JP2003280128A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high contrast silver halide photographic sensitive material having high sensitivity and high processing stability. <P>SOLUTION: In the silver halide photographic sensitive material having at least one silver halide emulsion layer on a support, a metal complex having a cyanide ligand is contained in silver halide contained in the silver halide emulsion and a hydrazine compound having an onium group in each molecule is also contained. <P>COPYRIGHT: (C)2004,JPO

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.

The silver halide photographic light-sensitive material used in such an image forming system has a high processing stability such as a change in sensitivity due to a change in the activity of the hydrazine derivative and the nucleation accelerator due to fatigue of the processing solution. I have a problem. As a measure for improving the processing stability, there is a method of increasing the contrast of the emulsion, but there has been a problem that the sensitivity decreases with the increase of the contrast. Therefore, there has been a demand for technological development with high sensitivity and excellent processing stability.

[0008]

In view of these problems of the prior art, the present invention is to provide a silver halide photographic light-sensitive material having high contrast, high sensitivity and good processing stability. Intended.

[0009]

As a result of intensive studies, the present inventor has found that the following means can provide a silver halide photographic light-sensitive material that meets the purpose. [1] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a metal complex having a cyanide ligand is contained in silver halide contained in the silver halide emulsion layer. A silver halide photographic light-sensitive material containing the hydrazine compound having an onium group in the molecule.

[2] The silver halide photographic light-sensitive material described in [1], wherein the hydrazine compound having an onium group in the molecule is represented by the following formula (1) or (2).

[Chemical 5] [In the formulas (1) and (2), R ¹ represents an arylene group or a divalent heterocyclic group, Q represents an onium group, J represents a divalent linking group, and G ¹ represents —CO—. Group, -S
O ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or ^{-P (O) (G 2 R} 4) -
Represents a group, G ² represents a single bond, an —O— group, a —NR ⁴ — group, R ⁴ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and R ² represents a hydrogen atom, an alkyl group. , An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a carbamoyl group, R ³ represents an aryl group or a heterocyclic group, and A ¹ and A ² are both hydrogen atoms or Is a hydrogen atom and the other is an acyl group,
Represents either a sulfonyl group or an oxalyl group. [3] The silver halide photographic light-sensitive material according to [2], wherein the hydrazine compound having an onium group in the molecule is represented by the formula (1). [4] The silver halide photographic light-sensitive material according to [2] or [3], wherein the atom of J directly bonded to R ¹ in the formula (1) is not a nitrogen atom. [5] In the formula (1), the group represented by -G ¹ is -C.
O-, wherein the group represented by R ² is an onium-group-free alkyl group or an onium-group-free carbamoyl group, according to any one of [2] to [4]. Silver halide photographic light-sensitive material. [6] In the formula (1), the group represented by -G ¹ -R ² is -COCF ₂ H or -COCF ₂ CF ₂ COOM (M represents a hydrogen atom or a counter cation). The silver halide photographic light-sensitive material according to any one of [2] to [5]. [7] In the formula (1), the linking group represented by R ¹ is an unsubstituted phenylene group [2] to
The silver halide photographic light-sensitive material according to any one of [6].

[8] The compound of the formula (1) is represented by the following formula (1-
a) or a silver halide photographic light-sensitive material described in any one of [2] to [7], which is represented by the following formula (1-b).

[Chemical 6] [In the formula (1-a) and ^{(1-b), -G 1} -
R ² is —COCF ₂ H or —COCF ₂ CF ₂ COOM.
(M represents a hydrogen atom or a counter cation), J is an alkylene group, and Q is a pyridinium group or a quinolinium group. [9] The silver halide has a structure consisting of an inside and a surface layer, and the inside is 99 mol% of silver of silver halide crystals.
A metal complex containing the following and also containing one or more cyanide ligands: [1] to
The silver halide photographic light-sensitive material according to any one of [8]. [10] A silver halide emulsion contains silver 1 in silver halide.
Any one of [1] to [9], characterized by containing 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol of a metal complex containing at least one cyanide ligand per mol. The described silver halide photographic light-sensitive material. [11] The silver halide has a structure consisting of an inside and a surface layer, and the inside is 95 mol of silver of a silver halide crystal.
% Or less and also includes a metal complex containing one or more cyanide ligands [1] to
The silver halide photographic light-sensitive material according to any one of [10]. [12] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide contained in the silver halide emulsion layer contains a Group VIII metal compound and has the following formula ( In 1), -G ¹ -R ² contains a hydrazine compound having an onium group in the molecule, which is -COCF ₂ H or -COCF ₂ CF ₂ COOM (M represents a hydrogen atom or a counter cation). And a silver halide photographic light-sensitive material.

[Chemical 7] [In Formula (1), R¹Is an arylene group or divalent
Represents a heterocyclic group, Q represents an onium group, and J represents a divalent group.
Represents a linking group, G¹Is a -CO- group, -SO₂-Group, -SO
-Group, -COCO- group, thiocarbonyl group, iminomethyi
Ren group or -P (O) (G²R^Four) -Represents a group, G²Is
Single bond, -O- group, -NR^FourRepresents a group, R ^FourIs hydrogen
Represents a child, an aliphatic group, an aryl group or a heterocyclic group, and R
²Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Alkoxy, aryloxy, amino or cal
Represents a vamoyl group, A¹And A²Are both hydrogen atoms
Or one is a hydrogen atom and the other is an acyl group, sulfo
Represents either a nyl group or an oxalyl group. ] [13] In the formula (1), R¹J's directly associated with
It is noted in [12] that the atom is not a nitrogen atom.
The listed silver halide photographic light-sensitive material. [14] In the formula (1), R¹The linking group represented by
[12] characterized by being an unsubstituted phenylene group
Alternatively, the silver halide photographic light-sensitive material described in [13]. [15] The compound of formula (1) is represented by the following formula (1-a) or
[12] -characterized by being represented by the formula (1-b)
[14] The silver halide photographic light-sensitive material according to any one of [14].
material.

[Chemical 8] [In the formula (1-a) and ^{(1-b), -G 1} -
R ² is —COCF ₂ H or —COCF ₂ CF ₂ COOM.
(M represents a hydrogen atom or a counter cation), J is an alkylene group, and Q is a pyridinium group or a quinolinium group. [16] The group VIII metal compound is a rhodium compound, an iridium compound, a rhenium compound, a ruthenium compound or an osmium compound [12] to
The silver halide photographic light-sensitive material according to any one of [15]. [17] The proportion of silver bromide in the silver halide contained in the silver halide emulsion in the silver halide emulsion layer is from 45 to 45.
75 mol% [1] to [16]
The silver halide photographic light-sensitive material as described in any one of 1.

[0012]

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.

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer on a support. The silver halide photographic light-sensitive material of the present invention contains a metal complex having a cyanide ligand in the silver halide contained in the silver halide emulsion layer and a hydrazine compound having an onium group in the molecule. It is characterized by doing. The hydrazine compound having an onium group in the molecule used in the silver halide photographic material of the present invention may be any compound, but is preferably a compound represented by formula (1) or formula (2). .

