ R _b ^FourMay have a substituent if possible.
r and s represent 0 or 1. ) R_b1Is more preferably an aromatic group, especially an aryl group.
Preferred is a thiol group.

R _b1 may be substituted with a substituent. Examples of the substituent include, for example, an alkyl group, an aralkyl group,
Alkenyl, alkynyl, alkoxy, aryl, substituted amino, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen, cyano, sulfo and Carboxyl group, alkyl and aryloxycarbonyl group, acyl group,
In addition to an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, a nitro group, an alkylthio group, an arylthio group and the like, a group represented by the following general formula (c) can be mentioned.

Formula (c)

[0039]

Embedded image

In the formula (c), Y_cIs -CO-, -SO
_Two-, -P (O) (R_c ^Three)-(Wherein, R _c ^ThreeIs alkoki
Represents a silyl group or an aryloxy group. ) Or-
OP (O) (R_c ^Three)-, L is a single bond, -O-,
-S- or -NR_c ^Four-(Where R_c ^FourIs a hydrogen atom,
Represents an alkyl group or an aryl group. ). R_c ¹
And R_c ^TwoRepresents a hydrogen atom, an aliphatic group, an aromatic group or
Represents a ring group, which may be the same or different, and
They may be bonded to each other to form a ring.

R _b1 may include one or more of the general formula (c). In the general formula (c), the aliphatic group represented by R _c ¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _c ¹ is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group. The hetero ring of R _c ¹ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, and S atoms, which may be a single ring, May form a condensed ring with the aromatic or heterocyclic ring of the above. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a benzothiazolyl group. Are preferred.

R _c ¹ may be substituted with a substituent.
Examples of the substituent include the following. These groups may be further substituted. For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Examples include a sulfo group, a carboxyl group, an alkyl and aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a nitro group, an alkylthio group, and an arylthio group.

When possible, these groups may be linked to each other to form a ring. The aliphatic group represented by R _c ² in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _c ² is a monocyclic or bicyclic aryl group, such as a phenyl group.

R _c ² may be substituted with a substituent.
Examples of the substituent include those listed as R _c ¹ and the substituent in the general formula (c). Further, if possible, R _c ¹ and R _c ² may be linked to each other to form a ring. R _c ² is more preferably a hydrogen atom. The Y _c in the general formula (c) -CO -, - SO 2 - is particularly preferred, L is a single bond and -NR _c ⁴ - are preferred.

The aliphatic group represented by R _c ⁴ in the general formula (c) is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c ⁴ is a monocyclic or bicyclic aryl group, such as a phenyl group. R _c ⁴ may be substituted with a substituent. Examples of the substituent include those listed as R _c ¹ and the substituent in the general formula (c).

R _c ⁴ is more preferably a hydrogen atom.
As G _{b1 in the} general formula (2), a —CO— group is most preferable. R _{b2 in the} general formula (2) represents a substituted alkyl group in which a carbon atom substituted by G _b1 is substituted with at least one electron withdrawing group, preferably two electron withdrawing groups, and particularly preferably three electron withdrawing groups. Represents a substituted alkyl group substituted with a suction group.

The electron-withdrawing group for substituting the carbon atom substituted with G _b1 of R _b2 preferably has an δ _p value of 0.2 or more and a δ _m value of 0.3 or more, for example, halogen, cyano, nitro , Nitroso, polyhaloalkyl, polyhaloaryl,
Alkyl or arylcarbonyl group, formyl group,
Alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate ester group, phosphone It represents an acid amide group, an arylazo group, an amidino group, an ammonio group, a sulfonyl group, or an electron-deficient heterocyclic group.

R _{b2 in the} general formula (2) particularly preferably represents a trifluoromethyl group. R _b1 and R _b2 of the general formula (2)
May have incorporated therein a ballast group or a polymer commonly used in immobile photographic additives such as couplers. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. As a polymer, for example,
No. 100530.

R _b1 and R _{b2 in} the general formula (2) may have a group in which a group that enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include thiourea group, heterocyclic thioamide group, mercapto heterocyclic group, triazole group and the like, US Pat. Nos. 4,385,108 and 4,459,347, and JP-A-59-195,233.
Nos. 59-200, 231 and 59-201, 04
No. 5, 59-201, 046, 59-201, 0
No. 47, 59-201, 048, 59-201,
Nos. 049, 61-170, 733, 61-27
Nos. 0,744, 62-948, 63-234,2
No. 44, No. 63-234, No. 245, No. 63-234,
No. 246.

The compounds represented by the general formula (2) used in the present invention are listed below, but the present invention is not limited thereto.

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

Next, the compound represented by formula (3) will be described in detail.

[0061]

Embedded image

In the formula, A _c1 and A _c2 are each a hydrogen atom or one is a hydrogen atom and the other is a sulfinic acid residue or an acyl group, and R _c1 is an aliphatic group, an aromatic group or a heterocyclic group. , R _c2 represents a hydrogen atom, an alkyl group, an aryl group,
G _c1 represents an alkoxy group, an aryloxy group, or an amino group, and G _c1 represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group. Here, at least one of R _c1 and R _c2 has an adsorption promoting group for silver halide.

In the general formula (3), the aliphatic group represented by R _c1 is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c1 is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group. The heterocyclic ring of R _c1 is a 3-10 negatively saturated or unsaturated heterocyclic ring containing at least one of N, O, and S atoms, which may be a single ring, May form a condensed ring with the aromatic or heterocyclic ring of the above. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, for example, pyridine, imidazolyl, quinolinyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolinyl, thiazolyl, benzothiazolyl, and the like. preferable.

R _c2 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted. For example, an alkyl group,
Aralkyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, aryl, alkylthio, arylthio, sulfonyl, sulfinyl , A hydroxy group, a halogen atom, a cyano group, a sulfo group and a carboxyl group.

When possible, these groups may be linked to each other to form a ring. Preferred as R _c1 is an aromatic group, more preferably an aryl group. Among the groups represented by R _c2 , when G _c1 is a carbonyl group, a hydrogen atom or an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl) is preferable. 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, a 4-methanesulfonylphenyl group), and the like. Particularly, a hydrogen atom is preferable.

When G _c1 is a sulfonyl group, R _c2
Is preferably an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxyphenylmethyl group), an aryl group (eg, a phenyl group), or a substituted amino group (eg, a dimethylamino group). G _c1
Is a sulfoxy group, preferred R _c2 is a cyanobenzyl group, a methylthiobenzyl group, and the like. When G _c1 is a phosphoryl group, R _c2 is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group. Phenoxy groups are particularly preferred.

When G _c1 is an N-substituted or unsubstituted iminomethylene group, preferred R _c2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. As the substituent of R _{c2, in addition to} the unsubstituted groups listed for R _c1 , for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, and the like can also be applied.

These substituents are further substituted with these substituents.
It may be replaced. Where possible, these groups
A mutually connected ring may be formed. R_c1Or R_c2
The group capable of promoting adsorption to silver halide which can be substituted with_c1− (L
_c1) _qIt can be represented by-. Where X_c1Is halogenated
A group that promotes adsorption to silver;_c1Is a divalent linking group.
q is 0 or 1.

