JPH09211802A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic image ultrahigh in contrast and excellent in dot image quality and little in black spots and to prevent contamination of silver. SOLUTION: A silver halide photographic sensitive material having at least one emulsion layer containing silver halide which contains >=50mol% silver chloride and is sensitized with selenium or tellurium on a base body is exposed for an image and developed in the presence of a compd. expressed by a formula. In the formula, Z<1> is a represents nonmetal atoms necessary to form an aromatic heteroring containing nitrogen and Z<1> has R<1> and (SX<2> )n as substituents.

Description

Detailed Description of the Invention

[0001]

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

[0002]

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

[0003] In order to improve the reproduction of continuous tone images or the reproduction of line images using halftone images, an image forming system exhibiting ultra-high contrast (especially γ of 10 or more) photographic properties is required. As a method for obtaining high-contrast photographic characteristics, a lith developing system using a so-called "contagious developing effect" has been used for a long time, but has a drawback that a developing solution is unstable and difficult to use. There is a demand for an image forming system which can be developed with a processing solution having good storage stability and obtain ultra-high contrast photographic characteristics.
Nos. 166,742, 4,168,977, 4,221,857, 4,224,401, 4,243,739, 4,269,922,
Nos. 4,272,606 and 4,311,781
No. 4,332,878, No. 4,618,57
No. 4, No. 4,634, 661, No. 4,681, 8
No. 36 and No. 5,650,746 are disclosed. These are surface latent image type silver halide photographic light-sensitive materials to which a hydrazine derivative is added.
Is a system that obtains a super-high contrast negative image in which γ exceeds 10 by processing with a stable MQ or PQ developer. According to this method, super-high contrast and high-sensitivity photographic characteristics can be obtained, and Since the concentration of sulfite can be added, the stability of the developing solution against air oxidation is dramatically improved as compared with the conventional lith developer.

However, in the above-mentioned method, although the stability of the developing solution can be enhanced by a high-concentration sulfurous acid preservative, a relatively high p-value is required to obtain a super-high contrast photographic image.
It was necessary to use a developing solution having an H value, and therefore, the developing solution was easily oxidized by air, and a large amount of the developing solution had to be replenished. Therefore, attempts have been made to realize a super-high contrast photographic image forming system using nucleation development of a hydrazine compound with a developer having a lower pH. Further, in the above method, there is a problem that sandy fog called black spots occurs in the unexposed portion.

US Patent No. 4,269,929
1-267759), US Pat. No. 4,737,452 (JP-A-60-179734), and US Pat.
4,769,4,798,780, JP-A-1-1-1
No. 79939, No. 1-179940, U.S. Pat.
98,604, 4,994,365, Japanese Patent Application No. 7-
No. 37817 discloses a method of using a highly active hydrazine nucleating agent and a nucleation accelerator in order to obtain a super-high contrast image by using a stable developing solution having a pH of less than 11.0. It is also disclosed that a silver halide emulsion having a high silver chloride content and subjected to chemical sensitization has high nucleation activity. However, even in this method, the replenishment amount of the developing solution is required to be about 320 to 450 ml when processing 1 square meter of the silver halide photographic light-sensitive material, and a further replenishment amount reduction method and a stable processing method have been desired.

Further, when the replenishment amount is reduced, there arises a problem that silver sludge in a developing tank called silver stain increases and adheres to the photosensitive material. This problem is aggravated by using a silver halide emulsion having a high silver chloride content, which is advantageous in terms of nucleation activity. The method to suppress silver stain is
JP-A-56-24347, JP-B-56-46585
No. 62-2849, JP-A-4-295847,
A lot of them are disclosed in JP-A-4-305649, JP-A-56-72441, JP-A-56-24347, JP-A-3-53244, JP-A-3-282457, and JP-A-4-31852.

However, since these methods strongly suppress nucleation development and deteriorate the halftone dot quality, further improvement of the silver stain prevention technique has been desired.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to obtain a photographic image having super-high contrast, excellent halftone dot quality, and little black spots, and to provide a photographic image forming method in which silver stain is less likely to occur. It is to be.

[0009]

The object of the present invention is to provide at least one emulsion containing selenium-sensitized or tellurium-sensitized silver halide having a silver chloride content of 50 mol% or more on a support. A silver halide photographic light-sensitive material having a layer is subjected to image-wise exposure and then subjected to development processing in the presence of a compound represented by the general formula (1). General formula (1)

[0010]

Embedded image

In the formula, Z ¹ represents a nonmetallic atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle in cooperation with N and C, and Z ¹ represents R ¹ and ( S
X ² ) _n . Here, R ¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. X ¹ and X ² are hydrogen atoms or cations, and n is 0, 1 or 2. Further, two kinds of radicals obtained by removing one arbitrary hydrogen atom from Z ¹ may combine to form a bis type structure.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the general formula (1) will be described in detail.

[0013]

Embedded image

Z ¹ is 5 or 6 in collaboration with N and C
Represents a non-metal atomic group necessary for forming a nitrogen-containing aromatic heterocycle. The 5-membered nitrogen-containing aromatic heterocycle formed of Z ¹ , N and C is a combination of elements selected from carbon, oxygen and sulfur in addition to nitrogen, and is further a hydrocarbon ring or heterocycle. May be condensed with, for example, pyrazole, imidazole, oxazole,
Thiazole, triazole, thiadiazole, oxadiazole, indazole, benzimidazole, benzoxazole, benzothiazole, pyrazolotriazole, pyrrolotriazole and the like can be mentioned. The 5-membered nitrogen-containing aromatic heterocycle is preferably triazole, thiadiazole, oxadiazole, benzimidazole, benzoxazole, benzothiazole, pyrazolotriazole, or pyrrolotriazole, and more preferably triazole, thiadiazole, oxadiazole, or benzozole. Imidazole, most preferably triazole. The 6-membered nitrogen-containing aromatic hetero ring formed by Z ¹ , N and C is a monocyclic ring or a ring condensed with a carbocyclic or heterocyclic ring, for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline Phthalazine, quinoxaline, quinazoline, sinoline, phenanthridine, phenanthroline, naphthyridine, pteridine, purine, triazolopyrimidine, imidazolopyridine, triazolopyridine, imidazolotriazine, and triazolotriazine. As the 6-membered nitrogen-containing aromatic heterocycle, preferably, pyrazine, pyrimidine, pyridazine, triazine, phthalazine, quinoxaline, quinazoline, naphthyridine, pteridine, purine,
Triazolopyrimidine, imidazolopyridine, triazolopyridine, imidazolotriazine, triazolotriazine, more preferably pyrimidine, pyridazine, triazine, pteridine, purine, triazolopyrimidine, imidazolotriazine, triazolotriazine, most preferably Preferred are pyrimidine, triazine and purine.

R ¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. As the group bonded by the carbon atom of R ¹ , an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carboxyl group,
A cyano group and a heterocyclic group, which are bonded by an oxygen atom, are a hydroxy group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, and sulfonyloxy group are bonded to each other by a nitrogen atom, such as acylamino group, amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, and sulfamoyl group. The amino group, the alkoxycarbonylamino group, the aryloxycarbonylamino group, the sulfonamide group, the imide group, and the heterocyclic group, which are bound by a sulfur atom, include an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, and an alkoxysulfonyl group. Group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group, and a sulfinyl group. These may be further substituted with the groups mentioned as R ¹ . R ¹ may be plural, and if possible, two R ¹ may combine to form a ring.

The R ¹ will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, t-butyl, benzyl and cyclopentyl. The alkenyl group has 2 to 10 carbon atoms, for example vinyl, 1-
Examples include propenyl, 1-hexenyl and styryl.
The alkynyl group has 2 to 10 carbon atoms and includes, for example, ethynyl, 1-butynyl and phenylethynyl. The aryl group is an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 8 carbon atoms, for example, carbamoyl, N-ethylcarbamoyl,
It is N-phenylcarbamoyl. The alkoxycarbonyl group has 2 to 8 carbon atoms, such as methoxycarbonyl and benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 12 carbon atoms,
For example, phenoxycarbonyl. The acyl group has 1 to 8 carbon atoms, such as acetyl and benzoyl. The heterocyclic group linked by a carbon atom on the ring is a 5- or 6-membered saturated or unsaturated heterocycle having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, The number of hetero atoms constituting the ring and the number of elements may be one or plural, and examples thereof include 2-furyl, 2-thienyl, 2-pyridyl, and 2-imidazolyl.

The alkoxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and includes, for example, methoxy, 2-
Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 12 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m-.
(3-hydroxypropionamide) phenoxy. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or more, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy,
2-pyridyloxy. The acyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy, and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has a carbon number of 1 to 8, and examples thereof include methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 10 carbon atoms,
It preferably has 1 to 6 carbon atoms, such as acetylamino and benzoylamino. The alkylamino group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylamino, N- (2-hydroxyethyl) amino and N- (3-dimethylaminopropyl).
It is Amino. Arylamino group has 6 to 1 carbon atoms
Those of 0 are, for example, anilino and N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-oxazolylamino, 2-tetrahydropyranylamino, and 4-pyridylamino. The ureido group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
10 to 10, preferably 0 to 5 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and is, for example, methoxycarbonylamino. The aryloxycarbonylamino group has 7 to 12 carbon atoms, such as phenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The sulfonamide group has 1 to 10 carbon atoms, preferably 1 carbon atom.
To 6, for example, methanesulfonamide and p-toluenesulfonamide. The imide group has 4 carbon atoms
And N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocyclic ring composed of a nitrogen atom and at least one of a carbon atom, an oxygen atom or a sulfur atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 10 carbon atoms,
Preferably, it has 1 to 5 carbon atoms, such as methylthio,
It is 2-carboxyethylthio. The arylthio group has 6 to 12 carbon atoms, for example, phenylthio, 2
-Carboxyphenylthio. The heterocyclic thio group is a 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and which constitutes a ring. The number of atoms and the number of elements may be one or plural, and examples thereof include 2-benzothiazolylthio and 2-pyridylthio.