In the formula (1), the arylene group represented by R ¹ is preferably a substituted or unsubstituted arylene group having a total carbon number of 6 to 30, more preferably a total carbon number of 6 to 20, for example, a phenylene group. , A naphthylene group and the like, and a particularly preferred one is a phenylene group. The divalent heterocyclic group represented by R ¹ preferably has a total carbon number of 2 to 3.
0, more preferably a 5- or 6-membered substituted or unsubstituted aromatic heterocycle containing at least one of N, O and S having a total carbon number of 2 to 20, such as a pyridine ring,
Examples thereof include a pyrimidine ring, an oxazole ring, a thiazole ring, a quinoline ring and an isoquinoline ring, and a pyridine ring is particularly preferable.

R ¹ may have one or more substituents, and examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), an alkyl group (straight chain, A branched or cyclic alkyl group, including a bicycloalkyl group and an active methine group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (regardless of the substituting position), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group Group, heterocyclic oxycarbonyl group, carbamoyl group, N-hydroxycarbamoyl group,
N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group, cyano group, carboximide Ill group (Carb
onimidoyl group), formyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group , Carbamoyloxy group, sulfonyloxy group, amino group, (alkyl,
Aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group,
N-hydroxyureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) Sulfonylureido group, N-acylureido group, N-acylsulfamoylamino group, hydroxyamino group, nitro group, isocyano group, imino group, mercapto group, (alkyl, aryl or heterocycle) thio group, (alkyl, aryl , Or heterocycle) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, N-acylsulfamoyl group, N-sulfonylsulfamoyl group or its Salt, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group,
Examples thereof include a silyl group. Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group here means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, It means an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, a carbonimidoyl group (Carbonimidoyl group). Here, the two electron-withdrawing groups may be bonded to each other to form a cyclic structure. In addition, salt is an alkali metal,
It means cations such as alkaline earth metals and heavy metals, and organic cations such as ammonium ions and phosphonium ions. These substituents may be further substituted with these substituents. Further, when two or more of these groups are substituted, these may be the same or different, and the substituents may be bonded to each other to form a ring.
R ^{1 in the} formula (1) is preferably an arylene group, more preferably a phenylene group, and particularly preferably an unsubstituted phenylene group.

In the formulas (1) and (2), Q represents an onium group, and the onium group includes onium groups of nitrogen atom, phosphorus atom and sulfur atom, preferably the following formulas (3) to (). It is a group represented by 7).

[Chemical 9] [In the formulas (3) to (7), R ⁵ represents a substituted or unsubstituted aliphatic group, an aryl group or a heterocyclic group, and Z represents a nitrogen atom in the formula to form a nitrogen-containing heteroaromatic ring. It represents a necessary atomic group, and X ⁻ represents a counter anion. ]

In the formulas (4) to (7), the aliphatic group represented by R ⁵ preferably has a total carbon number of 1 to 30, more preferably a total carbon number of 1 to 20 and is a linear, branched or cyclic substituent. Or an unsubstituted alkyl group, alkenyl group, and alkynyl group, such as a methyl group, an ethyl group, a hexyl group, a 2-ethylhexyl group, a benzyl group, a dodecyl group, a stearyl group, a 4-chlorobutyl group, a cyclohexyl group, and a tert group.
-Butyl group, ethenyl group, ethynyl group and the like can be mentioned, with preference given to an alkyl group. The aryl group represented by R ⁵ is preferably a substituted or unsubstituted aryl group having a total carbon number of 6 to 30, more preferably a total carbon number of 6 to 20, and examples thereof include a phenyl group, a 4-cyanophenyl group, and 4 −
Examples thereof include a butylphenyl group and a 2-naphthyl group, and a phenyl group is particularly preferable. The heterocyclic group represented by R ⁵ is preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group containing at least one of N, S and O, and more preferred Is a nitrogen-containing heteroaromatic ring (eg, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, etc.). R ⁵ may be further substituted with another substituent, and as the substituent, the groups enumerated as the substituents of R ^{1 in} the formula (1) can be applied. R ⁵ is more preferably an aliphatic group or an aryl group, and particularly preferably an alkyl group or a phenyl group. In addition, R ^{5 s} in the formulas (5) to (7) may be the same or different, and may be bonded to each other to form a ring.

The nitrogen-containing heteroaromatic ring formed by Z and the nitrogen atom in the formulas (3) and (4) is preferably a 5- or 6-membered substituted or unsubstituted nitrogen-containing heteroaromatic ring, which is Other rings (eg benzene ring, naphthalene ring,
(Pyridine ring, thiophene ring, furan ring, pyrrole ring, etc.)
It may be condensed with. Examples of the nitrogen-containing heteroaromatic ring include oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, pyridine ring, pyrimidine ring,
Examples thereof include a quinoline ring, an isoquinoline ring, a quinazoline ring, an acridine ring, an imidazole ring, and a benzimidazole ring. Preferred are a pyridine ring, a quinoline ring and an isoquinoline ring, and a pyridine ring is particularly preferred. Z
A substituent may be bonded to, for example, R of the formula (1)
Those enumerated as the substituents of ¹ are applicable. Formula (1)
And in the formula (2), Q is more preferably formulas (3), (4) and (6), and particularly preferably formulas (3) and (4).

X ⁻ represents a counter anion, for example, a halogen ion (chlorine, bromine, iodine, etc.), a carboxylate ion (trifluoroacetic acid, pentachlorobenzoic acid, etc.),
Sulfonate ions (methanesulfonate, such as toluene sulfonic acid), sulfate ion, perchlorate ion, carbonate ion, nitrate ion, tetrafluoroborate ion, PF ₆ ^- and the like, preferably a halogen ion, carboxylate ion, It is a sulfonate ion. When X ⁻ forms an inner salt, it represents a counter anion portion.

[0020] Equation (1) and formula (2), the divalent linking group represented by J _{is, -CH 2 -, - CH =} CH -, - C≡
_{C -, - C 6 H 4} -, - NH -, - O -, - S -, - CO
-, - SO -, - SO 2 -, - PO -, - CH = an N- or a group comprising a combination of these linking groups. Examples of combinations, -CONH -, - SO ₂ NH
-, - NHCONH -, - CONHSO 2 -, - COO
_{-, - (CH 2 CH 2} O) n- (n = 1~10), - CH
_{2 O -, - (CH 2} ) n- (n = 2~20), - CH 2 -
C ₆ H ₄ — (any of o, m, and p linkages), combinations of these, and combinations of these with the above-described linking groups are included. In formula (1), it is particularly preferable that the atom in J directly bonded to R ¹ is not a nitrogen atom.
In formulas (1) and (2), the linking group represented by J preferably has 1 to 20 total carbon atoms, and more preferably has 2 to total carbon atoms.
10, and these linking groups may be substituted with a substituent by removing the hydrogen atom thereof, and as the substituent, the groups enumerated as the substituents of R ¹ in formula (1) can be applied. A particularly preferred group is an alkylene group.

[0021] Equation (1) and in formula (2), G ¹ is _{-CO -, - SO 2 -,} - SO -, - COCO-, thiocarbonyl group, an iminomethylene group or -P (O) (G
² R ⁴⁾ - represents, G ² represents a single bond, -O -, - NR ⁴ - represents, R ⁴ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group.