Preferred examples of the group for promoting adsorption to silver halide represented by X _c1 include a thioamide group, a mercapto group, a group having a disulfide bond, and a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption promoting group represented by X _c1 is a divalent group represented by -CS-amino-, and may be a part of a ring structure or may be an acyclic thioamide group. . Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat. Nos. 4,030,925, 4,031,127, 4,080,207, 4,245,037, 4,255,511, 4,266,013 and 4,276,364,
And "Research Disclosure" (Rese
Arch Disclosure, Vol.
15162 (November 1976), and Volume 176 N
o. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, a thioureido group, a thiourethane group, and a dithiocarbamate group. Specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione, Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,3
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, and the like. It may be substituted.

The mercapto group of X _c1 is an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (—S
When the carbon atom to which the H group is bonded is a nitrogen atom which is the same as a cyclic thioamide group having a tautomeric relationship with the nitrogen atom, specific examples of this group are the same as those listed above.) Is mentioned. _Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by X _c1 include a 5- or 6-membered nitrogen-containing heterocyclic ring composed of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like. These may be further substituted with a suitable substituent.

_Examples of the substituent include those described as the substituent for R _c1 . Among those represented by X _c1 , preferred are thioamide groups (ie, mercapto-substituted nitrogen-containing heterocycles such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole) Group, 2-mercapto-
This is a case of a 1,3,4-oxadiazole group, a 2-mercaptobenzoxazole group or the like, or a nitrogen-containing heterocyclic group (eg, a benzotriazole group, a benzimidazole group, an indazole group or the like).

Further, two or more X _c1- (L _c1 ) _q -groups may be substituted, and may be the same or different. The divalent linking group represented by L _c1 is an atom or an atomic group containing at least one of C, N, S, and O. In particular,
For example, an alkylene group, alkenylene group, alkynylene group, arylene group, -O-, -S-, -NH-, -N
=, - CO -, - SO 2 - ( may have these groups the substituents), it is made of a single or a combination thereof and the like.

These may be further substituted with a suitable substituent. _Examples of the substituent include those described as the substituent of R _c1 . A _c1 and A _c2 represent a hydrogen atom and a carbon number of 20
The following alkylsulfonyl and arylsulfonyl groups (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more), an acyl group having 20 or less carbon atoms (preferably Is a benzoyl group, or a benzoyl group substituted such that the sum of Hammett's substituent constants is -0.5 or more,
Alternatively, a straight-chain, branched or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group). And the sulfinic acid residues represented by A _c1 and A _c2 specifically represent those described in US Pat. No. 4,478,928.

A _c1 and A _c2 are most preferably hydrogen atoms. As G _{c1 in the} general formula (3), a carbonyl group is most preferable. Among those represented by the general formula (3), preferred ones can be represented by the general formula (3-a). General formula (3-a)

[0076]

Embedded image

In the formula, R ′ _c1 is obtained by removing one hydrogen atom from R _{c1 in the} general formula (3). Here, R ′ _c1 , R _c2
Alternatively, at least one of L _{c1 has} a group or an amino group that can be dissociated into an anion having a pKa of 6 or more. pKa
Among the groups capable of dissociating into 6 or more anions, preferred are substituents capable of dissociating into pKa 8 to 13 anions, which are hardly dissociated in a neutral or weakly acidic medium and are alkaline aqueous solutions such as a developer. (Preferably pH 10.5-
What is necessary is just to dissociate sufficiently in 12.3), and there is no need to be a specific one.

For example, a hydroxyl group, a group represented by —SO ₂ NH—, a hydroxyimino group, an active methylene group, or an active methine group (for example, —CH ₂ COO—, —CH ₂ CO—,
—CH (CN) —COO—) and the like.
The amino group may be primary, secondary or tertiary, and preferably has a conjugate acid having a pKa of 6.0 or more.

A _c1 , A _c2 , G _c1 , R _c2 , L _c1 , X _c1 and q have the same _meanings as those described in the general formula (3). Among the compounds represented by the general formula (3), particularly preferable ones are represented by the general formula (3-b). General formula (3-b)

[0080]

Embedded image

In the formula, L _c2 has the same meaning as L _{c1 in} formulas (3) and (3-a), and Y _c1 has the same meaning as that of R _{c1 in} formula (3). And q represents 0 or 1, l represents 0, 1, or 2, and when l is 2, Y _c1
May be the same or different. A _c1 , A _c2 , G _c1 , R _c2 , L
_c1 and _Xc1 have the same _meanings as those described in the general formulas (3) and (3-a).

Further, preferably, X _c1- (L _c2 ) _q -S
O ₂ NH— is substituted at the p-position to the hydrazino group. The compound of the general formula (3) is disclosed in JP-A-56-6784.
3, ibid. 60-179733, Japanese Patent Application No. 60-78182,
Japanese Patent Application No. 60-111936, Japanese Patent Application No. 61-11503
6, etc. can be synthesized.

Specific examples of the compound represented by the general formula (3) are described below. However, the present invention is not limited to the following compounds.

[0084]

Embedded image

[0085]

Embedded image

In the present invention, the hydrazine compound is preferably added in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and more preferably 1 × 1 ^-6 mol per mol of silver halide.
The range is preferably from 0 ^-5 mol to 2 × 10 ^-2 mol. The hydrazine compound of the present invention can be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformylamide, dimethyl sulfoxide, and methyl cellosolve.

Also, by an already well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexane is used to dissolve and mechanically dissolve. An emulsified dispersion can be prepared and used. Alternatively, a hydrazine compound powder 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. Next, the nucleation accelerator represented by the general formula (X) used in the present invention will be described.

[0088]

Embedded image

In the general formula [X], R ₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residue. Q is a mere bond, a sulfur or selenium atom as a divalent group,
An oxygen atom as a divalent group, a disulfide group (-SS
−) NR ₄ ,

[0090]

Embedded image

Or NR ₄ CS. Where R ₄ is R
Synonymous with ₃ . R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue or an amino group. ₅ between R ₃ and R ₄ , R ₁ and R ₂ , or R ₁ and R ₃
A 6-membered or 6-membered heterocyclic ring may be formed. However, when a 5- or 6-membered heterocyclic ring is formed between R ₁ and R ₃ ,
Neither ₂ nor R ₄ represents a hydrogen atom.
Further, among the hetero rings formed between R ₁ and R ₂ , the rhodanine ring is excluded.

The alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ have 1 to 20 carbon atoms and include those substituted. Examples of the substituent include a halogen atom (eg, a chlorine atom), a cyano group, a carboxy group, a hydroxy group, an acyloxy group having 2 to 6 carbon atoms (eg, an acetoxy group), and an alkoxycarbonyl group having 2 to 22 carbon atoms (eg, an ethoxycarbonyl group). Butoxycarbonyl group, aryl group (monocyclic or bicyclic and may be substituted, for example, phenyl group, tolyl group, p-sulfophenyl group), etc. Examples of advantageous alkyl groups are as follows. A: methyl group, ethyl group, propyl group (n- or i-), butyl group (n-, i- or t-), amyl (may have a branch).
The same applies hereinafter), hexyl group, octyl group, dodecyl group, pentadecyl group, heptadecyl group, chloromethyl group, 2-
Chloroethyl group, 2-cyanoethyl group, carboxymethyl group, 2-carboxyethyl group, 2-hydroxyethyl group, 2-acetoxyethyl group, acetoxyethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-methoxycarbonylethyl group , Benzyl group, o
-Nitrobenzyl group, p-sulfobenzyl group, R ₁ , R
_The aryl group represented by ₂ , R ₃ and R ₄ is a monocyclic or bicyclic, preferably monocyclic aryl group, including substituted ones. The substituent has, for example, 1 to 20 carbon atoms.
(E.g., methyl, ethyl, nonyl), alkoxy having 1 to 20 carbon atoms (e.g., methoxy, ethoxy), hydroxy, halogen (e.g., chlorine, carbon), carboxy, sulfo There are groups. Specific examples of the aryl group include a phenyl group, p-
Tolyl, p-methoxyphenyl, p-hydroxyphenyl, p-chlorophenyl, 2,5-dichlorophenyl, p-carboxyphenyl, o-carboxyphenyl, 4-sulfophenyl, 2,4-diphenyl A sulfophenyl group, a 2,5-disulfophenyl group, a 3-sulfophenyl group, and a 3,5 disulfophenyl group.

