JP2003084384A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high contrast and high sensitivity silver halide photographic sensitive material. SOLUTION: The silver halide photographic sensitive material having at least one silver halide emulsion layer on a support contains at least one organic gold compound is characterized in that it has a characteristic curve whose gamma in the optical density range of 0.3-3.0 is >=5.0 as a characteristic curve shown on rectangular coordinate axes with equal unit lengths of logarithmic light exposure (x-axis) and optical density (y-axis).

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 ultrahigh contrast negative photographic light-sensitive material suitable for a silver halide light-sensitive material used in a photolithography process.

[0002]

2. Description of the Related Art In a photoengraving process in the field of graphic arts, a continuous tone photographic image is converted into a so-called halftone dot image that expresses the density of the image by the size of the halftone dot area, and an image in which characters and line drawings are taken. A method of making a printing original plate in combination with is performed. The silver halide light-sensitive material used in such applications has a super-high contrast photographic property capable of clearly distinguishing an image portion and a non-image portion in order to improve the reproducibility of characters, line images, and halftone images. Have been asked to have.

As a system that meets such a demand,
There is known a so-called lith development method in which an image having high contrast is formed by treating a silver halide light-sensitive material made of silver chlorobromide with a hydroquinone developer having an extremely low effective concentration of sulfite ion. However, in this method, since the concentration of sulfite ion in the developer is low, the developer is extremely unstable against air oxidation,
A large amount of developer had to be replenished in order to keep the liquid activity stable.

As an image forming system which eliminates the instability of image formation by the lith development method and obtains super-high contrast photographic characteristics by processing with a developer having good storage stability, for example, US Pat. No. 4,166 is used. , 742,
No. 4,168,977, No. 4,221,8
No. 57, No. 4,224,401, No. 4,243,739, No. 4,269,922.
No. 4,272,606, No. 4,272,606
311,781, 4,332,878, 4,618,574, 4,63
No. 4,661, No. 4,681,836, No. 5,650,746 and the like.
These are surface latent image type silver halide photographic light-sensitive materials to which a hydrazine derivative is added, and a sulfurous acid preservative of 0.15 m
It is a system for forming a super-high contrast negative image having a gamma of more than 10 by processing with a developing solution containing hydroquinone / methol or hydroquinone / phenidone having a pH of 11.0 to 12.3 containing ol / L or more as a developing agent. 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.

In order to form a sufficiently high contrast image with a hydrazine derivative, the pH is 11 or higher, usually 1.
It was necessary to process with a developer of 1.5 or more. Although it was possible to increase the stability of the developer by using a high concentration of sulfite preservative, it is necessary to use a developer having a high pH value as described above in order to obtain a super-high contrast photographic image. However, even if there is a preservative, the developer is likely to be air-oxidized and unstable, and therefore, attempts have been made to realize a super-high contrast image at a lower pH in order to further improve the stability.

For example, US Pat. No. 4,269,929 (JP-A-61-267759) and US Pat. No. 4,737,452 (JP-A-60-1797).
34), U.S. Pat. Nos. 5,104,769, 4,798,780, and JP-A 1-17.
No. 9939, No. 1-179940, U.S. Pat. No. 4,998,604, No. 4,994,36.
No. 5, JP-A-8-272023 discloses pH.
A method of using a highly active hydrazine derivative and a nucleation accelerator to obtain an ultrahigh contrast image using a developing solution of less than 11.0 is disclosed. Since the silver halide photographic light-sensitive material used in such an image forming system contains a highly active compound, it has problems of storage stability such as sensitivity fluctuation during storage and increased fog. Most of the causes are due to the high emulsion sensitivity, and there has been a demand for the development of a sensitizing technique having excellent storage stability.

[0007]

SUMMARY OF THE INVENTION In consideration of these problems of the prior art, the present invention has an object of providing a silver halide photographic light-sensitive material having high contrast and high sensitivity.

[0008]

As a result of extensive studies, the present inventors have found that a silver halide photographic light-sensitive material containing an organic gold compound and having a specific gamma can achieve the above object, The present invention has been provided. That is, the present invention provides a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, containing at least one organic gold compound, and having a logarithmic exposure amount (x
(Axis) and optical density (y-axis) in the characteristic curves shown on the orthogonal coordinate axes having the same unit length, the optical densities of 0.3 to 3.
There is provided a silver halide photographic light-sensitive material characterized by having a characteristic curve in which the gamma at 0 is 5.0 or more.

The organic gold compound used in the silver halide photographic light-sensitive material of the present invention preferably has a structure represented by the following general formula (1). Formula (1) [Au (L) ₂ ] ⁺ X ⁻ (In the formula, L represents a ligand, and two Ls may be the same or different from each other, and at least one is mesoionic coordinated. Represents a child, and X ⁻ represents an anion.)

The silver halide photographic light-sensitive material of the present invention preferably contains a hydrazine compound. The film surface pH on the emulsion layer side is preferably 6.0 or less.
It is more preferably 5 to 6.0.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The silver halide photographic light-sensitive material of the present invention will be described in detail below. In addition, in this specification, "-" means the range which includes the numerical value described before and behind that as a minimum value and a maximum value, respectively.

In the present invention, "gamma" means an optical density of 0.3 in a characteristic curve shown on an orthogonal coordinate axis having the same unit length represented by the optical density (y axis) and the common logarithmic exposure amount (x axis). It is the gradient when a straight line is drawn at two points of 3.0 and 3.0. That is, if the angle between the straight line and the x-axis is θ, ta
Indicated by nθ. In the present invention, in order to obtain the characteristic curve,
Using a developing solution (ND-1 from Fuji Photo Film Co., Ltd.) and a fixing solution (NF-1 from Fuji Photo Film Co., Ltd.),
An automatic developing machine (FG-680 manufactured by Fuji Photo Film Co., Ltd.) was used to develop a silver halide photographic light-sensitive material under the development conditions of 35 ° C. and 30 seconds.
AG).

The silver halide photographic light-sensitive material of the present invention has a characteristic curve having a gamma of 5.0 or more, preferably 5.0 to 100, more preferably 5.0 to 30. Although there are various methods for obtaining a silver halide photographic light-sensitive material having the characteristic curve specified in the present invention, for example, a silver halide emulsion containing a heavy metal (for example, a metal belonging to Group VIII) capable of realizing high contrast is used. Can adjust the gamma of the silver halide photographic light-sensitive material. Particularly, it is preferable to use a silver halide emulsion containing a rhodium compound, an iridium compound, a ruthenium compound and the like. It is also preferable that at least one compound such as a hydrazine derivative or an amine compound or a phosphonium compound is contained as a nucleating agent on the side including the emulsion layer.

The organic gold compound used in the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention contains at least one organic gold compound. In the present invention, the photosensitive silver halide emulsion is preferably chemically sensitized in the presence of an organic gold compound. As the organic gold compound, it is preferable to use a compound represented by the following general formula (1) (hereinafter, also referred to as “gold (I) compound”).

General formula (1) [Au (L) ₂ ] ⁺ X ⁻

In the general formula (1), L represents a ligand,
Two L's may be the same or different from each other,
At least one represents a mesoionic ligand. X ⁻ represents an anion such as a halogen ion and BF ₄ ⁻ . However, X
^- is not intended to be limited to monovalent anions.

These compounds can be dissolved in various solvents including water or organic solvents such as acetone or methanol, but the most preferred compounds are water-soluble compounds. As used herein, the term “water-soluble” means that a gold (I) compound has a standard pressure and temperature of 20.
Dissolves in water at a concentration of at least 10 ^-5 mol / L at ° C.

In the general formula (1), the mesoionic ligand represented by L is coordinate-bonded with the gold (I) ion, is water-soluble, and enables chemical sensitization of the silver halide photographic composition. To form a gold (I) compound. The mesoionic ligand is preferably a ligand represented by the following general formula.

[0019]

[Chemical 1]

In the formula, the circle having a + sign on the heterocycle is a symbolic representation of the six delocalized π-electrons associated with the partial positive charge on the heterocycle.

In the formula, a, b, c, d and e are method
Unsubstituted or substituted to complete the on-ligand
Selected atom, for example, the mesoionic triazolium or
The carbon and carbon needed to complete the tetrazolium 5-membered heterocycle
And nitrogen atom. Heterocyclic components (a, b, c,
d and e) are CR^FiveGroup, NR^Five'Group, nitrogen atom and
It can be selected from chalcogen atoms. Minus
The symbol is on the exocyclic group f, which is conjugated with 6 π electrons on the heterocycle.
Two additional electrons are shown. There is extensive delocalization and
The charge that is taken up is only part of the charge. The exocyclic group f is
S, Se and R ^FiveWhichever is selected from
preferable.

Here, R ⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group. R ⁵ 'represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group. R ⁵ "represents a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group. R ⁵ , R ⁵ 'and R ⁵ " may be bonded together to form another ring. be able to.

The mesoionic ligands include Ollis and R
amsden by Advances in Heterocyclic Chemistry, 19
Volume, Academic Press, London (1976) can also be used. The mesoionic ligand represented by the above general formula can be coordinated to gold (I) via the exocyclic group f. From the viewpoint of stability of the organic gold compound, the exocyclic group f is preferably not O (oxygen atom). The above general formula for the mesoionic ligand has a circle representing the six delocalized π-electrons of the heterocyclic moiety, but this does not imply aromaticity.

The compound represented by the general formula (1) includes
The compound represented by the following general formula (1a) is included.

[0025]

[Chemical 2]

In the formula, R ^6a , R ^7a and R ^8a each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group or a substituted or unsubstituted aryl group. (X ^{a) -} is a halogen ion or BF ₄ ^- represents a. Preferred compounds are shown in the table below.

[0027]

[Table 1]

The compounds represented by the general formula (1) include compounds represented by the following general formula (1b).

[0029]

[Chemical 3]

[0030] Here, R ^6b, R ^7b and (X ^{b) -} the above R ^6a, R ^7a and (X ^{a) -} and are each synonymous. Preferred compounds are shown in the table below.

[0031]

[Table 2]

The compound represented by the general formula (1) includes a compound represented by the following general formula (1c).

[0033]

[Chemical 4]

In the formula, R ^6c , R ^7c , R ^8c and R ^9c are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an amino group, a substituted or unsubstituted aryl group. the stands, (X ^{c) -} is halogen or BF ₄ ^- represents a. Preferred compounds are shown in the table below.

[0035]

[Table 3]

The mesoionic compound used as a starting material for preparing the gold (I) compound containing the mesoionic ligand is described in Altrand, Dedio and McSweeney, US Pat. No. 4,378,424 (1983). It can be prepared by the method described or by the method described in the general introduction of Ollis and Ramsden and references cited therein. Synthesis of gold (I) compounds can be performed by various techniques known in the art. For example, a method of reacting a gold (I) precursor compound with an appropriate amount of mesoionic compound is preferable. This reaction is generally at room temperature (about 2
(0 ° C.) or just above room temperature for a few minutes. In the subsequent reaction, the ligand of the gold (I) precursor compound is replaced with a mesoionic ligand having a higher affinity with gold (I). The product obtained can be separated and purified by crystallization techniques.

Various substituents on the mesoionic ligand affect the solubility of the final product gold (I) compound. The most desirable gold (I) compounds are those that are soluble in water and can be made in water. Further, an aqueous emulsion can be sensitized with a solvent that is soluble in an organic solvent such as acetone, and the emulsion can be sensitized with a non-aqueous medium. This gold compound is described in US Pat. No. 5,049,
Further details are provided in US Pat.

In the present invention, the gold (I) compound may be added to any layer on the silver halide emulsion layer side of the support. For example, it can be added to the silver halide emulsion layer or another hydrophilic colloid layer, but it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Further, two or more kinds of organic gold compounds can be added in combination. The organic gold compound of the present invention is preferably added at the time of preparing a silver halide emulsion. The addition amount of the organic gold compound in the present invention is preferably 10 ⁻⁹ to 10 ³ with ^respect to 1 mol of silver halide, and 1
More preferably, it is 0 ⁻⁷ to 10 ² mol.

The silver halide photographic light-sensitive material of the present invention preferably contains a hydrazine compound as a nucleating agent. In particular, it is preferable to contain at least one hydrazine derivative represented by the following general formula (D). General formula (D)

[Chemical 5]

Where R²⁰Is an aliphatic group, an aromatic group, or
Represents a heterocyclic group, R^TenIs a hydrogen atom or a blocking group
Represent, G^TenIs -CO-, -COCO-, -C (= S)-,
-SO₂-, -SO-, -PO (R³⁰) -Group (R³⁰Is R^Ten
R selected from the same range as the group defined in^TenUnlike
You may stay. ) Or an imino methylene group.
A ^Ten, A²⁰Are both hydrogen atoms, or one is a hydrogen atom
And the other is a substituted or unsubstituted alkylsulfonyl group,
Or a substituted or unsubstituted arylsulfonyl group, or
Or represents a substituted or unsubstituted acyl group.

In the general formula (D), the aliphatic group represented by R ²⁰ is preferably a substituted or unsubstituted linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms. is there. In the general formula (D), R ²⁰
The aromatic group represented by is a monocyclic or condensed-ring aryl group, and examples thereof include a benzene ring and a naphthalene ring. R
^The heterocyclic group represented by ²⁰ is a monocyclic or condensed ring, saturated or unsaturated, an aromatic or non-aromatic heterocyclic group, for example, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, Examples thereof include a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, a piperidine ring and a triazine ring. Preferred as R ²⁰ is an aryl group, and particularly preferred is a phenyl group.

The group represented by R ²⁰ may be substituted, and typical examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), an alkyl group (aralkyl group, cycloalkyl group). , An active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (for example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. Group, carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyleneoxy group Or contains repeating propyleneoxy group units , An aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, an (alkyl, aryl, or heterocyclic) amino group, N -Substituted nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, isothioureido group, imide group, (alkoxy or aryloxy)
Carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, N-acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle) thio group, ( Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoramide or phosphate ester structure And the like. These substituents may be further substituted with these substituents.

The substituent which R ²⁰ may have is preferably an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group,
Acylamino group, sulfonamide group, ureido group, sulfamoylamino group, imide group, thioureido group, phosphoramide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group Group, carbamoyl group, carboxy group (including its salt), (alkyl, aryl, or heterocycle) thio group, sulfo group (including its salt), sulfamoyl group, halogen atom, cyano group, nitro group, etc. ..

In the general formula (D), R ¹⁰ represents a hydrogen atom or a blocking group, and the blocking group is specifically an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
It represents a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.