In the formula (1), R ² is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having a total carbon number of 1 to 10, such as methyl group or difluoromethyl group). , Trifluoromethyl group, dichloromethyl group, pentafluoroethyl group, benzyl group,
o- hydroxybenzyl group, a methoxymethyl group, a benzenesulfonyl group, a hydroxymethyl group, benzenesulfonylamino methyl group, -CF ₂ CF ₂ COOK
Etc.), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms in total, such as a phenyl group, a hydroxymethylphenyl group, a chlorophenyl group, etc.), a heterocyclic group (preferably N, O, S 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group containing at least one of them, for example, pyridyl group, thienyl group, furyl group, imidazolyl group, piperidyl group, pyrrolidyl group, etc.), alkoxy group (Preferably having a total carbon number of 1 to
10 substituted or unsubstituted alkoxy groups such as methoxy group, ethoxy group, butoxy group), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms such as phenoxy group), It represents an amino group (preferably a substituted amino group having 1 to 10 total carbon atoms, such as a methylamino group, a dimethylamino group, a phenylamino group, etc.) or a carbamoyl group. R ² may have a substituent, and as the substituent, those enumerated as the substituents of R ¹ can be applied.

In the formula (1), the group represented by -G ¹ is -CO-, and the group represented by R ² is an alkyl group containing no onium group or a carbamoyl group containing no onium group. Is more preferable. In formula (1), a particularly preferred group represented by -G ¹ -R ² is -COCF.
₂ H or —COCF ₂ CF ₂ COOM (M represents a hydrogen atom or a counter cation).

In the formula (2), the aryl group represented by R ³ is preferably a substituted or unsubstituted aryl group having 6 to 30 total carbon atoms, more preferably 6 to 20 total carbon atoms,
Examples thereof include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable. The heterocyclic group represented by R ³ preferably contains at least one of N, O and S 5.
Alternatively, it is a 6-membered substituted or unsubstituted aromatic heterocycle, and examples thereof include a pyridine ring, a pyrimidine ring, an oxazole ring, a thiazole ring, a quinoline ring, and an isoquinoline ring, and a pyridine ring is particularly preferable. R ³ is preferably an aryl group, and particularly preferably a phenyl group. R ³ may have a substituent, and as the substituent, the groups enumerated as the substituents of R ¹ can be applied.

In the formulas (1) and (2), both A ¹ and A ² are hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg acetyl group, benzoyl group, etc.), sulfonyl group ( For example, it represents a methanesulfonyl group, a toluenesulfonyl group, etc.) or an oxalyl group (eg, an ethoxaryl group, etc.). It is particularly preferable that both A ¹ and A ² are hydrogen atoms.

The hydrazine compound having an onium group in the molecule is preferably a compound represented by the formula (1). Particularly, the compound represented by the formula (1-a) and the compound represented by the formula (1-b) are preferable. In formulas (1-a) and (1-b), -G ¹ -R ² is -COCF ₂ H or -COCF ₂ CF ₂ COOM (M represents a hydrogen atom or a counter cation), and J is an alkylene. And Q represents a pyridinium group or a quinolinium group. For specific examples and preferable ranges of J and Q,
As above. The total carbon number of the compounds represented by formulas (1) and (2) is preferably 10 to 200, more preferably 13 to 100, and particularly preferably 15 to 50. Further, a plurality of compounds represented by the formulas (1) and (2) may be bonded to each other via a linking group, and may have a bis or tris structure or a polymer structure having an average molecular weight of 500,000 or less.

Further, the compounds represented by the formulas (1) and (2) may incorporate an adsorptive group which adsorbs to silver halide. Such adsorption groups include alkylthio groups, arylthio groups, thiourea groups, thioamide groups,
U.S. Pat. Nos. 4,385,108, 4,459,347, mercapto heterocyclic groups and triazole groups, JP-A-59-195233 and 59-2.
00231, gazette 59-201045 gazette, gazette 5
9-201046, 59-201047, 59-201048 and 59-20104.
9, gazette 61-170733 gazette, gazette 61-27.
0744, 62-948, and 63-23.
No. 4244, No. 63-234245, No. 63.
The groups described in JP-A-234246 can be 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.

The compounds represented by the formulas (1) and (2) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. In particular, one having a ballast group incorporated therein is one of the preferable examples. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and examples thereof include an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from among alkylphenoxy groups and the like.
As the polymer, for example, JP-A-1-100530 is used.
Those described in Japanese Patent Publication No.

The compounds represented by the formulas (1) and (2) can be dissociated by a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, a (alkyl, aryl, or heterocycle) thio group, or a base. Functional group (carboxy group, sulfo group, acylsulfamoyl group,
Carbamoylsulfamoyl group etc.) may be contained. Particularly, a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, or a group containing a (alkyl, aryl, or heterocycle) thio group is one of the preferable examples.

Specific examples of the compounds of formulas (1) and (2) include, for example, US Pat. No. 4,994,365, JP-A-5-45761, JP-A-5-34853, and JP-A-5-34853. No. 45762, No. 5-45763, No. 5-45764, No. 5-150392, No. 5-204075, No. 5-204076, No. 5-216151, No. 5-333466.
No. 6-19032, No. 6-19031, No. 6-148777, No. 6-148778.
No. 6,16,01010, and No. 6-17525.
No. 3, gazette 10-232456 gazette, and gazette 11-19.
0887, DE 3829078, 400
Those described as specific examples in JP-A No. 6032 and JP-A No. 4-96035 are listed.

Specific examples of the compounds of formula (1) and formula (2) are shown below, but the compounds of formula (1) and formula (2) that can be used in the present invention are not limited thereto.

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

In the present invention, the hydrazine compound having an onium group in the molecule is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide. , Dimethyl sulfoxide, methyl cellosolve, etc. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

In the present invention, having an onium group in the molecule
The hydrazine compound
It may be added to any layer on the side of the agent layer. For example, halo
Addition to silver genide emulsion layer or other hydrophilic colloid layer
Can be a silver halide emulsion layer or it
Is preferably added to the hydrophilic colloid layer adjacent to
Yes. In addition, a polymer having an onium group in two or more kinds of molecules
It is also possible to use a dragin compound in combination. Starting
Hydrazine compound with onium group in Ming
The addition amount of the substance is 1 × 10 1 to 1 mol of silver halide.^-Five
~ 1 x 10^-2mol is preferable, 1 × 10 ^-Five~ 5 x 10
^-3mol is more preferable, 2 × 10^-Five~ 5 x 10^-3mo
l is most preferred. In the present invention, an onium group in the molecule
The hydrazine compound having is known in the art, for example
Easy according to the method described in Japanese Patent Laid-Open No. 10-232456
Can be synthesized.

