JPH0736140A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material with superhigh contrast having stable photographic performance by incorporating a hydrazine deriv. into a silver halide emulsion layer and spectrally sensitizing the silver halide emulsion with specified dyes. CONSTITUTION:This silver halide photographic sensitive material has at least one silver halide emulsion layer on a supporting body. At least one of the silver halide emulsion layer or other hydrophilic colloid layers contains a hydrazine deriv., and the silver halide emulsion is spectrally sensitized with dyes expressed by formula I and formula II. In formulae, X1-X4 are hydrogen atoms, cyano groups, etc., R1-R4 are alkyl or alkenyl groups and at least one of these is a group having a sulfo group, Y1 is a counter ion, n1 is 0 or 1 and is 0 for an inner salt, Q represents atoms necessary to form benzoxazole, R21 is acid substituent, R22 and R23 are alkyl groups, an L21-L24 are substd. or unsubstd. methine groups.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting super-high gradation (especially γ of 10 or more) is provided in order to improve reproduction of continuous tone images or line images by halftone dot images. is necessary. There is a demand for an image forming system which can be developed with a processing solution having good storage stability to obtain super-high photographic characteristics, and one of them is US Pat. Nos. 4,166,742 and 4,16.
No. 8,977, No. 4,221,857, No. 4,2
No. 24,401, No. 4,243,739, No. 4,
No. 272,606 and No. 4,311,781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added is added with a sulfite preservative in an amount of 0.15 mol / liter or more. Including pH 11.0-12.
A system for forming a super-high contrast negative image having a γ value of more than 10 by treating with a developing solution of No. 3 has been proposed. This new image forming system can be used with silver iodobromide and silver iodochlorobromide, whereas the conventional ultrahigh contrast image forming system can only use silver chlorobromide with a high silver chloride content. There are features. Another feature of the conventional lith developer is that it can contain a large amount of sulfite preservative, whereas it can contain a very small amount of sulfite preservative.

However, since a developer having a pH of 11 or more is easily oxidized by air and is unstable and cannot withstand long-term storage or use, a silver halide photographic light-sensitive material containing a hydrazine compound is developed with a developer having a lower pH. However, attempts have been made to create a high contrast image. For example, Japanese Patent Laid-Open No. 1-1799
No. 39 and No. 1-179940, a nucleation development accelerator having an adsorption group for silver halide emulsion grains;
Similarly, using a light-sensitive material containing a nucleating agent having an adsorption group, p
A processing method of developing with a developing solution of H11.0 or less is described.

Further, the nucleation-hardening light-sensitive material using a hydrazine derivative has a large range of change in photographic property with a change in pH of the developing solution. The pH of the developer greatly changes due to air oxidation of the developer and increase due to concentration by evaporation of water, or decrease due to absorption of carbon dioxide in the air. Therefore, attempts have been made to reduce the dependence of photographic performance on the pH of the developer. Further, in a nucleation-hard-tone / high-tone negative image system using a hydrazine derivative, one of the points to be improved is that it causes undesired development called black spots, which is a problem in the photolithography process. ing. The black spot is a black spot made of minute developed silver that originally occurs in a portion that should be non-imaged when it is not exposed. Black spots frequently occur due to a decrease in sulfite ion, which is generally used as a preservative in a developing solution, and an increase in pH value, and the commercial value as a photosensitive material for photoengraving is remarkably reduced. For this reason, great efforts have been made to improve the black spots, but the improvement of the black spots is often accompanied by a decrease in sensitivity and gamma (γ), resulting in a high-sensitivity high-contrast (for example, 1 for γ).
There is a strong demand for a system that maintains 0 or more) and improves black spots.