The alkyl group represented by R ¹⁰ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, a trifluoromethyl group, a difluoromethyl group or 2-
Carboxytetrafluoroethyl group, pyridiniomethyl group, difluoromethoxymethyl group, difluorocarboxymethyl group, 3-hydroxypropyl group, methanesulfonamidomethyl group, benzenesulfonamidomethyl group,
Examples thereof include a hydroxymethyl group, a methoxymethyl group, a methylthiomethyl group, a phenylsulfonylmethyl group and an o-hydroxybenzyl group. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, a 2,2-dicyanovinyl group, a 2-ethoxycarbonylvinyl group and a 2-trifluoro-2-methoxycarbonylvinyl group. . The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed ring aryl group is preferable, and a group containing a benzene ring is particularly preferable. Examples thereof include a phenyl group, a 3,5-dichlorophenyl group, a 2-methanesulfonamidophenyl group, a 2-carbamoylphenyl group, a 4-cyanophenyl group and a 2-hydroxymethylphenyl group.

The heterocyclic group is preferably a 5- or 6-membered one containing at least one nitrogen, oxygen and sulfur atom.
Saturated or unsaturated, a monocyclic or condensed ring heterocyclic group, which may be a heterocyclic group containing a quaternized nitrogen atom, for example, a morpholino group, a piperidino group (N-substituted), a piperazino group, Imidazolyl group, indazolyl group (4-nitroindazolyl group, etc.), pyrazolyl group, triazolyl group, benzimidazolyl group, tetrazolyl group,
Examples thereof include a pyridyl group, a pyridinio group (N-methyl-3-pyridinio group and the like), a quinolinio group and a quinolyl group. A morpholino group, a piperidino group, a pyridyl group, a pyridinio group and the like are particularly preferable.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, a 2-hydroxyethoxy group and a benzyloxy group. The aryloxy group is preferably a phenoxy group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized (Including a nitrogen-containing heterocyclic group containing a nitrogen atom) is preferable. Examples of the amino group include 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolyl group. Lumino group, N-benzyl-3-pyridinioamino group and the like. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (4-benzenesulfonamidophenylhydrazino group etc.) is particularly preferable.

The group represented by R ¹⁰ may be substituted, and preferable examples of the substituent include those exemplified as the substituent of R ²⁰ .

In the general formula (D), R^TenIs G^Ten-R^Tenof
Split the part from the rest of the molecule, ^Ten-R^TenPart of atom
Such as causing a cyclization reaction to produce a cyclic structure containing
For example, Japanese Unexamined Patent Application Publication No. Sho 6
Examples thereof include those described in JP-A-3-29751.

The hydrazine derivative represented by the general formula (D) may have an adsorptive group adsorbing to silver halide incorporated therein. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups and triazole groups, which are described in U.S. Pat. No. 4,385,108 and 4,459,347.
Specification, JP-A-59-195233 and 59-
No. 200231, No. 59-201045, No. 59-201046, No. 59-201047, No. 59-201048, and No. 59-20104.
No. 9, JP-A-61-170733, JP-A 61-170733.
270744, 62-948, and 63-.
The groups described in JP-A-234244, JP-A-63-234245 and JP-A-63-234246 are mentioned. The adsorbing group for these silver halides may be a precursor. Examples of such precursors include the groups described in JP-A-2-285344.

R ¹⁰ or R ^{20 in} the general formula (D) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. In the present invention, the ballast group is a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio having 6 or more carbon atoms. Represents a group or a group having these as a partial structure, and more preferably has a carbon number of 7 or more and 24 or less, a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), It represents an alkylamino group (or alkyleneamino group), an alkylthio group, or a group having these as a partial structure. Examples of the polymer include those described in JP-A No. 1-100530.

R ¹⁰ or R ²⁰ in the general formula (D) may contain a plurality of hydrazino groups as a substituent. At this time, the compound represented by the general formula (D) is a multimer with respect to the hydrazino group. And specifically, for example, JP-A-64-86
134, JP-A-4-16938, JP-A-5
-197091, WO95-32452, International Publication WO95-32453, JP-A-9-1792.
29, JP-A-9-235264, JP-A-9
The compounds described in JP-A-235265, JP-A-9-235266, JP-A-9-235267 and the like can be mentioned.

R ¹⁰ or R ^{20 in} the general formula (D) includes a cationic group (specifically, a group containing a quaternary ammonio group, a group containing a quaternized phosphorus atom, or A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, an (alkyl, aryl, or heterocycle) thio group, or a dissociative group (alkaline group) A group or partial structure having a proton with low acidity that can be dissociated in a developing solution,
Alternatively, it means a salt thereof, specifically, for example, a carboxyl group (—COOH), a sulfo group (—SO ₃ H),
Phosphonic acid group (-PO ₃ H), phosphoric acid group (-OPO
₃ H), hydroxy group (-OH group), mercapto group (-
SH), - SO ₂ NH ₂ group, N- substituted sulfonamide groups (-SO ₂ NH- group, -CONHSO ₂ - group, -CONH
SO ₂ NH- group, -NHCONHSO ₂ - group, -SO ₂ N
HSO ₂ — group), —CONHCO— group, active methylene group, —NH— group in the nitrogen-containing heterocyclic group, or salts thereof) may be included. Examples of these groups include, for example, JP-A-7-234471, JP-A-5-333466, and JP-A-6-190.
32, JP-A-6-19031, and JP-A-5-
45761, U.S. Pat. No. 4,994,365, U.S. Pat. No. 4,988,604, JP-A-7-259240, JP-A-7-5610,
JP-A-7-244348, German Patent 4006032
The compounds described in JP-A No. 11-7093 and the like are mentioned.

In the general formula (D), A^Ten, A²⁰Is hydrogen
Child, alkyl or aryl sulfoni with 20 or less carbon atoms
Group (preferably phenylsulfonyl group, or
The total of the substituent constants of the
Phenylsulfonyl group), acyl having 20 or less carbon atoms
Group (preferably benzoyl group or Hammett's substituent
Benzo substituted such that the sum of constants is −0.5 or more.
Or a linear, branched, or cyclic substitution
Is an unsubstituted aliphatic acyl group (wherein the substituent is, for example,
For example, halogen atom, ether group, sulfonamide group,
Rubonamide group, hydroxy group, carboxy group, sulfo group
Groups and the like))). A^Ten, A ²⁰As hydrogen
Atoms are most preferred.

Next, the hydrazine derivative which is particularly preferably used in the present invention will be described. R ²⁰ is particularly preferably a substituted phenyl group, and as the substituent, a sulfonamide group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group, an N-acylsulfamoylamino group and the like are particularly preferable. A sulfonamide group and a ureido group are more preferable, and a sulfonamide group is most preferable. The hydrazine derivative represented by the general formula (D) is a group containing a ballast group, a silver halide adsorption group, a quaternary ammonio group as a substituent, in R ²⁰ or R ¹⁰ , as a substituent. A nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, a group containing a repeating unit of an ethyleneoxy group, (alkyl, aryl,
Or heterocyclic) thio group, at least one substitution of an alkali dissociative group capable of dissociation by developing solution or hydrazino group capable of forming a multimer (group represented by -NHNH-G ¹⁰ -R ¹⁰⁾ Is particularly preferable. Furthermore, it is preferable that R ²⁰ has, as a substituent of any one of the above groups, directly or indirectly, most preferably, R ²⁰ represents a phenyl group substituted with a benzenesulfonamide group, This is a case where the benzenesulfonamide group has any one of the groups described above as a substituent on the benzene ring directly or indirectly.

Preferred among the groups represented by R ¹⁰ are:
When G ¹⁰ is a —CO— group, a hydrogen atom, an alkyl group,
An alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, a substituted aryl group (as a substituent, an electron withdrawing group or an o-hydroxymethyl group is particularly preferable), Most preferably, it is a hydrogen atom or an alkyl group. When G ¹⁰ is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferable, and a substituted amino group, particularly an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is preferable. . Also G ¹⁰
When is a —SO ₂ — group, R ¹⁰ is preferably an alkyl group, an aryl group or a substituted amino group.

In the general formula (D), G ¹⁰ is preferably-
A CO- group or a -COCO- group, particularly preferably a -CO- group.

Specific examples of the compound represented by formula (D) are shown below. However, the compound that can be used in the present invention is not limited to the following specific examples.

[0059]

[Chemical 6]

[0060]

[Chemical 7]

[0061]

[Chemical 8]

[0062]

[Chemical 9]

[0063]

[Chemical 10]

[0064]

[Chemical 11]

[0065]

[Chemical 12]

[0066]

[Chemical 13]

[0067]

[Chemical 14]

[0068]

[Chemical 15]

[0069]

[Chemical 16]

[0070]

[Chemical 17]

[0071]

[Chemical 18]

[0072]

[Chemical 19]

[0073]

[Chemical 20]

[0074]

[Chemical 21]

[0075]

[Chemical formula 22]

[0076]

[Chemical formula 23]

[0077]

[Chemical formula 24]

[0078]

[Chemical 25]

[0079]

[Chemical formula 26]

[0080]

[Chemical 27]

[0081]

[Chemical 28]

[0082]

[Chemical 29]

[0083]

[Chemical 30]

[0084]

[Chemical 31]

[0085]

[Chemical 32]

[0086]

[Chemical 33]

[0087]

[Chemical 34]

As the hydrazine derivative used in the present invention, the following hydrazine derivative is preferably used in addition to the above. The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following publications.

Compounds represented by (Chemical formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the publication; described in JP-B-6-93082. A compound represented by the general formula (I), specifically, the same publication 8
1 to 38 compounds described on pages 18 to 18; JP-A-6-23
Compounds represented by the general formula (4), the general formula (5) and the general formula (6) described in JP-A-0497, specifically, compounds 4-1 to 4-1 described on pages 25 and 26 of the publication. 4-1
0, compounds 5-1 to 5-42 described on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7: compounds represented by the general formula (1) and the general formula (2) described in JP-A-6-289520, specifically Compound 1-1 described on pages 5 to 7 of the same. ~ 1-1
7) and 2-1); compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same; JP-A-6
A compound represented by (Chemical Formula 1) described in JP-A-313951, specifically a compound described on pages 3 to 5 of the same; a compound represented by formula (I) described in JP-A-7-5610; Specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same publication; compounds represented by general formula (II) described in JP-A-7-77783. Specifically, the compounds II-1 to II-10 described on pages 10 to 27 of the publication.
2; compounds represented by formula (H) and formula (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H described on pages 8 to 15 of the publication. −
44; a compound characterized by having an anionic group or a nonionic group which forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, particularly in the general formula (A), general formula (B), general formula (C), general formula (D), general formula (E),
Compounds represented by formula (F), specifically compounds N-1 to N-30 described in the same publication; JP-A-9-22082
Examples of the compound represented by the general formula (1) described in JP-A No. 2004-96242 include compounds D-1 to D-55 described in the same. In addition, international publication WO95-32452
Publication, International Publication WO95-32453, JP-A-9-179229, JP-A-9-235264, JP-A-9-235265, JP-A-9-235.
No. 266, No. 9-235267, No. 9-319019, No. 9-319020, No. 10-130275, No. 11-7.
093, JP 6-332096 A, JP 7-209789 A, JP 8-6193 A,
JP-A-8-248549 and JP-A-8-24855.
No. 0, JP-A-8-262609, JP-A-8-
314044, JP-A-8-328184,
JP-A-9-80667 and JP-A-9-127632
JP-A-9-146208 and JP-A-9-1
No. 60156, JP-A-10-161260,
JP-A-10-221800 and JP-A-10-213
871, JP-A-10-254082, JP-A-10-254088, and JP-A-7-120864.
JP-A-7-244348, JP-A-7-3
33773, JP 8-36232, JP 8-36233, JP 8-36234, JP 8-36235, and JP 8-2720.
No. 22, JP-A-9-22083, JP-A 9-
The hydrazine derivatives described in JP-A-22084, JP-A-9-54381 and JP-A-10-175946 can also be mentioned.

In the present invention, the hydrazine nucleating agent is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methyl cellosolve or the like. Further, by well-known emulsion dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It is possible to dissolve it using an auxiliary solvent such as ethyl acetate or cyclohexanone and mechanically prepare an emulsified dispersion for use. Alternatively, by a method known as a solid dispersion method, a hydrazine derivative powder is ball-milled in water,
A colloid mill or ultrasonic waves may be used for dispersion.

In the present invention, the hydrazine-based nucleating agent may be added to any layer provided that it is on the silver halide emulsion layer side of the support. For example, it can be added to the silver halide emulsion layer or another hydrophilic colloid layer, but it is preferably added to the silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Further, two or more kinds of hydrazine-based nucleating agents can be used in combination. The addition amount of the nucleating agent in the present invention is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol per 1 mol of silver halide, and 1 × 1.
0 ^{−5 to} 5 × 10 ⁻³ mol is more preferable, and 2 × 10 ⁻⁵ to
Most preferred is 5 × 10 ⁻³ mol.

A nucleation accelerator can be incorporated in the silver halide photographic light-sensitive material of the present invention. Examples of the nucleation accelerator used in the present invention include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. Specifically, JP-A-7-77783
JP-A No. 48, lines 2 to 37, specifically compounds A-1) to A-7 described on pages 49 to 58.
3); (Chemical Formula 2) described in JP-A-7-84331.
1), (compound 22) and (compound 23), specifically the compounds described on pages 6 to 8 of the same; the general formula [Na] described in JP-A-7-104426. And compounds represented by general formula [Nb], specifically, compounds Na-1 to Na-22 and compounds Nb-1 to Nb-12 described on pages 16 to 20 of the same publication; -2
General formula (1), general formula (2), general formula (3), general formula (4), general formula (5)
A compound represented by the general formula (6) or the general formula (7),
Specifically, the compounds 1-1 to 1-19 described in the publication,
Compounds 2-1 to 2-22, Compounds 3-1 to 3-36, Compounds 4-1 to 4-5, Compounds 5-1 to 5-41, Compounds 6-1 to 6-58, And 7-1 to 7-3
Compound of 8; p55 of JP-A-9-297377,
The nucleation accelerator described in line 8 of column 108 to p69 and line 44 of column 136 can be mentioned.

The nucleation accelerator used in the present invention includes
The quaternary salt compounds represented by the following general formulas (a) to (f) are preferable, and the compound represented by the general formula (b) is most preferable.