The silver halide composition for the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited, and examples thereof include silver chloride, silver bromide, silver chlorobromide, silver iodobromide,
Any composition selected from silver iodobromide and silver iodochlorobromide can be used. In the present invention, silver bromide 40 m
It is preferable to use silver chlorobromide or silver iodochlorobromide containing ol% or more. Furthermore, silver bromide 45 mol% to 75 m
It is preferable to use silver chlorobromide or silver iodochlorobromide containing 1% by weight. The shape of silver halide grains may be cubic, tetradecahedron, octahedron, amorphous, or plate-like, but the aspect ratio (circle equivalent diameter / thickness) is preferably 2 or less,
Most preferably, it is a cube. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.1 to 0.5 μm. The coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is preferably 15% or less,
A narrow particle size distribution of 10% or less is more preferable. 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 P. Glafk.
ides Chimie et Physique Photographique (Pau
l Montel, 1967), Photog by GF Dufin
raphic Emulsion Chemistry (The Forcal Press, 1
966), by VL Zelikman et al Making and Coati
ng Photographic Emulsion (The Forcal Press, 19
64) and the like. That is, any of an acidic method and a neutral method may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. 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 a 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, Japanese Patent Publication No. 48-36890, and Japanese Patent No. 52-16364.
No. 4,242,445, JP-A-55-158124, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate as described in JP-A-55-158124. It is preferable to use the method of changing the concentration of the aqueous solution as described in (1) to grow rapidly within a range not exceeding the critical saturation.

The silver halide emulsion used in the present invention is
A metal complex containing one or more cyanide ligands is contained in silver halide in an amount of 1 × 10 ⁻⁶ mol or more per mol of silver. 5 × 10 per mol of silver in silver halide
^-6 mol or more and 1 x 10 ^-2 mol are preferably contained. Furthermore, in 1 mol of silver in the silver halide, 5
It is particularly preferable that the content is not less than ^{x10 -6} mol and not more than ^{5x10 -3} mol. The metal complex containing at least one cyanide ligand used in the present invention is added in the form of a water-soluble complex salt. Particularly preferred are hexacoordinated complexes represented by the following formulas. [M (CN) _n1 L _6-n1 ] ^n- wherein M represents a metal belonging to groups V to VIII, in particular Ru,
Re, Os and Fe are preferable. L represents a ligand other than a cyan compound, and is preferably a halide ligand, a nitrosyl ligand, a thionitrosyl ligand, or the like. n1 is 1
6 and n represents 0, 1, 2, 3 or 4. n1 is preferably 6. In this case, the counterion has no significance and ammonium or alkali metal ions are used. 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.

[0053]

[Chemical formula 24]

The metal complex used in the present invention may be present in any part of the silver halide grain as long as it is a grain. When the silver halide crystal is composed of the inside and the surface layer, it is preferable that the inside contains a metal complex. In the present invention, the silver halide has a structure consisting of the inside and the surface layer, and the inside is 99 mol of silver of silver halide crystals.
%, And a metal complex containing one or more cyanide ligands is preferably included. Further, the silver halide has a structure composed of an inside and a surface layer, and the inside contains a metal complex containing 95 mol% or less of silver of the silver halide crystal and at least one cyanide ligand. It is more preferable to include.

The silver halide emulsion provided from one aspect of the present invention comprises a rhodium compound and iridium compound in order to achieve high contrast and low fog in addition to a metal complex containing one or more cyanide compound ligands. Compounds, rhenium compounds, ruthenium compounds, osmium compounds, etc.
Contains a Group VIII metal compound. 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 halogen, amines, oxalate, aco, etc. as a ligand, for example, hexachlororhodium (III) complex salt, pentachloroacorodium complex salt, tetrachlorodiaco Examples thereof include rhodium complex salt, hexabromorhodium (III) complex salt, hexaamine rhodium (III) complex salt, and trizalatrodium (III) complex salt. 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 an alkali halide (eg KC
1, NaCl, KBr, NaBr, 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.

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- Here, M represents Ru, Re, or Os, L is a ligand, and n is 0, 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Further, preferred ligands include halide ligands, nitrosyl ligands, thionitrosyl ligands and the like. 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.

[0057]

[Chemical 25]

The addition amount of these compounds is 1
The range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol per mol is preferable, and 1 × 10 ⁻⁸ mol to 1 × 1 is particularly preferable.
It is 0 ^-6 mol. Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, hexaammineiridium, pentachloronitrosyliridium and the like.

The silver halide emulsion used in the present invention is preferably chemically sensitized. Sulfur sensitization, selenium sensitization,
Known methods such as the tellurium sensitization method and the noble metal sensitization method can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitization method and gold sensitization method, sulfur sensitization method and selenium sensitization method and gold sensitization method,
The sulfur sensitizing method, tellurium sensitizing method, gold sensitizing method and the like 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.
Particularly, the general formula (VII in JP-A-4-324855) is used.
It is preferable to use the compounds represented by I) and (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to be 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.) 6
35 (1980), ibid 1102 (1979),
ibid 645 (1979), Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.) 1,191 (198)
0), S. S.Patai, The Chemistry
The Chemistry of Organic Serenium
and Tellunium Compounds), Vol 1 (198
6) and the compound described in Vol 2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in JP-A-4-324855.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, 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. A thiosulfonic acid compound may be added to the silver halide emulsion used in the present invention by the method disclosed in European Patent Publication EP 293,917A. The silver halide emulsion in the silver halide photographic light-sensitive material used in the present invention is preferably used in combination of 1 type to 3 types. When two or more kinds are used in combination, those having different average particle sizes, different halogen compositions, different amounts and kinds of metal complexes contained, different crystal habits, different chemical sensitization conditions, and sensitivity. It is preferable to use different ones 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 used in the present invention is spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye depending on the use of the light-sensitive material. May be. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye,
Complex merocyanine dyes, holoholer cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. Useful sensitizing dyes used in the present invention are, for example, Resear
ch Disclosure Item Item 17643IV-A (Dec. 1978, p.23), Item 18341X Item (1979)
August p. 437) or cited therein.

Particularly, 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, A)
Japanese Patent Application Laid-Open No. 60-162 discloses an argon laser light source.
(I) -1 to (I) -8 compounds described in JP-A No. 247, I-1 to I described in JP-A-2-48653.
-28 compound, compounds I-1 to I-13 described in JP-A-4-330434, U.S. Pat. No. 2,16
Example 1 to Ex described in No. 1,331
compound of sample 14, compounds 1 to 7 described in West German Patent No. 936,071; B) for a helium-neon laser and a red laser diode light source,
I-1 to I- described in JP-A-54-18726
38 compound, I described in JP-A-6-75322
-1 to I-35 compounds and JP-A-7-28733
Compounds I-1 to I-34 described in Japanese Patent No. 8 and 2-1 to 2-1 described in Japanese Patent No. 2822138.
4, 3- (1) to 3- (14), 4-1 to 4-6 compounds; C) Japanese Patent Publication No. 55-398 for LED light sources.
Dyes 1 to 20 described in JP-A-18, JP-A-62-28
The compounds I-1 to I-37 described in Japanese Patent No. 4343, the compounds I-1 to I-34 described in Japanese Patent Laid-Open No. 7-287338, and the compounds 2-1 to 2 described in Japanese Patent No. 2822138. -14,3- (1) to 3- (1
4), Compounds 4-1 to 4-6; D) Compounds I-1 to I-12 described in JP-A-59-191032, and JP-A-60-8084 for semiconductor laser light sources.
Compounds I-1 to I-22 described in JP-A No. 1, a compound of I-1 to I-29 described in JP-A-4-335342 and I-1 described in JP-A-59-192242. To I-18 compound; E) JP-A-55-45 for tungsten and xenon light sources for plate making cameras.
Compounds (1) to (19) represented by General Formula [I] described in JP-A No. 015, 4-A to 4-S compounds and 5-A to 5 described in JP-A-6-242547. -Q compound, 6-A to 6-T compound and JP-A-9-1
The compounds I-1 to I-97 described in JP-A-60185 are advantageously selected, but the present invention is not limited thereto.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially 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, paragraph J, or the aforementioned Japanese Examined Patent Publication No. 49-255.
No. 00, No. 43-4933, JP-A-59-1
9032, 59-192242 and the like.