US Pat. Nos. 4,988,604 and 4,9
94,365 and 5,041,355 describe hydrazine compounds having repeating units of ethylene oxide,
And hydrazine compounds having a pyridinium group are disclosed. However, from the description of the examples,
In these inventions, the high contrast is not sufficient, and it is difficult to obtain the high contrast and the required Dmax under practical development processing conditions. An example using chemically sensitized silver chlorobromide in a system using a hydrazine derivative is disclosed in, for example, JP-A-53-20921.
No. 60, No. 60-83028, No. 60-140339,
63-46437, 63-103232, Japanese Patent Application Nos. 2-98387, 2-98391, 2-30.
No. 2077 and No. 3-188230. On the other hand, examples in which a hydrazine derivative and a silver halide emulsion containing a heavy metal complex such as rhodium or iridium are used in combination are disclosed in JP-A-60-83028 and 61-47942.
No. 61, No. 61-47943, No. 61-29837, No. 62-201233, No. 62-235947, No. 63-.
No. 103232 is disclosed.

It is well known to use a sensitizing dye to extend the photosensitive wavelength of a silver halide photographic emulsion, that is, to spectrally sensitize it. The sensitizing dye is required to have sensitivity at a required wavelength, less residual color after processing, and high safety against safelight light. further,
It is widely known by those skilled in the art that the change in photographic performance with respect to the pH change of the developer largely depends on the photographic characteristics during PQ development under the condition that hydrazine nucleating infectious development does not occur. In order to improve the dependence, it is essential to improve the photographic performance during PQ development by the spectral sensitization technique. An example of a system using a hydrazine derivative and containing a cyanine dye is 5,5′-dichloro-9-ethyl-
A large number of alkali salts of 3,3'-bis (3-sulfopropyl) oxacarbocyanine have been disclosed, and examples thereof include JP-A-61-29837 and 62-62.
No. 235947, No. 62-280733, No. 62-
280734, JP-A Nos. 2-40 and 2-12456.
No. 0, No. 2-262653, No. 3-53549, No. 3-63641 and the like.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a halogen having a photographic performance which is stable when the developer is stable and has a gamma of more than 10 and which is stable against pH fluctuation of the developer. A silver halide photographic light-sensitive material is provided. A second object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, less residual color after processing, and high safety in safelight.

[0008]

SUMMARY OF THE INVENTION The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer or another hydrophilic colloid layer is formed. And a hydrazine derivative in at least one layer, and the silver halide emulsion is spectrally sensitized with a dye of the following general formulas [I] and [II]. It was General formula [I]

[0009]

[Chemical 3]

In the formula, X ₁ , X ₂ , X ₃ and X ₄ represent a hydrogen atom, a cyano group, an alkyl group, a halogen atom, a halogen-substituted alkyl group, an alkylthio group, an alkoxycarbonyl group and a carbamoyl group. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents a substituted or unsubstituted alkyl or alkenyl group, and R ₁ , R ₂ ,
At least one of R _{3 and} R ₄ is a group having a sulfo group or a carboxy group. Y ₁ represents a counter ion necessary for neutralizing the electric charge. n ₁ represents 0 or 1, and is 0 in the case of an inner salt. General formula (II)

[0011]

[Chemical 4]

In the formula, Q represents an atom necessary for forming a substituted or unsubstituted benzoxazole or thiazoline nucleus, R ₂₁ is an acid-substituted or acid salt-substituted alkyl group, and R ₂₂ and R ₂₃ are respectively Is an alkyl group, or R ₂₂ and R ₂₃ together form an alkylene unit that forms a heterocycle with the nitrogen atom to which they are attached, and L ₂₁ , L ₂₂ , L ₂₃ and L ₂₄ are Each is a substituted or unsubstituted methine group.