[0094]

[Chemical 35]

[0095]

[Chemical 36]

In the general formula (a), Q ¹ represents a nitrogen atom or a phosphorus atom, R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ each represent an aliphatic group, an aromatic group or a heterocyclic group, which are bonded to each other. You may form a cyclic structure. M is a carbon atom contained in M and represents an m ¹⁰ -valent organic group which is bonded to Q ¹ .
Here, m ¹⁰ represents an integer of 1 to 4. In the general formula (b), the general formula (c), or the general formula (d), A ¹ , A ² ,
A ³ , A ⁴ and A ⁵ each represent an organic residue for completing an unsaturated heterocycle containing a quaternized nitrogen atom,
L ¹⁰ and L ²⁰ represent a divalent linking group, and R ¹¹¹ , R ²²² ,
R ³³³ represents a substituent. General formula (a), general formula (b),
The quaternary salt compound represented by the general formula (c) or the general formula (d) has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups in the molecule,
This may be provided over a plurality of locations.

In the general formula (e), Q ² represents a nitrogen atom or a phosphorus atom. R ²⁰⁰ , R ²¹⁰ , and R ²²⁰ represent the same groups as R ¹⁰⁰ , R ¹¹⁰ , and R ^{120 in the} general formula (a). In general formula (f), A ⁶ represents a group having the same meaning as A ¹ or A ² in general formula (b). However, the nitrogen-containing unsaturated heterocycle formed by A ⁶ may have a substituent, but does not have a primary hydroxyl group on the substituent. In formulas (e) and (f), L ³⁰ represents an alkylene group, and Y represents —C.
(= O) - or -SO ₂ - represents, L ⁴⁰ represents a divalent linking group containing at least one hydrophilic group. In the general formulas (a) to (f), ^Xn- represents an n-valent counter anion, and n represents an integer of 1 to 3. However, when it has an anion group in the molecule and forms an intramolecular salt with (Q ¹ ) ⁺ , (Q ² ) ⁺ or N ⁺ , X ^n- is not necessary.

In the general formula (a), R ¹⁰⁰ , R ¹¹⁰ , R
^The aliphatic group represented by ¹²⁰ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
sec-butyl group, tert-butyl group, octyl group,
2-ethylhexyl group, dodecyl group, hexadecyl group,
A linear or branched alkyl group such as octadecyl group;
An aralkyl group such as a substituted or unsubstituted benzyl group;
Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group; allyl group, vinyl group, 5-
Examples thereof include an alkenyl group such as a hexenyl group; a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group; and an alkynyl group such as a phenylethynyl group. The aromatic group is a phenyl group, a naphthyl group, an aryl group such as a phenanthryl group, and the heterocyclic group is a pyridyl group, a quinolyl group, a furyl group, an imidazolyl group, a thiazolyl group, a thiadiazolyl group, a benzotriazolyl group,
Examples thereof include a benzothiazolyl group, a morpholyl group, a pyrimidyl group, and a pyrrolidyl group.

Examples of the substituents substituted on these groups include, in addition to the groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, Nitro group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, carbonamido group, carbamoyl group, ureido group, thioureido group, sulfonylureido group, sulfonamide group, sulfamoyl group, Hydroxyl group, sulfonyl group, carboxyl group (including carboxylate), sulfo group (including sulfonate), cyano group, oxycarbonyl group, acyl group, heterocyclic group (heterocyclic group containing a quaternized nitrogen atom (Including) and the like. These substituents may be further substituted with these substituents. The groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ in the general formula (a) may be bonded to each other to form a cyclic structure.

As an example of the group represented by M in the general formula (a),
Is m^TenWhen represents 1, R¹⁰⁰, R^{1 Ten}, R¹²⁰Synonymous with
Groups. m^TenIs an integer of 2 or more, M is M
Q in the carbon atom contained in¹Combined with m^TenValent linking group
Represents, specifically, an alkylene group, an arylene group, and
B ring group, and further, these groups and -CO- group, -O- group,
-N (RN)-group, -S- group, -SO- group, -SO₂-,
M formed by combining -P = O- groups^TenValuable linking group
Represents (RN is a hydrogen atom or R¹⁰⁰, R¹¹⁰, R¹²⁰
When a plurality of RNs are present in the molecule,
These may be the same or different, and
May be combined with each other). M has an optional substituent
And the substituent may be R¹⁰⁰, R¹¹⁰, R
¹²⁰The same as the substituent that the group represented by may have
Is mentioned.

In the general formula (a), R ¹⁰⁰ , R ¹¹⁰ , R
¹²⁰ is preferably a group having 20 or less carbon atoms, particularly preferably an aryl group having 15 or less carbon atoms when Q ¹ represents a phosphorus atom, and an alkyl group having 15 or less carbon atoms when Q ¹ represents a nitrogen atom. , Aralkyl groups and aryl groups are particularly preferable.
m ¹⁰ is preferably 1 or 2, and when m ¹⁰ is 1, M is preferably a group having 20 or less carbon atoms, and an alkyl group, aralkyl group or aryl group having 15 or less carbon atoms is particularly preferable. When m ¹⁰ represents 2, the divalent organic group represented by M is preferably an alkylene group, an arylene group, and further these groups and a —CO— group, a —O— group, a —N (RN) group.
It is a divalent group formed by combining a — group, a —S— group and a —SO ₂ — group. When m ¹⁰ represents 2, M is preferably a divalent group having a total carbon number of 20 or less, which is a carbon atom contained in M and is bonded to Q ¹ . In addition, M, or R ¹⁰⁰ , R
^{When 110} and R ¹²⁰ each include a plurality of repeating units of ethyleneoxy group or propyleneoxy group, the preferred range of the total number of carbon atoms is not limited thereto. Also m ¹⁰
Is an integer of 2 or more, R ¹⁰⁰ , R ¹¹⁰ , R in the molecule
There are a plurality of ¹²⁰ , respectively, but the plurality of R ¹⁰⁰ , R
¹¹⁰ and R ¹²⁰ may be the same or different.

The quaternary salt compound represented by the general formula (a) is
There are a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups in the molecule, which may be substituted at one position or may be distributed over a plurality of positions. When m ¹⁰ represents an integer of 2 or more, M
It is more preferable that the linking group represented by has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups.

In the general formula (b), general formula (c) or general formula (d), A ¹ , A ² , A ³ , A ⁴ and A ^{5 each} contain a quaternized nitrogen atom and are substituted or non-substituted. It represents an organic residue for completing a substituted unsaturated heterocycle, which may contain a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a hydrogen atom, and may further have a condensed benzene ring.
Examples of unsaturated heterocycles formed by A ¹ , A ² , A ³ , A ⁴ and A ⁵ include pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, thiazole ring, thiadiazole ring, benzotriazole ring, benzothiazole. Examples thereof include a ring, a pyrimidine ring, a pyrazole ring and the like. Particularly preferred are a pyridine ring, a quinoline ring, and an isoquinoline ring. The unsaturated heterocycle formed by A ¹ , A ² , A ³ , A ⁴ , and A ⁵ together with the quaternized nitrogen atom may have a substituent. Examples of the substituent in this case include the same substituents that the groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ of the general formula (a) may have. The substituent is preferably a halogen atom (particularly a chloro atom), an aryl group having 20 or less carbon atoms (particularly preferably a phenyl group),
Alkyl group, alkynyl group, carbamoyl group, (alkyl or aryl) amino group, (alkyl or aryl) oxycarbonyl group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, hydroxy group, mercapto group, carbonamide group , Sulfonamide group, sulfo group (including sulfonate), carboxyl group
(Including carboxylate), cyano group, and the like. Particularly preferably, a phenyl group, an alkylamino group,
A carbonamido group, a chloro atom, an alkylthio group and the like, and a phenyl group is most preferable.

The divalent linking group represented by L ¹⁰ and L ²⁰ includes alkylene, arylene, alkenylene, alkynylene,
A divalent heterocyclic _{group, -SO 2 -, - SO -} , - O -, -
It is preferable that S-, -N (RN ')-, -C (= O)-, and -PO- are used alone or in combination. However, RN 'represents an alkyl group, an aralkyl group, an aryl group, or a hydrogen atom. The divalent linking group represented by L ¹⁰ and L ²⁰ may have any substituent. Examples of the substituent include the same substituents that the groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ of the general formula (a) may have. L ¹⁰ , L
^As particularly preferable examples of ²⁰ , alkylene, arylene,
-C (= O) -, - O -, - S -, - SO 2 -, - N
(RN ')-may be used alone or in combination.

R ¹¹¹ , R ²²² , and R ³³³ are preferably an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and they may be the same or different. R ¹¹¹ , R ²²² , and R ³³³ may have a substituent, and the substituent may be a group represented by R ¹⁰⁰ , R ¹¹⁰ , and R ¹²⁰ of the general formula (a). The same thing as a substituent is mentioned. Particularly preferably, R
¹¹¹ , R ²²² , and R ³³³ are each an alkyl group having 1 to 10 carbon atoms or an aralkyl group. Examples of preferable substituents include carbamoyl group, oxycarbonyl group, acyl group, aryl group, sulfo group (including sulfonate), carboxyl group (including carboxylate), hydroxy group, (alkyl or aryl) amino group, An alkoxy group can be mentioned. However, when R ¹¹¹ , R ²²² , and R ³³³ contain a plurality of repeating units of ethyleneoxy group or propyleneoxy group, the above R ¹¹¹ , R ²²² , and R ^{333 can be used.}
The preferred range of the number of carbons mentioned above is not limited to this.

The quaternary salt compound represented by the general formula (b) or the general formula (c) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule. It may be substituted or may be substituted at a plurality of positions, A ¹ , A ² , A ³ , A ⁴ , R
^111, R ^222, L ^10, may be substituted in any of the L ²⁰ but, preferably, the linking group represented by L ¹⁰ or L ^20, repeating units of ethyleneoxy group or propyleneoxy group in total 20 It is preferable to have one or more.

The quaternary salt compound represented by the general formula (d) is
It has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups in the molecule, which may be substituted at one position or at multiple positions, and is either A ⁵ or R ³³³ . The group represented by R ³³³ preferably has a total of 20 or more repeating units of ethyleneoxy groups or propyleneoxy groups.

The quaternary salt compound represented by the general formula (a), the general formula (b), the general formula (c) and the general formula (d) contains an ethyleneoxy group and a propyleneoxy group simultaneously and repeatedly. You can leave. Further, when a plurality of repeating units of ethyleneoxy group or propyleneoxy group is contained, the repeating number may take exactly one value or may be given as an average value. In the latter case, quaternary salt The compound is a mixture having a certain molecular weight distribution. In the present invention, it is more preferable to have a total of 20 or more ethyleneoxy repeating units, and it is more preferable to have a total of 20 to 67 total repeating units.

In the general formula (e), Q ² , R ²⁰⁰ ,
R ²¹⁰ and R ²²⁰ are each Q ¹ in the general formula (a),
It represents a group having the same meaning as R ¹⁰⁰ , R ¹¹⁰ and R ^120, and the preferred ranges are also the same. In the general formula (f), A ⁶ is
Represents a group having the same meaning as A ¹ or A ² in the general formula (b),
The preferable range is also the same. However, the nitrogen-containing unsaturated heterocycle formed by A ^{6 of} the general formula (f) together with the quaternized nitrogen atom may have a substituent,
It does not have a substituent containing a primary hydroxyl group.

In formulas (e) and (f), L ³⁰ represents an alkylene group. The alkylene group is preferably a linear, branched, or cyclic, substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Further, not only saturated one represented by ethylene group but also -CH ₂
It may contain an unsaturated group represented by C ₆ H ₄ CH ₂ — and —CH ₂ CH═CHCH ₂ —. When L ³⁰ has a substituent, examples of the substituent include the substituents which the groups represented by R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ of the general formula (a) may have. L ³⁰ has 1 to 1 carbon atoms
0, straight-chain or branched, saturated groups are preferred. More preferably, it is a substituted or unsubstituted methylene group, ethylene group or trimethylene group, particularly preferably a substituted or unsubstituted methylene group or ethylene group, and most preferably a substituted or unsubstituted methylene group.

In the general formulas (e) and (f), L ⁴⁰ represents a divalent linking group having at least one hydrophilic group. Here -SO the hydrophilic group ₂ -, - SO-,
-O-, -P (= O) =, -C (= O)-, -CONH
_{-, - SO 2 NH -,} - NHSO 2 NH -, - NHCON
H-, an amino group, a guadinino group, an ammonio group, each group of a heterocyclic group containing a quaternized nitrogen atom, or a group composed of a combination of these groups. L ⁴⁰ is constituted by appropriately combining these hydrophilic groups with an alkylene group, an alkenylene group, an arylene group and a heterocyclic group. Groups such as an alkylene group, an arylene group, an alkenylene group, and a heterocyclic group that form L ⁴⁰ may have a substituent.
Examples of the substituent include R ¹⁰⁰ , R ¹¹⁰ and R ¹²⁰ of the general formula (a).
Examples of the substituent that the group represented by may have include the same ones. Also the hydrophilic group in L ⁴⁰ is present in the form of dividing the L ^40, may it be present as part of a substituent on L ^40, that are present in the form of dividing the L ⁴⁰ Is more preferable. For example, -C (= O)-, -SO
_2- , -SO-, -O-, -P (= O) =, -CONH
_{-, - SO 2 NH -,} - NHSO 2 NH -, - NHCON
H-, a cationic group (specifically, a quaternary salt structure of nitrogen or phosphorus, or a nitrogen-containing heterocycle containing a quaternized nitrogen atom), an amino group, a guadinino group, or a group of these groups. This is the case where a divalent group consisting of a combination is present in a form that divides L ⁴⁰ .

L⁴⁰Of a preferred example of the hydrophilic group of
One is a combination of an ether bond and an alkylene group,
Repeating units of ethyleneoxy and propyleneoxy groups
Is a group having a plurality of Degree of polymerization or average polymerization
The degree is preferably 2 to 67. L⁴⁰With a hydrophilic group
Also, -SO₂-, -SO-, -O-, -P (=
O) =, -C (= O)-, -CONH-, -SO₂NH
-, -NHSO₂NH-, -NHCONH-, amino
Group, guadinino group, ammonio group, quaternized nitrogen source
As a result of combining groups such as a heterocyclic group containing a child,
Or or L⁴⁰A dissociative group as a substituent of
It is also preferable to include. Here, the dissociative group is alkaline
Having a low-acidic proton that can be dissociated in the developer of
Or a partial structure, or a salt thereof,
Specifically, for example, a carboxy group (—COOH), a sulfo group
(-SO₃H), phosphonic acid group (-PO₃H), phosphate group
(-OPO₃H), hydroxy group (-OH group), merca
Put group (-SH), -SO₂NH ₂Group, N-substituted sulfo
Amide group (-SO₂NH-group, -CONHSO₂-Base,
-SO₂NHSO₂-Group), -CONHCO- group, active group
Or a -NH- group inherent in a nitrogen-containing heterocyclic group,
Or these salts.