The heterocyclic residue of R ₁ , R ₂ , R ₃ or R ₄ is preferably a 5- to 7-membered heterocyclic residue such as pyrrolidine, pyrrole, tetrahydrofuran, furan,
Tetrahydrothiophene, thiophene, thiazole, thiadiazoline, oxazole, oxazoline, imidazole, imidazoline, triazole, tetrazole, thiadiazole, oxadiazole, benzothiazole,
Examples include benzoxazole, benzimidazole, morpholine, pyridine, quinoline, quinoxaline, azepine and the like. These may be substituted with the groups described as substituents for R ₁ to R ₃ .

The 5- or 6-membered ring formed by R ₃ and R ₄ or R ₁ and R ₂ includes, for example, a piperidine ring, a piperazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring and a triazole ring. Preferred are a piperidine ring, a pyrrole ring, a piperazine ring and a morpholine ring. The 5- or 6-membered hetero ring formed between R ₁ and R ₃ is, for example, a thiazoline ring, a thiazolidine ring, a selenazoline ring, an oxazoline ring, an oxazolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazoline ring, a pyrazolidine ring, 1,3,4-thiadiazoline ring, 1,3,4-
Examples include an oxadiazoline ring, a 1,3,4-triazoline ring, a tetrazoline ring, a thiohydantoin ring, a dihydropyridine ring, a dihydropyrimidine ring, and a dihydrotriazine ring. These heterocycles also include those having a 5- to 7-membered carbon ring or heterocycle bonded thereto.

That is, a benzothiazoline nucleus, a naphthothiazoline nucleus, a dihydronaphthothiazoline nucleus, a tetrahydrobenzothiazoline nucleus and the like for a thiazole ring; a benzoselenazoline nucleus and the like for a selenazole ring; a benzoxazoline nucleus and a naphthooxazoline nucleus for an oxazoline ring; For the benzimidazoline nucleus, dihydroimidazolopyrimidine nucleus, etc .; for the triazoline ring, dihydrotriazolopyridine nucleus, dihydrotriazolopyrimidine nucleus, etc .; for the pyrazoline ring, dihydropyrazolopyridine nucleus, dihydropyrazolopyrimidine nucleus, etc .; for the dihydropyrimidine ring, dihydropyrimidine nucleus. Zolopyrimidine nucleus, dihydropyrrolopyrimidine nucleus,
A dihydrotriazolopyrimidine nucleus and the like are included.

Various substituents can be provided on carbon atoms of these heterocyclic nuclei. For example, carbon number 1
20 alkyl groups (for example, methyl group, ethyl group, n-
Butyl group, t-butyl group, heptyl group, heptadecyl group), C1-C20 alkoxy group (for example, methoxy group, ethoxy group, dodecyloxy group, heptadecyloxy group), C1-C20 alkylthio group ( For example, methylthio group, ethylthio group, butylthio group), hydroxy group, mercapto group, amino group (including not only unsubstituted but also substituted amino groups, such as dimethylamino group, methylamino group, diethylamino group, butylamino group, benzylamino group) An alkyl-substituted amino group such as a group; an aryl-substituted amino group such as an anilino group or a diphenylamino group;
Acylamino groups such as acetylamino group, cabilloylamino group, benzoylamino group, methylsulfonylamino group, benzenesulfonylamino group and p-toluenesulfonylamino group; thioamide groups such as acetylthioamide group and propionylthioamide group), aryl group (E.g., phenyl, naphthyl, tolyl), alkenyl having 2 to 20 carbons (e.g., allyl and methallyl), aralkyl having 1 to 4 carbons in the alkyl portion (e.g., benzyl, phenethyl, halogen) (Eg, chlorine, bromine), cyano group, carboxy group, sulfo group, carbamoyl group (including substituted carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group), thioca Bamoyl group (including those substituted, for example, thiocarbamoyl group, methylthiocarbamoyl group, dimethylthiocarbamoyl group, ethylthiocarbamoyl group, phenylthiocarbamoyl group, alkoxycarbonyl group having 2 to 22 carbon atoms), for example, methoxycarbonyl group , An ethoxycarbonyl group, a butoxycarbonyl group), an aryloxycarbonyl group (eg, a phenoxycarbonyl group), an alkylcarbonyl group having 2 to 22 carbon atoms (eg, an acetyl group, a cabilloyl group), an oxygen atom, and the like. The alkyl group further includes a carboxy group, a sulfo group, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an acyloxy group (for example, an acetoxy group), an aryl group (for example, a phenyl group, and a nitrophenyl group which may be substituted. ) May be substituted.

The substituents on the substitutable nitrogen atom in the heterocyclic chain may have the substituents as described for R _{1 to} R ₄ . When Q represents a NR _4, alkyl group represented by R ₄ include those having 1 to 20 carbon atoms, substituted. Examples of the substituent for the alkyl group include a halogen atom, a cyano group, a carboxy group, a sulfo group, a sulfato group, a phospho group, a carbamoyl group,
An aminosulfonyl group, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group; including substituted ones, for example, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms ( For example, a methoxy group, an ethoxy group, a propoxy group), an acyloxy group having 2 to 8 carbon atoms (for example, acetoxy group, propionoxy group), a sulfo group, a sulfoalkoxy group having 1 to 6 carbon atoms (for example, 2-sulfoethoxy group, 3 -Sulfopropoxy group), etc.), having 2 carbon atoms
To 22 acyloxy groups (eg, acetoxy group, propionoxy group), alkenyl group having 2 to 22 carbon atoms (eg, vinyl group), alkoxycarbonyl group having 2 to 22 carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group) Group, dodecyloxycarbonyl group), aryl group (monocyclic or bicyclic, which may have a substituent, for example, phenyl group, p-sulfophenyl group), heterocyclic residue [for example, thiazole ring residue, oxazole Ring residue, imidazole ring residue, thiadiazole ring residue, oxadiazole ring residue, triazole ring residue, tetrazole ring residue, pyrimidine ring residue, etc.
Especially

[0098]

Embedded image

(In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered ring. Examples of the ring formed by Z are the same as the heterocyclic ring formed by R ₁ and R _2. The group represented by the following is preferable. 〕and so on. Specific examples of the alkyl group represented by R ₂ are as follows: methyl group, ethyl group, propyl group (n
-Or i-), a butyl group (n-, sec-, i- or t
-), N-hexyl group, dodecyl group, heptadecyl group,
Chloromethyl group, 2-chloroethyl group, 2-cyanoethyl group, carboxymethyl group, 2-carboxyethyl group,
2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-sulfatoethyl group, 2-phosphoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 3 -Methoxypropyl group, 2-ethoxyethyl group,
2- (2-hydroxyethoxy) ethyl group, 2- (2-
Acetoxyethoxy) ethyl group, 2- (2-sulfoethoxy) ethyl group, 2- (2- (3-sulfopropoxy)
Ethoxy) ethyl group, 2-acetoxyethyl group, 4-propionyloxybutyl group, allyl group, methoxycarbonylmethyl group, 2- (methoxycarbonyl) ethyl group,
4- (ethoxycarbonyl) butyl group, butoxycarbonylmethyl group, benzyl group, 2-phenylethyl group, p
-A sulfobenzyl group, a 2- (2-mercapto-3-benzimidazolyl) ethyl group.