The sulfamoyl group has 0 to 1 carbon atoms
It has 0, preferably 0 to 6 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. The alkoxysulfonyl group has 1 to 1 carbon atoms
It preferably has 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methoxysulfonyl. The aryloxysulfonyl group has 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

R ¹ is preferably hydrogen atom, alkyl group, aryl group, carbamoyl group, acyl group, cyano group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, sulfone. Amido group, alkylthio group, arylthio group, sulfamoyl group, sulfonyl group, more preferably hydrogen atom, alkyl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, alkylthio group, most preferably A hydrogen atom, an alkyl group, an alkoxy group, an amino group, and an alkylthio group.

X ¹ and X ² are hydrogen atoms or cations. Examples of the cation include sodium, potassium, lithium, calcium, ammonium, tetrabutylammonium and triethylammonium. X
¹ and X ² are preferably a hydrogen atom, sodium,
Potassium and ammonium. n is preferably 1 or 2.

From the general formula (1), a radical having two arbitrary hydrogen atoms bonded to each other to form a bis type structure is preferably represented by the following general formula (2). General formula (2)

[0026]

Embedded image

In the formula, Z ²¹ and Z ²² each represent a group obtained by removing one hydrogen atom from Z ^{1 in the} formula (1), and X ²¹ and X ²² have the same meaning as X ¹ . L ² is a divalent linking group (alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group and -O-, -S-, -NH-, -CO.
-, --SO _2-, etc., which are linked by a group consisting of a single or a combination thereof. These preferred ones are also the same as in the formula (1).

Examples of the alkylene group for L ² include ethylene, trimethylene, pentamethylene, propylene and 2
-Butene-1,4-yl, 2-butene-1,4-yl,
p-xylylene. The alkenylene group is, for example, ethene-1,2-yl. The alkynylene group is ethyn-1,2-yl. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ² represents an alkylene group, a —NH (alkylene) NH— group, —O
(Alkylene) O-group, -S (alkylene) S-group,-
NH (alkylene) CONH (alkylene) NH- group,
-NH (alkylene) O (alkylene) NH- is preferable, and -NH (alkylene) NH- group and -O (alkylene) O- group are more preferable.

Of the compounds of the present invention represented by the general formula (1), those represented by the following general formulas (3) to (9) are preferable. General formula (3)

[0030]

Embedded image

In the formula, R ³¹ and X ³¹ have the same meanings as R ¹ and X ^{1 in} formula (1), respectively. R ³¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an optionally substituted amino group, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an alkyl group, a hydroxy group, An optionally substituted amino group and a mercapto group are preferred, and a hydrogen atom, an alkyl group and a mercapto group are most preferred. R ³² is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group or an optionally substituted amino group. R ³² is preferably a hydrogen atom, an alkyl group, a hydroxy group,
It is an optionally substituted amino group, more preferably a hydrogen atom or an alkyl group. General formula (4)

[0032]

[Chemical 6]

In the formula, R ⁴¹ , R ⁴² and X ⁴¹ have the same meanings as R ³¹ , R ³² and X ^{31 in} formula (3), respectively, and the preferred ranges are also the same. General formula (5)

[0034]

Embedded image

In the formula, R ⁵¹ and X ⁵¹ have the same meanings as R ³¹ and X ^{31 in} formula (3), respectively. R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an optionally substituted amino group, a mercapto group or an alkylthio group, more preferably an alkyl group or an optionally substituted group. An amino group, a mercapto group and an alkylthio group are preferred, and a mercapto group and an alkylthio group are most preferred. General formula (6)

[0036]

Embedded image

In the formula, R ⁶¹ , R ⁶² and X ⁶¹ have the same meanings as R ³¹ , R ³¹ and X ^{31 in} formula (3), respectively. R ⁶¹
Preferably a hydrogen atom, an alkyl group, an aryl group,
A heterocyclic group, a hydroxy group, an alkoxy group, an optionally substituted amino group, a mercapto group, an alkylthio group, more preferably a hydroxy group, an alkoxy group,
An amino group which may be substituted, a mercapto group and an alkylthio group are preferred, and a hydroxy group, an amino group which may be substituted and a mercapto group are most preferred. R ⁶² is preferably a mercapto group. General formula (7)

[0038]

Embedded image

In the formula, R ⁷¹ , R ⁷² and R ⁷³ have the same meanings as R ⁶¹ , R ⁶² and R ^{62 in} formula (6), respectively, and the preferred ranges are also the same. However, at least one of them is a mercapto group. More preferably, R ⁷³ is a mercapto group. General formula (8)

[0040]

Embedded image

In the formula, R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ have the same meanings as R ⁶¹ , R ⁶² , R ⁶¹ and R ^{62 in} formula (6), respectively, and the preferred ranges are also the same. However, at least one of them is a mercapto group. R ⁸³ is most preferably an optionally substituted amino group or a hydrogen atom. More preferably, R ⁸⁴ is a mercapto group. General formula (9)

[0042]

Embedded image

In the formula, R ⁹¹ , R ⁹² and R ⁹³ have the same meanings as R ⁶¹ , R ⁶¹ and R ^{61 in the} general formula (6), respectively, and their preferable ranges are also the same. However, at least one of them is a mercapto group. More preferably, R ⁹² or R ⁹³ is a mercapto group.

Of the general formulas (3) to (9), the general formulas (3), (5) to (9) are more preferable, and the general formulas (3), (6) and (8) are most preferable. Next, specific examples of the compound represented by the general formula (1) in the present invention will be shown, but the compound is not limited thereto.

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

[Chemical 21]

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

The compounds represented by the general formula (1) of the present invention are described in the following patents and patents / literatures cited therein. That is, JP-A-4-301837,
5-61159, 6-230525 and JP-A-58-58.
169147, 62-56959, U.S. Pat.
892, JP-A-3-53244, and JP-A-3-282457,
5-61159, 5-303179, 4-362
942, JP-B-46-11630, JP-A-6-1753
02, 6-258787 and the like.

When the compound represented by the general formula (1) of the present invention is added to a developing solution, the compound is added in an amount of 0.1 to 1 liter of the developing solution.
A range of 01 to 10 mmol is preferred, 0.1 to 5
The millimolar range is particularly preferred. When it is added to a silver halide photosensitive material, it is preferably added to a non-photosensitive layer such as a back layer or the uppermost protective layer. The amount of the compound of the present invention added is 1 × 10 ⁻⁶ to 5 × 10 ⁶ per 1 m ² of the light-sensitive material.
The range of ^-3 mol is preferable, and the range of ^{1x10 -5} to ^{1x10 -3} mol is particularly preferable.

The method of adding the compound represented by the general formula (1) of the present invention to a silver halide light-sensitive material is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol). ), Ketones (acetone, methylethylketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can also be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, the powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The hydrazine derivative used in the present invention is
A compound represented by the following general formula (H) is preferable. General formula (H)

[0064]

Embedded image

In the formula, R ₁ represents an aliphatic group, an aromatic 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 Represents a hydrazino group, G ₁ is -C
O- group, -SO ₂ - group, -SO- group,

[0066]

Embedded image

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (H), the aliphatic group represented by R ₁ is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms. . In the general formula (H), R
_The aromatic group represented by ₁ is a monocyclic or bicyclic aryl group, for example, a benzene ring or a naphthalene ring. The heterocyclic group represented by R ₁ is a monocyclic or bicyclic aromatic or non-aromatic heterocycle, which may be condensed with an aryl group to form a heteroaryl group. Examples thereof include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring and a benzothiazole ring. R ₁
Are preferably aryl groups. R ₁ may be substituted. Representative examples of the substituent include an alkyl group (including an active methine group), an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring and a quaternized nitrogen atom. A group containing a heterocyclic ring (eg, a pyridinio group),
A hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit),
Aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group,
A group containing an amino group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group, a sulfamoylamino group, a semicarbazide group, a thiosemicarbazide group, a hydrazino group, a group containing a quaternary ammonium group, (alkyl,
Aryl, or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl)
Sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, nitro group, phosphoric acid amide group, phosphate ester structure And a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like. Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms), aralkyl groups (preferably having 1 to 20 carbon atoms), and alkoxy groups (preferably having 1 to 20 carbon atoms). 20), substituted amino group (preferably having 1 to 20 carbon atoms), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms) ), A ureido group (preferably having 1 to 30 carbon atoms), a carbamoyl group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) and the like. .

In formula (H), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, a benzene ring. Is included. As the heterocyclic group, at least one nitrogen, oxygen,
And a 5- to 6-membered ring compound containing a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group, a quinolinio group,
There is a quinolinyl group. Pyridyl or pyridinio groups are particularly preferred. Alkoxy group has 1 to 8 carbon atoms
And the aryloxy group is preferably a monocyclic one, and the amino group is preferably an unsubstituted amino group, or an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a heterocyclic amino group. . R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ . Preferred among the groups represented by R ₂ are hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, difluoromethyl group, 2-carboxytetrafluoroethyl group) when G ₁ is —CO— group. Group, pyridiniomethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methane) Sulfonamidophenyl group, o-carbamoylphenyl group, 4-cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom or an alkyl group. When G ₁ is a —SO ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group). Alternatively, a substituted amino group (eg, a dimethylamino group, etc.) and the like are preferable. When G ₁ is a —COCO— group, it is preferably an alkoxy group, an aryloxy group or an amino group, particularly a substituted amino group (eg 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group). , Anilino group, o-hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc.) are preferred. Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms For example, Japanese Patent Laid-Open No. 63-297
No. 51 and the like.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear or branched, or cyclic, unsubstituted and substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group,
A sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group)). A ₁ ,
Most preferably, A ₂ is a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (H) may be further substituted, and preferable examples include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ...
, Etc. may be substituted multiple times, and preferred examples also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (H) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (H) may have an adsorptive group adsorbing to silver halide incorporated therein. Examples of the adsorptive group include an alkylthio group, an arylthio group, a thiourea group, a thioamide group,
U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045 and JP-A-59-201045, such as mercapto heterocyclic groups and triazole groups. 201046, 5
Nos. 9-201047, 59-201048, 59
-201049, JP-A-61-170733, and 6
1-270744, 62-948, 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246. These adsorbing groups to silver halide may be precursors. As such a precursor, JP-A-2-285
No. 344.