L ⁴⁰ is preferably an alkylene group or an arylene group, and -C (= O)-, -SO _2- , -O-,-.
_{CONH -, - SO 2 NH -} , - NHSO 2 NH -, - N
An appropriate combination of HCONH- and an amino group is used. More preferably -C alkylene group having 2 to 5 carbon atoms (= O) -, - SO 2 -, - O -, - CON
_{H -, - SO 2 NH -} , - NHSO 2 NH -, - NHCO
An appropriate combination of NH- is used. Y is -C
(= O) - or -SO ₂ - represents a. Preferably -C
(= O)-is used.

In the general formulas (a) to (f), X ^n-
Examples of the counter anion represented by are halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion, carboxylate ion such as benzoate ion, p-
Examples thereof include sulfonate ion such as toluene sulfonate, methane sulfonate, butane sulfonate, and benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion, and nitrate ion. 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. As ^Xn- , a chloro ion or a bromo ion is particularly preferable, and a chloro ion is most preferable. However, having another anion group in the molecule,
When forming an intramolecular salt with (Q ¹ ) ⁺ , (Q ² ) ⁺ or N ⁺ , X ^n- is not necessary.

The quaternary salt compound used in the present invention is represented by the general formula (b), the general formula (c) or the general formula (f).
The quaternary salt compounds are more preferable, and among them, the quaternary salt compounds represented by the general formulas (b) and (f) are particularly preferable.
Further, in the general formula (b), it is preferable that the linking group represented by L ¹⁰ has 20 or more ethyleneoxy repeating units, and particularly preferably 20 to 67 repeating units. In the general formula (f), the unsaturated heterocyclic compound formed by A ⁶ is 4-phenylpyridine,
It is particularly preferable when it represents isoquinoline or quinoline.

Specific examples of the quaternary salt compounds represented by the general formulas (a) to (f) are shown below. In the following, Ph represents a phenyl group. However, the present invention is not limited to the following compound examples.

[0117]

[Chemical 37]

[0118]

[Chemical 38]

[0119]

[Chemical Formula 39]

[0120]

[Chemical 40]

[0121]

[Chemical 41]

[0122]

[Chemical 42]

[0123]

[Chemical 43]

[0124]

[Chemical 44]

4 represented by the general formulas (a) to (f)
The graded salt compound can be easily synthesized by a known method. Specifically, Synthesis Examples 1 to 6 described later can be referred to.

The nucleation accelerator which can be used in the present invention is a suitable water-miscible organic solvent such as alcohols (methanol,
It can be used by dissolving it in ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like.

Further, by well-known emulsification-dispersion method, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically dissolved. An emulsified dispersion can be prepared 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 which can be used in the present invention is preferably added to the non-photosensitive layer consisting of a hydrophilic colloid layer containing no silver halide emulsion on the side of the silver halide emulsion layer with respect to the support. It is preferably added to a non-photosensitive layer consisting of a hydrophilic colloid layer between the silver halide emulsion layer and a support. The addition amount of the nucleation accelerator of the present invention is preferably ^{1 × 10 -6 ~2 × 10 -2} mol to silver halide 1 mol, more preferably ^{1 × 10 -5 ~2 × 10 -2} mol, 2
Most preferably, it is x10 ^-5 to 1 x 10 ^-2 mol. Also, 2
It is also possible to use more than one type of nucleation accelerator together.

The silver halide for the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited. Silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide can be used, but silver chlorobromide and silver iodochlorobromide containing 50 mol% or more of silver chloride are used. Is preferred. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of silver halide is 0.1 μm to 0.7 μm
Is preferable, but more preferably 0.1 to 0.5 μm. Also, {(standard deviation of particle size) / (average particle size)} × 1
The coefficient of variation represented by 00 is preferably 15% or less, and more preferably 10% or less with a narrow particle size distribution. The silver halide grains may be composed of a uniform phase in the inside and the surface layer or may be different. In addition, a localized layer having a different halogen composition may be provided inside or on the surface of the grain.
The photographic emulsion used in the present invention is described by P. Glafkides Ch
imie et PhysiquePhotographique (Paul Montel, 1967), GF Dufin, PhotographicEmulsion
Chemistry (The Forcal Press, 1966), VL Zeli
By kman et al Making and Coating Photographic Emulsi
on (The Forcal Press, 1964) and the like. That is, the acidic method,
Any method such as 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, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.

As one form of the simultaneous mixing method, a method of keeping pAg in the liquid phase where silver halide is formed 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. Tetra-substituted thiourea compounds are more preferred as the silver halide solvent, and are described in JP-A Nos. 53-82408 and 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The amount of the silver halide solvent added varies depending on the kind of the compound used, the intended grain size and the halogen composition, but it is 10 ^-5 to 10 per 1 mol of the silver halide.
^-2 mol is preferred.

The controlled double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and are used in the present invention. It is a useful tool for making silver halide emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-36890 and 52-163.
64, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, British Patent No. 4,242,445 and JP-A-55-158124. It is preferable to use the method of changing the concentration of the aqueous solution as described in the official gazette and to grow it quickly in a range not exceeding the critical saturation.

The silver halide emulsion used in the present invention is
It may contain a metal belonging to Group VIII. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound and the like. In addition, for higher sensitivity, K
₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ], K ₃ [C
Doping with a metal hexacyanide complex such as r (CN) ₆ ] is effective.

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, aco, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, tetrachlorodiaco Rhodium complex salt, hexabromorhodium (II
Examples thereof include I) complex salts, hexaaminerhodium (III) complex salts, and trisalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or alkali halides (eg KCl, NaCl, KBr, NaB
r etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The rhenium, ruthenium and osmium used in the present invention are disclosed in JP-A-63-2042, JP-A-1-285941 and JP-A-20-20852.
It is added in the form of a water-soluble complex salt described in JP-A-2-20855. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^n- where M
Represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands and thionitrosyl ligands. Specific examples of the complex used in the present invention are shown below, but the complex usable in the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O ) ₂ (CN) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^1- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CO) ₃ Cl ₃ ] ^2- [Ru (CO) Cl ₅ ] ^2- [Ru (CO) Br ₅ ] ^2- [OsCl ₆ ] ^3- [OsCl ₅ (NO)] ^2- [Os (NO) (CN) ₅ ^2- [Os (NS) Br _5] ^2- [Os (CN) _6] ^4- _{[Os (O) 2 (CN)} 4 ] ^4-

The addition amount of these compounds is 1
1 x 10 per mol^-9mol ~ 1 x 10^-Fiverange of mol
Is preferable, and particularly preferably 1 × 10^-8mol ~ 1x
10 ^-6mol. Iridium used in the present invention
As a compound, hexachloroiridium, hexabromo
Iridium, hexaammine iridium, pentachrome
Examples include ronitrosyl iridium. Used in the present invention
The iron compound used is potassium hexacyanoferrate (II).
Examples include um and ferrous thiocyanate.

The silver halide emulsion used in the present invention is preferably chemically sensitized. As the method of chemical sensitization, in addition to the method using the organic gold compound, 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. Used alone or in combination. When used in combination, for example,
The sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing 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. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are thiosulfates and thiourea compounds. As the thiourea compound, the specific tetra-substituted thiourea compound described in US Pat. No. 4,810,626 is particularly preferable. 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, but is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻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. Unstable selenium compounds are disclosed in JP-B-44-15748 and 43-13489.
JP-A-4-109240 and JP-A-4-324.
The compounds described in Japanese Patent No. 855 can be used.
In particular, the general formula (VIII) in JP-A-4-324855
It is preferable to use the compounds represented by and (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of silver halide grains. Regarding the formation rate of silver telluride in a silver halide emulsion, the method disclosed in JP-A-5-187
It can be tested by the method described in JP-A-313284. Specifically, US Pat. Nos. 1,623,499, 3,320,069 and 3,773.
No. 2,031 specification, British patent No. 235,211 specification, No. 1,121,496 specification, No. 1,29.
5,462, 1,396,696, Canadian Patent 800,958, and JP-A-4-
No. 204640, No. 4-271341, No. 4
-333043, 5-303157, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 63
5 (1980), ibid 1102 (1979), ibid
645 (1979), Journal of Chemical Society Perkin Transactions (J. Chem. So
c.Perkin.Trans.) 1,191 (1980), edited by S. Patai, The Chemistry of Organic Serenium and Tellunium
Compounds), Vol 1 (1986), Vol 2 (198)
The compounds described in 7) can be used. In particular, the general formulas (II), (III), (I) in JP-A-4-324855
Compounds represented by V) are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 1 mol of silver halide is used.
10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10
^Use about ^-3 mol. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, pA
The g is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 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 chloroaurate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol can be used per mol of silver halide. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of forming silver halide grains or physically ripening.

Reduction sensitization can be used in the present invention. As reduction sensitizers, stannous salts, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication EP 293,917. The silver halide emulsion in the silver halide photographic light-sensitive material used in the present invention may be of only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions,
Different crystal habits, different chemical sensitization conditions, different sensitivities) may be used together. Above all, in order to obtain a high contrast, it is preferable to coat an emulsion having a higher sensitivity as it is closer to the support, as described in JP-A-6-324426.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. Furthermore, JP-A-5
Compounds of general formula [I] described in JP-A-5-45015,
Further, the compound of the general formula [I] described in JP-A-9-160185 is preferable, and particularly, JP-A-9-1601.
The compounds of general formula [I] described in JP-A-85 are preferred.
Specifically, the compounds (1) to (19) described in JP-A-55-45015, the compounds I-1 to I-40 and I-5 described in JP-A-9-160185.
6 to I-85 and the like.

Other sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes,
Complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. Other useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-A (19).
December 1978 p. 23), Item 18341X item (19)
August 1979 p. 437) or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate-making cameras can be advantageously selected.

For example, as for A) an argon laser light source, (I) described in JP-A-60-162247.
-1 to (I) -8 compounds, I-1 to I-28 compounds described in JP-A-2-48653, JP-A-4-
Compounds I-1 to I-13 described in JP-A-330434 and Ex described in US Pat. No. 2,161,331
compounds of samples 1-14, West German Patent 936,071
Compounds 1 to 7 described in JP-A No. 6-78, and B) helium-neon laser light source, compounds I-1 to I-38 described in JP-A-54-18726, JP-A-6-7.
The compounds I-1 to I-35 described in Japanese Patent No. 5322 and the compounds I-1 to I-34 described in JP-A-7-287338, C) Japanese Patent Publication No.
Dyes 1 to 20 described in JP-A-5-39818, JP-A-6-26
Compounds I-1 to I-37 described in JP-A-2-284343 and I described in JP-A-7-287338.
-1 to I-34 compound, D) semiconductor laser light source, I-described in JP-A-59-191032.
1 to I-12 compounds, I-1 to I-22 compounds described in JP-A-60-80841, JP-A-4-3
Compounds I-1 to I-29 described in JP 35342 and I-1 described in JP-A-59-192242.
In addition to the compounds described above, the compounds of I-41 to I-55 and the compounds of I-55 described in JP-A No. 9-160185 are used for the tungsten and xenon light sources of the plate-making camera. Compounds 86 to I-97, compounds 4-A to 4-S, compounds 5-A to 5-Q, and 6-A described in JP-A-6-242547.
Compounds from 6 to T can be advantageously selected.

These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclos
ure) 176, 17643 (issued in December 1978), page 23, IV, item J, or the aforementioned Japanese Patent Publication No. 49-2550.
0, 43-4933, JP-A-59-19
032 and 59-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more kinds. To add the sensitizing dyes to the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3. Solvents such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, etc. Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent and the solution is dispersed in water or a hydrophilic colloid. As disclosed in JP-B-44-23389, JP-B-44-27555, JP-B-57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion. A method of adding or adding to an emulsion as an aqueous solution in the coexistence of an acid or a base, US Pat. No. 3,8
No. 22,135, No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in which a surfactant coexists into an emulsion. JP-A-53-102733, JP-A-58-58
A method in which a dye is directly dispersed in a hydrophilic colloid as disclosed in JP-A-105141, and the dispersion is added to an emulsion, as disclosed in JP-A-51-74624, It is also possible to use a method in which the dye is dissolved using the compound to be added and the solution is added to the emulsion. Ultrasonic waves can also be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion at any stage in the preparation of emulsions which has been found to be useful so far.
For example, U.S. Pat. Nos. 2,735,766, 3,628,960, and 4,183,756.
No. 4,225,666.
As disclosed in JP-A No. 8-184142 and JP-A No. 60-196749, chemical ripening is carried out during the silver halide grain formation step and / or before desalting, during the desilvering step and / or after desalting. Before the start of the process, JP-A-5
As disclosed in Japanese Patent Application Laid-Open No. 8-113920, it may be added at any time or step immediately before chemical ripening or during the step, after chemical ripening, and before the emulsion is coated before the coating. Good. Also, US Pat.
25,666, JP-A-58-7629, etc., the same compound alone or in combination with a compound having a different structure, for example, during the grain forming step and the chemical ripening step or It may be added in divided portions such as after completion of chemical aging or before or after chemical aging or after completion of the process. You may.

In the present invention, the amount of the sensitizing dye added varies depending on the shape and size of the silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, etc.
4 × 10 ⁻⁶ to 8 × 10 ⁻³ per mol of silver halide
It can be used in mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−7 to} 3.5 × 10 per 1 m ² of the surface area of the silver halide grain.
The addition amount of ^-6 mol is preferable, and it is 6.5 × 10 ^{-7 to} 2.0.
The addition amount of × 10 ^-6 mol is more preferable.