Among the compounds represented by the formula (X), more preferred compounds are represented by the following formula (Xa).

[0101]

Embedded image

Q¹To complete a 5- or 6-membered heterocycle
The required atomic group is shown. R_FourIs the same as in the general formula [X].
Righteous. Where R_FourDoes not represent a hydrogen atom
Q ¹Adjacent to the thioketo group in the group of atoms
Atoms are not bonded to hydrogen atoms. Q¹Completed in
Specific examples of the heterocyclic ring represented by₁And R_TwoFormed by
Is the same as that shown for the heterocycle.

The heterocycle completed by Q ¹ has a divalent substituent such as an oxo group (＝ O), a thioxo group (＝ S),
An ethylidene group (CH ₃ CH =), a substituted ethylidene group (for example, a benzoxazolylideneethylidene group, a thiazolinylideneethylidene group, a pyridylideneethylidene group, a quinolylidenethylidene group, etc.), a heterocyclic divalent residue (for example, A benzoxazolylidene group, a benzothiazolylidene group, a thiazolinylidene group, a pyridylidene group, a quinolilidene group, or the like.

Compounds represented by formula (X) {including formula (Xa)} are described in, for example, JP-B-48-34169 (Compounds Nos. 1 to 8, 31, 32), Pharmaceutical Journal 7
4 1365 to 1369 (1954) (Compound Example-No.
9), Seinstein XIII, 394, IV12
1 (Compound Examples-Nos. 12 and 13), JP-B-47-18
008 (Compound Example-No. 19), JP-B-48-341
88 (Compound Example-No. 25) and the like.

Hereinafter, the formula (X) used in the present invention ｛the formula (X
Specific examples of the thioamide compound as a nucleation accelerator represented by｝ including a) are shown below, but the present invention is not limited thereto.

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

When the compound represented by the general formula (X) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-light-sensitive hydrophilic colloid layers (for example, a protective layer) , An intermediate layer, a filter layer, an antihalation layer, etc.). Specifically, a hydrophilic colloid solution is used as an aqueous solution when the compound used is water-soluble, or as a solution of an organic solvent miscible with water such as alcohols, esters, and ketones when the compound is poorly water-soluble. May be added. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but is preferably added after chemical ripening and before coating. Particularly, it is preferable to add it to a coating solution prepared for coating. The addition amount is preferably 1 × 10 ⁻⁶ mol to 5 × 10 ⁻² mol per mol of silver halide, more preferably 3 × 10 ⁻⁵ to 1 × 10 ⁻² mol.

Next, the compound of the formula (M) will be described. As the p-aminophenol used in the present invention, a compound represented by the following formula (M) is preferable. General formula (M)

[0113]

Embedded image

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

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

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

The aryl group is an aryl group having 6 to 10 carbon atoms, such as phenyl, naphthyl and p-methoxyphenyl. The aralkyl group has 7 to 7 carbon atoms.
And 10 aralkyl groups such as benzyl.
The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. One or more may be used, for example, 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 may have 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, such as ureide, methylureide, and N, N-dimethylureide. The acyl group has 1 to 1 carbon atoms.
An acyl group having 0, preferably 1 to 6 carbon atoms, such as acetyl and benzoyl. The oxycarbonyl group is an oxycarbonyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. The carbamoyl group has 1 to 1 carbon atoms.
0, preferably a carbamoyl group having 1 to 6 carbon atoms such as carbamoyl, N, N-dimethylcarbamoyl, N
-Ethylcarbamoyl. The sulfonyl group is a sulfonyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and ethanesulfonyl. The sulfinyl group is a sulfinyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfinyl. The sulfamoyl group has 0 to 0 carbon atoms.
10, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl and dimethylsulfamoyl.

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

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

[0121]

Embedded image

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

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

Further preferred compounds in the formula (MB) are those in which 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,
A compound in which R ₅₅ and R ₆₆ are alkyl groups. here,
Alkyl group, alkoxy group, carbonamido group, sulfonamido group, sulfamoylamino group, ureido group,
Also included are those substituted by a hydroxy group, an alkoxy group, an amino group, an alkylamino group, an ammonium group, a carbonamido group, a sulfonamido group, or a ureido group.

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

The most preferred compound is represented by the general formula (M
In B), R ₁₁ is a hydrogen atom, and R ₂₂ has 1 carbon atom.
To 3 alkyl group, an alkoxy group having 1 to 4 carbon atoms, a carbonamido group having 1 to 3 carbon atoms, a sulfonamido group having 1 to 3 carbon atoms, a ureido group having 1 to 3 carbon atoms, R _55, R
A compound in which ₆₆ is a methyl group. Here, the alkyl group and the alkoxy group represented by R ₂₂ include those substituted with a hydroxy group or an alkoxy group.

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

[0128]

[Table 1]

[0129]

[Table 2]

[0130]

[Table 3]

[0131]

[Table 4]

[0132]

[Table 5]

[0133]

[Table 6]

[0134]

[Table 7]

[0135]

[Table 8]

[0136]

[Table 9]

The compound represented by the general formula (M) 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.

In the present invention, the term "substantially free of dihydroxybenzenes" means that substantially no dihydroxybenzenes are contained, or "substantially free of dihydroxybenzenes" means that they do not contain allergic action or developing effect. Say,
In the present invention, those not containing at all are preferable.

Next, the compound represented by formula (G) will be described. Compound represented by general formula (G)

[0140]

Embedded image

In the general formula (G), D and E represent -CH =
Group, -CR₀= Represents a group or a nitrogen atom, where R₀Is
Represents a substituent. L₁, L_Two, L_ThreeIs a hydrogen atom, a halogen atom
Or a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom,
Represents any substituent attached to the ring at any of the phosphorus atoms
Then L₁~ L_ThreeMay be the same or different. However
L₁, L_Two, L_Three, And R₁At least one of -SM
Group (M is an alkali metal atom, hydrogen atom, ammonium
Group). E and D are one nitrogen atom and one charcoal
When representing an elementary atom, E is a nitrogen atom and D is a carbon atom (-C
H = group or -CR ₀= Group), in which case L_TwoAnd
And L_ThreeDoes not represent a hydroxy group.