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 colloidal dispersion in the presence of a surfactant to 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 the specifications of JP-A No. 8-184142, JP-A No. 60-196749, etc., the time before the grain formation step of silver halide and / or before desalting, during the desilvering step and / or after desalting From the time before the start of chemical aging,
As disclosed in the specification of JP-A-58-113920 and the like, immediately before chemical ripening or during the process, after chemical ripening and before coating, at any time before the emulsion is coated, It may be added in the process. Also,
U.S. Pat. No. 4,225,666, JP-A-58-
As disclosed in the specification of Japanese Patent No. 7629, etc., the same compound alone or in combination with a compound having a different structure, for example, divided into a grain forming step and a chemical ripening step or after completion of chemical ripening, It may be added in divided portions such as before chemical aging or during the process and after completion,
You may change and add the compound and the kind of combination of the compound which are added by dividing.

The addition amount of the sensitizing dye in the present invention varies depending on the shape, size, halogen composition, method and degree of chemical sensitization of silver halide grains, kind 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.

A nucleation accelerator may 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, Japanese Patent Laid-Open No. 2001-343
Nos. 725 to 725, and compounds represented by the general formula (1), the general formula (2), the general formula (3) and the general formula (4), specifically A-1 to A described in the same publication. -42, B-1 to B-4
1, C-1 to C-14 compounds; 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 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 and dispersion method, oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are used to dissolve and mechanically dissolve. 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 comprising a silver halide emulsion-free hydrophilic colloid layer 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 10 ⁻⁵ to 1 × 10 ⁻² mol. Further, two or more kinds of nucleation accelerators can be used in combination.

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 (I
II) -1 to 25 compounds); JP-A-1-118832
Compounds having substantially no absorption maximum in the visible region represented by the general formula (I) described in Japanese Patent Publication (specifically, compounds I-1 to I-26 described in the Publication); JP-A-2-
No. 103536, page 17, lower right line 19 to gazette 18
Antifoggant described in the fourth line on the upper right of the page; JP-A-2-103
JP-A No. 9-179228, which is described in JP-A 536, page 18, lower left line 12 to lower left line 20;
Polymer latex having an active methylene group represented by formula (I) described in JP-A-9-179228 (specifically compounds I-1 to I-16 described in JP-A-9-179228);
Polymer latex having a core / shell structure described in JP-A No. 1994- (specifically, compounds P-1 to P-
55); acidic polymer latex described in JP-A-7-104413, page 14, left first line to page right, 30th line (specifically, compound II-1 described in page 15 of the same).
II-9)); Japanese Patent Application Laid-Open No. 2-103536, page 19, upper left line, line 15 to page 19, upper right line, line 15; matting agents, slip agents, plasticizers; 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 Compound; JP-A-2-18542, page 2, lower left line 13-
Conductive substances described on page 3, upper right line, page 3 of the same publication (specifically, metal oxides described on page 2, lower right line, second page to lower right line, 10 of the same publication, and Described compounds P-1 to P
-7 conductive polymer compound); JP-A-2-103536
No. 1, page 17, lower right line, to page 18, upper right line, water-soluble dyes; general formula (FA), general formula (FA1), and general formula (FA2) described in JP-A-9-179243. , A solid disperse dye represented by the general formula (FA3) (specifically, compounds F1 to F34 described in the publication, JP-A-7-15211).
No. 2 (II-2) to (II-24), and JP-A No. 7-152112 (III-5) to (II).
I-18) and (I) described in JP-A-7-152112.
V-2) to (IV-7), solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382); and development by oxidation described in JP-A-5-274816. A redox compound capable of releasing an inhibitor, preferably a redox compound represented by the general formula (R-1), the general formula (R-2) or the general formula (R-3) described in the publication (specifically, , Compounds R-1 to R described in the publication
Compounds of -68); and the binders described in JP-A-2-18542, page 3, lower right, lines 1 to 20.

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 usable 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, but 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.

The developing solution used in the present invention (hereinafter, both the developing starting solution and the developing replenishing solution are collectively referred to as a developing solution).
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 that exhibits superadditivity therewith, and 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 preferably used usually 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 in an amount of usually 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 used for processing the silver halide photographic light-sensitive material of the present invention contains additives usually used (eg, developing agent, alkaline agent, pH buffer, 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 (eg sodium salt, potassium salt) and the like are used, and carbonate is preferably used. The amount of buffering agent, especially carbonate, used is preferably 0.05 mol / L or more, particularly 0.08 to 1.0 m.
ol / L.

In the present invention, it is preferable that both the development starter solution and the development replenisher solution have a pH increase of 0.8 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 0.8 or less, it is determined that the liquid has the properties specified above. In the present invention, it is particularly preferable to use a development starter solution and a development replenisher solution that have a pH value increase of 0.7 or less when the above test is performed.

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 may be added as an antifoggant or a black spot (black pe).
pper) inhibitor may be included. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6
-Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,3,4
-Thiadiazol-2-yl) thio) butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. it can. 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 the aminopolycarboxylic acid 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, JP-A-52-25632, 55- 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, etc., and hydroxyalkylidene-diphosphonic acid, Research Disclosure Vol. 181, Item 1
8170 (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 and JP-A-57-208554, 5
The compounds described in 4-61125, 55-29883, 56-97347 and the like can also be mentioned.

Examples of the organic phosphonocarboxylic acid include those disclosed in 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 developing solution,
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 to 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 470 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material, and it is 30 to 325.
ml is 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 hardening agent, 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 such as sulfite, bisulfite, metabisulfite, etc.
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 (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. .. 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 more preferably 80 to 1 m ² per 1 m ^{2 of the} silver halide photographic light-sensitive material.
Particularly preferred is 325 ml. The replenisher 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 preferably stored in a packaging material having a low oxygen permeability as described in, for example, 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 in the present invention can be adjusted in solubility by changing the surface condition (smoothness, porosity, etc.) or partial thickness, or forming a hollow donut shape.
Further, it is possible to have 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 permeability to oxygen and water, and the packaging material may have a known shape such as a bag shape, a cylinder shape or a box shape. 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
You may attach an aluminum seal or heat seal the packaging material, but you may use other known ones,
There is no particular limitation. Further, in terms of environmental protection, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent in the present invention is not particularly limited, and a known method can be used. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolution having a dissolving portion and a portion for stocking a completed liquid as described in JP-A-9-80718. Method of melting with an apparatus and replenishing from a stock part, JP-A-5-11
No. 9454, No. 6-19102, No. 7-26
A method in which a processing agent is added to a circulation system of an automatic developing machine to dissolve and replenish it as described in Japanese Patent No. 1357, and processing is performed in accordance with the processing of a silver halide photographic light-sensitive material with an automatic developing machine incorporating a dissolution tank. 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 possible to use the method described in JP-A-9-
It may be automatically opened and automatically charged by a dissolving device or an automatic processor having an opening mechanism as described in JP-A-138495, and the latter is preferable from the viewpoint of working environment. Specifically, there are a method of piercing the take-out port, a method of peeling, a method of cutting and a method of pushing, and a method described in JP-A-6-19102 and JP-A-6-95331.