There are no particular restrictions on the various additives used in the silver halide photographic light-sensitive material of the present invention. For example, JP-A-3-39948, page 10, lower right, line 11 to the same, page 12 lower left. The polyhydroxybenzene compound described in line 5 (specifically, the compound (II
I) -1 to 25 compounds); compounds represented by the general formula (I) described in JP-A No. 1-118832, which have substantially no absorption maximum in the visible region (specifically, the same publications). Compounds I-1 to I-26 described in JP-A 2-1;
Antifoggant described in JP-A-03536, page 17, lower right line 19 to page 18, upper right line 4; JP-A No. 2-1035.
No. 36, page 18, lower left line 12 to lower left, line 20; polymer latex described in JP-A No. 9-179228; polymer latex having an active methylene group represented by formula (I) (specifically, Specifically, compounds I-1 to I-16 described in the publication; polymer latex having a core / shell structure described in JP-A-9-179228 (specifically, compound P-1 described in the publication). ~ P-5
5); JP-A-7-104413, page 14, left first line to page right 30, line 30 (specifically, compounds II-1 to II- described in page 15 of the same).
9)); JP-A-2-103536, page 19, upper left 1
The matting agent described in the 5th line to the 15th line on the upper right of page 19 of the same gazette,
Lubricants, plasticizers; JP-A-2-103536, No. 18
Hardeners described on page 5, upper right line to page 17, upper right line 17; having acid groups described in JP-A-2-103536, page 18, lower right line 6, to page 19, upper left line 1 Compounds; JP-A-2-18542, page 2, lower left, line 13 to JP-A-3-18542
Conductive substances described in line 7 in the upper right of the page (specifically, metal oxides described in line 2 in the lower right of page 2 to line 10 in the lower right of the same publication, and compound P described in the same publication). -1-P-7 conductive polymer compounds); JP-A-2-103536, No. 1
Water-soluble dyes described on page 7, lower right line 1 to upper right line, line 18; general formula (F) described in JP-A-9-179243.
A), the general formula (FA1), the general formula (FA2), and the solid disperse dyes represented by the general formula (FA3) (specifically, the compounds F1 to F34 described in the publication and JP-A-7-152112). (II-2) to (II-24), JP-A-7-15
(III-5) to (III-18) described in JP-A No. 2112 and (IV-2) to (IV- described in JP-A-7-152112.
7), JP-A-2-294638 and JP-A-5-294638.
11382, a solid disperse dye); a redox compound capable of releasing a development inhibitor by being oxidized, as described in JP-A-5-274816, preferably the general formula (R-1) described in the publication. , A redox compound represented by the general formula (R-2) or the general formula (R-3) (specifically, compounds R-1 to R-68 described in the same publication); Issue, page 3, lower right, first line ~
The binder described in the 20th line can be mentioned.

The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 8
The range of 0 to 150% is preferable, and more preferably 90 to
It is in the range of 140%. The swelling ratio of the hydrophilic colloid layer is
The thickness (d ₀ ) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material was measured, and the silver halide photographic light-sensitive material was swollen by immersing it in distilled water at 25 ° C. for 1 minute. The thickness (Δd) is measured, and the swelling rate (%) =
It is obtained by the calculation formula of (Δd ÷ d ₀ ) × 100.

The film surface pH of the silver halide photographic light-sensitive material of the present invention on the side coated with the silver halide emulsion layer is 6.0.
It is preferably the following, more preferably 4.5 to 7.5, still more preferably 4.8 to 6.0. If it is less than 4.5, the hardening of the emulsion layer tends to be delayed.

Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, 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. Further, JP-A-7-234478 and US Pat. No. 5,55
A support made of a styrene-based polymer having a syndiotactic structure described in 8,979 is also preferably used.

The processing agents and processing methods such as the developing solution and the fixing solution in the present invention will be described below. Needless to say, the present invention is not limited to the following description and specific examples.

Any known method can be used for the development processing of the silver halide photographic light-sensitive material of the present invention.
As the developing solution, a known developing solution can be used.

Developer used in the present invention (hereinafter, both the development starter and the development replenisher are collectively referred to as a developer).
The developing agent used in (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives and hydroquinone monosulfonate, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent exhibiting superadditivity therewith, a combination of dihydroxybenzenes or ascorbic acid derivatives and 1-phenyl-3-pyrazolidones, or dihydroxybenzenes or Examples thereof include a combination of an ascorbic acid derivative and p-aminophenols. Among the developing agents used in the present invention, examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferable. Ascorbic acid derivative developing agents include ascorbic acid, isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferable from the viewpoint of material cost.

The developing agent for 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.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention,
There are o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol and the like. Among them, N-methyl-p-aminophenol, or JP-A-9- Aminophenols described in JP-A-297377 and JP-A-9-297378 are preferable.

The dihydroxybenzene type developing agent is usually preferably used in an amount of 0.05 mol / L to 0.8 mol / L. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 m
ol / L to 0.6 mol / L, preferably 0.10 mo
1 / L to 0.5 mol / L, the latter 0.06 mol / L
Below, preferably 0.03 mol / L to 0.003 mo
It is preferably used in an amount of 1 / L.

The ascorbic acid derivative developing agent is preferably used usually in an amount of 0.01 mol / L to 0.5 mol / L, and preferably 0.05 mol / L to 0.3 mol / L.
L is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is 0.01 mol / L to 0.5 mol / L, 1-phenyl-3-pyrazolidones Alternatively, it is preferable to use p-aminophenols in an amount of 0.005 mol / L to 0.2 mol / L.

The developer for processing the silver halide photographic light-sensitive material of the present invention contains additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent, etc.). be able to. Specific examples of these are shown below, but those usable in the present invention are not limited thereto. As a buffering agent used in the developing solution at the time of development processing, carbonate, JP-A-62-186
No. 259, the boric acid described in JP-A-60-93433.
Saccharides (eg saccharose), oximes (eg acetoxime), phenols (eg 5
-Sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The amount of buffering agent, especially carbonate, used is preferably 0.05 mol / L or more, particularly 0.08.
~ 1.0 mol / L.

In the present invention, it is preferable that both the development starter solution and the development replenisher solution have a pH increase of 0.5 or less when 0.1 mol of sodium hydroxide is added to 1 L of the solution. As a method for confirming that the developing starter solution or developing replenisher solution used has this property, the pH of the developing starter solution or developing replenisher solution to be tested is adjusted to 10.5, and then 1 L of this solution is adjusted to 0. 1mo
1 is added, and the pH value of the liquid at this time is measured. If the increase in pH value is 0.5 or less, it is determined that the liquid has the properties defined above. 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 0.4 or less when the above test is carried out.

Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably used in an amount of 0.2 mol / L or more, particularly 0.3 mol / L or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is 1.
It is desirable to set it to 2 mol / L. Particularly preferably,
It is 0.35-0.7 mol / L. As a preservative for the dihydroxybenzene-based developing agent, a small amount of the above-mentioned ascorbic acid derivative may be used in combination with sulfite. Of these, sodium erythorbate is preferably used from the viewpoint of material cost. The addition amount is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Additives other than those mentioned above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide,
Alkanolamines such as diethanolamine and triethanolamine, development accelerators such as imidazole and its derivatives, heterocyclic mercapto compounds (for example, 3- (5
-Mercaptotetrazol-1-yl) benzenesulfonate sodium salt, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A No. 62-212651 can be added as a physical development unevenness preventing agent. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound is used as an antifoggant or a black pepper.
It may be included as an inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2- Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4. -Thiadiazole-2
-Thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these additives is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol per 1 L of the developing solution.

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

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, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and others. 67747, 57-102624.
Examples thereof include compounds described in JP-B No. 53-40900.

Examples of the organic phosphonic acid include, for example, US Pat. Nos. 3,214,454 and 3,794,59.
No. 1 and West German Patent Publication No. 2227369, and the like, hydroxyalkylidene-diphosphonic acid, Research Disclosure Vol. 181, Item 181.
70 (May 1979 issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to the above, Research Disclosure 18170, JP-A-57-208554, and JP-A-57-208554.
-61125, 55-29883, and 5
The compounds described in 6-97347 and the like can also be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A Nos. 52-102726 and 53-42730.
No. 54-112127, No. 55-402.
4, gazette 55-4025 gazette, gazette 55-1262.
41, 55-65955, 55-65.
Examples thereof include compounds described in Japanese Patent Publication No. 956 and Research Disclosure 18170 described above.

These organic and / or inorganic chelating agents are not limited to those mentioned above. Also,
You may use it in the form of an alkali metal salt or an ammonium salt. The amount of these chelating agents added is 1 L of developer.
It is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

Further, as a silver stain preventing agent in the developer,
For example, JP-A-56-24347 and JP-B-56-4
In addition to the compounds described in JP-A-6585, JP-B-62-2849, JP-A-4-362942, and JP-A-8-6215, a triazine having one or more mercapto groups (for example, JP-B-6-23830). Gazette, Japanese Patent Laid-Open No. Hei 3
-282457, JP-A-7-175178, and pyrimidines having one or more mercapto groups (for example, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5 , 6-Diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine, JP-A-9-1999
-274289, etc.), pyridine having one or more mercapto groups (for example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine). , Compounds described in JP-A-7-248587), pyrazines having one or more mercapto groups (for example, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2, 3, 5-trimercaptopyrazine and the like), pyridazine having one or more mercapto groups (for example, 3-mercaptopyridazine,
3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc., compounds described in JP-A-7-175177, and US Pat. No. 5,457,011. The polyoxyalkylphosphonates described in the book can be used. These silver stain preventing agents can be used alone or in combination of two or more, and the addition amount is 0.
05-10 mmol is preferable and 0.1-5 mmol is more preferable. Further, as a dissolution aid, JP-A-61-26
The compounds described in 7759 can be used. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

The preferable pH of the developer is 9.0 to 12.0.
And particularly preferably in the range of 9.0 to 11.0, and more preferably 9.5 to 11.0. As the alkali agent used for pH adjustment, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As the cation of the developing solution, potassium ion does not suppress development as compared with sodium ion, and there is less jaggedness around the blackened portion called fringe. Further, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixing to the same extent as silver ions.Therefore, if the concentration of potassium ions in the developer is high, the potassium halide in the fixer will be brought in because the developer is brought in by the silver halide photographic light-sensitive material. The concentration becomes high, which is not preferable. From the above, the molar ratio of potassium ion and sodium ion in the developer is 2
It is preferably between 0:80 and 80:20. The ratio of potassium ion to sodium ion is pH buffer,
Counter cations such as pH adjusters, preservatives, chelating agents,
It can be arbitrarily adjusted within the above range.

The replenishing amount of the developing solution is 390 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material, and it is 30 to 325.
ml is preferred and 120-250 ml is most preferred.
The development replenisher may have the same composition and / or concentration as the development starter, or may have a different composition and / or concentration from the starter.

Ammonium thiosulfate, sodium thiosulfate, and ammonium ammonium thiosulfate can be used as the fixing agent of the fixing processing agent in the present invention. The amount of the fixing agent used can be appropriately changed, but is generally about 0.7 to
It is about 3.0 mol / L.

The fixing solution in the present invention may contain a water-soluble aluminum salt or a water-soluble chromium salt which acts as a hardener, and the water-soluble aluminum salt is preferable. For example, aluminum chloride, aluminum sulfate, potassium alum,
Examples include ammonium aluminum sulfate, aluminum nitrate, and aluminum lactate. These have an aluminum ion concentration of 0.01 to 0.15 mo in the liquid used.
It is preferably contained in 1 / L. When the fixing solution is stored as a concentrated solution or a solid agent, it may be composed of a plurality of parts including a hardener or the like as a separate part, or may be a one-pack type composition containing all components.

Preservatives (for example, sulfite, bisulfite, metabisulfite, etc. 0.01
5 mol / L or more, preferably 0.02 mol / L-
0.3 mol / L), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc., 0.1 mol / L to 1)
mol / L, preferably 0.2 mol / L to 0.7 mo
1 / L), a compound capable of stabilizing aluminum and softening water (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, Benzoic acid, salicylic acid, tyrone, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, their derivatives, their salts, sugars, etc. are added at 0.001 mol / L to 0.
5 mol / L, preferably 0.005 mol / L-0.
3 mol / L), but from the viewpoint of environmental protection in recent years, it is preferable not to include a boron compound.

In addition, the compounds described in JP-A-62-78551, pH adjusting agents (eg sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be contained. . As a surfactant,
For example, anionic surfactants such as sulfated sulfone oxides, polyethylene-based surfactants, JP-A-57-6840.
The amphoteric surfactants described in JP-A No. 1994-200242 are mentioned, and known defoaming agents can also be used. Wetting agents include alkanolamines and alkylene glycols. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, and JP-A-58-122.
Thiourea derivatives described in JP-A Nos. 535 and 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat. No. 4,126,459, and JP-A-64-4739. Japanese Patent Laid-Open No. 1-4
No. 739, No. 1-159645, and No. 3-
The mercapto compound described in JP 101728, the same 4-
The mesoionic compound and thiocyanate described in Japanese Patent No. 170539 can be included.

The pH of the fixing solution in the present invention is preferably 4.0 or higher, more preferably 4.5 to 6.0. The pH of the fixing solution rises due to the mixing of the developing solution during the treatment, but the pH in this case is 6.
It is preferably 0 or less, more preferably 5.7 or less, and in the non-hardening fixer, it is preferably 7.0 or less, more preferably 6.7 or less.

The replenishing amount of the fixing solution is preferably 500 ml or less, more preferably 390 ml or less, and 320 per 1 m ^{2 of the} silver halide photographic light-sensitive material.
It is particularly preferably about 80 ml. The replenishing solution may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration as the starting solution.

The fixing solution can be recycled and used by a known fixing solution recycling method such as electrolytic silver recovery. As a reproducing device, for example, FS-2000 manufactured by Fuji Photo Film Co., Ltd.
and so on. It is also preferable to remove the dye and the like using an adsorption filter such as activated carbon.

When the developing and fixing processing agent in the present invention is a liquid agent, it is preferable to store it in a packaging material having low oxygen permeability as described in JP-A-61-73147. Further, when these solutions are concentrated solutions, they are used by diluting 1 part of the concentrated solution with 0.2 to 3 parts of water so as to have a predetermined concentration.

Even if the development processing agent and the fixing processing agent in the present invention are solid, the same results as the liquid agent can be obtained. The solid processing agent will be described below. In the present invention, solid agents having a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film in order to separate the components that react with each other when they come into contact with each other, or may have a multi-layer structure to separate the components that react with each other. , And these may be used together.

Known coating agents and granulating aids can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and vinyl compounds are preferably used. In addition, reference can be made to column 48, line 2 to column 13, line 13 of JP-A-5-45805.

