JPH09281666A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain ultrahigh contrast, to ensure superior processing stability and to prevent the occurrence of black spots by incorporating a specified developing agent into a developing soln. for developing a photographic sensitive material contg. a specified hydrazine deriv. in a hydrophilic colloidal layer. SOLUTION: A silver halide photographic sensitive material contg. at least one kind of hydrazine deriv. represented by formula I in at least one of the silver halide emulsion layers or other hydrophilic colloidal layers is imagewise exposed and developed with a developing soln. under replenishment. The developing soln. contains a developing agent represented by formula III but does not practically contain a dihydroxybenzene developing agent. In the formula I, A is a combining group, B is a group represented by formula II and (m) is an integer of 2-6. In the formula II, each of Ar1 and Ar2 is an arom. group, etc., each of L1 and L2 is a combining group, R1 is H, etc., and G1 is -CO-, etc. In the formula III, each of R1 and R2 is hydroxy, amino, etc., each of P and Q is hydroxy, hydroxyalkyl, etc., Y is =O, etc., and R3 is H, alkyl, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultra-high contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

2. Description of the Related Art In recent years, in the field of photoengraving, a photographic light-sensitive material having good original reproducibility and a processing system capable of reducing processing waste liquid have been developed in order to cope with the variety and complexity of printed matter and due to an increase in environmental awareness. Was wanted.

[0003] In order to improve the reproduction of continuous tone images or the reproduction of line images using halftone images, an image forming system exhibiting ultra-high contrast (especially γ of 10 or more) photographic properties is required. As a method for obtaining high-contrast photographic characteristics, a lith developing system using a so-called "contagious developing effect" has been used for a long time, but has a drawback that a developing solution is unstable and difficult to use. Meanwhile, U.S. Pat. No. 4,1
66,742, 4,168,977, 4,
221,857, 4,224,401, 4,243,739, 4,269,922, 4,272,606, 4,311,781,
No. 4,332,878, No. 4,618,574
No. 4,634,661, No. 4,681,83
No. 6, No. 5,650,746, etc., a surface latent image type silver halide photographic light-sensitive material containing a hydrazine derivative is treated with a stable MQ or PQ developer having a pH of 11.0 to 12.3. , Γ of more than 10 is disclosed to obtain a super-high contrast negative image. According to this method, ultra-high contrast and high-sensitivity photographic characteristics can be obtained, and since a high concentration of sulfite can be added to the developer, the stability of the developer against air oxidation is higher than that of the conventional lith developer. And dramatically improve.

However, in the above-mentioned method, although the stability of the developing solution can be enhanced by a high-concentration sulfurous acid preservative, a relatively high p-value is required to obtain a super-high contrast photographic image.
It was necessary to use a developing solution having an H value, and therefore, the developing solution was easily oxidized by air, and a large amount of the developing solution had to be replenished. Therefore, attempts have been made to realize an ultrahigh contrast photographic image forming system using a hydrazine derivative with a developer having a lower pH.

[0005] US Patent No. 4,269,929 (JP-A-61-267759), US Patent No. 4,737,45.
No. 2 (JP-A-60-179734), U.S. Pat.
Nos. 104,769 and 4,798,780;
Nos. 179939 and 1-179940, U.S. Pat. Nos. 4,998,604, 4,994,365 and Japanese Patent Application No. 7-37817, using a stable developer having a pH of less than 11.0. A method using a highly active hydrazine nucleating agent and a nucleation accelerating agent to obtain a super-high contrast image is disclosed. It is also disclosed that a silver halide emulsion having a high silver chloride content and subjected to chemical sensitization has high nucleation activity.

Further, a hydrazine nucleating agent having two or more hydrazine groups in the molecule is disclosed in JP-A-4-16938,
5-1997091, 5-127287, 5-
No. 142688, No. 6-148777 and the like.

However, the known method requires a replenishing amount of the developing solution of about 150 to 450 ml when processing 1 square meter of the silver halide photographic light-sensitive material, and there is a growing concern about environmental problems. There has been a strong demand for improvement in processing stability, particularly in the developer pH dependence of photographic sensitivity, which has always been a problem in hydrazine nucleation systems.

Further, there is a problem that when the highly active hydrazine nucleating agent as described above is used, sandy fog called black spots is likely to occur in the unexposed area.

[0009]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide an image forming method using a silver halide photographic light-sensitive material which is super-high contrast, excellent in processing stability, and free from black spots.

[0010]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, said silver halide emulsion layer or another hydrophilic layer. Of at least one hydrazine derivative represented by the general formula (NB) in at least one of the photosensitive colloid layers, the method of developing a silver halide photographic light-sensitive material after imagewise exposure while replenishing a developing solution. In the image forming method, the developing solution is substantially free of a dihydroxybenzene-based developing agent and is developed with a developing solution containing a developing agent represented by the general formula (1). It was General formula (NB)

[0011]

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In the formula, A represents a linking group, B represents a group represented by the following general formula (B-1), and m represents an integer of 2 to 6. General formula (B-1)

[0013]

[Chemical 6]

In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents —CO
- group, -SO ₂ - group, -SO- group,

[0015]

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It represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group. R ₂ is selected from the same range as the groups defined in R _1, may be different from R _1. General formula (A-1)

[0017]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group, an alkoxy group, a mercapto group, or
P and Q are bonded to each other to form an atomic group forming a 5- to 7-membered ring together with the two vinyl carbon atoms substituted by R ₁ and R ₂ and the carbon atom substituted by Y. Y represents ＝ O or ＮN—R ₃ . R ₃ is a hydrogen atom, a hydroxyl group,
Represents an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. The hydrazine derivative (nucleating agent) used in the present invention will be described in detail. The hydrazine derivative used in the present invention is represented by the general formula (NB). General formula (NB)

[0020]

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In the formula, A represents a linking group, B represents a group represented by the following general formula (B-1), and m represents an integer of 2 to 6. General formula (B-1)

[0022]

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In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents —CO
- group, -SO ₂ - group, -SO- group,

[0024]

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It represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group. R ₂ is selected from the same range as the groups defined in R _1, may be different from R _1.

In the general formula (B-1), Ar₁, Ar
_TwoThe aromatic group represented by is a monocyclic or bicyclic aryl.
A benzene ring, a naphthalene ring,
Ar ₁, Ar_TwoThe aromatic heterocyclic group represented by
A cyclic or bicyclic aromatic heterocyclic group, other aryl
May be condensed with a group, for example, a pyridine ring,
Ring, imidazole ring, pyrazole ring, quinoline ring,
Soquinoline ring, benzimidazole ring, thiazole ring,
And a benzothiazole ring. Ar₁, Ar
_TwoIs preferably an aromatic group, more preferably
It is a phenylene group.

Ar ₁ and Ar ₂ may be substituted,
Representative substituents include, for example, alkyl groups (including active methine groups), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, heterocyclic groups containing quaternized nitrogen atoms (eg, pyridinio groups), hydroxy Groups, alkoxy groups (including groups that repeatedly contain ethyleneoxy or propyleneoxy group units), aryloxy groups, acyloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, urethane groups, carboxyl groups (the Salts), imide groups, amino groups,
Carbonamido group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group (including its salt), sulfamoyl group, acylsulfamoyl group, (alkyl or aryl)
Sulfonylureido group, (alkyl or aryl)
Sulfonylcarbamoyl group, halogen atom, cyano group,
Nitro group, phosphoric amide group, group containing phosphate ester structure, acylureide group, group containing selenium or tellurium atom, group having tertiary sulfonium structure or quaternary sulfonium structure, group containing quaternized phosphorus atom And the like. These substituents may be further substituted with these substituents.

Preferred substituents are those having 1 to 20 carbon atoms.
Alkyl group, aralkyl group, heterocyclic group, substituted amino group, acylamino group, sulfonamide group, ureido group,
Sulfamoylamino group, imido group, thioureido group,
Phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxyl group (including salts thereof), (alkyl,
Examples thereof include aryl or heterocycle) thio group, sulfo group (including salts thereof), sulfamoyl group, halogen atom, cyano group, nitro group and the like. Ar ₁ is preferably an unsubstituted phenylene group.