The silver halide photographic light-sensitive material which has been developed and fixed is then washed or stabilized (hereinafter, unless otherwise specified, it is called washing including stabilizing, and the liquid used for these is referred to as 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.

[0117] 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 scale preventing means may be provided in the washing step. 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 water stain preventing 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 condition, or may be carried out only during the non-working period 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 the 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. JP-A-11-23148
The method of Japanese Patent Publication No. 5 may be used. The antifungal agent is not particularly limited and known ones can be used. In addition to the above-mentioned oxidizing agents, there are, for example, glutaraldehyde, chelating agents such as aminopolycarboxylic acids, cationic surfactants, mercaptopyridine oxides (such as 2-mercaptopyridine-N-oxide), and the like, and they may be used alone or in combination of two or more. But it's okay. As a method for energizing, the methods described in JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, JP-A-4-18980 and the like can be used.

In addition, a known water-soluble surfactant or defoaming agent may be added to prevent unevenness of water bubbles and stain transfer. 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 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.

There are also cases where a stabilizing treatment is carried out 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. is there.

When the replenishment amount of the treatment agent is reduced, it is preferable to reduce the opening area of the treatment tank to prevent the evaporation of liquid and the oxidation of air. Regarding the roller-conveying type automatic developing machine, U.S. Pat. Nos. 3,025,779 and 3,
545,971 and the like, and is simply referred to as a roller-conveying type automatic developing machine in this specification. This developing machine comprises four steps of development, fixing, water washing and drying. In the present invention, other steps (for example, stopping step) are not excluded, 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 development and fixing time is 40 seconds or less, preferably 6 to 6 seconds.
35 seconds, the temperature of each liquid is preferably 25 to 50 ° C., 30 to
40 ° C. is preferred. Washing temperature and time is 0 ~ 50 ℃
And preferably 40 seconds or less. The silver halide photographic light-sensitive material that has been developed, fixed and washed with water may be dried by squeezing out washing water, that is, passing through a squeeze roller. Dry about 4
It is performed at 0 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, but it is disclosed in warm air drying, JP-A-4-15534, JP-A-5-2256, and JP-A-5-289294. Such as heat roller drying, far infrared ray drying,
You may use multiple methods together.

[0127]

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.

<Example 1> In this example, a silver halide photographic light-sensitive material satisfying the conditions of the present invention and a silver halide photographic light-sensitive material of a comparative example were prepared and evaluated. First, the emulsion used for preparing these silver halide photographic light-sensitive materials and the preparation of non-light-sensitive silver halide grains are described, and then the preparation of silver halide photographic light-sensitive materials and their evaluation are described.

[0129] << 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

[0130] 2 liquid   300 ml of water   Silver nitrate 150g

Three-liquid water 300 ml Sodium chloride 22 g Potassium bromide 58 g K ₃ IrCl ₆ Amount shown in Table 1 (concentration in a 20% KCl aqueous solution is 0.005%) (NH ₄ ) ₃ [RhCl ₅ (H ₂ O) ] Amount shown in Table 1 (concentration in a 20% NaCl aqueous solution is 0.001%)

K ₃ IrCl ₆ (0.005 used for the third liquid)
%), (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] (0.001
%) Are powders of 20% KCl aqueous solution and 20% N, respectively.
It was dissolved in an aCl 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 was added simultaneously with stirring for 20 minutes to form 0.19 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.

[0134]   4 liquid     100 ml of water     Silver nitrate 50g

5-Liquid Water 100 ml Sodium Chloride 8.6 g Potassium Bromide 19.3 g K ₄ [Fe (CN) ₆ ] .3H ₂ O (Yellow Blood Salt) Amount shown in Table 1.

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 was precipitated (pH 3.2 ± 0.2 range). Met). 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, 45 g of gelatin was added to adjust the pH to 5.6 and pAg to 7.5, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, sodium thiosulfate pentahydrate 15 mg and chloroauric acid. 4 mg was added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity.
Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene (100 mg) and an antiseptic (ICI Co., Ltd., Proxel) (100 mg) were added. Finally 55m of silver bromide
A silver iodochlorobromide cubic grain emulsion having an average grain size of 0.21 .mu.m and a coefficient of variation of 9% containing ol% and 0.08 mol% of silver iodide was obtained. The final emulsion was pH = 5.7, pA
g = 7.5, conductivity = 40 μS / m, density = 1.2 to
The viscosity was 1.25 × 10 ³ kg / m ³ and the viscosity was 50 mPa · s.

[0137]

[Chemical formula 26]

[0138] << 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

[0139]   2 liquid     300 ml of water     Silver nitrate 150g

Three-liquid water 300 ml Sodium chloride 22 g Potassium bromide 58 g K ₃ IrCl ₆ Amount shown in Table 1 (concentration in 20% KCl aqueous solution 0.005%) (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] Amount shown in Table 1 (concentration in 20% NaCl aqueous solution is 0.001%)

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

For one solution kept at 38 ° C. and pH 4.5, 2
90% each of the liquid and 3 liquid was added simultaneously with stirring for 20 minutes to form 0.17 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 0.19 μm. Further, 0.15 g of potassium iodide was added and aged for 5 minutes to complete grain formation.

[0143]   4 liquid     100 ml of water     Silver nitrate 50g

5-Liquid Water 100 ml Sodium Chloride 8.6 g Potassium Bromide 19.3 g K ₄ [Fe (CN) ₆ ] 3H ₂ O (Yellow Blood Salt) Amount shown in Table 1.

After that, 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 4 mg of chloroauric acid were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity.
6-methyl-1,3,3a, 7-tetraazaindene 1
00 mg, antiseptic (ICI, Proxel) 10
0 mg was added.

Finally, a silver iodochlorobromide cubic grain emulsion containing 55 mol% of silver bromide and 0.08 mol% of silver iodide, having an average grain size of 0.19 μm and a coefficient of variation of 10% was obtained. Finally, as an emulsion, pH = 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 × 10 ³ kg / m ³ ,
The viscosity was 50 mPa · s.

<< Preparation of Emulsions C to H >> Emulsion A was prepared in the same manner as Emulsion A, except that the halogen composition, grain size, type of heavy metal to be doped, and addition amount were changed as shown in Table 1. The halogen composition was adjusted by changing the amounts of sodium chloride and potassium bromide added in the third and fifth liquids, and the particle size was adjusted by changing the amount of sodium chloride added in the first liquid and the adjustment temperature.