In the case of forming a plurality of layers, components which do not react even when they come into contact with each other may be sandwiched between components which react with each other and processed into tablets or briquettes. It may be packaged in the same layer structure. These methods are described, for example, in JP-A-61-259921.
It is shown in JP-A-4-16841, JP-A-4-78848, JP-A-5-93991 and the like.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferred, especially tablets 1.0-5.0 g / c
m ³ is preferred, and the granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, JP-A-4-32837, JP-A-4-78848, JP-A-5-93991, and JP-A-5-93991. -85533, 4-85534, 4-85535, 5-134362, 5-197070, 5-204098, 5-224361, 6- 138604
No. 6-138605 and No. 8-28632.
Reference can be made to, for example, No. 9 publication.

More specifically, rolling granulation method, extrusion granulation method, compression granulation method, crushing granulation method, stirring granulation method, spray drying method, melt coagulation method, briquetting method, roller compaction method. The Ting method or the like can be used.

The solid agent of the present invention can be adjusted in solubility by changing the surface condition (smoothness, porosity, etc.) or partial thickness, or by forming a hollow donut shape.
Further, it is possible to take a plurality of shapes in order to give different solubilities to a plurality of granules or to adjust the solubilities of materials having different solubilities. Further, a multi-layered granule having different compositions on the surface and inside may be used.

The packaging material of the solid agent is preferably a material having low oxygen and water permeability, and the packaging material may have a known shape such as a bag, a cylinder, or a box. In addition, JP-A-6-242
585 to 6-242588 and 6-24.
No. 7432, No. 6-247448, No. 6-3
No. 01189, No. 7-5664, No. 7-56
The foldable shape disclosed in Japanese Patent Nos. 66 to 7-5669 is also preferable for reducing the storage space of the waste packaging material. These packaging materials include screw caps, pull tops, and
An aluminum seal may be attached or the packaging material may be heat-sealed, but other known materials may be used without any particular limitation. Further, in terms of environmental protection, it is preferable to recycle or reuse the waste packaging material.

The method of dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. Examples of these methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and Japanese Patent Application Laid-Open No. H9-96952.
Japanese Patent Application Laid-Open No. 5-1194, a method of dissolving with a dissolving device having a dissolving portion and a portion for stocking a finished liquid and replenishing from a stock portion, as described in JP-A-80718.
No. 54, No. 6-19102, No. 7-2613.
No. 57, a method of adding a processing agent to the circulation system of an automatic developing machine to dissolve and replenish it, and processing according to processing of a silver halide photographic light-sensitive material with an automatic developing machine having a dissolution tank built-in. Although there is a method of adding an agent and dissolving it, any other known method can be used. In addition, the treatment agent may be manually added, and it is disclosed in JP-A-9-13.
It may be automatically opened and automatically charged by a dissolving device or an automatic processor having an opening mechanism as described in Japanese Patent No. 8495, and the latter is preferable from the viewpoint of working environment. Specifically, the method of breaking through the outlet, the method of peeling, the method of cutting,
The method of pushing down, JP-A-6-19102, and JP-A-6-19102
The method described in Japanese Patent No. 95331 is available.

The silver halide photographic light-sensitive material which has been developed and fixed is then washed with water or stabilized (hereinafter, referred to as washing including stabilizing, unless otherwise specified. Water or wash water). The water used for washing may be tap water, ion-exchanged water, distilled water or stabilizing solution. The replenishing amount of these is generally about 8 L to about 17 L per 1 m ^{2 of} silver halide photographic light-sensitive material.
However, the amount of replenishment may be less than that. Especially 3L or less replenishment amount (including 0. That is, washing with water)
Then, not only the water saving process becomes possible, but also the pipe for installing the automatic processor can be eliminated. When the washing with water is carried out with a low replenishing amount, JP-A Nos. 63-18350 and 62-62
It is more preferable to provide a washing tank for a squeeze roller and a crossover roller described in JP-A-287252. In addition, various oxidizers (eg ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

[0191] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example two-stage, three-stage, etc.) than older are known, washing replenishing amount 50~200ml per silver halide photographic material 1 m ² Is preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without countercurrent flow).

Further, a means for preventing scales may be added to the washing step by the method of the present invention. Known means can be used as the scale prevention means, and there is no particular limitation, but a method for adding an antifungal agent (so-called scale prevention agent), a method for energizing, a method for irradiating ultraviolet rays or infrared rays or far infrared rays, There are methods of applying a magnetic field, ultrasonic treatment, heating, and emptying the tank when not in use. These scale prevention means may be carried out according to the processing of the silver halide photographic light-sensitive material, may be carried out at regular intervals irrespective of the use situation, or may be carried out only during a non-processing time such as at night. Good. Alternatively, it may be preliminarily rinsed with water and then replenished. Further, it is also preferable to carry out different scale preventive means at regular intervals in order to suppress the generation of resistant bacteria. As a water saving scale preventing device, a device AC-1000 manufactured by FUJIFILM Corporation and AB-5 manufactured by FUJIFILM Corporation may be used as a scale preventing agent.
The method of Japanese Patent No. 1485 may be used. The antifungal agent is not particularly limited and known ones can be used. In addition to the above-mentioned oxidizing agents, for example, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-mercaptopyridine-N
-Oxide etc.) and the like, and may be used alone or in combination of two or more. As a method of energizing, Japanese Patent Application Laid-Open No. 3-2246
No. 85, No. 3-224687, No. 4-162.
The methods described in JP-A No. 80, JP-A No. 4-18980 and the like can be used.

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

A part or all of the overflow liquid from the water washing step can be mixed and used in a processing liquid having a fixing ability, as described in JP-A-60-235133. In addition, microbial treatment (for example, sulfur-oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic, etc.) or oxidization treatment with electricity or an oxidant to obtain biochemical oxygen demand Quantity (B
OD), chemical oxygen demand (COD), iodine consumption, etc., and then drained, or a filter that uses a polymer having an affinity for silver, or a compound that forms a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of conservation of the natural environment to reduce the silver concentration in the wastewater by adding silver to precipitate silver and filter it with a filter.

Further, there is a case where a stabilizing treatment is performed after the water washing treatment, and examples thereof include JP-A-2-201357, JP-A-2-132435, JP-A-1-102553 and JP-A-46-44446. A bath containing the compound described in the publication may be used as the final bath of the silver halide photographic light-sensitive material. In this stabilizing bath, if necessary, an ammonium compound, a metal compound such as Bi or Al, an optical brightener,
Various chelating agents, film pH adjusting agents, hardening agents, bactericides, antifungal agents, alkanolamines and surfactants can also be added.

Additives such as antifungal agents and stabilizers to be added to the washing and stabilizing baths may be solid agents like the above-mentioned developing and fixing processing agents.

Waste liquids of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention are preferably incinerated. Further, these waste liquids can be concentrated or liquefied by a concentrating device as described in, for example, Japanese Examined Patent Publication No. 7-83867, US Pat. No. 5,439,560, etc., and then disposed. .

When the replenishment amount of the processing agent is reduced, it is preferable to reduce the opening area of the processing tank to prevent evaporation of liquid and air oxidation. Regarding the roller transport type automatic developing machine, U.S. Pat. Nos. 3,025,779 and 3,5
45,971 specification and the like, and is simply referred to as a roller transport type automatic developing machine in the present specification. This developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Further, a rinsing bath, a water washing tank or a washing tank may be provided between the development and fixing and / or the fixing water washing.

In the development processing of the present invention, the dry to dry period is preferably 25 to 160 seconds, and the developing and fixing time is 40 seconds or less, preferably 6 to 35 seconds.
Second, the temperature of each liquid is preferably 25 to 50 ° C., 30 to 40
C is preferred. Washing temperature and time are 0 to 50 ° C and 4
0 second or less is preferable. According to the method of the present invention, the silver halide photographic light-sensitive material which has been developed, fixed and washed with water may be dried by squeezing the washing water, that is, passing through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions. The drying method may be any known method and is not particularly limited,
Hot air drying, JP-A-4-15534, and JP-A-5-22
No. 56 and No. 5-289294, there are heat roller drying, far infrared ray drying and the like, and a plurality of methods may be used in combination.

[0200]

EXAMPLES The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials shown in the following examples,
The usage amount, ratio, processing content, processing procedure, etc. can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.

<Synthesis Example 1> Synthetic polyethylene glycol of Exemplified Compound 3 (average molecular weight 2000, 800
g), thionyl chloride (584 ml) and DMF (4 ml)
Were mixed at room temperature, then heated to 90 ° C. and stirred for 5 hours.
After distilling off excess thionyl chloride, 4-phenylpyridine (372 g) was added and the mixture was reacted at 150 ° C. for 7 hours.
The reaction mixture was treated with ethyl acetate / 2-propanol (10 /
The solution of 1) was prepared, cooled, and the precipitated solid was collected by filtration. This was dried to obtain the target Exemplified Compound 3 (584).
g, yield 62%).

<Synthesis Example 2> Synthetic polyethylene glycol (average molecular weight 2000, 10
g), thionyl chloride (7.3 ml) and DMF (0.1 m)
l) was mixed at room temperature, then heated to 90 ° C. and stirred for 5 hours. After distilling off excess thionyl chloride, isoquinoline (4.0 g) was added and the mixture was reacted at 150 ° C. for 7 hours. The reaction mixture was made into a solution of ethyl acetate / 2-propanol (10/1), cooled, and the precipitated solid was collected by filtration. This was dried to obtain the target Exemplified Compound 6 (7.1 g, yield 60%).

<Synthesis Example 3> Synthesis of Exemplified Compound 4 Exemplified Compound 4 was prepared in the same manner as in Synthesis Example 1 except that polyethylene glycol (average molecular weight of 2000) was used instead of polyethylene glycol (average molecular weight of 2000). Got 4.

<Synthesis Example 4> Synthesis of Exemplified Compound 65 1,10-Diamino-4,7-dioxadecane (17.
6 g, 0.1 mol), potassium carbonate (27.6 g,
0.2 mol), ethyl acetate (100 ml), water (50
ml) was vigorously stirred at room temperature, and chloroacetyl chloride (34 g, 0.3 mol) was added dropwise thereto. The reaction solution was separated, the ethyl acetate layer was dried over sodium sulfate,
When concentrated, 1,10-bis (chloroacetylamino)-
4,7-Dioxadecane was obtained (23 g, yield 70)
%). 3.3 g of this compound and triphenylphosphine (7.9 g) were mixed and heated at 150 ° C. for 5 hours. The reaction mixture was cooled and washed three times with ethyl acetate to give 5.4 g of Exemplified Compound 65 as a brown viscous liquid (yield 63
%)was gotten.

<Synthesis Example 5> Synthesis of Exemplified Compound 62 Instead of triphenylphosphine in Synthesis Example 4, 4
-Except that phenylpyridine was used, the same operation was performed to obtain Exemplified Compound 62.

<Synthesis Example 6> Synthesis of Exemplified Compound 71 Instead of 1,10-diamino-4,7-dioxadecane in Synthesis Example 4, O, O'-bis (2-aminopropyl) polyethylene glycol (average molecular weight 800) Was used and the same operation was performed except that 4-phenylpyridine was used instead of triphenylphosphine to obtain Exemplified Compound 71.

Example 1 In this example, a silver halide photographic light-sensitive material satisfying the conditions of the present invention (Samples 5, 10) was used.
26 to 26) and a silver halide photographic light-sensitive material of Comparative Example (Sample 1)
~ 4, 6-9) were manufactured and evaluated. First, the emulsion used for producing these silver halide photographic light-sensitive materials and the production method of the non-photosensitive silver halide grains are described, and then the production method of the silver halide photographic light-sensitive material and its evaluation are described.

[0208] << Preparation of Emulsion A >> 1 liquid   750 ml of water   20 g of gelatin   Sodium chloride 3g   1,3-Dimethylimidazolidine-2-thione 20 mg   Sodium benzenethiosulfonate 10 mg   Citric acid 0.7g

[0209] 2 liquid   300 ml of water   Silver nitrate 150g

Three-liquid water 300 ml Sodium chloride 38 g Potassium bromide 32 g K ₃ IrCl ₆ (0.005%, 20% aqueous solution of KCl) Amount shown in Table 4 (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] ( 0.001%, 20% NaCl aqueous solution)

K ₃ IrCl ₆ (0.005 used for the third liquid)
%), (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] (0.001
%) Is a 20% aqueous solution of KCl, NaC
It was dissolved in 1 of 20% aqueous solution and heated at 40 ° C. for 120 minutes to prepare.

To one solution kept at 38 ° C. and pH 4.5, 2
90% each of the liquid and 3 liquid were added simultaneously with stirring for 20 minutes to form 0.16 μm core particles. Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and the remaining 10% amounts of 2 liquid and 3 liquid were added over 2 minutes to grow to 0.21 μm. further,
0.15 g of potassium iodide was added and aged for 5 minutes to complete grain formation.

[0213] 4 liquid   100 ml of water   Silver nitrate 50g

5 liquids 100 ml sodium chloride 13 g potassium bromide 11 g K ₄ [Fe (CN) ₆ ] 3H ₂ O (yellow blood salt) Amount shown in Table 4

Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of an anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide precipitated.
(PH was in the range of 3.2 ± 0.2) Next, about 3 L of the supernatant was removed (first washing with water). An additional 3 L of distilled water was added and then sulfuric acid was added until the silver halide settled.
Again, 3 L of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process. Gelatin 45 after washing and desalting
g to adjust pH to 5.6 and pAg to 7.5, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, sodium thiosulfate 15
mg and chloroauric acid (addition amounts shown in Table 4) were added, and chemical sensitization was performed at 55 ° C. so as to obtain optimum sensitivity, and 4-hydroxy-6-methyl-1,3,3a, 7 was used as a stabilizer. -Tetraazaindene 100 mg and an antiseptic (manufactured by ICI Corporation,
Proxel) 100 mg was added. Finally, add silver chloride to 7
A silver iodochlorobromide cubic grain emulsion containing 0 mol%, 0.08 mol% of silver iodide, an average grain size of 0.22 μm, and a coefficient of variation of 9% was obtained (finally, the emulsion was pH = 5.7, pA).
g = 7.5, conductivity = 40 μS / m, density = 1.2 to
1.25 × 103 kg / m ³ , viscosity = 50 mPa · s).