R ₁ or R ₂ in the general formula (H) may contain a plurality of hydrazino groups as a substituent, and in this case, the compound represented by the general formula (H) is a multimer with respect to the hydrazino group. And specifically, for example, JP-A-64-86
134, JP-A-4-16938, JP-A-5-197.
No. 091.

Next, a particularly preferred hydrazine derivative in the present invention will be described. R ₁ is particularly preferably a substituted phenyl group, a ballast group through a sulfonamide group, an acylamino group, a ureido group, or a carbamoyl group, an adsorption group to silver halide, a group containing a quaternary ammonio group,
A group containing a repeating unit of an ethyleneoxy group, alkyl,
It may be substituted with an aryl or heterocyclic thio group, a group capable of dissociating in an alkaline developing solution (carboxyl group, sulfo group, acylsulfamoyl group, etc.), or a hydrazino group capable of forming a multimer. preferable. R ₁ is most preferably a phenyl group substituted with a benzenesulfonamide group, and the substituent of the benzenesulfonamide group preferably has any of the groups described above. G ₁ is preferably a -CO- group or a -COCO- group, and particularly preferably a -CO- group. In R ₂ , G ₁ is -CO
A -group is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or an o-hydroxymethyl group), and when G ₁ is a -COCO- group, a substituted amino group is Particularly preferred.

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

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

[Table 6]

[0083]

[Table 7]

[0084]

[Table 8]

As the hydrazine derivative used in the present invention, in addition to the above, the following hydrazine derivatives are preferably used. The hydrazine derivative used in the present invention can also be obtained by various methods described in the following patents.
Can be synthesized. A compound represented by (Chemical Formula 1) described in JP-B-6-77138.
Compounds described on pages 4 and 4. Compounds represented by the general formula (1) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP-A-6
Compounds represented by formulas (4), (5) and (6) described in JP-A-230497, specifically, compounds 4-1 to 4 described on pages 25 and 26 of the same publication. -1
0, compounds 5-1 to 5-42 on pages 28 to 36,
And compounds 6-1 to 6 described on pages 39 and 40.
-7. General formula (1) described in JP-A-6-289520
And compounds represented by formula (2), specifically, compounds 1-1) to 1-17) and 2-1) described on pages 5 to 7 of the same publication. Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3139
A compound represented by Chemical Formula 1 described in No. 51, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-561
A compound represented by formula (1) described in No. 0, specifically, compounds 1-1 to 1-3 described on pages 5 to 10 of the publication.
8. Compounds represented by the general formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the publication. JP-A-7-10442
Compounds represented by General Formula (H) and General Formula (Ha) described in No. 6, specifically Compounds H-1 to H-44 described on pages 8 to 15 of the same publication.

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

The hydrazine nucleating agent of the present invention may be added to any of the silver halide emulsion layer or other hydrophilic colloid layer on the silver halide emulsion layer side of the support. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 × with ^respect to 1 mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferred, and 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol is most preferred.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives. Examples are listed below. Compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described in pages 49 to 58. JP-A-7-84
No. 331, (Chem. 21), (Chem. 22) and (Chem. 2)
The compounds represented by 3), specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 described on pages 16 to 20 of the same publication.
To Nb-12 and compounds of Nb-1 to Nb-12. General formula (1) described in Japanese Patent Application No. 7-37817,
Compounds represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7). 1-1 to 1-19 described
2-1 to 2-22, 3-1 to 3-3
6, compound 4-1 to 4-5, 5-1 to 5-4
1 compound, 6-1 to 6-58 compound and 7-1 to
Compounds 7-38.

The nucleation accelerator most preferably used in the present invention are onium salt compounds represented by the general formulas (2), (3), (4) and (5). This will be described in detail below.

First, the general formula (2) will be described in detail.

[0091]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have. Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s
an aralkyl group such as a linear or branched alkyl group such as an ec-butyl group, a tert-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group or an octadecyl group, a substituted or unsubstituted benzyl group; Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, aryl groups such as phenyl group, naphthyl group, phenanthryl group; alkenyl groups such as allyl group, vinyl group, 5-hexenyl group; cyclopentenyl group,
Cycloalkenyl groups such as cyclohexenyl group; heterocyclic residues such as pyridyl group, quinolyl group, furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group, morpholyl group, pyrimidyl group, pyrrolidyl group Is mentioned. Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 ,
A secondary or tertiary amino group, an alkyl or aryl ether group,
Alkyl or aryl thioether group, carbonamido group, carbamoyl group, sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group,
Examples thereof include a carboxyl group, a sulfonic acid group, a cyano group or a carbonyl group. Examples of the group represented by L include R
₁ , R ₂ , R ₃ in addition to the same group, trimethylene group, tetramethylene group, hexamethylene group, pentamethylene group, octamethylene group, polymethylene group such as dodecamethylene group, phenylene group, biphenylene group, naphthylene group, etc. Divalent aromatic group, trimethylenemethyl group, polyvalent aliphatic group such as tetramethylenemethyl group, phenylene-
1,3,5-toluyl group, phenylene-1,2,4,5
-A polyvalent aromatic group such as a tetrayl group may be mentioned.
Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion,
Carboxylate ion such as benzoate ion, p
-Toluene sulfonate, methane sulfonate, butane sulfonate, benzene sulfonate and other sulfonate ions, sulfate ions, perchlorate ions, carbonate ions,
An example is nitrate ion. In the general formula (2),
R ₁ , R ₂ and R ₃ are preferably groups having 20 or less carbon atoms, and aryl groups having 15 or less carbon atoms are particularly preferred. m is preferably 1 or 2, and when m represents 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or an aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and a -CO- group. ,
—O— group, —NR ₄ — group (wherein R ₄ represents a hydrogen atom or a group having the same meaning as R ₁ , R ₂ and R ₃ and when a plurality of R _4's are present in the molecule, they are the same. Or different, and may be bonded to each other), -S
- is a divalent group formed by combining groups - group, -SO- group, -SO _2. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more,
There are a plurality of R ₁ , R ₂ and R _{3 in the} molecule,
The plurality of R ₁ , R ₂ and R ₃ may be the same or different. n is preferably 1 or 2 and m is preferably 1 or 2. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt. Many of the compounds represented by the general formula (2) of the present invention are known and are commercially available as reagents. As a general synthesis method, there is a method in which a phosphinic acid is reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester, or a method in which a counter anion of a phosphonium salt is exchanged by a conventional method. Specific examples of the compound represented by the general formula (2) are shown below. However, the present invention is not limited to the following compounds.

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

General formulas (3) and (4) will be described in more detail.

[0098]

Embedded image

In the formula, A represents an organic group for completing the heterocycle, and may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A can be a 5- or 6-membered ring, and a more preferred example is a pyridine ring. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂ -, -
SO -, - O -, - S -, - N (R 5) - those constituted alone or in combination are preferred. However, R ₅ represents an alkyl group, an aryl group, or a hydrogen atom. As particularly preferred examples, B and C are alkylene, arylene, -O
-, -S- may be used alone or in combination. R ₁ and R ₂ are preferably an alkyl group having 1 to 20 carbon atoms, and may be the same or different. A substituent may be substituted on the alkyl group, and as the substituent,
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl) Group), a substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group and an arylthio group. As a particularly preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. X represents an anion group, but in the case of an inner salt, X
Is not required. Examples of X include chlorine ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (1
962). )

Specific compounds of the general formulas (3) and (4) are shown below, but the invention is not limited thereto.

[0101]

Embedded image

[0102]

Embedded image

General formula (5) will be described in more detail.

[0104]

Embedded image

The nitrogen-containing heteroaromatic ring represented by Z may contain a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom in addition to the nitrogen atom, and the benzene ring may be condensed. The heteroaromatic ring formed is preferably a 5- or 6-membered ring, more preferably a pyridine ring, a quinoline ring, or an isoquinoline ring. R ₅ is preferably an alkyl group having 1 to 20 carbon atoms, and may be a straight chain, branched chain, or cyclic alkyl group. More preferred is an alkyl group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms
Is most preferred. X ⁻ represents an anion group, but in the case of an intramolecular salt, X ⁻ is not necessary. Examples of X ⁻ include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The groups represented by Z and R ₅ may be substituted and preferred substituents include a halogen atom (eg chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg phenyl group, Tolyl group, p-chlorophenyl group, etc.), substituted or unsubstituted acyl group (for example, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group,
Represents an alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group, nitro group, alkylthio group, arylthio group . Particularly preferred examples of the substituent include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. Other examples of the substituent of A include a substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.) and a substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.). preferable. Next, specific compounds of the present invention are described, but are not limited thereto. Further, the compound of the present invention can be easily synthesized by a generally well-known method, and the following documents are helpful. (See Quart. Rev., 16, 163 (196
2). ) Specific compounds of the general formula (5) are shown below, but the present invention is not limited thereto.

[0107]

Embedded image

[0108]

Embedded image

Amino compounds are also preferably used as the nucleation accelerator, and the following compounds are particularly preferably used.

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

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

The nucleation accelerator of the present invention may be added to any of the silver halide emulsion layer on the silver halide emulsion layer side of the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleation accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × 10 per mol of silver halide.
^-2 mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

The silver halide emulsion used in the present invention has a silver chloride content of 50 mol% or more, preferably 80 mol% or more. The halogen composition is preferably silver chloride, silver chlorobromide or silver chloroiodobromide. The content of silver iodide is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, the light-sensitive material suitable for high-illuminance exposure such as scanner exposure and the light-sensitive material for line drawing are
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaaminerhodium ( III) Complex salt, Trizalatrodium (II
I) Complex salts and the like. 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 (for example, KCl, 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. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograph by P. Glafkides.
ique (Published by Paul Montel, 1967) by GFDufin
Photographic Emulsion Chemistry (The Focal Press
, 1966), by VL Zelikman et al Making and
Coating Photographic Emulsion (The Focal Press
Ed., 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase where silver halide is produced, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 5,163,364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, or a method disclosed in British Patent No. 4,242,44.
No. 5, JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Average grain size of grains in monodisperse silver halide emulsion is 0.5 μm
It is below, and particularly preferably 0.1 μm to 0.4 μm.