In formula (B-1), the alkyl group represented by R ₁ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. It contains a benzene ring. At least one nitrogen, oxygen as a heterocycle,
And a 5- to 6-membered ring compound containing a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group, a quinolinio group,
There is a quinolinyl group. Pyridyl or pyridinio groups are particularly preferred. Alkoxy group has 1 to 8 carbon atoms
Alkoxy groups are preferred, aryloxy groups are preferably monocyclic, amino groups are unsubstituted amino groups, and C1-10 alkylamino groups, arylamino groups, saturated or unsaturated hetero groups. A ring amino group is preferred. R ₁ may be substituted, and preferable substituents include those exemplified as the substituents of Ar ₁ and Ar ₂ .

Preferred among the groups represented by R ₁ are hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, difluoromethyl group, 2-carboxy group) when G ₁ is --CO-- group. Tetrafluoroethyl group, pyridiniomethyl group, 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group) , O-carbamoylphenyl group, 4
-Cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom and an alkyl group. When G ₁ is a —SO ₂ — group, R ₁ is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group). Or a substituted amino group (for example,
And a dimethylamino group. G ₁ is -CO
In the case of a CO- group, an alkoxy group, an aryloxy group,
An amino group is preferable, and an alkylamino group, an arylamino group, or a heterocyclic amino group (including a heterocyclic group containing a quaternized nitrogen atom) is particularly preferable. Methylpiperidin-4-ylamino group, propylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-
And a benzyl-3-pyridinioamino group.
R ₁ also splits the G ₁ -R ₁ moiety from the remaining molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the —G ₁ —R ₁ — moiety, and examples thereof include those described in JP-A-63-29751. There are things.

The compound represented by the general formula (NB) may incorporate an adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups.
Nos. 5,108 and 4,459,347;
Nos. 195233, 59-200231 and 59-2
No. 01045, No. 59-201046, No. 59-20
No. 1047, No. 59-201048, No. 59-201
No. 049, JP-A-61-170733 and 61-27.
Nos. 0744, 62-948 and 63-234244
And groups described in JP-A-63-234245 and JP-A-63-234246. The adsorbing group for these silver halides may be a precursor. Examples of such a precursor include groups described in JP-A-2-285344.

In the general formula (B-1), L₁, L_Twoso
The linking group represented is -O-, -S-, -N (R_N)-
(R_NRepresents a hydrogen atom, an alkyl group, or an aryl group.
You. ), -CO-, -C (= S)-, -SO_Two-, -S
O-, -P = O-, an alkylene group alone, or these
Is a group consisting of a combination of groups. Combine here
Specifically, a group consisting of -CON (R_N)-,-
SO_TwoN (R_N)-, -COO-, -N (R_N) CON
(R_N)-, -N (R_N) CSN (R_N)-, -N (R
_N) SO_TwoN (R_N)-, -SO_TwoN (R_N) CO-,
-SO_TwoN (R _N) CON (R_N)-, -N (R_N) C
OCON (R_N)-, -CON (R_N) CO-, -S-
Alkylene group -CONH-, -O-alkylene group -CO
Groups such as NH- and -O-alkylene-NHCO-;
Can be These groups are linked from either the left or right.
May be. L in the general formula (B-1)₁, L_TwoRepresented by
When the linking group includes a trivalent or higher valent group,₁Is the general formula
-Ar in (B-1)₁-NHNH-G₁-R₁so
Two or more represented groups may be linked, and L_TwoIs
In the general formula (B-1), -Ar_Two-L₁-Ar₁-N
HNH-G₁-R₁Connecting two or more groups represented by
May be. In this case, L₁, L_TwoContains three or more
Specifically, the linking group is an amino group or an alkylene group.
is there. L in the general formula (B-1)₁Is preferably-
SO_TwoNH-, -NHCONH-, -NHC (= S) N
H-, -OH-, -S-, -N (R_N)-, Active methine
A group, and particularly preferably --SO_TwoNH- group. L
_TwoIs preferably -CON (R_N)-, -SO_TwoN
(R_N)-, -COO-, -N (R_N) CON (R_N)
-, -N (R_N) CSN (R_N)-Group.

In the general formula (NB), the linking group represented by A is a divalent to hexavalent linking group capable of linking the groups represented by B from 2 to 6, and is --O--, -S-, -N
( _RN ')-( _RN ' represents a hydrogen atom, an alkyl group, or an aryl group), -N ⁺ ( _RN ') _2- (two R
_{N'may be} the same or different, and may be bonded to form a ring), -CO-, -C (= S)-,-
SO ₂ —, —SO—, —P═O—, an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heterocyclic group alone, or a group consisting of a combination of these groups, or a single bond is there. Here, the heterocyclic group may be a heterocyclic group containing a quaternized nitrogen atom such as a pyridinio group.

In the general formula (NB), the linking group represented by A may be substituted, and the substituent is represented by the general formula (B).
Examples of the substituents which may be possessed by Ar ₁ and Ar _{2 in} -1) are the same.

When n is 0, the linking group represented by A is a benzene ring, a naphthalene ring, a saturated or unsaturated heterocycle, a heterocycle containing a quaternized nitrogen atom such as a pyridinio group, It preferably contains at least one of a quaternized nitrogen atom such as an ammonio group and a cycloalkylene group. When n is 1, the linking group represented by A includes a single bond, a benzene ring, a naphthalene ring, a saturated or unsaturated heterocyclic ring, a heterocyclic ring containing a quaternized nitrogen atom such as a pyridinio group, It preferably contains at least one of a quaternized nitrogen atom such as an ammonio group and a cycloalkylene group.

In the general formula (NB), m represents an integer of 2 to 6, preferably 2, 3 or 4, and particularly preferably 2 or 3.

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

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine derivative of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the emulsion layer or the hydrophilic colloid layer adjacent thereto.

The addition amount of the hydrazine derivative of the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, based on 1 mol of silver halide.
X10 ^{-5 to} 5 × 10 ^-3 mol is most preferred.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described in pages 49 to 58. JP-A-7-10
General formula [Na] and general formula [N]
b], specifically 16 to 2
Compounds of Na-1 to Na-22 described on page 0 and Nb
Compounds of -1 to Nb-12.

The nucleation accelerator used in the present invention is represented by the general formulas (A-1), (A-2), (A-3) and (A-
The onium salt compound represented by 4) is most preferably used. This will be described in detail below.

First, the general formula (A-1) will be described in detail.

[0052]

[Chemical 12]

In the formula, R ₁₀ , R ₂₀ , and R _{30 each} represent an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or a heterocyclic group, each of which further has a substituent. You may have. L
Represents an m-valent organic group bonded to Q ⁺ at its carbon atom, and m represents an integer of 1 to 4. X ^n- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when R ₁₀ , R ₂₀ , R ₃₀ or L has an anion group as a substituent and forms an intramolecular salt with Q ⁺ , X ^n- is not necessary.

Examples of the groups represented by R ₁₀ , R ₂₀ , and R ₃₀ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, octyl group. A linear or branched alkynyl group such as a 2-ethylhexyl group, a dodecyl group, a hexadecyl group or an octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or the like Alkyl group; aryl group such as phenyl group, naphthyl group, phenanthryl group; alkenyl group such as allyl group, vinyl group, 5-hexenyl group; cycloalkenyl group such as cyclopentenyl group, cyclohexenyl group; phenylethynyl group, etc. Alkynyl group; pyridyl group, quinolyl group, furyl group, imidazolyl group, thiazo Ryl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group, morpholyl group,
Heterocyclic groups such as a pyrimidyl group and a pyrrolidyl group can be mentioned.

Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁₀ , R ₂₀ , and R ₃₀ , halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and nitro. A group (alkyl or aryl) amino group,
Alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group,
Examples thereof include sulfoxy group, sulfonyl group, carboxyl group (including carboxylate), sulfonic acid group (including sulfonate), cyano group, oxycarbonyl group, acyl group and the like.

Examples of the group represented by L include the groups having the same meanings as R ₁₀ , R ₂₀ and R ₃₀ when m represents 1.
In addition, when m represents an integer of 2 or more, a trimethylene group,
Polymethylene group such as tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, dodecamethylene group, arylene group such as phenylene group, biphenylene group, naphthylene group, trimethylenemethyl group, polyvalent such as tetramethylenemethyl group Alkylene group, phenylene-1,3,5-toluyl group, phenylene-1,2,4
Examples thereof include polyvalent arylene groups such as 5-tetrayl group.