Next, the compound of the general formula (G) will be described in detail.
This will be described in detail. In the general formula (G), D and E are -CH
= Group, -CR₀= Represents a group or a nitrogen atom, where R₀
Represents a substituent. L₁, L_Two, L_ThreeIs hydrogen atom, halogen
Atom, or carbon atom, nitrogen atom, oxygen atom, sulfur atom
Any substituent attached to the ring at either the
Represents, L₁~ L_ThreeMay be the same or different. Where L
₁, L_Two, L_Three, And R₁At least one of the -SM group
(M is an alkali metal atom, hydrogen atom, ammonium group)
Represents E and D are one nitrogen atom and one carbon source
When E is a nitrogen atom, D is a carbon atom and D is a carbon atom (-CH =
Group or -CR ₀= Group), in which case L_TwoAnd L
_ThreeDoes not represent a hydroxy group. L₁, L_Two, L_ThreeIn table
Optional substituents and R₀As a substituent represented by
Is, specifically, a halogen atom (a fluorine atom,
Atom, bromine atom or iodine atom), alkyl group (aral
Including a kill group, a cycloalkyl group, an active methine group),
Alkenyl group, alkynyl group, aryl group, heterocyclic group,
Heterocyclic groups containing a quaternized nitrogen atom (eg
Dinio group), acyl group, alkoxycarbonyl group, ant
Oxycarbonyl group, carbamoyl group, carboxy
Group or salt thereof, sulfonylcarbamoyl group, acylca
Rubamoyl group, sulfamoylcarbamoyl group, carb
Zoyl group, oxalyl group, oxamoyl group, cyano group,
Thiocarbamoyl, hydroxy, alkoxy (d
Repeating a Tyleneoxy or Propyleneoxy unit
), Aryloxy group, heterocyclic oxo
Si group, acyloxy group, (alkoxy or aryl
Oxy) carbonyloxy group, carbamoyloxy group,
Sulfonyloxy group, amino group, (alkyl, aryl
Or heterocycle) amino group, hydroxyamino group, N-
Substituted saturated or unsaturated nitrogen-containing heterocyclic group, acyl
Amino group, sulfonamide group, ureido group, thiourei
Group, imide group, (alkoxy or aryloxy
B) carbonylamino group, sulfamoylamino group,
Micarbazide group, thiosemicarbazide group, hydrazino
Groups, quaternary ammonium groups, oxamoylamino groups, (A
Alkyl or aryl) sulfonyluureido, reed
Luureido group, acylsulfamoylamino group, nitro
Group, mercapto group, (alkyl, aryl or hetero
Ring) thio group, (alkyl or aryl) sulfonyl
Group, (alkyl or aryl) sulfinyl group, sulf
Ho group or its salt, sulfamoyl group, acyl sulfa
Moyl group, sulfonylsulfamoyl group or a salt thereof,
Groups containing phosphoric acid amide or phosphoric ester structure, etc.
Is raised. These substituents are further substituted with
May be substituted with a group. E is a nitrogen atom and D is
Carbon atom (-CH = group or -CR₀= Group)
Hour, L_Two, L_ThreeDoes not represent a hydroxy group.

The optional 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 hetero ring) thio group, sulfo group or salt thereof, and sulfamoyl group, and more preferably, alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, carbamoyl group, carbamoyl group or salt thereof, or 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 is Na, K, Li, Mg, Ca, etc., they -S ^- present as a counter cation.
M is preferably a hydrogen atom, an ammonium group, Na
⁺ Or K ⁺ , and particularly preferably a hydrogen atom.
Among the compounds of the general formula (G), the following general formula (GA):
The compound represented by (GB) is preferred.

[0145]

Embedded image

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.

[0149]

Embedded image

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,
Examples include an arylthio group, an alkylamino group, and an arylamino group. 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. Has a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonio 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 is 2
A methyl group substituted with two electron-withdrawing groups specifically includes groups such as dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, and α-acetyl-α-ethoxycarbonylmethyl. The substituent represented by X in the general formula (GA-1) is the above-described water-soluble group or a substituent substituted with the above-described water-soluble group, and the substituent has 0 to 15 carbon atoms. Alkyl, aryl, heterocyclic, alkoxy, aryloxy, heterocyclic oxy, acyloxy, (alkyl, aryl or heterocyclic) amino, acylamino, sulfonamide, ureido Group, thioureido group, imide group,
Sulfamoylamino group, (alkyl, aryl or heterocycle) thio group, (alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like, preferably an alkyl group having 1 to 10 carbon atoms (especially amino group) , An aryl group, an aryloxy group, an amino group, an (alkyl, aryl, or heterocycle) amino group, and an (alkyl, aryl, or heterocycle) thio group.

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

[0153]

Embedded image

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 optional substituent. Here, 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 the general 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 preferable 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.

[0159]

Embedded image

[0160]

Embedded image

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 in general formulas (GA-1) to (GA-3). It is a water-soluble group as defined for Y ₁ and Y ₂ or a group substituted with a water-soluble group. Further, among the compounds of the general formula (GB-1), the compound represented by the general formula (GB-1-a) is most preferred.

[0162]

Embedded image

In the general formula (GB-1-a), R ₅₁ , 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.

Hereinafter, specific examples of the compound represented by formula (G) of the present invention will be shown, but it goes without saying that the present invention is not limited thereto.

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

[0168]

Embedded image

The compound of the general formula (G) is added in an amount of 0.01 to 10 mmol, preferably 0.1 to 1 mmol per liter of the working solution.
５5 mmol.

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

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

The developer used in the present invention will be described below, but the present invention is not limited to the following description and specific examples. As the developing agent of the ascorbic acid derivative used in the present invention, a compound represented by the following formula (S) is preferable. General formula (S)

[0173]

Embedded image

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

[0175]

Embedded image

[0176]

Embedded image

[0177]

Embedded image

The ascorbic acids used in the developer used in the present invention include an endiol type (Endiol), an enaminol type (Enaminol), an endamine type (Endiamin), a thiol-enol type (Thiol-Enol) and an enamine-thiol type.
(Enamin-Thiol) is commonly known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,549;
It is described in JP-A-62-237443. Methods for synthesizing these ascorbic acids are also well known,
For example, Tsuguo Nomura and Hirohisa Omura, "Reducton Chemistry"
(Uchida Lao Tsuruho Shinsha 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.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / l to 0.5 mol / l, preferably 0.05 mol / l to 0.5 mol / l.
0.3 mol / l is more preferred. In the combination of the ascorbic acid derivative and the p-aminophenol, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or more.
0.5 mol / l, p-aminophenols in 0.
It is preferably used in an amount of from 005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention may contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto.

As the buffer used in the developer for developing the light-sensitive material in the present invention, carbonates,
Boric acid described in JP-A-286259;
(E.g., saccharose), oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalicylic acid), tertiary phosphates (e.g., sodium salt, potassium salt), and the like, preferably carbonate, Boric acid is used. It is preferable that the carbonate is not used alone, but is used in combination with the bicarbonate. If it is attempted to set the pH of the developer from 9.0 to 10.5 using only carbonate, the stability of the developer is impaired, and the activity of the developer is likely to be reduced by running. Therefore, the carbonate is preferably less than 0.8 mol / l, more preferably 0.1 mol / l.
Less than 5 mol / liter, and 0.1 mol /
Liter or more, and more than 0.1 mol / liter and 1.5
More preferably, it is not more than mol / liter. In the present invention, the concentration of bicarbonate in the developer is 0.1 mol /
Liters or more, and the total concentration of bicarbonate and carbonate is 0.5
Mol / liter or more, and the pH is 9.0 to 10.
It is preferably 5.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. The concentration of the sulfite is preferably 0.01 mol / L or more and 0.2 mol / L or less. If the concentration of sulfurous acid is high, the amount of silver eluted from the light-sensitive material into the developing solution increases, which is undesirable because it causes silver staining. The replenishing amount of the developing replenisher is preferably 300 ml or less, more preferably 30 ml or more and 250 ml or less per m ² of the photographic material. The development replenisher may have the same composition as the development starter except for the pH, or may have a different composition.