The silver halide emulsion of the present invention is selenium-sensitized or tellurium-sensitized. The chemical sensitization method may be used alone or in combination with a sulfur sensitization method, a noble metal sensitization method, a reduction sensitization method or the like. When used in combination, for example, sulfur sensitization method, selenium sensitization method and gold sensitization method, sulfur sensitization method, tellurium sensitization method and gold sensitization method are preferable.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
No., Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-2930
It is preferable to use the compounds described in No. 0 or the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Skilled artisans say that an unstable selenium compound as a sensitizer for photographic emulsions is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and has no role other than to make it present in the emulsion in an unstable form. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-344.
No. 92 and Japanese Patent Publication No. 52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (A) and (B) are preferable.

[0118]

Embedded image

In the formula, Z ₁ and Z ₂ may be the same or different, and an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, pentane group) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
A naphthyl group), a heterocyclic group (e.g., a pyridyl group, a cyenyl group, a furyl group, an imidazolyl group), -NR
₁ (R _2), - represents the OR ₃ or -SR _4. R ₁ , R
₂ , R ₃ and R ₄ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl group, an aralkyl group, the same examples as Z ₁ is exemplified as an aryl group or a heterocyclic group.
Here, R ₁ and R ₂ represent a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group,
-Nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group). In general formula (A), preferably Z ₁ represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂ is —NR ₅ (R ₆ ).
Represents R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In the general formula (A), more preferably N, N-dialkylselenourea, N, N, N ′.
-Trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

[0120]

Embedded image

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, —OR ₇ , —NR ₈ (R ₉ ), —SR ₁₀ , -Se
R ₁₁ , X represents a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom , X represents a halogen atom. In the general formula (B), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ ,
The aliphatic group represented by R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-
Propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, Propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (B), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. (For example, a pyridyl group, a cyenyl group, a furyl group, a thiazolyl group, an imidazolyl group, a benzimidazolyl group). In the general formula (B), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In formula (B), preferably Z ₃ , Z ₄ or Z ₅
Represents an aliphatic group, an aromatic group or —OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (B), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (A) and (B) are shown below, but the invention is not limited thereto.

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297449, No. 3320069, No. 3408196, No. 34
08197, 3434453, 34206
No. 70, No. 3591385, French Patent No. 269
No. 3038, No. 2093209, Japanese Patent Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
No. 57-22090, JP-A-59-180536,
59-185330, 59-181337, 59-187338, 59-192241 and 6
0-150046, 60-151637, 61
Japanese Patent Application No. Hei.
287380, 1-250950, 1-254
No. 441, No. 2-34090, No. 2-110558
Nos. 2-130976, 2-139183, 2-229300, and further, British Patent No. 255846,
No. 861984 and HE Spencer et al., Journal
of Photographic Science, Volume 31, 158-16
9 (1983).

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or they are disclosed in Japanese Patent Application Nos. 2-264447 and 2-26.
No. 4448, added during chemical sensitization.
Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one, and two or more of the above-described selenium sensitizers can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used in combination.

The tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499 and 3,320.
Nos. 069 and 3,772,031, British Patent No. 23
Nos. 5,211, 1,121,496 and 1,29
5,462, 1,396,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemical Communication (J. Che.
m. Soc. Chem. Commun.) 635 (1980), ibi
d 1102 (1979), ibid 645 (197)
9), Journal of Chemical Society
Perkin Transaction (J. Chem. Soc. Perkin
Trans.) 1,191 (1980) and the like are preferably used. Specific tellurium sensitizers include colloidal tellurium, telluroureas (eg, allyl tellurourea, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ′, N′-dimethyltelurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isotellurocyanates (for example, allyl isotellurocyanate), telluroketones (for example, telluroacetone, telluroacetonephenone), telluroamides (for example, telluro) Acetamide, N, N-dimethyl tellurobenzamide),
Tellurohydrazide (eg, N, N ′, N′-trimethyltelulobenzhydrazide), telluroester (eg, t
-Butyl-t-hexyl telluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium Compounds (eg British Patents 1,29
Examples thereof include negatively charged telluride ion-containing gelatin described in No. 5,462, potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, and allyl tellurocyanate). Of these tellurium compounds, the following general formulas (C) and (D) are preferable.

[0133]

Embedded image

In the formula, R ₂₁ , R ₂₂ and R ₂₃ are aliphatic groups,
Aromatic group, heterocyclic group, OR ₂₄ , NR ₅ (R ₆ ), S
It represents R ₇ , OSiR ₈ (R ₉ ) (R ₁₀ ), X or a hydrogen atom. R ₄ and R ₇ are an aliphatic group, an aromatic group, a heterocyclic group,
Represents a hydrogen atom or a cation, R ₅ and R ₆ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom,
R ₈ , R ₉ and R ₁₀ represent an aliphatic group, and X represents a halogen atom.

[0135]

Embedded image

In the formula, R ₁₁ represents an aliphatic group, an aromatic group, a heterocyclic group or —NR ₁₃ (R ₁₄ ), and R ₁₂ represents —NR ₁₅ (R _14
16), - represents a _{N (R 17) N (R} 18) R 19 or -OR _20. R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group. Where R ₁₁ and R ₁₅ , R ₁₁ and R ₁₇ , R ₁₁
And R ₁₈ , R ₁₁ and R ₂₀ , R ₁₃ and R ₁₅ , R ₁₃ and R ₁₇ , R ₁₃ and R _18, and R ₁₃ and R ₂₀ may combine to form a ring.
Specific examples of the compounds represented by formulas (C) and (D) of the present invention are shown below, but the present invention is not limited thereto.

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

The compounds represented by the general formulas (C) and (D) of the present invention can be synthesized according to already known methods. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969, 2927;
Journal of Organometallic Chemistry (J. Organomet. Chem.) 4,320 (1965); i
bid, 1,200 (1963); ibid, 113,
C35 (1976); Phosphorus Sulfur (P
hosphorus Sulfur) 15, 155 (1983); Chemist Ber. 109, 2996 (1)
976); Journal of Chemical Society Chemical Communication (J.Chem. Soc. Che
m. Commun.) 635 (1980); ibid, 1102.
(1979); ibid, 645 (1979); ibi
d, 820 (1987); Journal of Chemical Society Perkin Transaction (J. Che.
m.Soc. Perkin. Trans. ) 1,21
91 (1980); The Chemistry of Organo Selenium and Tellurium Campounds (T
he Chemistry of Organo Selenium and Tellurium Comp
ounds) 2 volumes 216-267 (1987). The addition amount of the selenium sensitizer and tellurium sensitizer used in the present invention is different depending on the activity of the sensitizer used, the type and size of silver halide, the temperature and time of ripening, etc., but preferably, Silver halide 1
It is at least 1 × 10 ^-8 mol per mol. More preferably 1
It is not less than ^10-7 mol and not more than 1 ^10-5 mol. The temperature of chemical ripening when a sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or more and 80 ° C. or less.
pAg and pH are arbitrary. For example, the effect can be obtained in a wide range of pH from 4 to 9. Selenium sensitization and tellurium sensitization are more effective when performed in the presence of a silver halide solvent.

Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide, and about 10 ^-7 to 10 ^-2 mol per mol of silver halide. Can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts as reduction sensitizers,
Amines, formamidinesulfinic acid, silane compounds and the like can be used. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication (EP) -293,917.
The silver halide emulsion in the light-sensitive material used in the present invention is
Only one kind may be used, or two or more kinds (for example, different average grain sizes, different halogen compositions, different crystal habits, different chemical sensitization conditions) may be used in combination.

In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 to 10%. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

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

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof. (Ammonium salt, sodium salt, potassium salt, etc.).
The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.
0 × 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

The following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (NO) ₂ Cl ₄ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl ₅ ] ^-2 6 [Re (NO) CN ₅ ] ^-2 7 [Re (NO) ClCN ₄ ] ^-2 8 [Rh (NO) ₂ Cl ₄ ] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl ₅ ] ^-2 14 [Cr (NO) Cl ₅ ] ^-3 15 [Re (NO) Cl ₅ ] ^-1 16 [Os (NS) Cl ₄ (TeCN)] ^-2 17 [Ru (NS) I ₅ ] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

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

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
No. 62247, JP-A-2-48653, U.S. Pat.
No. 161,331, West German Patent 936,071, Simple Merocyanines described in Japanese Patent Application No. 3-189532,
B) For a helium-neon laser light source, see JP-A-50-62425, JP-A-54-18726, and JP-A-59-62426.
No. 102229, trinuclear cyanine dyes, C) L
Japanese Patent Publication No. 48 for ED light source and red semiconductor laser
-42172, 51-9609, 55-398
18, JP-A-62-284343, JP-A-2-10.
JP-A-59-1910 for thiacarbocyanines described in 5135 and D) infrared semiconductor laser light source.
No. 32, tricarbocyanines described in JP-A No. 60-80841, and those described in the general formula (IIIa) and the general formula (IIIb) of JP-A Nos. 59-192242 and 3-67242. -Dicarbocyanines and the like containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Resear
ch Disclosure) Vol. 176, 17643 (published December 1978), page 23, IV, section J.

Regarding the argon laser light source, specifically, S1-1 to S described in (Japanese Patent Application No. 7-104647).
The dyes 1 to 13 are particularly preferably used.