Examples of the counter anion represented by X ^n- are halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion,
Examples include carboxylate ions such as fumarate ions and benzoate ions, sulfonate ions such as p-toluenesulfonate, methanesulfonate, butanesulfonate, and benzenesulfonate; sulfate ions; perchlorate ions; carbonate ions; and nitrate ions.

In the general formula (A-1), R ₁₀ , R ₂₀ ,
R ₃₀ is preferably a group having 20 or less carbon atoms, and when Q represents a phosphorus atom, an aryl group having 15 or less carbon atoms is particularly preferred. When Q represents a nitrogen atom, an alkyl group having 15 or less carbon atoms, aralkyl And aryl groups are particularly preferred. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group, an aralkyl group, or an aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or an aralkylene group, and further these groups and a —CO— group, an —O— group or an N group.
(NR ′)-group (NR ′ is a hydrogen atom or R ₁₀ , R ₂₀ ,
When a plurality of NR's are present in the molecule, which represents a group having the same meaning as R ₃₀ , these may be the same or different,
Further, they may be bonded to each other), -S- group, -S
O- group, -SO ₂ - is a divalent group formed by combining groups. When m represents 2, L is preferably a divalent group having a total number of carbon atoms of 20 or less, which is bonded to Q ^{+ at the} number of carbon atoms. When m represents an integer of 2 or more, R ₁₀ , R in the molecule
₂₀ and R ₃₀ respectively exist in plural, and the plural R ₁₀ ,
R ₂₀ and R ₃₀ may be the same or different.

The counter anion represented by X ^n- is preferably a halogen ion, a carboxylate ion, a sulfonate ion or a sulfate ion, and n is preferably 1 or 2.

Many of the compounds represented by formula (A-1) of the present invention are known and are commercially available as reagents. As a general synthesis method, when Q is a phosphorus atom, a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. is there. Further, when Q is a nitrogen atom, there is a method of reacting a primary, secondary, or tertiary amino compound with an alkylating agent such as alkyl halides and sulfonates.

Specific examples of the compound represented by formula (A-1) are shown below. However, the present invention is not limited to the following compounds.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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Next, the general formula (A-2) and the general formula (A-
3) will be described in more detail.

[0069]

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In the formula, A ₁ , A ₂ , A ₃ and A ₄ represent an organic residue containing a quaternized nitrogen atom for completing a substituted or unsubstituted unsaturated heterocycle, and a carbon atom. ,
It may contain a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. A ₁ , A
Examples of the unsaturated hetero ring formed by ₂ , A ₃ and A ₄ include a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a thiazole ring, a thiadiazole ring, a benzotriazole ring, a benzothiazole ring, a pyrimidine ring and a pyrazole ring. And the like. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.

The divalent group represented by B and C is an alkyle
, Arylene, alkenylene, alkynylene, -SO
_Two-, -SO-, -O-, -S-, -N (R_N)-,-
C = O-, -P = O- are used alone or in combination.
Are preferred. Where R _NIs an alkyl group, aralkyl
Represents a hydrogen atom, an aryl group, or a hydrogen atom. Particularly preferred example
, B and C are alkylene, arylene, and -C = O
-, -O-, -S-, -N (R_N)-Alone or in combination
It is possible to cite those configured by

R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), a substituent or An unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, etc.), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.),
(Alkyl or aryl) oxycarbonyl group, sulfo group (including sulfonate), carboxy group (including carboxylate), mercapto group, hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, etc.),
Aryloxy group, carbonamido group, sulfonamide group, sulfamoyl group, carbamoyl group, ureido group,
Examples thereof include thioureido group (alkyl or aryl) amino group, cyano group, nitro group, alkylthio group, arylthio group and the like. Particularly preferably, R ₁ and R ₂ are each an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include a carbamoyl group, an oxycarbonyl group, an acyl group, an aryl group, a sulfo group (including sulfonate), a carboxy group (including carboxylate), and a hydroxy group.

The unsaturated heterocycle formed by A ₁ , A ₂ , A ₃ and A ₄ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . The substituent preferably has 0 to 10 carbon atoms.
Aryl group, alkyl group, carbamoyl group, (alkyl or aryl) amino group, oxycarbonyl group,
Alkoxy, aryloxy, (alkyl or aryl) thio, hydroxy, carbonamido,
Sulfonamide group, sulfo group (including sulfonate),
And carboxy groups (including carboxylate).

For the counter anion represented by X ^n- ,
The formula is the same as the formula (A-1), and the preferred range is also the same.

The compound of the present invention can be easily synthesized by a generally well-known method, but the following documents are helpful. (Reference, Quart. Rev., 16,163 (1962).)

Specific compounds represented by formulas (A-2) and (A-3) are shown below, but the invention is not limited thereto.

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[0078]

[Chemical 21]

[0079]

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[0080]

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Next, the general formula (A-4) will be described.

[0082]

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The nitrogen-containing unsaturated heterocycle containing Z may contain a carbon atom, a hydrogen atom, an oxygen atom or a sulfur atom in addition to the nitrogen atom, and may further have a condensed benzene ring.
Further, it may have a substituent. Examples of the hetero ring formed include general formulas (A-2) and (A-3)
The same as the examples of the nitrogen-containing unsaturated heterocycle formed by A ₁ , A ₂ , A ₃ and A ₄ of the above. The preferred range is also the same, and a pyridine ring, a quinoline ring and an isoquinoline ring are preferred. When the nitrogen-containing unsaturated heterocycle containing Z has a substituent, examples of the substituent include those represented by general formula (A-2) and general formula (A-3) in which A ₁ , A ₂ , A ₃ , and A ₄ are Examples of the substituent which the nitrogen-containing unsaturated heterocycle to be formed may have are the same, and the preferable range is also the same.

R ₃ represents an alkyl group or an aralkyl group, which may have 1 to 20 carbon atoms, may be substituted or unsubstituted, and may be linear, branched or cyclic. Examples of the substituent include R ₁ and R in the general formula (A-2).
_The same examples as the examples of the substituent that the alkyl group represented by ₂ may have are mentioned, and the preferable ranges are also the same.

For the counter anion represented by X ^n- ,
The formula is the same as the formula (A-1), and the preferred range is also the same.

The compound represented by the general formula (A-4) of the present invention can be easily synthesized by a well-known method, and the following documents are helpful. (See, Quar
t.Rev., 16,163 (1962).)

Next, specific examples of the compound represented by formula (A-4) of the present invention are shown below, but the present invention is not limited thereto.

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An amino compound is also preferably used as the nucleation accelerator. Specifically, the following compounds are preferably used.

[Chemical formula 2] described in JP-A-7-84331
1) Compounds represented by (Chemical Formula 22) and (Chemical Formula 23), specifically, compounds described on pages 6 to 8 of the same publication. Compounds represented by the general formula [Na] described in JP-A-7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the same. Japanese Patent Application No. 7-37817
Compounds represented by general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) described in Specifically, the compounds of 1-1 to 1-19 described in the same specification, 2-1 to 2-
22 compounds, 3-1 to 3-36 compounds, 4-1 to 4
-5 compound, 5-1 to 5-41 compound, 6-1 to 6
Compounds of -58 and 7-1 to 7-38.

The nucleation accelerator of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl. It can be used by dissolving it in cellosolve or the like. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the powder of the nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The nucleation accelerator of the present invention may be added to any one of the silver halide emulsion layer on the silver halide emulsion layer side of the support or another hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto.

The amount of the nucleation accelerator added in the present invention is silver halide.
1 x 10 for 1 mol^-6~ 2 x 10 ^-2Mole is preferred,
1 × 10^-Five~ 2 x 10^-2More preferably 2 × 10
^-Five~ 1 × 10^-2Molar is most preferred.

The silver halide emulsion according to the present invention may contain any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide and silver iodobromide as the silver halide, but the silver chloride content is 30. It is preferably at least mol%, more preferably at least 50 mol%.
The content of silver iodide is preferably at most 5 mol%, more preferably at most 2 mol%.

The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and tabular, but cubic or tabular is preferred.