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

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

As aminopolycarboxylic acids, for example,
Aspartic acid acetic acid, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine Hexacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others, JP-A-52-25632, JP-A-55-67747, and JP-A-57-10
2624, and compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene compounds described in, for example, US Patents 3,214,454 and 3,794,591 and West German Patent Publication 2,227,396.
Diphosphonic acid and Research Disclosure No. 181
Vol., Item 18170 (May 1979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like.
4, 54-61125, 55-29883, 56
-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-211127, JP-A-55-4024 and JP-A-55-40.
25, 55-126241, 55-65555, 55-65556, and the compounds described in Research Disclosure 18170 described above.

These organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer. As the fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate, and sodium ammonium thiosulfate can be used. The amount of the fixing agent to be used can be changed as appropriate, but is generally about 0.7 to about 3.0.
Mol / l.

The fixing solution in the present invention 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 0.01 to 0.1 as an aluminum ion concentration in the working solution.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

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

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

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0. The replenishment rate of the fixing solution is 500 ml or less, preferably 390 ml or less, per 1 m ² of the photosensitive material, and 320 to 30 ml.
Milliliters are more preferred. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution. The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is Reclaim R-60 manufactured by Fuji Hunt.

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

The solid processing agent in the present invention may be in a known form (powder, granule, granule, block, tablet, compactor, briquette, plate, crushed product, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or coating film to separate components that react with each other upon contact,
Components that react with each other may be separated into a plurality of layers, or they may be used in combination.

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

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described, for example, in JP-A-61-25992.
1, JP-A-4-15641, 4-16841, 4-
32837, 4-78848 and 5-93991. The bulk density of the solid processing agent is 0.5 to 6.0.
g / cm ³ is preferable, and particularly, a tablet is 1.0 to 5.0 g / cm ^3.
3 is preferred, granules preferably 0.5 to 1.5 g / cm ^3. As a method for producing the solid processing agent in the present invention, any known method can be used. For example, as a packaging method, JP-A-61-259921, JP-A-4-1684
1, the method described in 4-78848 can be used. As a method for solidification, JP-A-4-8553
3, 4-85534, 4-85535, 5-13
4362, 5-197070, 5-204098,
5-224361, 6-138604, 6-13
8605 and Japanese Patent Application No. 7-89123 can be used.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used. The particle size and shape of the granulated material suitable for the present invention vary depending on the desired properties, but generally the solubility desired for the photographic processing agent and the amount of residual powder in the waste packaging material after preparation or vibration during transportation. In consideration of the durability against the destruction of the granulated material by the method, in the case of granules, the spherical equivalent particle size is about 0.5 to 50 mm, preferably 1 to 50 mm.
The shape is cylindrical, spherical, cubic, rectangular, or the like, and more preferably spherical or cylindrical. The roller compacted product may be crushed or sieved to a diameter of about 2 mm to 1 cm. In the case of briquettes and tablets, the particle size and shape also differ depending on the desired properties, but a diameter of about 2 mm to 5 cm is preferable, and the shape is cylindrical, spherical, cubic, rectangular, etc., and more preferably spherical or cylindrical. It is.
When the solubility is desired to be improved, a plate having a reduced thickness, a plate having a further reduced center portion, a hollow donut, and the like are also useful. Conversely, the diameter and thickness may be further increased for the purpose of slowly dissolving,
It can be adjusted arbitrarily. Further, the surface state (smooth, porous, etc.) may be changed in order to control the solubility. Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid processing agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also,
JP-A-6-242555-JP-A 6-242588, JP-A-6-242588
247432, 6-247448, Japanese Patent Application No. 5-306
64, JP-A-7-5664, 7-5666 to 7-5
It is also preferable to use a foldable shape as disclosed in US Pat. For these packaging materials, a screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and these materials are limited to these. Do not. In addition, recycling or reusing the waste packaging material is preferable in terms of environmental conservation.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for storing a completed solution as described in Japanese Patent Application No. 7-235499. Dissolve in
Replenishment method from stock section,
4, a method for introducing and dissolving and replenishing a processing agent into a circulating system of an automatic developing machine as described in 6-19102 and 7-261357, and processing a photosensitive material with an automatic developing machine having a dissolving tank built therein. There is a method of adding and dissolving the treating agent according to the method, but any other known method can be used. In addition, the processing agent may be manually opened and charged, or may be automatically opened and automatically loaded by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferable from the viewpoint of the working environment. More specifically, a method of piercing the take-out port, a peeling method, a cutting method, a pushing method, and a method described in JP-A-6-19
102, 6-95331.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, this is referred to as washing including the stabilization processing, and the liquid used for these is water or washing water. .) Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. If washing with a low replenishment volume,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration. As a method for reducing the replenishing amount of washing, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time.
The replenishing amount of washing with water is preferably 200 to 50 ml per 1 m ² of the light-sensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

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

In addition, known water-soluble surfactants and defoamers 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 the washing system to prevent contamination by the dye eluted from the photosensitive material. A part or all of the overflow solution from the washing step can be mixed and used with a processing solution having a fixing ability, as described in JP-A-60-235133. In addition, microbial treatment (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 ceramic), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining or forming a filter using a polymer having affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath may also contain a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a deterrent, an alkanolamine or a surfactant. Agents can also be added. Additives such as deodorants and stabilizers to be added to the washing and stabilizing baths may be solid agents as in the case of the above-mentioned developing and fixing processing 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. These waste liquids are, for example,
-83867, US Pat. No. 5,439,560, etc. It is also possible to condense or solidify with a concentrating device and then dispose.

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

In the development processing of the present invention, dry to dry
The development and fixing time is preferably 30 seconds or less, preferably 6 to 20 seconds, and the temperature of each liquid is 25 to 50 ° C.
Is preferable, and 30 to 40 ° C. is more preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.
Heat roller drying, drying by far infrared rays, and the like as disclosed in JP-A-2256 and 5-289294, and a plurality of methods may be used in combination.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the corresponding places shown below can be preferably used. Item 1) Silver halide emulsion and page 12, lower right column, line 12 in JP-A-2-97937, page 14 and lower left column, line 14 in JP-A-2-97937, and from JP-A-2-2236. From page 19, upper right column, line 19 to page 8, lower left column, line 12, JP-A-4-330430 and JP-A-5-11389. 2) Spectral sensitizing dyes JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; JP-A-2-39042, page 7, lower right column, line 8, Page 13, lower right column, 5th line. JP-A-2-12236, page 8, lower left column, line 13 to lower right column, JP-A-2-103536, page 16 lower right column, line 3 to page 17, lower left column, line 20 And JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, JP-A-5-11389, and JP-A-4-330434. 3) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) and compound examples II- 1 to II-22, compounds described in JP-A-1-179939.

4) Surfactant From page 7, upper right column, line 7 to lower right column, line 7 of JP-A-2-12236. 5) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1, and JP-A-2-55349, page 8, lower right column, line 13 From the eye, page 11, line 8 in the upper left column. 6) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and JP-A-1-237538. Thiosulfinic acid compounds described in the official bulletin. 7) Polyhydroxyl JP-A-2-55349, page 11, upper left column, page 9 or benzenes, right lower column, line 17; 8) Slip agent, plasticizer From page 6, upper right column, line 6 to page 19, upper right column, line 15 of JP-A-2-103536. 9) Hardener JP-A-2-103536, page 18, line 5 to line 17, upper right column.