The general formula [I] will be described in detail below. In the formula, R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, R ₁ , R ₂ ,
At least one of R ₃ and R ₄ is a group having a sulfo group or a carboxy group. More preferable substituents of the alkyl group and the alkenyl group include, for example, a sulfo group, a carboxy group, a halogen atom, a hydroxy group, an alkoxy group having 6 or less carbon atoms (eg, a methoxy group, an ethoxy group, etc.), and a substituent having 8 or less carbon atoms. Optionally substituted aryl group (eg, phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, etc.), heterocyclic group (eg, furyl group, cenyl group, etc.), optionally substituted aryl having 8 or less carbon atoms An oxy group (for example, a chlorophenoxy group,
Phenoxy group, sulfophenoxy group, hydroxyphenoxy group, etc.), acyl group having 8 or less carbon atoms (eg, benzenesulfonyl group, methanesulfonyl group, acetyl group, propionyl group, etc.), alkoxycarbonyl group having 6 or less carbon atoms (eg, ethoxy). Carbonyl group, butoxycarbonyl group, etc.), C6 or less alkylcarbonyl group (eg, methylcarbonyl group, ethylcarbonyl group, etc.), cyano group, C6 or less alkylthio group (eg, methylthio group, ethylthio group, etc.), carbon C8 or less optionally substituted arylthio group (eg, phenylthio group, tolylthio group, etc.), C8 or less optionally substituted carbamoyl group (eg, carbamoyl group, N-ethylcarbamoyl group, etc.), carbon number Acylamino groups of 8 or less (eg acetylamino , Methanesulfonylamino group). It may have one or more substituents. R
Specific examples of the group represented by ₁ , R ₂ , R ₃ and R ₄ include:
For example, methyl group, ethyl group, propyl group, isopropyl group, allyl group, pentyl group, hexyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, ethoxypropyl group,
Methylthiomethyl group, methylthioethyl group, methylthiopropyl group, ethylthiomethyl group, ethylthioethyl group, methylcarbonylmethyl group, methylcarbonylethyl group, ethylcarbonylmethyl group, ethylcarbonylethyl group, benzyl group, naphthyl group, 4- Carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group, phenethyl group, tolylethyl group, sulfophenethyl group, 2-pyridyl group, 2-thiazolyl group, 2,2-difluoroethyl group, 2 , 2,2-
Trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2- (2-hydroxyethoxy) ethyl group, carboxymethyl group, carboxyethyl group, ethoxycarbonylmethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group, sulfoethyl group, 2-chloro-3-sulfopropyl group, 3-sulfo Propyl group, 2-hydroxy-3-
Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- (2,3-dihydroxypropyloxy)
Ethyl group, 2- [2- (3-sulfopropoxy) ethoxy] ethyl group, 2-pyrrolidin-2-one-1-ylethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group, 2-acetoxyethyl group, carbo Methoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group, 3-sulfatopropyl group, 4-sulfatobutyl group and the like can be mentioned.

X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), and an alkyl group having 6 or less carbon atoms (eg, Methyl group, ethyl group, propyl group,
Butyl group, cyclohexyl group, etc.), aryl group (eg phenyl group etc.), alkoxy group having 4 or less carbon atoms (eg methoxy group, ethoxy group, butoxy group etc.), aryloxy group (eg phenoxy group etc.), carbon number 6 The following acyl groups (eg, acetyl group, propionyl group, benzoyl group, etc.), acyloxy groups having 3 or less carbon atoms (eg, acetoxy group, etc.), alkoxycarbonyl groups having 8 or less carbon atoms (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxy). Carbonyl group, benzyloxycarbonyl group, etc.), carbamoyl group having 8 or less carbon atoms (eg, carbamoyl group, NH-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group having 8 or less carbon atoms (eg, sulfamoyl) Base,
N, N-dimethylsulfamoyl group, morpholinylsulfonyl group, piperidinosulfonyl group, etc.), hydroxy group, cyano group, trifluoromethyl group, alkylthio group, preferably a hydrogen atom, a halogen atom, a cyano group, It is a trifluoromethyl group. Y represents an ion necessary for neutralizing the charge, n is 1 or 2, and is 1 when forming an intramolecular salt. Specific examples are shown below, but the present invention is not limited thereto.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