For the helium-neon light source, in addition to the above, it is represented by the general formula (I) described in Japanese Patent Application No. 4-228745, page 8, line 1 to page 13, line 4 to line 13. Particularly preferred are sensitizing dyes. In addition, Japanese Patent Application No. 4-2287
The compounds described in General Formula (I) of No. 45 are also preferably used. Specifically, S described in (Japanese Patent Application No. 7-104647)
The dyes 2-1 to S2-10 are particularly preferably used.
Further, it is a sensitizing dye represented by the general formula (I) of Japanese Patent Application No. 6-103272, specifically, I-1 to I-described in the specification.
The dye of I-34 is also preferably used.

For the LED light source and the infrared semiconductor laser, specifically, the dyes S3-1 to S3-8 described in (Japanese Patent Application No. 7-104647) are particularly preferably used.

For the infrared semiconductor laser light source, specifically, S4-1 to S4-1 described in (Japanese Patent Application No. 7-104647).
The dye of S4-9 is particularly preferably used.

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

There are no particular restrictions on the various additives used in the photographic material of the present invention, and for example, those described in the following sections can be preferably used.

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

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

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

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

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

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

Compounds having an acid group described in JP-A-2-103536, page 18, lower right line, line 6 to page 19, upper left line, line 1.

JP-A-2-18542, page 2, lower left 1
From the 3rd line to the 7th line on the upper right side of page 3 of the same publication, specifically, the metal oxides from the 2nd lower right line on the 2nd page to lower right 10th line of the same publication, And conductive polymer compounds of compounds P-1 to P-7 described in the same publication.

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

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

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

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

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass 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.

The developer used in the development processing of the light-sensitive material of the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . Any of known methods can be used for the developing treatment of the present invention, and known developing treatment solutions can be used. There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable that the developing agent contains dihydroxybenzenes or an ascorbic acid derivative. Further, in view of developing ability, dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones,
Combination of dihydroxybenzenes and p-aminophenols, combination of ascorbic acid derivative and 1-phenyl-3-pyrazolidones, or ascorbic acid derivative and p
-Aminophenols combinations are preferred, most preferred combinations are ascorbic acid derivatives and p-aminophenols.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone,
Isopropyl hydroquinone, methyl hydroquinone,
There are hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. The ascorbic acid derivative developing agent preferably used in the present invention is Japanese Patent Application No. 7-12738.
The compound of the general formula (1) according to 5, specifically,
The compounds 1-1 to 1-31 described in the publication are preferably used.

Of these, a particularly preferred compound is ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid). The general range of ascorbic acid derivative developing agent is 5 per liter of developing solution.
× 10 ⁻³ mol to 1 mol, particularly preferably 10 ⁻² mol to
It is 0.5 mol.

Further, 1-phenyl-3-used in the present invention
As developing agents for pyrazolidone or its derivatives, there are 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. . Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. Among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 to 0.8 mol / liter. Particularly preferably, it is in the range of 0.2 to 0.6 mol / liter. Dihydroxybenzenes and 1
When using a combination of -phenyl-3-pyrazolidones or p-aminophenols, the former is 0.05 to
0.6 mol / liter, more preferably 0.2-0.
5 mol / liter, the latter is preferably used in an amount of 0.06 mol / liter or less, more preferably 0.03 mol / liter or less. The ascorbic acid derivative developing agent is usually preferably used in an amount of 0.05 to 1.0 mol / liter. Particularly preferably, it is in the range of 0.1 to 0.5 mol / liter. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
~ 1.0 mol / liter, more preferably 0.1
It is preferred to use 0.5 mol / liter, the latter 0.2 mol / liter or less, more preferably 0.1 mol / liter or less.

Preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like.
When a dihydroxybenzene type developing agent is used, the amount of sulfite is 0.20 mol / liter or more, particularly 0.3 mol / liter.
It is used in an amount of 1 liter or more, but if added in an excessively large amount, it causes silver stain in the developing solution, so the upper limit is preferably 1.2 mol / liter. Particularly preferably 0.35
~ 0.7 mol / l. On the other hand, when an ascorbic acid derivative developing agent is used, the amount of sulfite may be small and may be 0.5 mol / liter or less.

When a dihydroxybenzene type developing agent is used, a small amount of an ascorbic acid derivative may be used in combination with sulfite as a preservative. Examples of the ascorbic acid derivative include ascorbic acid, its stereoisomer, erythorbic acid, and alkali metal salts (sodium and potassium salts) thereof, and sodium erysorbate is preferably used from the viewpoint of material cost. The addition amount is 0.03 in molar ratio with respect to the dihydroxybenzene type developing agent.
To 0.12 is preferable, and 0.05 is particularly preferable.
The range is from 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; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole or its derivatives; mercapto Compounds, indazole compounds, benzotriazole compounds, and benzimidazole compounds may be included as antifoggants or black pepper inhibitors. Specifically, 5-nitroindazole,
5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5- Nitrobenztriazole, 4
-[(2-Mercapto-1,3,4-thiadiazole-
Examples thereof include sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution.

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

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

As the organic phosphonic acid, US Pat.
Nos. 4454 and 3794591, and West German Patent Publication 2
227639 and the like, hydroxyalkylidene-diphosphonic acid and Research Disclosure (Research
Disclosure) Volume 181, Item 18170 (1979)
May, 2002) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid. In addition, the above Research Disclosure 18170, JP-A-57-208554 and 54- 61125, 5
Examples thereof include compounds described in JP-A Nos. 5-29883 and 56-97347.

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

Further, as a development unevenness preventive agent, JP-A-62-
Compounds described in No. 212,651 as dissolution aids
The compound described in 1-267759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent,
It may contain a hardener or the like.

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

In the present invention, both the development starter solution and the development replenisher solution have the property that "the pH increase when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.25 or less". It is preferable. As a method for confirming that the developing solution or replenisher used has this property, the pH of the developing solution or replenisher to be tested is adjusted to 10.0, and then sodium hydroxide is added to 1 liter of the solution. .1 mol was added, and the pH value of the liquid at this time was measured. If the increase in the pH value was 0.25 or less, it was determined that the solution had the properties specified above. In the present invention, it is particularly preferable to use a development starter solution and a development replenisher solution which have a pH value increase of 0.2 or less when the above test is carried out.

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

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

In the present invention, the pH of the development initiating solution is 8.5 to 12.0, preferably 8.5 to 11.0.
It is particularly preferably in the range of 9.0 to 10.0. The pH of the developer replenisher and the pH of the developer in the developing tank during continuous processing are also in this range. As the alkali agent used for setting the pH, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate) can be used.

When processing 1 square meter of the silver halide photographic light-sensitive material, the replenisher amount of the developing solution is 225 ml or less, preferably 225 to 30 ml, especially 1.
80 to 50 ml. The development replenisher may have the same composition as the development start solution, or may have a higher concentration of components consumed in development than the start solution.

It is preferable to concentrate the processing liquid and dilute it at the time of use for the purpose of transporting the processing liquid, packaging material cost, space saving, and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. It is particularly preferably 0.2 to 1.5 mol / liter. The fixing solution may optionally contain a hardening agent (eg, a water-soluble aluminum compound), a preservative (eg, a sulfite,
Bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, ammonia, sulfuric acid), a chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B Nos. 45-35754 and 58-122535.
No. 58-122536, alcohols having a triple bond in the molecule, U.S. Pat.
A thioether compound described in JP-A-126449;
And the like, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffer include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid; and inorganic acids such as boric acid, phosphate, and sulfite. Buffers can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffering agent is used for the purpose of preventing the pH of the fixing agent from increasing due to carry-in of the developing solution, and 0.01 to
1.0 mol / liter, more preferably 0.02 to 0.1.
Use about 6 mol / l. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 can also be used.

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

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. In the washing or stabilizing treatment, the washing water amount is usually ² m ² per m ^{2 of the} silver halide photosensitive material.
It is performed at 0 liters or less, and a replenishment amount (0 liters or less
In other words, it can also be carried out by washing with water. That is, not only water saving processing can be performed, but also piping for installing the automatic processing machine can be eliminated. As a method for reducing the replenishing amount of washing water, a multi-stage countercurrent method (for example, 2
Stage, three stage, etc.) are known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the normal direction, that is, the processing solution which is not stained with the fixing solution is sequentially contacted, so that the efficiency is further improved. Washing is performed. When the washing with water is carried out with a small amount of water, JP-A-63-18
It is more preferable to provide washing tanks for squeeze rollers and crossover rollers described in No. 350 and No. 62-287225. Alternatively, various oxidizing agents may be added or a filter may be combined to reduce the pollution load which is a problem when washing with a small amount of water. Further, part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath by the method of the present invention according to the treatment is disclosed in 23
As described in JP-A No. 5133, it can be used for a processing solution having a fixing ability which is a preceding processing step. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent unevenness of water bubbles which are easily generated at the time of washing with a small amount of water and / or to prevent a treatment agent component adhering to a squeeze roller from being transferred to a treated film. Good. Further, in order to prevent contamination by the dye eluted from the photosensitive material, JP-A-63-16345
The dye adsorbent described in No. 6 may be installed in a washing tank. In addition, a stabilization process may be performed following the water washing process,
Examples thereof include JP-A-2-201357 and JP-A-2-132.
No. 435, No. 1-102553, JP-A-46-444.
A bath containing the compound described in No. 46 may be used as a final bath of the light-sensitive material. If necessary, metal compounds such as ammonium compounds, Bi, and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines, and surfactants may be used in this stabilizing bath. Agents can also be added. The water used in the washing step or the stabilization step includes tap water, deionized water, halogen, ultraviolet sterilizing lamp, and water sterilized by various oxidizing agents (ozone, hydrogen peroxide, chlorate, etc.). It is preferable to use, and washing water containing the compounds described in JP-A-4-39652 and JP-A-5-241309 may be used. Washing or stabilizing bath temperature and time are 0-5
0 ° C. and 5 seconds to 2 minutes are preferred.