The photographic emulsion used in the present invention is P. Glafki.
by des Chimie et Physique Photographique (Paul Mont
el, 1967), Photographic Emulsi by GFDufin
on Chemistry (The Focal Press, 1966), VLZeli
Making and Coating Photographic Emuls by kman et al
ion (published by The Focal Press, 1964) and the like.

That is, any of an acidic method and a neutral method may be used, and as a method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Is also good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. The amount of the silver halide solvent to be added depends on the type of the compound used, the intended grain size, and the halogen composition, but is preferably from 10 ^-5 to 10 ^-2 mol per mol of silver halide.

In the controlled double jet method and the method for forming grains using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and it is used in the present invention. It is a useful tool for making silver halide emulsions. In order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445, JP-A-55-15812
It is preferable to use the method of changing the concentration of the aqueous solution as described in No. 4 to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} ×
The coefficient of variation represented by 100 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm to 0.4 μm.

The silver halide emulsion used in the present invention is
It may contain a metal belonging to Group VIII. In particular, the light-sensitive material suitable for high-intensity exposure such as scanner exposure and the light-sensitive material for line image photography preferably contain a rhodium compound, an iridium compound, a ruthenium compound, etc. in order to achieve high contrast and low fog. Further, it is preferable to contain an iron compound for higher sensitivity. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example,
Examples thereof include hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium (III) complex salt, and trisalatrodium (III) complex salt. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of rhodium compounds, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or alkali halides (eg KCl, NaCl, KBr, Na)
A method of adding Br or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, and hexaammineiridium. Examples of the ruthenium compound used in the present invention include hexachlororuthenium and pentachloronitrosylruthenium. Examples of the iron compound used in the present invention include potassium hexacyanoferrate (II),
Ferrous thiocyanate is mentioned.

The addition amount of these compounds is 1 × 10 ^{-8 to} 5 × 10 ^-6 mol, preferably 5 × 10 ^-8 to 1 × 10 ^-6 mol, per 1 mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

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

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer.For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening.
It is 10 ⁻⁷ to 10 ⁻² mol per mol, and more preferably 1
0 ^-5 to 10 ^-3 mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
Compounds described in JP-A-121798 can be used. In particular, it is preferable to use the compounds represented by formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to serve as a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, see Japanese Patent Application No.
It can be tested by the method described in No. 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33.
No. 3819, No. 3-53693, No. 3-131598
No. 4-129787, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 635 (1980), ibid 1102 (19
79), ibid 645 (1979), Journal of Chemicals
Society Parkin Transaction (J.Che
m.Soc.Perkin.Trans.) 1,2191 (1980), S. Pata
i) Ed., The Chemical of Organic Selenium and Tellurium, The Chemistr
y of Organic Serenium and Tellunium Compounds), Vol
The compounds described in 1 (1986) and Vol 2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferable.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions, etc., but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide, and about 10 ^-7 to 10 ^-2 mol per mol of silver halide. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physically ripening them.

Reduction sensitization can be used in the present invention. As reduction sensitizers, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The silver halide emulsion of the present invention can be prepared by the method described in European Patent Publication (EP) -293,917.
A thiosulfonic acid compound may be added.

The silver halide emulsion in the light-sensitive material used in the present invention may be of one kind or two or more kinds (for example,
(Those having different average grain sizes, different halogen compositions, different crystal habits, and different chemical sensitization conditions)
You may use together.

In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, and more preferably 95 mol% or more of silver chloride. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

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

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

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NS) Cl ₅ ] ^-2 5 [Rh (NO) Cl ₅ ] ^-2 6 [Re (NO) CN ₅ ] ^-2 7 [Re (NO) ClCN ₄ ] ^-2 8 [Rh (NO) ₂ Cl ₄ ] ^-2 9 [Rh (NO ) (H ₂ O) Cl ₄ ] ^-1 10 [Ru (NO) CN ₅ ] ^-211 [Ru (NO) Br ₅ ] ^-2 12 [Rh (NS) Cl ₅ ] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 (Cr (NO) Cl ₅ ) ^-3 15 (Re (NO) Cl ₅ ) ^-1 16 (Os (NS) Cl ₄ (TeCN)) ^-2 17 (Ru (NS) l ₅ ) ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

The silver halide emulsion used for the light-returning light-sensitive material is also preferably chemically sensitized by the above method.

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

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized with a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes used in the present invention are described or cited in, for example, RESEARCH DISCLOSURE Item 17643 IV-A (Dec. 1978, p. 23) and Item 1831X (August 1978, p. 437). It is described in. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
18, JP-A-62-284343, JP-A-2-10.
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
32, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242 and JP-A-3-67242, and general formulas (IIIa) and (IIIb). -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure).
Disclosure) Vol. 176, 17643 (issued December 1978), page 23, IV, paragraph J.

For the argon laser light source, specifically, S1-1 to S1 described in Japanese Patent Application No. 7-104647.
The dye of -13 is particularly preferably used.

For the helium-neon light source, in addition to the above, the formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to line 13 is used. The sensitizing dyes represented are particularly preferred. In addition, Japanese Patent Application No. 4-228
The compounds described in General Formula (I) of No. 745 are also preferably used. Specifically, S2 described in Japanese Patent Application No. 7-104647
The dyes -1 to S2-10 are particularly preferably used. Further, it is a sensitizing dye represented by the general formula (I) of Japanese Patent Application No. 6-103272, specifically, I-1 to I described in the specification.
The dye of -34 is also preferably used.

Regarding the LED light source and the infrared semiconductor laser, specifically, S described in Japanese Patent Application No. 7-104647 is used.
The dyes 3-1 to S3-8 are particularly preferably used.

For the infrared semiconductor laser light source, specifically, S4-1 to S described in Japanese Patent Application No. 7-104647.
The dyes 4-9 are particularly preferably used.

The sensitizing dye of the general formula (IV) described in Japanese Patent Application No. 5-201254 (from page 20, line 14 to page 22, line 23) is preferably used for a white light source for camera photography and the like. . Specifically, the dyes S5-1 to S5-20 described in Japanese Patent Application No. 7-104647 are particularly preferably used.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following sections can be preferably used.

Polyhydroxybenzene compounds described in JP-A-3-39948, page 10, lower right line 11, to page 12, lower left line 5, specifically, compound (III) described in the same publication. -1 to 25 compounds.

A compound represented by the general formula (I) described in JP-A-1-118832, which has substantially no absorption maximum in the visible region. Specifically, compound I-
Compounds of 1-26.

The antifoggant described in JP-A-2-103536, page 17, lower right line, line 17 to page 18, upper right line, fourth line.

Polymer latices described in JP-A-2-103536, page 18, lower left line 12 to lower left line 20, same page.

Matting agents, slip agents, and plasticizers described in JP-A-2-103536, page 19, upper left line, line 15 to page 19, upper right line, line 15.

Hardeners described in JP-A-2-103536, page 18, upper right, line 5 to upper right, line 17 of the same page.

Compounds having an acid group described in JP-A-2-103536, page 18, lower right line, line 6 to page 19, upper left line, first line.

JP-A-2-18542, page 2, lower left 1
Conductive substances from the third line to the seventh line on the upper right of page 3 of the publication. Specifically, the metal oxides described on page 2, lower right line 2 to page 10, lower right line, and the conductive polymer compounds of compounds P-1 to P-7 described in the same publication .

Water-soluble dyes described in JP-A-2-103536, page 17, lower right line, line 1 to upper right line, line 18 of the same page.

Solid disperse dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773.

JP-A-2-12236, page 9, upper right corner 7
The surfactant described in the third line from the line on the lower right side of the same page. JP 2
PEG-based surfactants described in JP-A-103536, page 18, lower left line, line 4 to lower left line, line 7; JP-A-3-399
No. 48, page 12, lower left line, line 6 to page 13, lower right line, line 5 fluorine-containing surfactants. Specifically, compounds VI-1 to VI-15 described in the publication. Japanese Patent Laid-Open No. 5-
Redox compounds capable of releasing a development inhibitor by being oxidized as described in 274816. Preferably, a redox compound represented by the general formula (R-1), the general formula (R-2) or the general formula (R-3) described in the publication. Specifically, compounds of compounds R-1 to R-68 described in the publication.

JP-A-2-18542, page 3, lower right corner 1
The binder described in lines 20 to 20.