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

[0209]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Example 1 <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.
H6.0, adjusted to pAg7.5, 2 mg per mole of silver
Of sodium thiosulfate and 4 mg of chloroauric acid
Chemical sensitization was carried out at 0 ° C. to obtain the optimum sensitivity. Then, 4-hydroxy-6-methyl-1,3,3, as a stabilizer
150 mg of a, 7-tetrazaindene was added, and 100 mg of compound (a) was further added as a preservative. The obtained particles were silver chlorobromide cubic particles each having an average particle size of 0.25 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%)

[0211]

Embedded image

Preparation of Coated Sample A polyethylene terephthalate film support having a moisture-proof layer undercoat 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 at 0.5 g / m ² .

[0213] 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), 5 × 10 ⁻⁴ mol of a nucleation promoting agent and a comparative compound shown below and a compound shown in Table 10 as 5 × 10 ^-4 mol was added. Further, 100 mg of hydroquinone and sodium salt of N-oleyl-N-methyltaurine were added so as to be applied at 30 mg / m ² . Next, the hydrazine derivative shown in Table 10 was added at 0.8 × 10 ⁻⁵ mol /
m ² , the polymer latex represented by (f) was 200 mg /
m ^2, an average particle size 0.02μm colloidal silica (Nissan Chemical [lines] Ltd. SNOWTEX C) a 200 mg / m ^2, further 1,2-bis (vinylsulfonyl acetamide) as a hardener ethane 200 mg / m ² Was added. The pH of the solution was adjusted to 5.65 using acetic acid. They were coated silver amount2.
5 g / m ^2, it was coated to a gelatin 0.8 g / m ^2.

[0214]

Embedded image

(PC layer) The following surfactant (g) was added to an aqueous gelatin solution at 5 mg / m ² and 1,5-dihydroxy-2-benzaldoxime was added at 10 mg / m ² so as to be coated. It was applied so as to be 0.5 g / m ² . (OC layer) gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 40 mg / m ² with an average particle size of about 3.5 μm, colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.)
0.1 g / m ^2, polyacrylamides 100 mg / m ² and a sliding agent (h) Fluorine surfactant 5 mg / m ² and dodecylbenzenesulfonic acid represented as 20 mg / m ² and coating aids by the following structural formula (i) 100 mg / m ² of sodium was applied.

[0216]

Embedded image

Then, the following conductive layer and back layer were simultaneously coated on the opposite side of the support. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 250 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 100 {compound- (a) 7} sodium dodecylbenzenesulfonate Salt 20〃Dihexyl-α-sulfosuccinate sodium salt 20〃Polystyrene sulfonate sodium salt 20〃 <Back layer> Gelatin (Ca ⁺⁺ content 30 ppm) 2.6 g / m ² Dye Dye [a], Dye [b], Mixture of Dye [c] Dye [a] 70 mg / m ² Dye [b] 70 染料 Dye [c] 90 ナ ト リ ウ ム Dodecylbenzenesulfonic acid sodium salt 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

[0218]

Embedded image

After the obtained sample was stored for one week in an atmosphere of 25 ° C. and 55% RH, the following running stability was evaluated. The results are shown in Table-10. Table-10
As is clear from the graph, the level of the present invention has extremely high photographic characteristics and excellent running stability.

[0220]

[Table 10]

(1) Evaluation of running stability The sample was passed through an interference filter having a peak at 480 nm.
Exposure was performed with a xenon flash light having an emission time of 10 ^-5 sec through a step wedge, and the drive gear was changed to a high-speed drive using an FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd. using a developer having the following composition. After developing at 35 ° C. for 15 seconds, fixing, washing and drying were performed. As the running conditions, the photosensitive material described above was continuously treated at a rate of 20 m ² per day at a blackening rate of 80% for 5 days, and the performance of the fresh solution and the fatigue solution after running was evaluated.
The sensitivity was determined from the exposure amount giving fog + density = 1.5 in the characteristic curve. Index (gamma) indicating the contrast of the image
In the characteristic curve, the point of fog + density of 0.3 on the characteristic curve is connected by a straight line to the point of fog + density of 3.0, and the slope of this line is expressed as a gamma value. That is, gamma = (3.0−0.3)
/ [Log (exposure amount giving density 3.0)-(density 0.
Exposure amount giving 3)], and the larger the gamma value, the harder the photographic characteristics. As a graphic arts photosensitive material, gamma is preferably 10 or more, and more preferably 15 or more.

The composition of the developer per liter of working solution is shown below. Developer Potassium hydrogen carbonate 0.40 mol Potassium carbonate / monohydrate 0.40 mol Diethylenetriamine / pentaacetic acid 4 g Sodium sulfite 5 g (0.04 mol) Potassium bromide 2 g 5-Methylbenzotriazole 0.08 g Sodium erythorbrate monohydrate 45 g Compound Example A-24 shown in Table 2 2.5 g Trimercaptotriazine 0.03 g The pH was adjusted to 9.7. The replenishment rate was 120 ml / m ² .

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

Example 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 coated. <Back Layer> Gelatin (Ca ⁺⁺ content 3000ppm) 2.0 g / m ² Compound - 3 mg / m ² Compound - 40 〃 compound - 40 〃 compound - 155 〃 compound - 150 〃 sodium dodecylbenzenesulfonate 7 〃 dihexyl - α-Sulfosuccinate sodium 30 １，２ 1,2-bis (vinylsulfonylacetamide) ethane 140 ナ ト リ ウ ム Sodium sulfate 180 化合物 Compound-5 微粒子 Fine particles of polymethyl methacrylate (average particle size 4.7 μm) 10 微粒子

[0225]

Embedded image

[0226]

Embedded image

Then, an emulsion first and second layers having the following composition, a lower layer and an upper layer of a protective layer were simultaneously coated on the opposite side of the support. The hydrazine compound described in Table 11 was added to this emulsion in an amount of 0.
8 × 10 ⁻⁵ mol / m ² , nucleation accelerator 5 × 10 ⁻⁴ mol / m ²
m ² , 4-hydroxy-6-methyl-1,3,3a, 7-
30 mg / m ² of tetrazaindene, the following compounds-,-
Each ^{40mg / m 2, 10mg / m} 2, as an additive to a hardener, 1,1-bis (vinylsulfonyl) methane added gelatin 1g per 55mg on the side having emulsion layers, silver 1.6
g / m ² and gelatin at 0.6 g / m ² .
An aqueous sodium chloride solution containing 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was simultaneously added over 14 minutes, and the average particle size was adjusted by controlling the potential to 95 mV. Silver chloride cubic grains of 15 μm were prepared. The hydrazine compound described in Table 11 was added to this emulsion at 0.8 × 10 ^−5.
Mol / m ^2, hard gradation accelerator 5 × 10 ^-4 mol / m ^2, 4-hydroxy-6-methyl-1,3,3a, 7- tetrazaindene the 30 mg / m ^2, the following compounds -, -For each 4
0 mg / 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 silver was coated at 1.6 g / m ² and gelatin was coated at 0.6 g / m ² .