Next, the general formula [II] will be described in detail. In the formula, Q represents an atom necessary for forming a substituted or unsubstituted benzoxazole or thiazoline nucleus, R ₂₁ is preferably an acid-substituted or acid salt-substituted alkyl group having 1 to 6 carbon atoms, and R _{21 22} and R ₂₃ are each preferably an alkyl group having 1 to 6 carbon atoms, or R ₂₂ and R ₂₃ together form an alkylene unit which forms a heterocycle with the nitrogen atom to which it is bonded. Formed, L ₂₁ , L
₂₂ , L ₂₃ and L ₂₄ are each a substituted or unsubstituted methine chain. Specific examples of the substituted alkyl group R ₂₁ include a sulfoalkyl group (eg, sulfopropyl, sulfobutyl, etc.), a carboxyalkyl group (eg, carboxyethyl, carboxybutyl, etc.), a sulfatoalkyl group (eg, sulfatoethyl, sulfatobutyl, etc.). ) Is mentioned. The methine groups L _{21 to} L ₂₄ may be substituted with a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, but are preferably unsubstituted. The alkyl groups R ₂₂ and R ₂₃ preferably form pyrrolidine or piperidine with the nitrogen atom to which they are attached. Examples of substituents on the benzoxazole nucleus include one or more halogens, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, alkoxy groups and other substitutions commonly incorporated in sensitizing dyes. A group can be mentioned. General formula (I
Specific examples of I] are shown below, but the present invention is not limited thereto. In the formula, SP ⁻ represents 3-sulfopropyl, 4SP ⁻ represents 4-sulfobutyl, and 3
SB ^- represents a 3-sulfobutyl.

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

The sensitizing dyes represented by the general formulas [I] and [II] are known, and WO93 / 02384 and JP-A-5-12, respectively.
It can be synthesized or obtained by the method described in 7288.

To add the sensitizing dyes used in the present invention to the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or alternatively, water, methanol,
Ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol,
2,2,2-trifluoroethanol, 3-methoxy-
1-propanol, 3-methoxy-1-butanol, 1
It may be added to the emulsion by dissolving it in a solvent such as -methoxy-2-propanol, N, N-dimethylformamide or the like alone or in a mixed solvent. Also, US Pat. No. 3,469,98
No. 7, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. 44-23389, 44-25555, 57-
As disclosed in 22091 and the like, a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexistent to be added to the emulsion as an aqueous solution, US Pat. No. 135, No. 4,006,025, etc., a method of adding an aqueous solution or colloidal dispersion in which a surfactant coexists into an emulsion, as disclosed in JP-A-53-102733. , Ibid. 58-105
No. 141, a method in which a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. To dissolve the dye,
A method of adding the solution into the emulsion can also be used.
In addition, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step of emulsion preparation which has been found to be useful so far. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666 and JP-A-58-184142,
As disclosed in the specification of JP-A-60-196749 and the like, the period before the grain forming step or / and desalting of the silver halide, during the desalting step and / or after the desalting to before the start of chemical ripening. No., as disclosed in the specification of JP-A-58-113920, immediately before or during chemical ripening, at any time before the emulsion is coated, until the coating after chemical ripening. , May be added in the step. In addition, as disclosed in the specifications of US Pat. No. 4,225,666 and JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure. It may be added dividedly by dividing into medium and during the chemical aging step or after completion of the chemical aging, or before chemical aging or during the step and after completion of the chemical aging. The kind of combination may be changed and added.

When the present invention is applied to a silver halide photographic light-sensitive material, it is preferable that an aggregate of sensitizing dyes is formed, and among the sensitizing dyes represented by the general formula [I], Particularly preferred are those that easily form so-called J aggregates. Further, for example, Japanese Patent Publication No. 49-46, 932, Japanese Patent Laid-Open No. 58-28,738, and US Pat.
The combined use of the water-soluble bromide and water-soluble additives (for example, bispyridinium salt compounds, mercapto-heterocyclic sulfonates, alkali metal salts, etc.) described in the specification of Japanese Patent No. 738 strengthens the J aggregate. preferable. These compounds are used in an amount of about 10 ^-5 to 1 mol per mol of silver halide.

The addition amount of the spectral sensitizing dyes represented by the general formulas [I] and [II] used in the present invention varies depending on the shape and size of the silver halide grains, but each is per mol of silver halide. It can be used at 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount 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, The addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable. Further, the spectral sensitizing dye of the general formula [I] and the spectral sensitizing dye of the general formula [II] are used at a molar ratio of the spectral sensitizing dye of the general formula [I]: the spectral sensitizing dye of the general formula [II]. The range of dye = 1: 10 to 10: 1, particularly 1: 5 to 5: 1 is preferable.