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

The light-sensitive material which has been developed and fixed is then washed with water or stabilized. Water used for the washing or stabilizing bath may be tap water, ion-exchanged water, or distilled water. These replenishment rate depends on the water pressure, generally but about 17 liters to about eight liter photosensitive material 1 m ^2, can also be carried out in less replenishing rate. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When the washing with water is carried out with a small amount of water, JP-A-63-18350 and JP-A-62-18350.
It is more preferable to provide a washing tank for the squeeze roller and the crossover roller described in US Pat. In addition, in order to reduce the pollution load that becomes a problem when washing with a small amount of water, addition of various oxidizers (eg ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) and filters You may combine filtration.

As a method of reducing the replenishment amount of washing water,
A multi-stage counter-current method (for example, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount for washing is 200 to ⁵ per 1 m ² of light-sensitive material.
0 ml is preferred. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will gradually move in the normal direction,
That is, since the treatment liquid which is not contaminated with the fixing liquid is sequentially contacted and processed, the water washing can be performed more efficiently. This effect can also be obtained by an independent multi-stage system (a method in which a new solution is replenished in a multi-stage washing tank or stabilizing bath without using countercurrent).

Further, the method of the present invention may be provided with a scale preventing means in the washing or stabilizing bath. As the means for preventing descaling, a known means can be used, and there is no particular limitation. Irradiating ultraviolet rays or infrared rays or far infrared rays, applying a magnetic field, sonicating, applying heat, and emptying the tank when not in use.
These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. For example, glutaraldehyde, chelating agent such as aminopolycarboxylic acid, cationic surfactant, oxidizing agent (eg ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.), Mercaptopyridine oxide (eg 2-
Mercaptopyridine-N-oxide, etc.)
They may be used alone or in combination of two or more. The protective agent may be added to the washing or stabilizing bath depending on the treatment, or may be added to the washing water or the stabilizing solution in advance and supplemented. Replenishment of the protective agent may be performed according to the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. Further, it is also preferable to use a different antiseptic agent for each fixed period in order to suppress the occurrence of resistant bacteria. As a method of energizing, there are JP-A-3-224685, JP-A-3-224687, and JP-A-4-162.
80, 4-18980, etc. can be used.

In order to prevent unevenness of water bubbles, which is likely to occur at the time of washing with a small amount of water, and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film,
Known water-soluble surfactants and defoamers may be added. Further, the dye adsorbent described in JP-A-63-163456 may be installed in a water washing tank to prevent contamination by dyes eluted from the light-sensitive material.

A part or the whole of the overflow solution from the washing or stabilizing bath can be mixed and used in a processing solution 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 supporting microorganisms on a porous carrier such as activated carbon or ceramics), or oxidization treatment with electricity or an oxidant to obtain biochemical oxygen demand Amount (BOD), chemical oxygen demand (COD), iodine consumption, etc. are reduced before draining or forming a sparingly soluble silver complex such as a filter or trimercaptotriazine using a polymer having an affinity for silver. It is also preferable from the viewpoint of conservation of the natural environment to reduce the silver concentration in the waste water by adding the compound described above to precipitate silver and filter it with a filter.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and examples thereof include JP-A-2-201357 and JP-A-2-201357.
JP-A-132435, JP-A-1-102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, antifungal agents, alkanolamines and surface active agents. Agents 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, the fixing solution, the washing water and the stabilizing solution used in the present invention are preferably burnt and disposed. These waste liquids are, for example, Japanese Patent Publication No. 7-83867, U.S. Pat.
It is also possible to condense or solidify with a concentrating device as described in S5439560 or the like before disposing.

When the replenishment amount of the processing agent is reduced, it is preferable to prevent the liquid from evaporating and oxidizing by reducing the contact area of the processing tank with the air. A roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,779 and 3,545,971, and is simply referred to as a roller-conveying type processor in this specification.
The roller transport type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Four steps by a stabilization step may be used instead of the water washing step.

In the developing treatment of the present invention, the developing and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each liquid is preferably 25 to 50 ° C, and preferably 30 to 40 ° C. The temperature and time of the washing or stabilizing bath are preferably 0 to 50 ° C and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed (or stabilized) may be washed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known method can be used for the drying method, and there is no particular limitation. For example, warm air drying or, for example, JP-A-4-15534 and JP-A-5-225 can be used.
6, drying by a heat roller as disclosed in the same 5-289294, drying by far infrared rays, etc.,
You may use a some method together.

[0206]

【Example】

<Preparation of Silver Halide Emulsion> [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride, and K ₃ corresponding to 3.5 × 10 ⁻⁷ mol per mol of silver.
IrCl ₆ and K ₂ Rh (H ₂ O) Cl ₅ equivalent to 2.0 × 10 ⁻⁷ mol
To a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione while stirring, by a double jet method, to give an average grain size of 0.25 μm and a silver chloride content of 70 mol%. Silver chlorobromide particles were prepared.

Then, according to a conventional method, the product was washed with water by the flocculation method, 40 g of gelatin was added per mol of silver, and further 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per mol of silver.
The pH was adjusted to 6.0 and pAg 7.5, and 1 mg of sodium thiosulfate, 4 mg of chloroauric acid and 1 mg of the sensitizer shown in Table 9 were added to 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Then, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.25 μm and a silver chloride content of 70 mol%.
(Coefficient of variation 10%)

[0208]

[Table 9]

[Emulsion B] Liquids 2 and 3 were simultaneously added over 24 minutes with stirring to Liquid 1 below, which was maintained at 38 ° C. and pH 4.5, to form grains of 0.18 μm. Subsequently, the following 4 liquid and 5 liquid were added over 8 minutes, and 0.15 g of potassium iodide was added to complete the particle formation. Then, according to a conventional method, the product was washed with water by a flocculation method, gelatin was added per mol of silver, and then pH was adjusted to 5.2.
Adjust to pAg 7.5, add 4 mg of sodium thiosulfate and 10 mg of chloroauric acid, 4 mg of sodium benzenethiosulfonate and 1 mg of benzenesulfinic acid and 2 mg of sensitizer shown in Table 10 per 1 mol of silver, and optimize at 55 ° C. It was chemically sensitized to obtain sensitivity. Furthermore, as a stabilizer, 4-hydroxy-
6-methyl-1,3,3a, 7-tetraazaindene 5
0 mg, 100 pp of phenoxyethanol as a preservative
Then, cubic silver iodochlorobromide cubic grains having a silver chloride content of 70 mol% and an average grain size of 0.20 μm were finally obtained. (Variation coefficient 9%)

<1 solution> Water 1.0 liter Gelatin 20 g Sodium chloride 2 g 1,3-Dimethylimidazolidin-2-thione 20 mg Sodium benzenethiosulfonate 3 mg <2 solution> Water 600 ml Silver nitrate 150 g <3 solution > Water 600 ml Sodium chloride 45 g Potassium bromide 21 g K ₃ IrCl ₆ (0.001% aqueous solution) 15 ml (NH ₄ ) ₃ RhBr ₆ (0.001% aqueous solution) 1.5 ml <4 solution> Water 200 ml Silver nitrate 50 g <5 liquid> Water 200 ml Sodium chloride 15 g Potassium bromide 7 g K ₄ Fe (CN) ₆ 30 mg

[0211]

[Table 10]

[Emulsion C] 250 ml of an aqueous silver nitrate solution in which 64 g of silver nitrate was dissolved, and 2.0 × per mol of silver in the finished emulsion.
^10-7 corresponding to a molar K ₃ IrCl ₆ and 1.0 × 10 ^-7 corresponding to a molar _{K 2 Rh (H 2 O)} Cl 5 halogen salt aqueous solution 250 prepared by dissolving potassium bromide 20g sodium chloride 14g including
ml to a 2% aqueous gelatin solution containing sodium chloride (0.3%), 1,3-dimethyl-2-imidazolidinethione (0.002%) and citric acid (0.05%) at 38 ° C. with stirring. By a double jet method for 12 minutes at an average particle size of 0.16 μm and a silver chloride content of 55.
Nucleation was performed by obtaining mol% silver chlorobromide grains. Then, a silver nitrate aqueous solution 3 in which 106 g of silver nitrate was dissolved
Particle formation was carried out by adding 300 ml of a halogen salt aqueous solution in which 00 ml, 28 g of potassium bromide and 26 g of sodium chloride were dissolved by the double jet method over 12 minutes.

Thereafter, 1.0 × 10 ⁻³ mol of KI was added to 1 mol of silver for conversion, and the product was washed with water by a flocculation method according to a conventional method. Then, 40 g of gelatin was added per mole of silver, and pH 6.0, pAg
After adjusting to 7.5, 3 mg of sodium benzenethiosulfonate, 1 mg of benzenesulfinic acid, 2 mg of sodium thiosulfate, 8 mg of chloroauric acid and 2 mg of the sensitizer shown in Table 11 were added per 1 mol of silver, and the mixture was added at 60 ° C. for 70 minutes. It was heated and chemically sensitized. Then, after adding 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene as a stabilizer and 100 mg of proxel as a preservative, 400 mg of a sensitizing dye (S-0) was added, After a minute, the temperature dropped. The obtained grains were silver iodochlorobromide cubic grains having an average grain size of 0.22 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10%)

[0214]

Embedded image

[0215]

[Table 11]

[Emulsion D] Sodium chloride kept at 30 ° C. and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per mol of silver, 5 × 10 ⁻³ mol of 4-hydroxy-
In a 1.5% gelatin aqueous solution containing 6-methyl-1,3,3a, 7-tetraazaindene and having a pH of 2.0, a silver nitrate aqueous solution and 4.0 × 10 ⁻⁵ mol of K ₂ Ru (per mol of silver) were added. N
An aqueous solution of sodium chloride containing O) Cl ₅ was simultaneously added by the double jet method at a potential of 95 mv for 3 minutes and 30 seconds to half the amount of silver of the final particles to adjust 0.10 μm of the particles at the core. Then, 4.0 mol per mol of silver nitrate aqueous solution and silver
An aqueous sodium chloride solution containing × 10 ^-5 mol of K ₂ Ru (NO) Cl ₅ was added in the same manner as above for 7 minutes to give an average particle size of 0.
13 μm silver chloride grains were prepared. (Coefficient of variation 13%)

Then, after washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added, and proxel was added as a preservative at a ratio of 6 per mol of silver.
After the addition of 0 mg, the pH was adjusted to 5.7 and pAg to 7.5, and 2 × 10 ⁻⁵ mol of sodium thiosulfate, 4 × 10 ⁻⁵ mol of chloroauric acid, and the sensitizer shown in Table 12 were added per mol of silver. 1 × 10 ⁻⁵ mol was added and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added as a stabilizer in an amount of 1 × 10 ⁻³ mol per mol of silver. As the final particles, p
H5.7, pAg 7.5, and Ru4 × 10 ⁻⁵ mol / Ag mol.