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

The developer used in the development processing of the light-sensitive material according to the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . For the developing treatment of the present invention, any known method can be used, and a known developing solution can be used.

The developing agent used in the developing solution used in the present invention is an ascorbic acid derivative and does not contain a dihydroxybenzene type developing agent.

The ascorbic acid derivative developing agent preferably used in the present invention is a compound represented by the general formula (1).

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In the general formula (1), R ₁ and R ₂ are respectively a hydroxy group and an amino group (having 1 carbon as a substituent).
To 10 alkyl groups such as methyl group, ethyl group, n-
Includes those having a butyl group, a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-
A toluenesulfonylamino group, an alkoxycarbonylamino group (a methoxycarbonylamino group, etc.), a mercapto group, and an alkylthio group (a methylthio group, an ethylthio group, etc.). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group,
Or an atom group necessary for bonding P and Q to form a 5- to 7-membered ring together with two vinyl carbon atoms substituted with R ₁ and R ₂ and a carbon atom substituted with Y. Represents
Specific examples of the ring structure, -O -, - C (R 4) (R 5) -,
_{-C (R 6) =, -} C (= O) -, - N (R 7) -, - N
= And are combined. However, R ₄ , R ₅ ,
R ₆ and R ₇ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, a sulfo group can be mentioned as the substituent), a hydroxy group,
Represents a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include dihydrofuranone ring, dihydropyrone ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolinone ring, pyridone ring, azacyclohexenone ring, uracil ring and the like. And preferred examples of the 5- to 7-membered ring are:
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azasiloxhexenone ring,
A lauryl ring can be mentioned.

Y is a group composed of ═O or ═N—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxy group. Represents an alkyl group (for example, carboxymethyl, carboxyethyl). Hereinafter, specific examples of the compound of the general formula (1) are shown, but the present invention is not limited thereto.

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Of these, ascorbic acid and erythorbic acid (diastereomers of ascorbic acid) are preferred. A general range of the amount of the compound of the general formula (1) used is 5 × 10 ⁻³ mol to 1 mol, particularly preferably 10 ⁻² mol to 0.5 mol, per liter of the developing solution.

The developer used in the present invention preferably contains 1-phenyl-3-pyrazolidone or a derivative thereof or a p-aminophenol derivative as an auxiliary agent. The most preferred combination is a combination of an ascorbic acid derivative and a p-aminophenol derivative.

1-Phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-. Hydroxymethyl-3-pyrazolidone and the like. P used in the present invention
-As aminophenol derivatives, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-
Hydroxyphenyl) glycine, etc., among which N
-Methyl-p-aminophenol is preferred.

The ascorbic acid derivative developing agent is usually 0.1%.
It is preferably used in an amount of from 0.5 to 1.0 mol / l. Particularly preferably, it is in the range of 0.1 to 0.5 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 to 1.0 mol / liter, more preferably 0.1 to 0.5 mol. /
It is preferable to use the liter and the latter in an amount of 0.2 mol / l or less, more preferably 0.1 mol / l or less.

Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formacdehyde sodium bisulfite.
If a large amount of sulfite is added, it causes silver contamination in the developing solution. It is particularly preferably 0.1 mol / liter or less.

Additives other than those mentioned above include
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or its derivatives; mercapto Compounds, indazole compounds, bendtriazole compounds, and benzimidazole compounds may be contained as antifoggants or black pepper inhibitors. Specifically, 5-nitroindazole,
5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5- Nitrobenztriazole, 4
-[(2-Mercapto-1,3,4-thiadiazole-
Examples thereof include sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution.

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

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

Examples of the organic phosphonic acid include US Pat.
Nos. 214,454, 3,794,591, and West German Patent Publication No. 2,227,639, and hydroxyalkylidene-diphosphonic acids and Research Disclosure Vol. 181, Item 181.
70 (May 1979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like.
No. 0, JP-A-57-208554 and JP-A-54-6112.
No. 5, No. 55-29883, No. 56-97347, etc. can be mentioned.

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

Further, as a silver stain preventing agent in the developing solution, JP-A-56-24347, JP-B-56-45685,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, a compound described in JP-A-62-212651 can be used as a development unevenness inhibitor, and a compound described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, and a hardener may be contained.

The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the development temperature is about 20 ° C. to about 50 ° C., preferably 25 to 45 ° C., and the development time is 5 seconds. ~ 2 minutes, preferably 7 seconds to 1 minute 30 seconds.

In the present invention, both the development starter solution and the development replenisher solution have the property that "the pH rise when adding 0.1 mol of sodium hydroxide to the solution liter is 0.25 or less". Is preferred. As a method for confirming that the development starter or development replenisher used has this property, the pH of the development starter or development replenisher to be tested is 1
After adjusting to 0.0, 0.1 mol of sodium hydroxide was added to 1 liter of this solution, and the pH value of the solution at this time was measured. Judge as having properties. In the present invention, it is particularly preferable to use a development starter solution and a development replenisher solution which have a pH value increase of 0.2 or less when the above test is carried out.

As a method for imparting the above-mentioned properties to the development starter solution and the development replenisher solution, it is preferable to use a buffer.
Examples of the buffer include carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93333 (eg, saccharose), oximes (eg, acetoxime), and phenols (eg, 5 -Sulfosalicylic acid), tertiary phosphates (e.g., sodium salts, potassium salts) and the like, preferably carbonates and boric acid. The amount of the buffer, especially carbonate, used is preferably 0.2 mol / liter or more, particularly 0.5 to 1.5 mol / l.
Liters.

As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

In the present invention, the pH of the development initiating solution is preferably 8.5 to 12.0, particularly preferably 8.5 to 11.0. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also in this range. Alkaline agents used for setting the pH include ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate)
Can be used.

When processing 1 square meter of a silver halide photographic light-sensitive material, the replenisher amount of the developing solution is 225 ml or less, preferably 225 to 30 ml, particularly 180 to 30 ml.
Milliliters. The development replenisher may have the same composition as the development start solution, or may have a higher concentration of components consumed in development than the start solution. In the present invention, since the pH of the developer decreases as the photographic material is processed, it is preferable to set the pH of the developing replenisher to a value higher than the pH of the developing solution. Specifically, it is preferable to set the pH of the developing replenisher to be higher than the pH of the developing solution by 0.05 to 1.0, particularly preferably 0.1 to 0.5.

It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like.

Further, in order to reduce the fatigue of the fixing solution due to the mixing of the developing solution into the fixing solution, it is preferable to keep the potassium ion concentration in the developing solution low. In particular,
It is preferred that all the salts added to the developer be added in the form of sodium salts.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. It is particularly preferably 0.2 to 1.5 mol / liter. The fixing solution may optionally contain a hardening agent (eg, a water-soluble aluminum compound), a preservative (eg, a sulfite,
Bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in US Pat. No. 4,126,459, mesoionic compounds described in JP-A-4-229860, etc. And the compounds described in JP-A-2-44355 may be used. Further, as the pH buffering agent, for example, acetic acid,
Organic acids such as malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid and adipic acid, and inorganic buffering agents such as boric acid, phosphate and sulfite can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing an increase in the pH of the fixer due to the carry-in of the developer,
1.0 mol / liter, more preferably 0.02 to 0.1.
Use about 6 mol / l. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The preferable addition amount is 0.01 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C. to about 50 ° C., preferably 25 ° C.
At ~ 45 ° C, the fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 500 ml / m ² or less, particularly preferably 200 ml / m ² or less, based on the processing amount of the photosensitive material.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A Nos. 350 and 62-28725. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means according to the process according to the method of the present invention is disclosed in JP-A-60-2351.
As described in No. 33, it can also be used for a processing solution having a fixing ability which is a processing step before that. Also,
A water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles, which is likely to occur when washing with a small amount of water, and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing tank to prevent contamination by the dye eluted from the photosensitive material. Further, there is a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and examples thereof include JP-A-2-2013357 and JP-A-2-132435.
The baths containing the compounds described in JP-A No. 1-102553 and JP-A No. 46-44446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides,
It is also possible to add fungicides, alkanolamines and surfactants. Water used in the washing or stabilizing process includes tap water, deionized water, halogen, ultraviolet germicidal lamps, and various oxidizers (ozone, hydrogen peroxide,
It is preferable to use water that has been sterilized with chlorate or the like. Further, JP-A-4-39652, JP-A-5
Rinsing water containing the compound described in No. 241309 may be used. Washing or stabilizing bath temperature and time is 0 to 50 ° C,
5 seconds to 2 minutes is preferable.