[0148] << 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

[0149]   2 liquid     400 ml of water     Silver nitrate 100g

3-liquid water 400 ml sodium chloride 13.5 g potassium bromide 45.0 g (NH ₄ ) ₃ [RhCl ₅ (H ₂ O)] 8.6 mg (4 × 10 ⁻⁵ mol / Agmol)

The 1st, 2nd and 3rd liquids kept at 70 ° C. and pH 4.5 were added simultaneously for 15 minutes while stirring,
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 unripened silver iodochlorochlorobromide cubic milk particles having an average particle size of 0.45 μm and a coefficient of variation of 10% was obtained, which contained mol% and silver iodide 0.08 mol%. The final emulsion is pH = 5.7, pAg = 7.5, conductivity = 40 μS.
/ M, density = 1.3 to 1.35 x 10 ³ kg / m ³ , and viscosity = 50 mPa · s.

<< 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 layer 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 solution Gelatin 0.3 g / m ² polyethyl acrylate latex 150 mg / m ² compound (Cpd-7) 40 mg / m ² compound (Cpd-14) 10 mg / m ² 5-methylbenzotriazole 40 mg / m ² Preservative (ICI, Proxel) 1.5 mg / m ²

Emulsion layer coating liquid Emulsion (kind shown in Table 2) Addition as shown in Table Sensitizing dye A 5.7 × 10 ⁻⁴ mol / Agmol KBr 3.4 × 10 ⁻⁴ mol / Agmol Compound (Cpd- 1) 2.0 × 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 (Table Compound shown in 2) Addition amount as shown in Table 2 Nucleation accelerator (Compound shown in Table 2) Addition amount as shown in Table 2,4-dichloro-6-hydroxy-1,3,5-triazinenaphthyl Umium 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 with respect to gelatin Mass% Latex copolymer of methyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate (weight ratio 88: 5: 7) 150 mg / m ² core-shell type latex 150 mg / m ² (core : Styrene / butadiene copolymer (weight ratio 37/63), shell: styrene / 2-acetoxyethyl acrylate (weight ratio 84/16), core / shell ratio = 50/50)

The pH of the coating solution was adjusted to 5.6 with citric acid. The emulsion layer coating solution thus prepared was coated on the following support so as to have the amounts of silver and gelatin shown in Table 2.

[0157]

[Chemical 27]

Coating solution for lower layer of protective layer Gelatin 0.5 g / m ² non-photosensitive silver halide grains 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 liquid 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 antiseptic (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.

[0160]

[Chemical 28]

Back Layer Coating Liquid Gelatin 3.0 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 30 mg / m ² (average particle size 6.5 μm) 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 based on gelatin Calcium nitrate 20 mg / m ² Preservative (ICI Co., Ltd., Proxel ) 12 mg / m ²

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

[0163]

[Chemical 29]

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

[0165] Undercoat 1 layer coating solution   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   0.12 g of colloidal silica having a particle size of 70 to 100 μm   (Nissan Chemical Co., Ltd., Snowtex ZL,)   Amount of water to reach 100g

Further, 10% by mass of KOH was added to adjust the pH.
The coating solution adjusted to 6 was dried at a drying temperature of 180 ° C. for 2 minutes and 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) Manufactured by Proxel) 3.5 × 10 ⁻³ g acetic acid 0.2 g water Total amount of 100 g

The coating solution was dried at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm.

[0169]

[Chemical 30]

<< Coating Method on Support >> On the support having the above-mentioned undercoat layer, the UL layer, the emulsion layer, the lower protective layer and the upper protective layer are formed in this order from the emulsion surface side closer to the support. 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 a 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 sequentially coated in this order by a curtain coater system while adding a hardener solution, and passed through a cool 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. At 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 a 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 with a cardboard that had been humidity-controlled for 2 hours at 25 ° C. and a relative humidity of 50% to prepare samples shown in Table 2.
When the humidity in the barrier bag was measured, it was 45%.
The film surface pH of the obtained sample on the emulsion layer side is 5.5 to 5.
The film surface pH on the back side was 6.0 to 6.5. 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 a developing solution (Fuji Photo Film Co., Ltd., QR-D1) and a fixing solution (Fuji Photo Film Co., Ltd., NF-1), an automatic processor (Fuji Photo Film Co., Ltd., FG-) was used. 680AG) at 35 ° C
Processing was carried out under developing conditions of 30 seconds.

<Evaluation> The sensitivity, gradation (gamma), practical density and processability 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.

(Gradation γ) 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 were obtained. A straight line connecting two points with 0.0 was drawn and the gradient was taken 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).

(Processing stability of silver halide photographic light-sensitive material) Each sample prepared as shown in Table 2 was used as a developing solution QR-
D1 with 15% blackening per day
(20 cm) was treated with 80 ml of the working solution per cm × 61 cm), and 20 sheets of all sizes were processed, and this was run for 6 days per week, and running was continued for 15 weeks. By processing a small amount of film in this manner, a small amount of processed developer was obtained. Further, each sample prepared as shown in Table 2 was subjected to 85% blackening per day with a developing solution QR-D1 and 8 times the working solution per size (50.8 cm × 61 cm).
300 sheets of all sizes were processed while replenishing with 0 ml, and this was continuously performed for 4 days. By processing a large amount of film in this way, a large quantity processed developer was obtained. The practical density was evaluated with these developers, and the practical density (small amount), practical density (large amount) and halftone dot when exposed at the LV value at which the halftone dot was 50% in the processing liquid before running. % (Small net%, large net%) was calculated.

Table 2 shows the results of these evaluations.
From Table 2, it can be seen that the samples satisfying the conditions of the present invention have high sensitivity and practical concentration and are excellent in processability.

[0179]

[Table 1]

[0180]

[Table 2]

Example 2 A developing solution (G101C, manufactured by Agfagewald Co., Ltd.) and a fixing solution (G333, manufactured by Agfagewald Co., Ltd.) were used, and 100 ml of the used solution was replenished for each size. For the sample described,
The same experiment as in Example 1 was performed. The results of these evaluations are summarized in Table 3. From Table 3, it can be seen that the samples satisfying the conditions of the present invention have excellent processability.

[0182]

[Table 3]

Example 3 Instead of sodium thiosulfate used for the chemical sensitization of Emulsion A in Examples 1 and 2, a carboxymethyltrimethylthiourea compound which is a tetra-substituted thiourea compound or dicarboxymethyl Dimethylthiourea compound is equivalent to sodium thiosulfate
When a sample was prepared in the same manner except that 1 was added, the sample having the constitution of the present invention showed good performance as in Examples 1 and 2.

<Example 4> The same experiment as in Example 1 was carried out using a developing solution (Kodak Polychrome Graphics Co., Ltd., R
A2000) and a fixing solution (RA3000, manufactured by Kodak Polychrome Graphics Co., Ltd.) were used, and the amount of the solution used was 144 per large size (50.8 cm × 61 cm).
When replenished with ml, the sample having the constitution of the present invention showed good performance as in Example 1.

<Example 5> The same experiment as in Example 1 was conducted using the following solid developer (Konica Corp., type 681) and fixing solution (Konica Corp., type 881). Similarly to Example 1, the sample having the constitution of the present invention showed good performance.

Example 6 The same experiment as in Example 1 was carried out by the following solid developer (Fuji Photo Film Co., Ltd., QR-D1).
PD) and fixer (Fuji Photo Film Co., Ltd., UR-
When F1 PD) was used, the sample having the constitution of the present invention showed good performance as in Example 1.

<Example 7> The same experiment as in Example 1 was conducted using the following solid developer (Konica Corp., 681Z) and a fixing solution (Konica Corp., 881Z).
Similar to Example 1, the sample having the constitution of the present invention showed good performance.