[0216]

[Chemical formula 45]

[0217] << Preparation of Emulsion B >> 1 liquid   750 ml of water   20 g of gelatin   Sodium chloride 1g   1,3-Dimethylimidazolidine-2-thione 20 mg   Sodium benzenethiosulfonate 10 mg   Citric acid 0.7g

[0218] 2 liquid   300 ml of water   Silver nitrate 150g

Three-liquid water 300 ml Sodium chloride 38 g Potassium bromide 32 g K ₃ IrCl ₆ (0.005%, 20% aqueous solution of KCl) Amount shown in Table 4 (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] ( 0.001%, 20% NaCl aqueous solution) Amount shown in Table 4

K ₃ IrCl ₆ (0.005 used for the third liquid)
%), (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] (0.001
%) Is a 20% aqueous solution of KCl, NaC
It was dissolved in 1 of 20% aqueous solution and heated at 40 ° C. for 120 minutes to prepare.

To one solution kept at 38 ° C. and pH 4.5, 2
90% each of the liquid and 3 liquid were added simultaneously with stirring for 20 minutes to form 0.16 μm core particles. Then 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetraazaindene 500mg,
Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and the remaining 10% of 2 liquid and 3 liquid were added over 2 minutes to grow to 0.18 μm. Further, 0.15 g of potassium iodide was added and aged for 5 minutes to complete grain formation.

[0222] 4 liquid   100 ml of water   Silver nitrate 50g

5 liquid water 100 ml sodium chloride 13 g potassium bromide 11 g K ₄ [Fe (CN) ₆ ] / 3H ₂ O (yellow blood salt) Amount shown in Table 4

Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitating agent-1 was added, and the pH was lowered with sulfuric acid until the silver halide precipitated (pH 3.2).
The range was ± 0.2). Next, about 3 L of the supernatant was removed (first washing with water). After adding 3L of distilled water,
Sulfuric acid was added until the silver halide had settled. Again, 3 L of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process. Add 45 g of gelatin to the emulsion after washing and desalting,
Adjusted to pH 5.6 and pAg 7.5, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, triphenylphosphine selenide 2
mg and chloroauric acid (addition amounts shown in Table 4) were added and chemical sensitization was performed at 55 ° C. so as to obtain optimum sensitivity, and 4-hydroxy-6-methyl-1,3,3a, 7 was used as a stabilizer. -Tetraazaindene 100 mg, antiseptic (manufactured by ICI Corporation,
Proxel) 100 mg was added. Finally, add silver chloride to 7
A silver iodochlorobromide cubic grain emulsion containing 0 mol% and 0.08 mol% of silver iodide and having an average grain size of 0.18 μm and a coefficient of variation of 10% was obtained (finally, the emulsion was pH = 5.7, p.
Ag = 7.5, conductivity = 40 μS / m, density = 1.2x
10 ³ kg / m ³ , viscosity = 50 mPa · s).

<< Preparation of Emulsions C to K >> For the emulsion B, the organic gold compounds shown in Table 4 are used in place of the grain size, the type of heavy metal to be doped, the addition amount, and chloroauric acid used for chemical sensitization. Other than the above, the same preparation as that for Emulsion B was performed. The particle size was adjusted by changing the addition amount of one liquid of sodium chloride and the adjusting temperature.

[0226] << Preparation of Non-Photosensitive Silver Halide Grains->> 1 liquid   Water 1L   20 g of gelatin   Sodium chloride 3.0g   1,3-Dimethylimidazolidine-2-thione 20 mg   Sodium benzenethiosulfonate 8mg

[0227] 2 liquid   400 ml of water   Silver nitrate 100g

Three-liquid water 400 ml Sodium chloride 13.5 g Potassium bromide 45.0 g (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] (0.001%, 20% aqueous solution of NaCl) 4 × 10 ⁻⁵ mol / Agmol

The 1st, 2nd and 3rd liquids kept at 70 ° C. and pH 4.5 were added simultaneously with stirring for 15 minutes,
Nuclear particles were formed. Then, the following 4 liquid and 5 liquid were added over 15 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation.

Thereafter, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitating agent-1 was added, and the pH was lowered using sulfuric acid until the silver halide precipitated (pH 3.2 ±).
It was in the range of 0.2). Next, about 3 L of the supernatant was removed (first washing with water). An additional 3 L of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 L of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process. To the emulsion after washing and desalting, add 45 g of gelatin and p
H5.7 and pAg were adjusted to 7.5, phenoxyethanol was added as a preservative, and the average silver chloride was finally adjusted to 30
A dispersion of undeveloped cubic silver iodochlorobromide cubic milk particles having an average particle diameter of 0.45 μm and a coefficient of variation of 10% was obtained, which contained mol% and silver iodide 0.08 mol%.
H = 5.7, pAg = 7.5, conductivity = 40 μS / m,
Density = 1.3-1.35 × 103 kg / m ³ , viscosity = 5
It became 0 mPa · s).

<Preparation of Non-Photosensitive Silver Halide Grains-> 1 Liquid Water 1 L Gelatin 20 g Potassium Bromide 0.9 g Citric Acid 0.2 g NH ₄ NO ₃ 20 g Hydrogen Peroxide 3.5 g Sodium Benzenethiosulfonate 15 mg

[0232] 2 liquid   400 ml of water   Silver nitrate 200g

Three-liquid water 400 ml Potassium bromide 140.0 g (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] (0.001%, 20% aqueous solution of NaCl) 4 × 10 ⁻⁵ mol / Agmol

While stirring one solution kept at 60 ° C. with Na
40 ml of OH (1 mol / L) was added, and further 0.7 g of an aqueous silver nitrate solution was added. Then, 1/2 of each of the 2nd and 3rd liquids was controlled by the double jet method.
With the silver potential kept at +24 mV, add over 20 minutes,
After physical aging for 2 minutes, the other half of the second and third solutions was added by the same control double jet method over 20 minutes to form particles.

Then, it was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitating agent-1 was added, and the pH was lowered using sulfuric acid until the silver halide precipitated (pH 3.1).
The range was ± 0.2). Next, about 3 L of the supernatant was removed (first washing with water). After adding 3L of distilled water,
Sulfuric acid was added until the silver halide had settled. Again, 3 L of the supernatant was removed (second washing with water). The same operation as the second water washing was repeated once (third water washing) to complete the water washing / desalting process. Add 45 g of gelatin to the emulsion after washing and desalting,
The pH was adjusted to 5.7 and pAg was adjusted to 7.5.
Phenoxyethanol was added, and finally the average silver chloride was reduced to 3
A dispersion of unpost-ripened silver tetradecahedral bromide emulsion grains having an average grain size of 0.8 μm and a coefficient of variation of 10% containing 0 mol% and 0.08 mol% of silver iodide was obtained (finally as an emulsion. , PH
= 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.3 × 10 ³ kg / m ³ , and viscosity = ³⁰ mPa · s).

<< Preparation of Non-Photosensitive Silver Halide Grains->>
Per 1 mol of KBr in the following X-1 to X-4 aqueous solution,
An amount of (NH ₄ ) ₃ [RhCl ₃ corresponding to 1 × 10 ⁻⁵ mol
₅ (H ₂ O)] (0.001%, 20% aqueous solution of NaCl) was added to form particles.

(Addition 1) 1300 m of an aqueous solution containing 0.6 g of KBr and 1.1 g of gelatin having an average molecular weight of 15,000.
1 was kept at 35 ° C. and stirred. To this, an Ag-1 aqueous solution (containing 4.9 g of AgNO ₃ in 100 ml) 24
ml and an X-1 aqueous solution (4.1 ml of KBr in 100 ml).
24 g and G-1 aqueous solution (100 ml)
It contains 3 g of gelatin having an average molecular weight of 15,000 in 1.8 g by a triple jet method at a constant flow rate.
Added over 0 seconds.

Thereafter, 1.3 g of KBr was added, and the temperature was raised to 75 ° C. After the aging step for 12 minutes after the temperature rise, G-2 aqueous solution (100 ml of an aqueous solution of alkali-treated ossein gelatin was added and reacted with trimellitic anhydride at 50 ° C. and pH 9.0 to cause a reaction, 300 ml of gelatin (containing 12.7 g of gelatin obtained by removing trimellitic acid) was added, and then disodium 4,5-dihydroxy-1,3-disulfonate monohydrate was added to 2.
1 g and 0.002 g of thiourea dioxide were sequentially added at intervals of 1 minute.

(Addition 2) Next, an Ag-2 aqueous solution (100
22.1 g of AgNO ₃ is contained in ml) 157 ml
And an X-2 aqueous solution (15.5 g of KBr in 100 ml)
Containing) was added by the double jet method over 14 minutes. At this time, the addition of the Ag-2 aqueous solution accelerated the flow rate so that the final flow rate was 3.4 times the initial flow rate, and the addition of the X-2 aqueous solution increased the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 3) Then, an Ag-3 aqueous solution (10
32.0 g of AgNO ₃ is contained in 0 ml) 329 m
1 and X-3 aqueous solution (21.5% of KBr in 100 ml).
g, containing 1.6 g of KI) by the double jet method
Added over 7 minutes. At this time, the addition of the Ag-3 aqueous solution accelerated the flow rate so that the final flow rate was 1.6 times the initial flow rate, and the addition of the X-3 aqueous solution increased the pAg of the bulk emulsion solution in the reaction vessel to 8.3. I went to keep it.

(Addition 4) Furthermore, an Ag-4 aqueous solution (10
32.0 g of AgNO ₃ is contained in 0 ml) 156 m
1 and X-4 aqueous solution (22.4 of KBr in 100 ml).
g) was added by the double jet method over 17 minutes. At this time, the Ag-4 aqueous solution was added at a constant flow rate, and the X-3 aqueous solution was added so that the pAg of the bulk emulsion solution in the reaction vessel was maintained at 8.3.

Thereafter, 0.0025 g of sodium benzenethiosulfonate and an aqueous solution of G-3 (containing 12.0 of alkali-treated ossein gelatin in 100 ml) 12
5 ml was sequentially added at intervals of 1 minute.

Next, 43.7 g of KBr was added to adjust the pAg of the bulk emulsion solution in the reaction vessel to 9.0, and
73.9 g of AgI fine particles (containing 13.0 g of AgI fine particles having an average particle diameter of 0.047 μm in 100 g) was added.

(Addition 5) Two minutes later, 249 ml of an Ag-4 aqueous solution and an X-4 aqueous solution were added by the double jet method. At this time, the Ag-4 aqueous solution was added at a constant flow rate for 16 minutes, and the X-4 aqueous solution was added so that the pAg was kept at 9.10.

(Addition 6) Subsequently, for 10 minutes, addition was carried out so that the pAg of the bulk emulsion in the reaction vessel was 7.5.

After that, desalting was carried out by an ordinary flocculation method, and then water, NaOH and alkali-treated ossein gelatin were added with stirring, and the pH was adjusted to 56 ° C.
It was adjusted to be 5.8 and pAg 8.9.

The obtained particles had an equivalent circle diameter of 1.0 μm, a particle thickness of 0.10 μm and an average AgI content of 3.94.
mol%, consisting of tabular silver halide grains whose parallel principal planes were (111) planes, and the variation coefficient of equivalent circle diameter of all grains was 24%.

<< Preparation of Coating Solution >> The silver halide photographic light-sensitive material prepared in this example was prepared by forming a UL layer / emulsion on one surface of a polyethylene terephthalate film support having a moisture-proof undercoat on both sides containing vinylidene chloride. It has a structure in which a layer / a protective layer lower layer / a protective layer upper layer is formed, and a conductive layer / back layer is formed on the opposite surface. The composition of the coating liquid used to form each layer is shown below.

UL layer coating liquid Gelatin 0.5 g / m ² polyethyl acrylate latex 150 mg / m ² compound (Cpd-7) 40 mg / m ² compound (Cpd-14) 10 mg / m ² preservative (manufactured by ICI Corporation) , Proxel) 1.5 mg / m ²

Emulsion Layer Coating Solution Emulsion Addition as shown in Table 5 Sensitizing Dye (SD-1) 5.7 × 10 ⁻⁴ mol / Agmol KBr 3.4 × 10 ⁻⁴ mol / Agmol Compound (Cpd-1) 2 0.0 * 10 < ^-4 > mol / Agmol compound (Cpd-2) 2.0 * 10 < ^-4 > mol / Agmol compound (Cpd-3) 8.0 * 10 < ^-4 > mol / Agmol 4-hydroxy-6-methyl-1. , 3,3a, 7-Tetraazaindene 1.2 × 10 ⁻⁴ mol / Agmol hydroquinone 1.2 × 10 ⁻² mol / Agmol citric acid 3.0 × 10 ⁻⁴ mol / Agmol hydrazine compound As shown in Table 5. Addition Nucleation accelerator (Cpd-5) 5.0 × 10 ⁻⁴ mol / Agmol 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 90 mg / m ² aqueous Latex (Cpd-6) 100 mg / m ² polyethyl acrylate latex 150 mg / m ² colloidal silica (particle size 10 μm) 15% by mass with respect to gelatin Compound (Cpd-7) 4% by mass with respect to gelatin Methyl acrylate and 2- Latex copolymer of acrylamide-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio 88: 5: 7) 150 mg / m ² core-shell type latex (core: styrene / butadiene copolymer (weight ratio 37 / 63), shell: styrene / 2-acetoxyethyl acrylate (weight ratio 84/16), core / shell ratio = 50/50) The coating solution pH was adjusted to 5.6 using 150 mg / m ² citric acid. The emulsion layer coating solution thus prepared was placed on the support described below in Table 5.
The amount of silver and the amount of gelatin shown in (4) were applied.

Coating solution for lower layer of protective layer Gelatin 0.5 g / m ² non-photosensitive silver halide grain 0.1 g / m ² compound (Cpd-12) 15 mg / m ² 1,5-dihydroxy-2-benz as silver amount Aldoxime 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² Compound (Cpd-13) 3 mg / m ² Compound (Cpd-20) 5 mg / m ² Preservative (ICI, Proxel) 1.5 mg / m ²

Protective layer upper layer coating solution Gelatin 0.3 g / m ² Irregular silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (Cpd-8) (gelatin dispersion) 20 mg / m ² Particle size 10 to 20 μm Colloidal silica (manufactured by Nissan Chemical Industries, Snowtex C) 30 mg / m ² compound (Cpd-9) 50 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (Cpd-10) 20 mg / m ² compound (Cpd-11) 20 mg / m ² preservative (ICI Co., Ltd., Proxel) 1 mg / m ^{2 The} viscosity of the coating solution for each layer was adjusted by adding the following thickener Z.