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

[0029]

[Chemical 12]

In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ₁ represents -CO- group, -SO ₂ - group, -
SO-group,

[0031]

[Chemical 13]

It represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, and 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 or unsubstituted alkylsulfonyl group. 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 (III), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have a substituent. In the general formula (III), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group. Preferred as R ₁ is an aryl group, and particularly preferred is one containing a benzene ring.
The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group and a ureido group. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl Group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoramide group, diacylamino group, imide group, R ₄ -NHCON
(R ₅ ) —CO— group (R ₄ and R ₅ are selected from the same groups as defined for R ₂ and may be different from each other), and the like, and a preferable substituent is an alkyl group (preferably C1 to C20), aralkyl groups (preferably C7 to C30), alkoxy groups (preferably C1 to C20), substituted amino groups (preferably C1 to C20 alkyl). An amino group substituted with a group), an acylamino group (preferably having 2 to 30 carbon atoms),
Examples thereof include a sulfonamide group (preferably having 1 to 30 carbon atoms), an ureido group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably having 1 to 30 carbon atoms), and the like. These groups may be further substituted.

In the general formula (III), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, benzene). Including rings). G
_{When 1} is a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom and an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group). , Phenylsulfonylmethyl groups, etc.), aralkyl groups (eg o-
A hydroxybenzyl group), an aryl group (eg, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, a 2-hydroxymethylphenyl group, etc.), and particularly hydrogen. Atoms are preferred. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

Most preferably, G in the general formula (III) is a --CO-- group. 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 Examples thereof include those described in JP-A-63-29751. A hydrogen atom is most preferable as A ₁ and A ₂ .

R ₁ or R _{2 in} the general formula (III) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, and examples thereof include an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group
It can be selected from phenoxy group, alkylphenoxy group and the like. Further, as a polymer, for example, JP-A-1
The thing described in No. 100530 is mentioned.

R ₁ or R _{2 in} the general formula (III) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
U.S. Pat. No. 4,459,347, JP-A-59-195233.
No. 59-202331, 59-201045
Issue 59-201046 Issue 59-201047
Issue 59-201048, Issue 59-201049.
No. 61-170733 and No. 61-270744.
No. 62-270948 and 63-234244.
No. 63-234245 and No. 63-234246.

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

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Nos. 4,459,347 and 4,560,638
No. 4,478,928, British Patent No. 2,011,
391B, JP-A-60-179734, and JP-A 62-2.
70948, 63-29751, 61-170.
No. 733, No. 61-270744, and European Patent No. 21.
7,310, 356,898, U.S. Pat.
86,167, JP-A-62-178246, 63.
-32538, 63-104047, 63-1
21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
245, 63-234246, 63-2945.
No. 52, No. 63-306438, No. 64-10233
, JP-A-1-90439, 1-100530,
1-105941, 1-105943, 1-
276128, 1-280747, 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962.
No. 35, No. 2-198440, No. 2-198441,
No. 2-198442, No. 2-220042, No. 2-
221953, 2-221954, 2-302
Nos. 750 and 2-304550 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, and particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

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

The silver halide photographic light-sensitive material of the present invention may contain a nucleation accelerator in the silver halide emulsion layer or other hydrophilic colloid layer. Nucleation accelerators include amine derivatives, onium salts, disulfide derivatives,
Alternatively, a hydroxymethyl derivative and the like can be mentioned. Examples of amine derivatives include those disclosed in JP-A-60-140,340.
Nos. 62-50,829 and 62-222,241.
No. 62, No. 62-250, 439, No. 62-280, 73
No. 3, No. 63-124,045, No. 63-133, 1
The compounds described in No. 45, No. 63-286,840 and the like can be mentioned. More preferably, the amine derivative is disclosed in JP-A Nos. 63-124,045 and 63-133.
No. 145, No. 63-286,840 and the like having a compound having a group capable of adsorbing to silver halide, or the total number of carbon atoms described in JP-A No. 62-222,241 is 20. The above compounds, US 4,975,354, E
Examples thereof include amine compounds having an ethylenoxy group described in P458,706A and the like, and compounds described in JP-A-62-50829. The onium salt is preferably a pyridinium salt, an ammonium salt or a phosphonium salt. Examples of preferable pyridinium salts include the compounds described in Japanese Patent Application No. 5-97866. Further, examples of preferable ammonium salts include JP-A Nos. 62-250,439 and 62-280.
The compound described in No. 733 etc. can be mentioned. Examples of preferable phosphonium salts are JP-A-61-167,939 and JP-A-62-280,733,
Examples thereof include compounds described in Japanese Patent Application No. 5-123273. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198,147. As the hydroxymethyl derivative, for example, US Pat. Nos. 4,693,956 and 4,777,
118, EP 231,850, JP-A-62-50,
No. 829 and the like can be mentioned, and more preferred are diarylmethanol derivatives. Examples of the acetylene derivative include the compounds described in JP-A-3-168735 and JP-A-2-271351. Examples of the urea derivative include JP-A-3-16873.
The compounds described in No. 6 can be mentioned.