The treatment liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. The treatment liquid used in the present invention may be in the form of a powder and solidified. Known methods can be used, but it is preferable to use the methods described in JP-A-61-259921, JP-A-4-85533, and JP-A-4-16841. Particularly preferred is the method described in JP-A-61-259921. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Regarding the roller-conveying type automatic developing machine, U.S. Pat. Nos. 3,025,779 and 3,545,971.
In this specification, it is simply referred to as a roller transport type processor. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the washing step.

[0172]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 The following developers were prepared.

<Developer A> Diethylenetriamine-5-acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium hydrogencarbonate 25 g Sodium erythorbate 45 g N-Methyl-p-aminophenol 7.5 g KBr 2 g 5-Methylbenzotriazole 0.004 g 1- Phenyl-5-mercaptotetrazole 0.02 g Sodium sulfite 2 g Water was added to make 1 liter, and the pH was adjusted to 9.7.

<Developer B> The same formulation as developer A, pH
Was adjusted to 11.5 with NaOH.

<Developer C> Diethylenetriamine-5-acetic acid 2 g Potassium carbonate 16.5 g Sodium carbonate 14 g Sodium hydrogencarbonate 13 g Hydroquinone 23 g N-Methyl-p-aminophenol 7.5 g KBr 2 g 5-Methylbenzotriazole 0.004 g 1- Phenyl-5-mercaptotetrazole 0.02 g Sodium sulfite 40 g Water was added to make 1 liter, and the pH was adjusted to 9.7 with NaOH.

Further, based on each of the developing solutions A, B and C,
Sodium hydroxide was added to raise the pH to 0.3. Developers A +, B +, C +, and acetic acid were added to raise the pH to 0.3.
The lowered developing solutions A-, B-, and C- were prepared.

<Preparation of Emulsion A> 1-liquid water 1-liter gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2-liquid water 400 ml silver nitrate 100 g 3-liquid water 400 ml sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridium (III) (0.001% aqueous solution) 6 ml

Solution 2 and solution 3 were added simultaneously to solution 1 kept at 42 ° C. and pH 4.5 over 15 minutes while stirring,
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4-liquid water 400 ml Silver nitrate 100 g 5-liquid water 400 ml Sodium chloride 27.1 g Potassium bromide 21.0 g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10 ml

Thereafter, the product was washed with water by the flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate were added and chemically sensitized at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion A having an average grain size of 0.25 μm was obtained.

<Preparation of coating sample> Sensitizing dye (1) was added to Emulsion A.
3.8 × 10 ^-4 mol / mol Ag was added for spectral sensitization. Further, KBr (3.4 × 10 ⁻⁴ mol / mol Ag), compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.
0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 1
0 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, and the hydrazine derivative shown in Table 9 at 1.0 × 10 ^−4.
Mol / mol Ag, compound (3) 6.0 × 10 ^-4 mol / mol Ag, and further 35 wt% polyethyl acrylate latex with gelatin, 20 wt% colloidal silica with 20 μm particle size and gelatin. Against 4
was added wt% of the compound (4), Ag2.5g / m ² on a polyester support was coated so as to gelatin 1.0 g / m ^2. A protective layer upper layer and a protective layer lower layer having the following compositions were coated thereon, and a UL layer having the following composition was coated thereunder. The following compounds were used as comparative examples of the hydrazine derivative of the present invention.

[0182]

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[0183]

[Table 9]

(Upper layer of protective layer) Gelatin 0.3 g / m ² Silica matting agent with an average of 3.5 μm 25 mg / m ² Compound (5) (Gelatin dispersion) 20 mg / m ² Colloidal silica with a particle size of 10 to 20 μm 30 mg / m ² compound (6) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (7) 20 mg / m ² (protective layer lower layer) gelatin 0.5 g / m ² compound (8) 15 mg / m ² 1,5 -Dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 150 mg / m ² (UL layer) gelatin 0.5 g / m ² polyethyl acrylate latex 150 mg / m ² compound (4) 40 mg / m ² compound (9 ) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following composition. (Back layer) Gelatin 3.3 g / m ² sodium dodecylbenzenesulfonate 80 mg / m ² compound (10) 40 mg / m ² compound (11) 20 mg / m ² compound (12) 90 mg / m ² 1,3-divinylsulfonyl 2-Propanol 60 mg / m ² Polymethylmethacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (4) 120 mg / m ² (conductive layer) Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ²

[0186]

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[0187]

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<Evaluation> (1) Exposure and Development Treatment The above sample was exposed to xenon flash light having an emission time of 10 ⁻⁵ sec through a step wedge through an interference filter having a peak at 633 nm. After developing with a developer FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd. at 32 ° C. for 15 seconds, fixing, washing with water,
A drying process was performed. The replenisher amounts of the developing solution and the fixing solution at the time of processing were 100 ml per 1 m ² of the sample.

The fixer used was the fixer A having the following formulation. <Fixer A> Ammonium thiosulfate 120 g Ethylenediamine / tetraacetic acid / 2Na / 2-hydrate 0.03 g Sodium thiosulfate / 5-hydrate 11 g Sodium metasulfite 19 g Sodium hydroxide 12.4 g Acetic acid (100%) 30 g Tartaric acid 2.9 g Glucon Sodium acid salt 1.7 g Aluminum sulfate 8.4 g pH 4.8

(2) Photographic sensitivity Sensitivity is expressed by the reciprocal of the exposure amount that gives a density of 1.5,
The relative value of the sensitivity of each sample when the comparative sample was 100 was calculated and set as S _1.5 . The larger the value, the higher the sensitivity.

(3) Gamma As an index (gamma) indicating the contrast of an image, a point of fog + density 0.1 to a point of fog + density 3.0 of the characteristic curve is connected by a straight line, and the slope of this straight line is the gamma value. Expressed as That is, gamma = (3.0-0.1) / [log (exposure amount giving density 3.0) -log (exposure amount giving density 0.1)], and the higher the gamma value, the harder the image. It shows that it is a characteristic. Practically, it should be 15 or more.

(4) Dependence of Photographic Sensitivity on Developer pH The photographic sensitivity of Developer A on pH of the developer was calculated by the following formula. pH dependency (ΔS _1.5 ) = S _1.5 (developing solution A +) − S _1.5 (developing solution A−) The smaller the value, the smaller the pH dependency of the developing solution, that is, the higher the processing stability. Similarly, for Developers B and C, the pH dependence of photographic sensitivity on developer pH was calculated. Practically, it should be 0.10 or more.

(3) Black spots The unexposed light-sensitive material was developed with developers A, B and C at 35 ° C. for 30 seconds, and the number of black spots generated was visually evaluated. "5"
Is the best quality, and "1" is the worst quality. "3" is the practical limit, and "2" and "1" are not practical.

The evaluation results are summarized in Table 10.

[0195]

[Table 10]

<Results> When the light-sensitive material containing the hydrazine derivative of the present invention and the developing solution of the present invention are combined, the pH dependence of photographic sensitivity is small, the activity is high, and black spots hardly occur. Photographic properties were obtained.

Example 2 The same results as in Example 1 were obtained by using the following photosensitive materials in place of the photosensitive material prepared in Example 1. However, this light-sensitive material was exposed through an interference filter having a peak at 780 nm. <Preparation of Emulsion B> 1-liquid water 1-liter gelatin 20 g sodium chloride 1.5 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2-liquid water 400 ml silver nitrate 100 g 3-liquid water 400 ml sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridium (III) (0.001% aqueous solution) 10 ml

To the 1st liquid kept at 40 ° C. and pH 4.5, the 2nd liquid and the 3rd liquid were added simultaneously with stirring for 15 minutes.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

Thereafter, it was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate were added and chemically sensitized at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion B having an average grain size of 0.22 μm was obtained.