[0253]

[Chemical formula 46]

Back Layer Coating Solution Gelatin 3.3 g / m ² compound (Cpd-15) 40 mg / m ² compound (Cpd-16) 20 mg / m ² compound (Cpd-17) 90 mg / m ² compound (Cpd-18) 40 mg / m ² compound (Cpd-19) 26 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 Liquid paraffin 78 mg / m ² Compound (Cpd-7) 120 mg / m ² Compound (Cpd-20) 5 mg / m ² Colloidal silica (particle size 10 μm) 15% by mass relative to gelatin Calcium nitrate 20 mg / m ² Preservative (ICI, Proxel) ) 12 mg / m ²

Conductive layer coating solution Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ² Preservative (ICI ( Ltd., Proxel) 0.3 mg / m ²

[0256]

[Chemical 47]

[0257]

[Chemical 48]

[0258]

[Chemical 49]

<Support> A biaxially stretched polyethylene terephthalate support (thickness 100 μm) was coated on both surfaces with a coating solution for the undercoat layer first layer and a coating solution for the undercoat layer second layer having the following compositions.

Undercoat layer 1-layer coating liquid 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 μm) 0.05 g Compound (Cpd -21) 0.20 g Colloidal silica (manufactured by Nissan Kagaku Co., Ltd., Snowtex ZL, particle size 70 to 100 μm) 0.12 g Water amount to make the total amount 100 g Further, 10% by mass KOH is added, pH = 6. The coating solution prepared as described above was dried at a drying temperature of 180 ° C. for 2 minutes, and then applied so that the dry film thickness would be 0.9 μm.

Undercoat layer Second layer coating solution Gelatin 1 g Methylcellulose 0.05 g Compound (Cpd-22) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Preservative (ICI Corporation) Proxel) 3.5 × 10 ⁻³ g acetic acid 0.2 g water Amount that makes the total amount 100 g So that the dry film thickness after drying this coating solution at 170 ° C. for 2 minutes is 0.1 μm Applied.

[0262]

[Chemical 50]

<Coating Method on Support> On the support having the above-mentioned undercoat layer, first, the emulsion layer side, from the side closer to the support, is the UL layer, the emulsion layer, the protective layer lower layer, and the protective layer upper layer in this order. The 4 layers were coated simultaneously with the addition of a hardener solution by the slide bead coater method while maintaining the temperature at 35 ° C, and after passing through the cold air set zone (5 ° C), the side opposite to the emulsion side was close to the support. From the side, a conductive layer and a back layer were applied in this order by a curtain coater method while adding a hardener solution, and simultaneously passed through a cold air set zone (5 ° C.). The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after applying the back surface side, it was conveyed in a state in which there was no contact with the roller and the rest until winding. The coating speed at this time is 200 m / min
Met.

<< Drying condition >> After setting, the product was dried with a drying air of 30 ° C. until the weight ratio of water / gelatin reached 800%, and
35% relative humidity 30% from 00% to 200%
Dry with the dry air of, and apply the air as it is, surface temperature 34
After 30 seconds from the time when the temperature reaches ℃ (which is considered as the end of drying),
It was dried in air at 48 ° C. and 2% relative humidity for 1 minute. This time,
The drying time is 50 seconds from the start of drying to 800% water / gelatin ratio, 35 seconds from 800% to 200%, 200%.
It took 5 seconds to complete the drying.

This silver halide photographic light-sensitive material was wound up at 25 ° C. and 55% relative humidity, and then cut in the same environment to obtain 6
8 in humidity controlled barrier bag at 25 ° C and 50% relative humidity
After the humidity was adjusted for a period of time, the sample was sealed together with a cardboard that had been humidity-controlled for 2 hours at 25 ° C. and a relative humidity of 50% to prepare samples 1 to 26 shown in Table 5. When the humidity in the barrier bag was measured, it was 45%. The pH of the film surface of the obtained sample on the emulsion layer side was 5.5 to 5.8, and the pH of the film surface on the back side was 6.0 to 6.5.
Met. The absorption spectra of the emulsion layer side and the back layer side were as shown in FIG.

<< Exposure and Development >> Each of the obtained samples was
It was exposed to xenon flash light with an emission time of 10 ⁻⁶ seconds through an interference filter having a peak at 7 nm and a step wedge. Then, using the developer (A) (ND-1 manufactured by Fuji Photo Film Co., Ltd.) and the fixer (B) (NF-1 manufactured by Fuji Photo Film Co., Ltd.) having the following formulations, an automatic processor (Fuji Photo Film Co., Ltd., FG-6
80AG), and processed under the developing conditions of 35 ° C. and 30 seconds.

Developer (A) [Composition per 1 L of concentrated solution] Potassium hydroxide 60.0 g Diethylenetriamine / pentaacetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60. 0 g 5-methylbenzotriazole 0.53 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.3 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.15 g 2-mercapto Sodium benzimidazole-5-sulfonate 0.45 g Sodium erythorbate 9.0 g Diethylene glycol 7.5 g pH 10.79 In use, the mother liquor was 1 part water to 2 parts of the above concentrate.
The pH of the mother liquor was 10.65.
The replenisher was diluted with 4 parts of the above concentrate at a ratio of 3 parts of water, and the pH of the replenisher was 10.62.

Fixer (B) [Formulation per 1 L of concentrated solution] Ammonium thiosulfate 360 g Ethylenediamine / tetraacetic acid / 2Na / 2-hydrate 0.09 g Sodium thiosulfate / 5-hydrate 33.0 g Sodium metasulfite 57.0 g Hydroxyl hydroxide Sodium 37.2g Acetic acid (100%) 90.0g Tartaric acid 8.7g Sodium gluconate 5.1g Aluminum sulphate 25.2g pH 4.85 When using, dilute at a ratio of 1 part of the above concentrate to 2 parts of water. did. The pH of the liquid used was 4.8.

<Evaluation> The sensitivity, gradation (gamma), practical density, and storage stability of each sample were measured by the following methods. (Sensitivity) Sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog +1.5, and is represented by Sample No. It was shown as relative sensitivity with a value of 1 being 100. The larger the value, the higher the sensitivity.

(Gamma) A characteristic curve shown on an orthogonal coordinate axis having the same unit length represented by the optical density (y axis) and the common logarithmic exposure amount (x axis) was prepared, and the optical densities of 0.3 and 3.0 were obtained.
A straight line connecting the two points with and was drawn and the gradient was defined as gamma.

(Density of practical skill) Images setter (manufactured by Fuji Photo Film Co., Ltd., RC5600V) is used for 175
The test step is output while changing the light amount in lines / inch, and development processing is performed under the above processing conditions.
The Dmax portion at the time of exposure with an LV value of 100% was measured and used as the practical density. In addition, the net% and the practical skill density are the densitometer (Ma
cbeth TD904).

(Storage stability of silver halide photographic light-sensitive material) Each sample prepared as shown in Table 5 was stored for 5 days under the condition of 50 ° C. and 45% relative humidity as a forced storage test. Totometry is evaluated and sensitivity S1.5
I asked (thermo). The sensitivity variation (ΔS1.5) with respect to the sensitivity (S1.5 (Fr)) of the sample which was not subjected to the forced test was calculated based on the following formula and shown as a percentage.

[0273]

[Equation 1] The value of the sensitivity fluctuation (ΔS1.5) is a positive value when the sensitivity is increased, and is a negative value when the sensitivity is decreased. It is desirable that the numerical value is small, it is practically necessary that the absolute value is within 25%, and it is more preferable that the absolute value is within 10%.

The results of these evaluations are summarized in Table 5.
From Table 5, it can be seen that the samples satisfying the conditions of the present invention have high sensitivity and practical concentration and are excellent in storability.

[0275]

[Table 4]

[0276]

[Table 5]

<Example 2> Emulsions A to K in Example 1
The same except that the tetra-substituted thiourea compound carboxymethyl trimethyl thiourea compound or dicarboxymethyl dimethyl thiourea compound was added in equimolar amount to sodium thiosulfate instead of sodium thiosulfate used for the chemical sensitization of When a sample was prepared, the sample having the constitution of the present invention showed good performance as in Example 1.

Example 3 An experiment similar to that of Example 1 was carried out using the following solid developer (C) and solid fixing agent (D), and a sample having the constitution of the present invention was obtained as in Example 1. Showed good performance.

[0279] Solid developer (C)   Sodium hydroxide (beads) 99.5% 11.5g   Potassium sulfite (bulk powder) 63.0g   Sodium sulfite (bulk powder) 46.0 g   62.0 g of potassium carbonate   Hydroquinone (briquette) 40.0g Briquette is summarized below.   Diethylenetriamine / pentaacetic acid 2.0g   5-methylbenzotriazole 0.35 g   4-hydroxymethyl-4-methyl-1-phenyl     -3-pyrazolidone 1.5g   4- (N-carboxymethyl-N-methylamino)     -2,6-dimercaptopyrimidine 0.2 g   3- (5-mercaptotetrazol-1-yl)     Sodium benzenesulfonate 0.1g   Sodium erythorbate 6.0 g   Potassium bromide 6.6g This was dissolved in water to make 1 L.   pH 10.65

Here, in the raw material form, the bulk powder was used as a general industrial product, and the beads of the alkali metal salt were commercial products. When the raw material form was briquette, it was used after being pressed and compressed into a plate shape using a briquetting machine and then crushed. For minor components, each component was blended before briquetting. The above treatment agent is 10L
The portion was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. Dissolution and replenishment are disclosed in JP-A-9-80718 and JP-A-9-13.
The dissolution replenishing device having an automatic opening mechanism disclosed in Japanese Patent No. 8495 was used.

Solid fixing agent (D) 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 / 2 dihydrate 0.03 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolved in water to make 50 ml. Fixer (D) was prepared by dissolving agent A and agent B in water to prepare 1 L. The pH was 4.8.

Ammonium thiosulfate (compact) was prepared by spray-drying flakes prepared by pressing under pressure with a roller compactor and crushing them into chips of irregular shape of about 4 to 6 mm, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. A 10 L portion of each of the agents A and B was filled in a foldable container made of high-density polyethylene, and the outlet of the agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. Japanese Patent Application Laid-Open No. 9-8 for dissolution and replenishment
The dissolution replenishing device having an automatic opening mechanism disclosed in JP-A-0718 and JP-A-9-138495 was used.

Example 4 The same experiment as in Example 1 was conducted by using the following developer (E) instead of the developer (A) in Example 1, and the present invention was obtained in the same manner as in Example 1. The silver halide photographic light-sensitive material having the above constitution showed good performance.

Developer (E) [Composition per 1 L of concentrated solution] Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75. 0 g 5-methylbenzotriazole 0.25 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.35 g 4- (N-carboxymethyl-N-methylamino) -2,6-dimercaptopyrimidine 0 0.3 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.45 g sodium erythorbate 9.0 g diethylene glycol 60.0 g pH 10.7 In use, 1 part of the above concentrated solution was diluted with 2 parts of water. . The pH of the used solution was 10.5.

<Example 5> With the developer (A) of Example 1,
A scanner film HL manufactured by Fuji Photo Film Co., Ltd., which is blackened by 20% per day, has a large size (50.8 cm x 61 c).
20 sheets of all size were treated while replenishing 50 ml of the used liquid per m), and this was run for 6 days per week for 15 consecutive weeks of running. By processing a small amount of film in this manner, a developer having a one-third reduction in sulfite concentration was obtained. With the developer (A) of Example 1, 1
A scanner film HL made by Fuji Photo Film Co., Ltd., which is 80% blackened per day, is printed in a large size (50.8 cm x 61 c
300 sheets of Daizen size were processed while replenishing 50 ml of the used solution per m), and this was continuously performed for 4 days. By processing a large amount of film in this manner, a developer having a pH lowered to 10.2 and an increased bromine ion concentration was obtained.

The same experiment as in Example 1 was carried out using the above-mentioned fatigue developing solution or a developing solution in the middle of fatigue, and as in Example 1, the silver halide photographic light-sensitive material of the constitution of the present invention was used. Showed good performance.

<Embodiment 6> In Embodiments 1 to 5, when the developing temperature was set to 38 ° C., the fixing temperature was 37 ° C., and the developing time was set to 20 seconds, the processing was carried out. The effect of the invention was not lost.

<Embodiment 7> In Embodiments 1 to 5, FG-680AS manufactured by Fuji Photo Film Co., Ltd. was used as a developing machine, and the conveying speed of the silver halide photographic light-sensitive material was set to a linear speed of 150.
Even when set to 0 mm / min and subjected to the same treatment, the sample having the constitution of the present invention similarly showed good performance.

<Embodiment 8> Instead of using Lux Setter RC-5600V manufactured by Fuji Photo Film Co., Ltd., Imagesetter FT manufactured by Dainippon Screen Co., Ltd.
-R5055, Select Set 5000 manufactured by Agfagewald Co., Avantra 25, or AccuSet 1000, Dreb 450 or Dreb 800 manufactured by Cytex Co., Rhino 630 manufactured by Heidel Co.,
Quasar, Hercules Elite, or Cigna Setter, Lux Setter Luxel F-9000, F-6000 made by Fuji Photo Film Co., Ltd. or Panther Pro 62 made by Prepress Co., Ltd. is used for the same evaluation. As a result, the sample having the constitution of the present invention showed good performance.

[0290]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity and high storage stability and high contrast.

[Brief description of drawings]

FIG. 1 is a diagram showing absorption spectra of an emulsion layer side and a back layer side of a silver halide photographic light-sensitive material according to an embodiment of the present invention.

[Explanation of symbols]

The vertical axis shows the absorbance (0.1 interval) and the horizontal axis shows 350 nm
Wavelengths up to 900 nm are shown. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
Contain at least one organic gold compound, and log exposure (x
(Axis) and optical density (y-axis) in the characteristic curves shown on the orthogonal coordinate axes having the same unit length, the optical densities of 0.3 to 3.
A silver halide photographic light-sensitive material having a characteristic curve having a gamma at 0 of 5.0 or more. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the organic gold compound is a compound represented by the following general formula (1). Formula (1) [Au (L) ₂ ] ⁺ X ⁻ (In the formula, L represents a ligand, and two Ls may be the same or different from each other, and at least one is mesoionic coordinated. Represents a child, and X ⁻ represents an anion.) 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material contains a hydrazine compound. 4. A film surface pH of the silver halide photographic light-sensitive material on the emulsion layer side is 6.0 or less.
4. The silver halide photographic light-sensitive material according to any one of 3 to 3.