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

[0056]

[Chemical formula 26]

[0057]

[Chemical 27]

[0058]

[Chemical 28]

[0059]

[Chemical 29]

The optimum addition amount of these compounds varies depending on the kind thereof, but is 1.0 × 1 per mol of the hydrazine compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is preferably used in the range of 10 ^-1 mol to 5.0 x 10 mol. These compounds are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. can be used after dissolving. 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. It is also possible to create and use things. Alternatively, the redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited as silver halide, and any of silver bromide, silver iodobromide, silver chlorobromide and silver iodochlorobromide can be used. It can be used, but preferably has a silver chloride content of 50.
Silver chlorobromide and silver iodochlorobromide containing at least mol%. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol% or less. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of silver halide is 0.
It is preferably 1 μm to 0.7 μm, more preferably 0.
2 to 0.5 μm, and the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, and more preferably 10% or less with a narrow particle size distribution. preferable. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers. The photographic emulsion used in the present invention is described by P. Glafkides in Chimie et Physi.
que Photographique (Published by Paul Montel, 1967
), GF Dufin Photographic Emulsion Chemist
ry (The Focal Press, 1966), VL Zelikm
by an et al Making and Coating Photographic Emulsio
n (published by The Focal Press, 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 the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which 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 preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

The silver halide photographic light-sensitive material of the present invention may contain a rhodium compound in order to achieve high contrast and low fog. As a rhodium compound,
Water-soluble rhodium compounds can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium ( III) complex salts, trizalatrodium (III) complex salts and the like. These rhodium compounds are used by dissolving them in water or a suitable solvent, and a method which is generally performed to stabilize the solution of the rhodium compound,
That is, a method of adding 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 total amount of the rhodium compound added is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-6 mol. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. .

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention can contain at least one metal selected from rhenium, ruthenium and osmium. This content is 1 × 1 for 1 mol of silver
The range of 0 ^-9 mol to 1 x 10 ^-5 mol is preferable, and the range of 1 x 10 ^-8 to 1 x 10 ^-6 mol is more preferable. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and they are disclosed in JP-A-63-29603 and JP-A-2-306236.
No. 3-167545, No. 4-76534, Japanese Patent Application No. 4
As described in No. 68305, No. 4-258187, etc., they may be contained in the particles with a distribution. Rhenium, ruthenium and osmium are disclosed in JP-A-6
No. 3-2042, JP-A Nos. 1-285941 and 2-2.
No. 0852, No. 2-20855 and the like are added in the form of water-soluble complex salts. Particularly preferred are the hexacoordination complexes shown below. [ML ₆ ] ^-n Here, M represents Ru, Re, or Os, n is 0,
Represents 1, 2, 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferable ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands, thionitrosyl ligands and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[0066] ^{_{ReCl 6 -3 ReBr 6 -3 ReCl 5}} (NO) -2 Re (NS) Br 5 -2 Re (NO) (CN) 5 -2 Re (O) 2 (CN) 4 -3 RuCl 6 - ³ RuCl ₄ (H ₂ O) ₂ ^-1 RuCl ₅ (NO) ^-2 RuBr ₅ (NS) ^-2 Ru (CN) ₆ ^-4 Ru (CO) ₃ Cl ₃ ^-2 Ru (CO) Cl ₅ ^-2 Ru (CO) Br ₅ ^-2 OsCl ₆ ^-3 OsCl ₅ (NO) ^-2 Os (NO) (CN) ₅ ^-2 Os (NS) Br ₅ ^-2 Os (CN) ₆ ^-4 Os (O) ₂ (CN ) ₄ ^-4