<Example 8> The same experiment as in Example 1 was conducted using the following solid developer (Konica Corp., 731G) and fixing solution (Konica Corp., 921G).
Similar to Example 1, the sample having the constitution of the present invention showed good performance.

<Embodiment 9> When the developing temperature was set to 38 ° C., the fixing temperature was 37 ° C., and the developing time was 20 seconds in each of Examples 1 to 8, the same results as in Examples 1 to 6 were obtained. The effect of the invention was not lost.

<Embodiment 10> In Embodiments 1 to 9, 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 15.
Even when the same treatment was carried out by setting it to 00 mm / min, the sample having the constitution of the present invention similarly showed good performance.

<Example 11> Instead of using Lux Setter RC-5600V manufactured by Fuji Photo Film Co., Ltd., PI-2800 manufactured by Fuji Photo Film Co., Ltd., and Imagesetter FT manufactured by Dainippon Screen Co., Ltd. -R50
55, select set 50 manufactured by Agfagewald Co., Ltd.
00, Avantra 25, or Accuset 100
0, Dreb 450 or Dreve 800 manufactured by Cytex Co., Ltd., Rhino 630 manufactured by Heidel Co., Ltd., Quasar, Hercules Elite, or Signa Setter, Lux Setter Laxel F-9000, F manufactured by Fuji Photo Film Co., Ltd. When the same evaluation was performed using either one of -6000 or Panther Pro 62 manufactured by Prepress Co., Ltd., the sample having the constitution of the present invention showed good performance.

[0192]

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

Continued front page    (72) Inventor Katsuyuki Watanabe             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. (72) Inventor Mitsunori Hirano             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H023 BA04 CA02 CD15

Claims (17)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photograph containing a metal complex having a cyanide ligand in the silver halide contained in the silver halide emulsion layer and a hydrazine compound having an onium group in the molecule. Photosensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrazine compound having an onium group in the molecule is represented by the following formula (1) or (2). [Chemical 1] [In the formulas (1) and (2), R ¹ represents an arylene group or a divalent heterocyclic group, Q represents an onium group, J represents a divalent linking group, and G ¹ represents —CO—. Group, -S
O ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or ^{-P (O) (G 2 R} 4) -
Represents a group, G ² represents a single bond, an —O— group, a —NR ⁴ — group, R ⁴ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and R ² represents a hydrogen atom, an alkyl group. , An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a carbamoyl group, R ³ represents an aryl group or a heterocyclic group, and A ¹ and A ² are both hydrogen atoms or Is a hydrogen atom and the other is an acyl group,
Represents either a sulfonyl group or an oxalyl group. ] 3. The hydrazine compound having an onium group in the molecule is represented by the formula (1).
The silver halide photographic light-sensitive material described in. 4. The formula (1), wherein the atom of J directly bonded to R ¹ is not a nitrogen atom.
Or the silver halide photographic light-sensitive material described in 3. 5. In the formula (1), the group represented by —G ¹ is —CO—, and the group represented by R ² is an alkyl group containing no onium group or a carbamoyl group containing no onium group. 5. The silver halide photographic light-sensitive material according to claim 2, wherein 6. In the formula (1), the group represented by —G ¹ —R ² is —COCF ₂ H or —COCF ₂ CF ₂ COOM.
(M represents a hydrogen atom or a counter cation), The silver halide photographic light-sensitive material according to any one of claims 2 to 5, wherein 7. The silver halide photographic light-sensitive material according to claim 2, wherein the linking group represented by R ¹ in the formula (1) is an unsubstituted phenylene group. material. 8. The halogen according to claim 2, wherein the compound of formula (1) is represented by the following formula (1-a) or the following formula (1-b). Silver halide photographic light-sensitive material. [Chemical 2] [In the formula (1-a) and ^{(1-b), -G 1} -
R ² is —COCF ₂ H or —COCF ₂ CF ₂ COOM.
(M represents a hydrogen atom or a counter cation), J is an alkylene group, and Q is a pyridinium group or a quinolinium group. ] 9. A silver halide having a structure comprising an inside and a surface layer, the inside being 99 m of silver of a silver halide crystal.
ol% or less and contains 1 cyanide ligand
9. The silver halide photographic light-sensitive material according to claim 1, which contains a metal complex containing one or more of them. 10. The silver halide emulsion contains 1 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol of a metal complex containing at least one cyanide ligand per 1 mol of silver in silver halide. 10. The silver halide photographic light-sensitive material according to claim 1. 11. A silver halide having a structure comprising an inside and a surface layer, the inside being 95% of silver of a silver halide crystal.
11. The silver halide photographic light-sensitive material according to claim 1, which contains a metal complex containing not more than mol% and containing at least one cyanide ligand. 12. At least one layer of halogen on a support.
Odor in silver halide photographic light-sensitive material having silver halide emulsion layer
The silver halide contained in the silver halide emulsion layer is
A group II metal compound is contained, and in the formula (1) below, -G
¹-R²Is -COCF ₂H or -COCF₂CF₂COO
A molecule that is M (M represents a hydrogen atom or a counter cation)
Containing a hydrazine compound having an onium group
And a silver halide photographic light-sensitive material. [Chemical 3] [In Formula (1), R¹Is an arylene group or divalent
Represents a heterocyclic group, Q represents an onium group, and J represents a divalent group.
Represents a linking group, G¹Is a -CO- group, -SO₂-Group, -SO
-Group, -COCO- group, thiocarbonyl group, iminomethyi
Ren group or -P (O) (G²R^Four) -Represents a group, G²Is
Single bond, -O- group, -NR^FourRepresents a group, R ^FourIs hydrogen
Represents a child, an aliphatic group, an aryl group or a heterocyclic group, and R
²Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
Alkoxy, aryloxy, amino or cal
Represents a vamoyl group, A¹And A²Are both hydrogen atoms
Or one is a hydrogen atom and the other is an acyl group, sulfo
Represents either a nyl group or an oxalyl group. ] 13. The silver halide photographic light-sensitive material according to claim 12, wherein the atom of J directly bonded to R ¹ in the formula (1) is not a nitrogen atom. 14. The silver halide photographic light-sensitive material according to claim 12, wherein the linking group represented by R ¹ in the formula (1) is an unsubstituted phenylene group. 15. A compound of formula (1) is represented by the following formula (1-a):
Alternatively, the silver halide photographic light-sensitive material according to any one of claims 12 to 14, which is represented by the formula (1-b). [Chemical 4] [In the formula (1-a) and ^{(1-b), -G 1} -
R ² is —COCF ₂ H or —COCF ₂ CF ₂ COOM.
(M represents a hydrogen atom or a counter cation), J is an alkylene group, and Q is a pyridinium group or a quinolinium group. ] 16. The group VIII metal compound is a rhodium compound,
The silver halide photographic light-sensitive material according to any one of claims 12 to 15, which is an iridium compound, a rhenium compound, a ruthenium compound or an osmium compound. 17. The ratio of silver bromide to silver halide contained in the silver halide emulsion in the silver halide emulsion layer is 45 to 75 mol%.
17. A silver halide photographic light-sensitive material according to any one of 16.