[0218]

[Table 12]

The formulations of the developer and fixer used are shown below.

<Developer formulation> Developer A Water 700 ml Sodium hydroxide 2.5 g Diethylenetriamine-5-acetic acid 4.0 g Potassium carbonate 55 g Sodium carbonate monohydrate 51 g Sodium sulfite 1.0 g Sodium erythorbate 30.0 g N-methyl- p-Aminophenol 7.5 g Potassium bromide 2.0 g Diethylene glycol 25.0 g Compound of the invention shown in Table 13 0.3 g Acetic acid (90%) 10 ml pH (adjusted with NaOH or acetic acid) 9.7 up-to (H ₂ O) 1 liter

Fixer Formulation Fixer A Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid / 2Na, dihydrate 0.09 g Sodium thiosulfate / 5-hydrate 32.8 g Sodium sulfite 75.0 g Sodium hydroxide 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 5.05 up-to (water) 1 liter 2 liters of water was added to 1 liter of the above liquid and used.

Example 1 (Preparation of coating sample) On a polyethylene terephthalate film (150 μm) support having an undercoat layer (0.5 μm) made of a vinylidene chloride copolymer, from the support side,
A sample was prepared by coating so as to have a layer structure of UL, EM, ML, and PC. The preparation method and application amount of each layer are shown below.

(UL) Water was added to gelatin and dissolved at 40 ° C., and then compound (W) was added at a concentration of 15 mg / m ^2, and further 70 wt% of latex copolymer (butyl acrylate; acrylic acid) to gelatin was added. 2-acetoacetoxyethyl methacrylate = 80: 4: 16 wt
Ratio), 3.0 wt% of compound (B) was added to gelatin, and the mixture was coated so that the gelatin became 0.3 g / m ² .

(EM) After the emulsion-A was dissolved at 40 ° C., the sensitizing dye (S-1) was added at 4.5 × 10 ⁻⁴ mol / mol Ag, and the sensitizing dye (S-2) was added at 1.5. × 10 ^-4 mol / mol A
g, KBr 4.5 × 10 ⁻³ mol / mol Ag, compound (A) 9.0 × 10 ⁻⁴ mol / mol Ag, compound (C)
3.2 × 10 ⁻⁴ mol / mol Ag, compound (D) 7.0 ×
10 ⁻⁴ mol / mol Ag, acetic acid 7.0 × 10 ⁻³ mol / mol Ag, hydroquinone 9.7 × 10 ⁻³ mol / mol Ag,
Compound (H) 1.4 × 10 ^-4 mol / mol Ag, compound (P) 2.6 × 10 ^-4 mol / mol Ag, and further 15 wt% of polyethyl acrylate latex to gelatin, to gelatin Latex copolymer of 15 wt% (butyl acrylate; acrylic acid; 2-acetoacetoxyethyl methacrylate = 80: 4: 16), compound (B) of 4 wt% with respect to gelatin was added, and Ag of 3.5 g /
It was applied so as to be m ² .

Compound (E) 7 was added to (ML) gelatin solution.
mg / m ² , 15 wt% of polyethyl acrylate with respect to gelatin and 3.5 wt% of compound (B) with respect to gelatin were added so that the gelatin became 0.5 g / m ² .

(PC) In a gelatin solution, an amorphous SiO ₂ matting agent having an average particle size of 3.5 μm 40 mg / m ² , silicone oil 20 mg / m ² and compound (F) 5 mg / m ² as a coating aid, dodecyl sodium benzenesulfonate 25 mg / m ² and the compound (G) 20mg / m ² was coated with the addition. Gelatin was 0.3 g / m ² .

[0227]

Embedded image

The back layer and the back protective layer were coated according to the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant Sodium P-dodecylbenzenesulfonate 40 mg / m ² Compound [B] 110 mg / m ² SnO ₂ / Sb (weight ratio 90 / 10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] Dye [a] 70 mg / m ² dye [b] 100 mg / m ² dye [c] 50mg / m ²

[0229]

Embedded image

[Back protective layer] Gelatin 0.8 mg / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonate sodium 15 mg / M ² Sodium acetate 40mg / m ²

The light-sensitive materials 1-1 to 1- created in this way
5, the development processing and the photographic performance evaluation were performed as follows. (Standard processing) Through a interference filter having a peak at 488 nm and a step wedge, light is exposed to xenon flash light with a light emission time of 10 ^-6 sec, and an FG-680A automatic processor (manufactured by Fuji Photo Film Co., Ltd.) is used. , 35 ° C 3
After 0 ″ development, fixing, washing with water and drying were subsequently carried out. The developing solution used was the developing solution prepared by adding the compound of the present invention to the developing solution A as shown in Table 13. A
Was used.

(Evaluation) The gamma of the light-sensitive material which had been subjected to the standard processing was evaluated. Gamma is expressed by the following equation. The larger this value, the harder the photographic characteristics. * Gamma = (3.0-0.3) / [log (exposure amount giving density 3.0) -log (exposure amount giving density 0.3)]

The halftone dot quality was evaluated as follows. Using a scanner suitable for the spectral wavelength of each light-sensitive material, output 50% flat mesh with 100 lines to the coated light-sensitive material, develop under the above-mentioned development conditions, and use half-fold magnifying paper to obtain halftone dot quality. It was visually evaluated. The evaluation result is expressed by a 5-point method of (good) 5 to 1 (bad).
Organized in 13. Practically, four points or more are required.

The evaluation of black spots was carried out by observing with a microscope, using an unexposed sample which had a developing time of 40 seconds under the above-mentioned developing conditions, and was evaluated in 5 stages. "5" represents the best level without black spots, and "1" represents the worst black spots and represents the worst quality. “3” is the limit level at which the generation of black spots is practically acceptable.

The silver stain was evaluated as follows. The light-sensitive material was exposed to a blackened area of 50% with a scanner, and under the above-mentioned developing conditions, a large size of 200 was applied per day.
The work of developing one sheet was carried out for 3 days, and after leaving it for 2 days, the unexposed sample was subjected to a development treatment, and the silver stain on the film surface was visually evaluated. The amount of developer replenished during processing was 30 ml per sheet of a large size photosensitive material, and the amount of fixer replenished was 30
ml. 5 is no silver stain, 4 is slightly generated,
3 was slightly generated, 2 was frequently generated, and 1 was generated in large amounts. 5 and 4 are levels that can be used satisfactorily without any problems, and 3 is a level that is slightly generated but is acceptable,
2 and 1 are practically problematic levels.

(Result)

[0237]

[Table 13]

It has been surprisingly found that the combination of the light-sensitive material of the present invention and the developing method makes it practically applicable from the viewpoint of contrast, halftone dot quality, black spots, and silver stain.

Example 2 (Preparation of coating sample) A sample was prepared in the same manner as in Example 1 except that the EM layer of Example 1 was changed as follows. (EM) After dissolving the emulsion-B together with gelatin at 40 ° C., KBr 3.6 × 10 ⁻³ mol / mol Ag, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene7. 6 × 10 ⁻⁴ mol / mol Ag, sensitizing dye (S
-2) 2.5 × 10 ^-4 mol / mol Ag, compound (H)
2.0 × 10 ⁻⁴ mol / mol Ag, compound (P) 5.7 ×
10 ⁻⁴ mol / mol Ag, compound (C) 5.0 × 10 ⁻⁴ mol / mol Ag, compound (D) 1.6 × 10 ⁻³ mol / mol Ag, 15 wt% colloidal silica based on gelatin, Furthermore, 15 wt% polyethyl acrylate latex for gelatin, 20 wt% latex copolymer for gelatin (butyl acrylate; acrylic acid; 2-acetoacetoxyethyl methacrylate = 8)
0: 4: 16), and 4 wt% of the compound (B) was added to gelatin to apply Ag 3.5 g / m ² . Compounds (B), (C), (D), (H),
(P) is the same as in Example 1.

[0240]

Embedded image

(Development Processing, Evaluation) The photosensitive materials 2-1 to 2-5 thus prepared were processed and evaluated using the same developer as in Example 1. However, the interference filter used during exposure had a peak at 633 nm.

(Results) As in Example 1, only when the photosensitive material of the present invention and the developing method are combined, it is possible to use the composition unexpectedly in terms of contrast, halftone dot quality, black spots, and silver stain. I understand.

Example 3 On a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides, from the side of the support,
EM (silver content 3.0 g / m ² , gelatin 1.5 g / m ² ), P
CU (gelatin 0.5 g / m ² ), PCO (gelatin 0.
4 g / m ² ). The film surface pH of the emulsion surface of the obtained sample was 5.8.

(EM) After dissolving the emulsion-C, 2 × 10 ^-4 mol of a short-wave cyanine dye represented by the following structural formula (a), and 5 × 10 ^-3 mol of bromide per mol of silver were dissolved. Potassium, 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 2 × 10 ⁻⁴ mol of the mercapto compound represented by the following structural formula (b), 3 × 10 ⁻⁴ mol of the following structural formula (c) ), A triazine compound represented by the formula (3), 3 × 10 ⁻⁴ mol of the compound (J), 4.4 × 10 ⁻⁴ mol of the compound (P) are added, and further hydroquinone 100 mg / m ² and p-dodecylbenzenesulfone are added. Sodium acid salt 10 mg / m ² , colloidal silica (Nissan Chemical Snowtex C) 150 mg /
m ² , a dispersion of polyethyl acrylate 500 mg / m ² ,
1,2-bis (vinylsulfonylacetamido) ethane was added so as to be coated at 80 mg / m ² to prepare an emulsion layer coating solution. The pH of the coating solution was adjusted to 5.6.