The addition 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 added especially at the time of forming the emulsion and incorporated into the silver halide grains. It is preferable. To incorporate these compounds into the silver halide grains by adding them during the formation of silver halide grains, a powder of a metal complex or an aqueous solution dissolved together with NaCl or KCl is used to form a water-soluble salt or a water-soluble salt during grain formation. Method in which a silver halide grain is prepared by adding it into a water-soluble halide solution, or by adding as a third solution when a silver salt and a halide solution are mixed at the same time, and a three-liquid simultaneous mixing method, or grain formation There is a method in which a necessary amount of an aqueous solution of a metal complex is charged into a reaction vessel. Particularly preferred is a method of adding powder or an aqueous solution dissolved together with NaCl and KCl to the water-soluble halide solution. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex may be added to the reaction vessel immediately after the particles are formed, during or during physical ripening, or at the time of chemical ripening.

The silver halide photographic light-sensitive material of the present invention may contain an iridium compound in order to achieve high sensitivity and high contrast. As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium 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 iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ⁻⁶ mol is suitable, and preferably 1 × 10 ⁻⁸ to 1 ×.
It is 10 ^-6 mol. The addition of these compounds can be appropriately carried out at each stage before the production of the silver halide emulsion grains and before the coating of the emulsion, but it is particularly preferable to add them at the time of forming the emulsion and to incorporate them into the silver halide grains. . The silver halide grain in the present invention may be doped with another heavy metal salt. In particular, doping with an Fe salt such as K ₄ [Fe (CN) ₆ ] is advantageously performed.

Further, the silver halide grains used in the present invention may contain metal atoms such as cobalt, nickel, palladium, platinum, gold, thallium, copper and lead. The above metal is 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ per mol of silver halide.
Molar is preferred. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention is preferably chemically sensitized, and sulfur sensitization, selenium sensitization, tellurium sensitization,
Known methods such as reduction sensitization and noble metal sensitization can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

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

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
No. 3489, Japanese Patent Application Nos. 2-130976 and 2-229.
The compounds described in No. 300, No. 3-121798 and the like can be used. It is particularly preferable to use the compounds represented by the general formulas (VIII) and (IX) in Japanese Patent Application No. 3-121798.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to become a sensitizing nucleus, on the surface or inside of silver halide grains. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, J. Chem. Soc. Chem. Comm.
un., 635 (1980), ibid. 1102 (1979), ibid. 645 (1979), J. Chem. Soc. Perkin. Trans.,
1, 191 (1980), edited by S. Patai, The Chemistr
y of Organic Serenium and Tellurium Compounds, Vol
1 (1986) and the same Vol 2 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in Japanese Patent Application No. 4-146739 are preferable.

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

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, 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. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of forming silver halide grains or physically ripening them. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in European Patent (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). Different conditions) may be used together.

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, poly A variety of synthetic hydrophilic polymer substances such as a single or copolymer such as acrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl butyral and the like can be used.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item 1) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 from general formula (II-m) without (II-p) and compounds II-1 to II-22, The compounds described in JP-A-1-179939. 2) Surfactant JP-A-2-12236, page 9, right upper column, line 7 to antistatic agent, right lower column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to 4 Lower right column, line 18 3) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 Stabilizer, page 18 to upper right column, line 4 and lower right column, line 1 to line 5 Furthermore, the thiosulfinic acid compounds described in JP-A-1-237538. 4) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 5) Compounds having an acid group JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 From page 11, page 11, upper left column, line 8. 6) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 or plasticizer, page 19 upper right column, line 15 7) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 8) Dyes, JP-A-2-103536, page 17, lower right column, line 1 to line 18, and JP-A-2-39042, page 4, upper right column, column 1 line to page 6, upper right column, line 5. Further, the solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773. 9) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 10) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 11) Redox compounds Compounds represented by formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), and general formulas described in pages 3 to 20 of JP-A 3-1 74143. (R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 12) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 13) Dihydroxyben Compounds described in JP-A-3-39948, page 11, upper left column to first zen, page 2, lower left column, and EP 452,772A.