<Preparation of coating sample> Sensitizing dye (2) was added to Emulsion B.
8.0 × 10 ⁻⁵ mol / mol Ag was added for spectral sensitization. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag, compound (3) 2.0 × 10 ⁻⁴ mol / mol Ag, compound (14) 1.
0 × 10 ⁻³ mol / mol Ag, hydroquinone 2.0 × 1
0 ⁻² mol / mol Ag, citric acid 2.0 × 10 ⁻³ mol / mol Ag, 1.5 × (hydrazine derivative) shown in Table 11
10 ^-4 mol / mol Ag, compound (16) 9.0 × 10 ^-4 mol / mol Ag, compound (17) 2.3 × 10 ^-4 mol / mol Ag, compound (18) 1.4 × 10 ⁻⁴ mol / mol Ag, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% based on gelatin, particle size 10 m
4 wt% of compound (19) was added to μ colloidal silica and gelatin, and Ag 3.2 was added on the polyester support.
It was coated at 5 g / m ² and gelatin at 1.4 g / m ² . An upper protective layer and a lower protective layer having the following composition were applied thereon.

[0201]

[Table 11]

(Upper layer of protective layer) Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (20) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² compound (21) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (22) 20 mg / m ² (protective layer lower layer) gelatin 0.8 g / m ² compound (23) 20 mg / m ² compound (24 ) 7 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 150 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. (Back layer) Gelatin 3.0 g / m ² Sodium dodecylbenzenesulfonate 40 mg / m ² Compound (24) 60 mg / m ² Compound (25) 30 mg / m ² 1,3-Divinylsulfonyl-2-propanol 60 mg / m ² Polymethylmethacrylate fine particles (average particle size 6.5 μm) 6 mg / m ² Polymethylmethacrylate fine particles (average particle size 3.5 μm) 25 mg / m ² Sodium sulfate 150 mg / m ² Compound (19) 110 mg / m ² (conductive layer) Gelatin 0.1 g / m ² Sodium dodecylbenzene sulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 200 mg / m ²

[0204]

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[0205]

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Example 3 The same results as in Example 1 were obtained by using the following photosensitive materials instead of the photosensitive material prepared in Example 1. However, this light-sensitive material was exposed through an interference filter having a peak at 488 nm. <Preparation of emulsion C> 1 liquid water 1 liter gelatin 20 g sodium chloride 2.0 g 1,3-dimethylimidazolidine-2-thione 20 mg sodium benzenesulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridium (III) (0.001% aqueous solution) 7 ml

Solution 2 and solution 3 were added simultaneously to solution 1 kept at 40 ° C. and pH 4.5 for 15 minutes while stirring,
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g

After that, it was washed with water by the flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and 2 mg of sodium benzenesulfinate were added and chemically sensitized at 55 ° C. so as to obtain the optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-
100 mg of tetrazaindene, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride,
A silver chloroiodobromide cubic emulsion C having an average grain size of 0.23 μm was obtained.

<Preparation of coating sample> Sensitizing dye (3) was added to Emulsion C.
2.0 × 10 ⁻⁴ mol / mol Ag, sensitizing dye (4) 7.0 ×
Spectral sensitization was carried out by adding 10 ⁻⁴ mol / mol Ag. Further, KBr 3.4 × 10 ⁻⁴ mol / mol Ag, compound (26)
5.0 × 10 ⁻⁴ mol / mol Ag, compound (27) 8.0 × 1
0 ^-4 mol / mol Ag, hydroquinone 1.2 × 10 ^-2 mol / mol Ag, (hydrazine derivative) shown in Table 12 1.8 × 10 ^-4 mol / mol Ag, compound (29) 3.5. ×
10 ^-4 mol / mol Ag, 30 wt% with respect to gelatin
% Polyethyl acrylate latex, 15 wt% of gelatin to colloidal silica having a particle size of 10 mμ, and 4 wt% of compound (30) to gelatin were added to obtain 3.4 g / m ² of Ag, gelatin on a polyester support. 1.5 g /
It was coated so as to be in m ^2. A protective layer upper layer and a protective layer lower layer having the following compositions were coated thereon, and a UL layer having the following composition was coated thereunder.

[0210]

[Table 12]

(Upper layer of protective layer) Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (31) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² compound (32) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (33) 20 mg / m ² (protective layer lower layer) gelatin 0.5 g / m ² compound (34) 15 mg / m ² 1,5 -Dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex 250 mg / m ² (UL layer) gelatin 0.5 g / m ² polyethyl acrylate latex 150 mg / m ² compound (30) 40 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (35) 90 mg / m ² Compound (36) 20 mg / m ² Compound (37) 40 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² Polymethylmethacrylate fine particles (average particle size 3.5 μm) 20 mg / m ² Compound (30) 120 mg / m ² Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ²

[0213]

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[0214]

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Example 4 A light-sensitive material was prepared in the same manner as in Example 3 except that the sensitizing dye in the emulsion layer of Example 3 was changed to the following sensitizing dye (5). evaluated. However, the exposure was performed with 3200 ° K tungsten light through a step wedge. Similar to Example 1, when the light-sensitive material containing the hydrazine derivative of the present invention and the developing solution of the present invention are combined, the photographic sensitivity has a small pH dependency, high activity, and black spots hardly occur. Photographic properties were obtained.

[0216]

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Example 5 <Preparation of Emulsion D> 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per ⁵ mol of sodium chloride and silver kept at 38 ° C., 5 × 10 ⁻³ mol of 4-hydroxy-6- PH including methyl-1,3,3a, 7-tetrazaindene =
An aqueous solution of sodium chloride containing 5 × 10 ^-5 mol of K ₂ Ru (NO) Cl ₅ per mol of silver in a 2.0% 1.5% gelatin aqueous solution was applied by the double jet method at a potential of 95 mV for 3 minutes 30. Simultaneously add half of the silver amount of the final grain in a second,
0.12 μm of core particles were prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 5 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes, and a silver chloride cube having an average grain size of 0.13 μm was added. Particles were prepared. (Coefficient of variation: 12%) After that, the product was washed with water by a flocculation method well known in the art to remove soluble salts, and gelatin was added to the compound-F as a preservative.
And 60 mg of phenoxyethanol were added per 1 mol of silver, and the pH was adjusted to 5.5 and pAg = 7.5.
4 × 10 ⁻⁵ mol of chloroauric acid, 1 × 10 ⁻⁵ mol of selenium compound SE and 1 × 10 ⁻⁵ mol of sodium thiosulfate were added per mol, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization. Then, 4-hydroxy-6-methyl-1, as a stabilizer,
3,3a, 7-tetrazaindene was added at 1 × 1 per mol of silver.
0 ^-3 mol was added (as final particles, pH = 5.7, p
The result was silver chloride containing Ag = 7.5 and Ru = 5 × 10 ⁻⁵ mol / Ag mol. )

[0218]

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<Preparation of Coating Sample> (Silver Halide Emulsion Layer) The following compound was added to Emulsion D to give a gelatin coating amount of 0.9 g on a support described below including an undercoat layer.
/ M ^2, the coating amount of silver coated with silver halide emulsion layer as a 2.75 g / m ^2. N-oleyl-N-methyltaurine sodium salt 19 mg / m ² Hydrazine derivative shown in Table 13 15 mg / m ² Nucleation accelerator Z 20 mg / m ² 3- (5-mercaptotetrazole) -benzenesulfonic acid sodium 11 mg / m ² Compound A 13 mg / m ² ascorbic acid 1 mg / m ² Compound B 15 mg / m ² Compound C 70 mg / m ² acetic acid Amount with which the film surface pH becomes 5.2 to 6.0 Compound D 950 mg / m ² Riborane-1400 (Lion Oil and fat) 47 mg / m ² Compound E (hardener) Amount that makes the swelling rate in water 80%

[0220]

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The following compounds were used as comparative examples of the hydrazine derivative of the present invention.

[0222]

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[0223]

[Table 13]

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer.