[0245]

Embedded image

(PCU) 10 mg / m ^{2 of} the compound represented by (d) was added to a gelatin solution containing proxel as a preservative,
The compound represented by (e) was added to 100 mg / m ² , and a dispersion of polyethyl acrylate was added so as to be applied at 300 mg / m ² to prepare. (PCO) In a gelatin solution containing proxel as a preservative, the compound represented by (d) was 10 mg / m ² , the compound represented by (e) was 100 mg / m ² , and the dispersion of polyethyl acrylate was 300 mg / m 2. ² Add so that it can be applied, and further, to a gelatin solution containing proxel as a preservative, an amorphous SiO ₂ matting agent 5 having an average particle size of about 3.5μ.
0 mg / m ² , colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd.) 100 mg / m ² , liquid paraffin 30 mg / m ² , and a fluorosurfactant 5 mg / m ² represented by the following structural formula (f) as a coating aid. 30 mg / m ^{2 of} p-dodecylbenzenesulfonic acid sodium salt was added so as to be applied.

[0247]

Embedded image

The back layer was coated according to the following formulation. (Back layer) Gelatin 1.5 g / m ² Surfactant p-Dodecylbenzenesulfonic acid sodium salt 30 mg / m ² Gelatin hardener 1,2-bis (vinylsulfonylacetamide) ethane 100 mg / m ² Dye g), (h), (i), (j) mixture Dye (g) 50 mg / m ² dye (h) 100 mg / m ² dye (i) 30 mg / m ² dye (j) 50 mg / m ² Proxel 1 mg / m ²

[0249]

Embedded image

(Back protective layer) Gelatin 1.5 g / m ² polymethylmethacrylate fine particles (average particle size 2.5 μ) 20 mg / m ² p-dodecylbenzenesulfonic acid sodium salt 15 mg / m ² dihexyl-α-sulfosuccinate Nato sodium salt 15 mg / m ² Sodium acetate 50 mg / m ² Proxel 1 mg / m ²

(Development Processing, Evaluation) The photosensitive materials 3-1 to 3-5 thus prepared were processed and evaluated using the same developer as in Example 1. However, a tungsten sensitometer was used for the exposure, and a filter having a color temperature of 3200 ° K was used. In addition, in the evaluation of the halftone dot quality, the quality of the halftone dot obtained by overlapping the contact screen during the exposure was visually evaluated.

(Results) As in Example 1, surprisingly, the combination of the light-sensitive material of the present invention and the developing method unexpectedly makes it possible to use the material in terms of contrast, halftone dot quality, black spots, and silver stain. I understand.

Example 4 <Preparation of Coating Solution for Emulsion Layer and Coating Thereof> The following compounds were added to Emulsion-D, and the coating amount of gelatin was 0.9 g / m ² on the following support including the undercoat layer, coated silver. The silver halide emulsion layer was coated so that the amount was 2.7 g / m ² . 1-Phenyl-5-mercapto-tetrazole 1 mg / m ² N-oleyl-N-methyltaurine sodium salt 10 mg / m ² compound-B 10 mg / m ² compound-C 8 mg / m ² compound-D 15 mg / M ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 760 mg / m ² compound-E (hardener) 105 mg / m ² sodium polystyrene sulfonate 57 mg / m ² compound-K 3 × 10 ^-5 mol / m ² compound-N 3 × 10 ^-5 mol / m ²

An emulsion protection lower layer and an upper layer were coated on the above emulsion layer. <Preparation of Emulsion Protecting Lower Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 0.6 g /
It was applied as a m ^2. Gelatin (Ca ⁺⁺ content 2700 ppm) 0.6 g / m ² Sodium p-dodecylbenzenesulfonate 10 mg / m ² Sodium polystyrene sulfonate 6 mg / m ² Compound-A 1 mg / m ² Compound-F 14 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 250 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Liquid and Its Coating>
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent 40 mg / m ² (average particle size 3.5 μ, pore diameter 25 mm, surface area 700 m ² / g) amorphous silica matting agent 10 mg / M ² (average particle size 2.5 μ, pore diameter 170 °, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycinepotadium 5 mg / m ² sodium p-dodecylbenzenesulfonate 30 mg / m ² Compound-A 1 mg / m ² Liquid paraffin 40 mg / m ² Solid disperse dye-G ₁ 30 mg / m ² Solid disperse dye-G ₂ 150 mg / m ² Sodium polystyrene sulfonate 4 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support. <Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution and coated so that the coating amount of gelatin was 0.06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² sodium p-dodecylbenzenesulfonate 13 mg / m ² dihexyl α-Sulfosuccinate sodium 12 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound-A 1 mg / m ²

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount was 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 1.94 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 15 mg / m ² compound-H 140 mg / m ² compound-I 140 mg / m ² compound-J 30 mg / m ² compound-K 40 mg / m ² sodium p-dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-L 5 mg / m ² N-perfluoro Octanesulfonyl-N-propyl glycine potassium 5 mg / m ² sodium sulfate 150 mg / m ² sodium acetate 40 mg / m ² compound-E (hardener) 105 mg / m ²

(Support, Undercoat Layer) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following compositions. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g Colloidal silica (Snow) Tex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd. 0.12 g Water was added to 100 g, KOH of 10% by weight was further added, and the coating solution adjusted to pH = 6 was dried at a drying temperature of 180 ° C. for 2 minutes. The film thickness is 0.
It was applied so as to be 9μ.

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

[0260]

Embedded image

[0261]

Embedded image

[0262]

Embedded image

(Development Processing, Evaluation) The photosensitive materials 4-1 to 4-5 thus prepared were processed and evaluated using the same developer as in Example 1. However, exposure was performed using a bright room printer P-627FM manufactured by Dainippon Screen Co., Ltd.
The developing conditions were 38 ° C. and 20 seconds.

(Results) As in Example 1, surprisingly, it was found that the combination of the light-sensitive material of the present invention and the developing method made it possible to put it into practical use from the viewpoint of contrast, black spots, and silver stain. .

Example 5 In Examples 1, 2, 3 and 4, the following developing solution D or E was used instead of the developing solution A, and the following fixing solution B was used instead of the fixing solution A. Also, Examples 1, 2, 3, 4
Similarly, it was found that the combination of the light-sensitive material of the present invention and the developing method surprisingly makes it practically possible from the viewpoints of contrast, black spots, and silver stain. However, the effect was smaller than that when the developing solution A was used.

<Developer D> Potassium hydroxide 40.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 60.0 g Sodium metabisulfite 70.0 g Potassium bromide 7.0 g Hydroquinone 40.0 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4 -Methyl-1 phenyl-3-pyrazolidone 1.50 g sodium 2-mercaptobenzimidazole-5-sulfonate 0.30 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.10 g sodium erythorbate 6.0 g diethylene glycol 5.0 g Add potassium hydroxide, add water to make 1 liter and adjust the pH to 10.65. 1 liter

<Developer E> The following storage form was made into a solid developer, and water was added to make 1 liter to prepare a use liquid. The composition of the solid developer is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (bulk powder) 63.0 g Sodium sulfite (bulk powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g Diethylenetriamine pentaacetic acid 2.0 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g 3- (5-Mercaptotetrazol-1-yl) Sodium benzenesulfonate 0.1 g Sodium erythorbate 6.0 g Potassium bromide 6.6 g Dissolve this in water to 1 liter. pH 10.65

Here, in the raw material form, the bulk powder was used as a general industrial product, and the beads of the alkali metal salt were commercial products. If the raw material is briquette, it is pressed and compressed using a briquetting machine to give an irregular length of 4 to 6
A rugby ball shape having a size of about mm was prepared, crushed and used. For minor components, each component was blended before briquetting.

<Fixing Solution B> The following solid agent and liquid agent were added to water to make 10 liters to prepare a working solution. The fixing solution is made of high-density polyethylene in the following formulation for both the solid agent portion and the liquid agent portion (average wall thickness = 500 μm, width 200-
What was filled in a container of 1000 μm) was used. The liquid volume after dissolution was 10 liters, and the pH was 4.85.

<Solid agent part> Ammonium thiosulfate 1200 g Sodium thiosulfate 150 g Sodium acetate 400 g Sodium metabisulfite 200 g <Liquid agent part> Aluminum sulfate (27%) 300 g Sulfuric acid (75%) 30 g Sodium gluconate 20 g EDTA 0.3 g citric acid 40 g solids parts are mixed and filled.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having, on a support, at least one emulsion layer containing selenium-sensitized or tellurium-sensitized silver halide having a silver chloride content of 50 mol% or more. An image forming method, which comprises developing after image exposure in the presence of a compound represented by the general formula (1). General formula (1) In the formula, Z ¹ represents a nonmetallic atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle together with N and C, and Z ¹ represents R ¹ and (SX ² ) as substituents _{has n} . Here, R ¹ represents a hydrogen atom, a halogen atom, or a substituent bonded to the ring by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. X ¹ and X ² are hydrogen atoms or cations, and n is 0, 1 or 2. Also, two radicals from which ^one arbitrary hydrogen atom has been removed from Z ¹ are bound,
A screw type structure may be formed. 2. The image forming method according to claim 1, wherein the silver halide photographic light-sensitive material contains a hydrazine derivative. 3. The image forming method according to claim 1, wherein the silver halide photographic light-sensitive material contains a hydrazine derivative and a nucleation accelerator. 4. The image forming method according to claim 1, 2 or 3, wherein the pH of the developing solution is 8.5 or more and less than 11.0.