[0228]

Embedded image

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

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

[0231]

Embedded image

Using the obtained sample, crushing running was performed as in Example 1, and running stability was evaluated as in Example 1. However, the photographic performance was evaluated as follows. <Evaluation of photographic performance> The emulsion of Example 1 was replaced with the following emulsion B, and the sensitizing dye for the EM layer was replaced with the following compound (S-3), and 2.1 × 10 ^-4 per mol of silver. A sample was prepared in the same manner as in Example 1 except that moles were added. Compound Example 4-1 was used as a hydrazine compound, and Compound Example X-1 was used as a nucleation accelerator (manufactured by Lum Co., Ltd., using the same amounts as in Example 1) under a developing condition of 35 ° C. for 20 seconds. . The results are shown in Table-11. As is clear from Table 11, the level of the present invention is excellent in running stability as in Example 1.

[0233]

[Table 11]

Example 3 The emulsion of Example 1 was replaced with the following emulsion B, and the sensitizing dye for the EM layer was replaced with the following compound (S-3), and 2.1 × 10 ^-4 per mol of silver. A sample was prepared in the same manner as in Example 1 except that moles were added. Compound Example 4-1 was used as the hydrazine compound, and Compound Example X-1 was used as the contrast enhancement accelerator in the same amount as in Example 1. [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 performed in the same manner as in Emulsion A of Example 1.

[0235]

Embedded image

The sample thus obtained was evaluated in the same manner as in Example 1. However, the evaluation of the photographic performance was based on the emission time of 10 ⁻⁶ , instead of the interference filter having a peak at 633 nm.
Exposure was performed with xenon flash light for 2 sec., and the developing treatment used the compounds shown in Table 12 instead of the compound A-24 in the developer formulation of Example 1. As the auxiliary developing agent, 2
The level of using a combination of the types was also tested. Table 12 shows the evaluation results.

[0237]

[Table 12]

As is evident from the evaluation results in Table 12, the p-aminophenols of the present invention have higher sensitivity, higher contrast and higher running stability than phenidone, pyrazolidone and monol as auxiliary developing agents having superadditivity. It turns out to be preferable. It can also be seen that, even when two or more auxiliary developing agents are used in combination, the level using the p-aminophenols of the present invention exhibits preferable performance.

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

[0240]

Embedded image

<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

[0242]

Embedded image

The sample thus obtained was evaluated in the same manner as in Example 3. However, evaluation of photographic performance is 780 nm
The test was performed in place of an interference filter having a peak at
As a result, as in Example 3, it was possible to obtain a photosensitive material for a semiconductor laser scanner having extremely high photographic characteristics and excellent running stability.

[0244]

As described above, according to the present invention, in an ascorbic acid-based developer not using hydroquinone, a change in photographic performance is small and an improved developing method can be provided.

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

Claims (4)

[Claims] 1. From the following general formulas (1), (2) and (3)
Selected hydrazine derivative and represented by the following general formula (X)
Silver halide photographic materials containing compounds
Qualitatively free of dihydroxybenzenes,
Acid and / or its derivatives as developing agents
Amides represented by the following general formula (M)
Develop with a developer containing a nophenol derivative
A developing method characterized by the following. General formula (1)Where R_a1Represents an aliphatic group or an aromatic group.
-O- (CH_TwoCH_TwoO)_n−,
-O- (CH_TwoCH (CH_Three) O)_n-Or -O-
(CH_TwoCH (OH) CH_TwoO)_n-(Where n is 3 or less
Containing a partial structure of the above integer) or one of the substituents
Group containing a quaternary ammonium cation as a part
You. G_a1Is a -CO- group, a -COCO- group, a -CS- group,
−C (= NG_a2R_a2) -Group, -SO-group, -SO_Two-Group
Or -P (O) (G_a2R_a2)-Represents a group. G_a2Is simple
Bond, -O- group, -S- group or -N (R_a2) -Group
And R_a2Represents an aliphatic group, an aromatic group, or a hydrogen atom.
Represents multiple Rs in the molecule_a2If they are the same
Or may be different. A_a1, A_a2One of them is a hydrogen source
And a hydrogen atom or an acyl or alkyl group
Or an arylsulfonyl group. General formula (2)Where R_b1Represents an aliphatic group, an aromatic group, or a heterocyclic group.
And may be replaced. G_b1Is a -CO- group, -SO
_Two-Group, -SO- group, -COCO- group, thiocarbonyl
Group, iminomethylene group or -P (O) (R_b3)-Group
Represents, R_b2Is G _b1At least one carbon atom substituted with
Represents a substituted alkyl group substituted with two electron-withdrawing groups. R
_b3Represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group,
Represents a reeloxy group or an amino group. General formula (3)Where A_c1, A_c2Are both hydrogen atoms or one is a hydrogen atom
And the other represents a sulfinic acid residue or an acyl group;
_c1Represents an aliphatic group, an aromatic group, or a heterocyclic group;
_c2Is a hydrogen atom, an alkyl group, an aryl group, an alkoxy
Group, aryloxy group, or amino group;_c1Is
Carbonyl, sulfonyl, sulfoxy, phosphoryl
And represents an iminomethylene group. Where R_c1, R_c2
At least one of them is adsorbed on silver halide
Has a promoting group. General formula (X)Where R_ThreeRepresents a hydrogen atom, an alkyl group, an aryl group or
Represents a ring residue. Q is a mere bond, sulfur as a divalent group
Atom or selenium atom, oxygen atom as divalent group,
Sulfide group (-SS-), NR_Four,Or NR_FourRepresents CS. Where R_FourIs R_ThreeSynonymous with
You. R₁And R_TwoIs a hydrogen atom, an alkyl group, an aryl
Group, heterocyclic group or amino group. R_ThreeAnd R_Four, R
₁And R_TwoOr R₁And R_ThreeA 5- or 6-membered heterocycle
It may be formed. Where R₁And R_ThreeBetween 5 and 6 members
When forming a terrorist ring, R_TwoAnd R_FourAre all hydrogen sources
I do not represent a child. Also, R₁And R_TwoFormed between
Among the heterocycles, the rhodanine ring is excluded. General formula (M)Where R₁, R_Two, R_Three, R_FourMay be the same or different
And each represents a hydrogen atom or a substituent. R_Five, R₆Are the same
And may be different, each of which is an alkyl group, an aryl
Group, aralkyl group or heterocyclic group. 2. A compound represented by the following general formula (G) in a developer.
2. The developing method according to claim 1, further comprising a silver stain inhibitor.
Processing method. General formula (G)In the general formula (G), D and E are -CH = group, -CR₀
= Represents a group or a nitrogen atom, where R₀Represents a substituent
You. L₁, L_Two, L_ThreeIs a hydrogen atom, a halogen atom, or
Carbon, nitrogen, oxygen, sulfur, phosphorus
Any substituent attached to the ring at any of₁~ L_Three
May be the same or different. Where L₁, L_Two, L_Three,
And R₁At least one of the -SM group (M is an
Li metal atom, hydrogen atom, ammonium group). Note that
When E and D represent one nitrogen atom and one carbon atom
Means that E is a nitrogen atom and D is a carbon atom (—CH ＝ group or
-CR ₀= Group), in which case L_TwoAnd L_ThreeIs hydro
It does not represent a xy group. 3. The bicarbonate concentration in the developer is 0.1 mol / l or more, and the total concentration of bicarbonate and carbonate is 0.1 mol / l.
5 mol / l or more and pH 9.0 to 1
3. The method according to claim 1, wherein the value is 0.5. 4. The developing method according to claim 1, wherein the replenishing amount of the developing replenisher is 300 ml / m ² or less.