(Emulsion Protecting Lower Layer) The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin would be 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.8 g / m ² compound F 1 mg / m ² 1,5-dihydroxy-2-benzaldoxime 14 mg / m ² C ₂ H ₅ SO ₂ SNa 3 mg / m ² compound C 3 mg / M ² p-dodecylbenzene sulfonate sodium 7 mg / m ²

(Preparation of Emulsion Protecting Upper Layer Coating Solution and Its Coating)
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent (average particle size 4.4 μm) 40 mg / m ² amorphous silica matting agent (average particle size 3.6 μm) 10 mg / m ² compound F 1 mg / m ² compound C 8 mg / m ² solid disperse dye -G ₁ 68mg / m ² Liquid paraffin 21 mg / m ² N-perfluorooctane sulfonyl -N- propyl glycine Potajiumu 5 mg / m ² p-sodium dodecyl benzene sulfonate 29 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

(Conductive layer) The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin would be 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 186 mg / m ² gelatin (Ca ⁺⁺ content 2700 ppm) 0.06 g / m ² sodium p-dodecylbenzenesulfonate 13 mg / m ² dihexyl- α-Sulfosuccinate sodium 12 mg / m ² Compound C 12 mg / m ² Compound F 1 mg / m ²

(Back layer) The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin would be 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94g / m ² of polymethyl methacrylate particles (average particle size 4.7μ) 7mg / m ² Compound H 233 mg / m ² Compound I 21 mg / m ² Compound G 146 mg / m ² Compound F 3mg / m ² p- sodium dodecylbenzenesulfonate 68 mg / m ² dihexyl -α- sulfosuccinates sodium _{^{21mg / m 2 C 8 F 17}} SO 3 Li 4mg / m 2 N- perfluorooctane sulfonyl -N- propyl glycine amount Potajiumu 6 mg / m ² sodium sulfate 177 mg / m ² compound -E (hardener) swelling rate in water is 90%

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate supports (thickness: 100 μm) were coated with the first and second undercoat layers having the following compositions on both sides. (Undercoat first layer) Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Colloidal silica (Snowtex) ZL; particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added, and the coating solution adjusted to pH = 6 was dried at a drying temperature of 180 ° C. for 2 minutes. Film thickness is 0.9
It was applied to be μ.

(Undercoat Layer Second Layer) Gelatin 1 g Methylcellulose 0.05 g Compound-J 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-F 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm, to prepare a support with an undercoat layer.

[0232]

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[0233]

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The coating method and drying conditions were as follows. <Coating method> On the support provided with the undercoat layer, an emulsion layer, an emulsion protective lower layer,
In the order of the emulsion protection upper layer, simultaneous multi-layer coating is performed while adding a hardener solution by a slide hopper method while maintaining at 35 ° C.
After passing through the cool air setting zone (5 ° C.), the conductive layer and the back layer are arranged in the order from the side closer to the support on the side opposite to the emulsion surface,
Similarly, simultaneous multi-layer coating was performed by adding a hardener solution by a slide hopper method, and a cold air setting zone (5 ° C.) was applied. At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time is 120 m / min
Met.

<Drying conditions> After setting, the product was dried with a drying air of 30 ° C. until the weight ratio of water / gelatin reached 800%, and then 8
Dry 200 to 200% with dry air at 35 ° C and 30%, apply air as it is, and after 30 seconds from when the surface temperature reaches 34 ° C (assuming the end of drying), dry for 1 minute at 48 ° C and 2% air. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 35 from 800 to 200%.
Seconds, 5% from 200% to the end of drying.

This sensitive material was wound up at 40 ° C. at 23 ° C., then cut in the same environment, and placed in a barrier bag conditioned for 6 hours to give 4 pieces.
After humidifying at 0 ° C. 10% for 8 hours, the sample was sealed with cardboard conditioned at 23 ° C. 40% for 2 hours to prepare a sample. When the humidity inside the barrier bag was measured, it was 40%.

<Evaluation> The above sample was exposed through a step wedge using a p-627FM printer manufactured by Dainippon Screen. Next, using the developing solution described in Example 1, the FG-680AG automatic developing machine manufactured by Fuji Photo Film Co., Ltd. was used.
After development at 20 ° C. for 20 seconds, fixing (fixing solution described in Example 2), washing with water, and drying were performed. The amount of replenisher of developer and fixer at the time of processing was 100 per m ² of sample.
ml.

Evaluations of gamma and photographic sensitivity on developer pH, and black spots were carried out in the same manner as in Example 2. Table 1 shows the evaluation results.
4

[0239]

[Table 14]

<Results> When the light-sensitive material containing the hydrazine derivative of the present invention and the developing solution of the present invention are combined, the pH dependence of photographic sensitivity is small, the activity is high, and black spots hardly occur. Photographic properties were obtained.

Example 6 A developer D having the following composition (the developer composition is the same as that of the developer A) and a fixer B having the following composition in which the storage form is a solid developer were prepared. Further, in order to investigate the pH dependence of photographic sensitivity, a developer D + in which sodium hydroxide was added to the developer D to raise the pH by 0.3, and a developer in which acetic acid was added to lower the pH by 0.3 D- was adjusted.

<Developer D> The following storage form was used as a working solution (pH 9.7) by adding water to a solid developer to make it 1 liter.

The composition of the solid developer is shown below. Sodium sulfite (bulk powder) 2 g Potassium carbonate (bulk powder) 33 g Sodium carbonate (bulk powder) 28 g Sodium hydrogen carbonate (bulk powder) 25 g The following are collectively briquetted. Diethylenetriamine-5-acetic acid 2 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-Methylbenzotriazole 0.004 g 1-phenyl-5-mercaptotetrazole 0.02 g

Here, in the raw material form, the bulk powder was used as a general industrial product. When the raw material was in the form of briquettes, it was pressurized and compressed using a briquetting machine to form an irregular shaped rugby ball type having a length of about 4 to 6 mm, which was then crushed and used. For minor components, each component was blended before briquetting.

<Fixing Solution B> The composition of the solid fixing agent is shown below. Agent A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (bulk powder) 19.0 g Sodium metabisulfite (bulk powder) 18.0 g Anhydrous sodium acetate (bulk powder) 42.0 g Agent B (liquid) Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.03 g Anhydrous citric acid 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 ml. Agent A and Agent B were dissolved in water to make 1 liter. pH 4.8

Ammonium thiosulfate (compact) was prepared by spray-drying a flake product, which was compressed under pressure with a roller compactor and crushed into irregularly shaped chips of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. Patent application Hei 7 for dissolution and replenishment
A dissolution replenishing device having an automatic opening mechanism disclosed in Japanese Patent Application No. 235499 and Japanese Patent Application No. 7-235498 was used.

In Examples 1, 2, 3, 4, 5, and 6,
Similar results were obtained by using the developing solution D instead of the developing solution A and using the fixing solution B instead of the fixing solution A.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer or at least one hydrophilic colloid layer is at least one kind. In the method of developing a silver halide photographic light-sensitive material after imagewise exposure while supplementing the developer with a hydrazine derivative represented by the general formula (NB), the developer is substantially dihydroxy. Contains no benzene-based developing agent,
An image forming method comprising developing with a developing solution containing a developing agent represented by the general formula (1). General formula (NB) In the formula, A represents a linking group, B represents a group represented by the following formula (B-1), and m represents an integer of 2 to 6. General formula (B-1) In the formula, Ar ₁ and Ar ₂ represent an aromatic group or an aromatic heterocyclic group, L ₁ and L ₂ represent a linking group, and n represents 0 or 1. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents a —CO— group, —SO ₂
-Group, -SO- group, It represents a -CO-CO- group, a thiocarbonyl group, or an iminomethylene group. R ₂ is selected from the same range as the groups defined in R _1, may be different from R _1. General formula (1) In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group. P and Q are a hydroxy group, a hydroxyalkyl group, a carboxyl group,
Carboxyalkyl group, sulfo group, sulfoalkyl group,
Represents an amino group, an aminoalkyl group, an alkyl group, an alkoxy group, or a mercapto group, or P and Q are bonded to each other, and two vinyl carbon atoms substituted by R ₁ and R ₂ are substituted by Y. Represents a group of atoms forming a 5- to 7-membered ring together with the carbon atoms. Y represents ＝ O or ＮN—R ₃ . R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. 2. The image forming method according to claim 1, wherein the pH of the developer is 8.5 or more and less than 11.0. 3. The image forming method according to claim 1, wherein at least one nucleation accelerator is contained in at least one of the emulsion layer and the other hydrophilic colloid layer of the silver halide photographic light-sensitive material. An image forming method comprising: 4. The image forming method according to claim 1, 2 or 3, wherein the silver halide emulsion is chemically sensitized. 5. The image forming method according to claim 1, claim 2, claim 3 or claim 4, wherein the silver halide emulsion has a silver chloride content of 50 mol% or more. Forming method.