The developer for developing the silver halide photographic light-sensitive material of the present invention has a pH of 1 when processing a light-sensitive material utilizing the conventional hydrazine nucleation infectious development effect.
It is not necessary to use a developing solution of 1.0 or more, and a stable developing solution having a pH of 9.6 or more and 11.0 or less can be preferably used.

The developing agent used in the developing solution used in the present invention is not particularly limited, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl are preferable. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, and hydroquinone is particularly preferable. The developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention is 1-phenyl-3-pyrazolidone or 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-
3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-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. Two
-Methyl-p-aminophenol, p-benzylaminophenol and the like are available, and among them, N-methyl-p-aminophenol is preferable. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Further, when a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / liter to 0.5 mol / liter and the latter is 0.06. Mol /
It is preferably used in an amount of liter or less. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. Sulfite is 0.3
It is preferably at least mol / liter, more preferably at least 0.4 mol / liter. The upper limit is preferably 2.5 mol / liter, particularly 1.2. Alkaline agents used to set the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate, and potassium silicate. Contains a buffer. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-5
Mercapto-tetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, and anti-foggant such as benztriazole-based compounds such as 5-methylbenztriazole Well, it may further contain a toning agent, a surfactant, an antifoaming agent, a water softening agent, a hardener, etc., if necessary. In particular, JP-A-56-1
No. 06244 amino compound, JP-B-48-35
The imidazole compound described in No. 493 is preferable from the viewpoint of promoting development or increasing sensitivity. In the developer used in the present invention, a silver stain preventing agent is disclosed in JP-A-56-24347.
And the compounds described in JP-A-4-362942, the compound described in JP-A-62-212651 as a development unevenness preventing agent, and JP-A-61-267759 as a dissolution aid.
The compounds described in No. 1 can be used. The developer used in the present invention has a buffering agent as disclosed in JP-A-62-1862.
59, boric acid, saccharides (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphates (for example, sodium salt) described in JP-A-60-93433. , Potassium salt) and the like, and boric acid is preferably used.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or salts thereof), if necessary, in addition to the fixing agent, and preferably It has a pH of 3.8 or higher, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed, and is generally about 0.1
It is about 5 mol / liter. The water-soluble aluminum salt, which mainly acts as a hardening agent in the fixing solution, is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, particularly 0.01 mol / liter to 0.03 mol / l.
The liter is particularly effective. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like can be given. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. If desired, the fixer may contain preservatives (eg, sulfite, bisulfite),
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image storage improving agent (eg, potassium iodide), and a chelating agent can be included. Here, since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter. The fixing temperature and time are the same as in the case of development, and about 2
0 seconds to about 50 ° C and 10 seconds to 1 minute are preferred.

For washing water, an antifungal agent (see, for example, Horiguchi, "Chemistry of Antibacterial and Antifungal", JP-A-62-115154).
Compound described in the specification), a water washing accelerator (such as sulfite), and a chelating agent. According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and it is preferably at about 20 ° C. to about 50 ° C. for 10 seconds to 3 minutes. Drying is performed at about 40 ° C to about 100 ° C,
The drying time can be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes and 3 seconds.

Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 3,54 are applicable.
5,971 and the like, and is simply referred to as a roller conveyance type processor in this specification. The roller conveyance type processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Here, the water washing step is 2 to
Water saving can be achieved by using a three-stage countercurrent washing method.

The developing solution used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. The replenishing system described in JP-A-62-91939 can be preferably used as the developer used in the present invention.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[0087]

【Example】

Example 1 <Emulsion preparation> An emulsion was prepared by the following method. Aqueous silver nitrate solution, potassium bromide and sodium chloride, and K ₂ Rh (H ₂ O) Cl corresponding to 2 × 10 ^-7 mol per mol of silver
₅ and K ₃ Ir equivalent to 2 × 10 ^-7 mol per mol of silver
An aqueous solution of a halogen salt containing Cl ₆ and sodium chloride,
Silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 70 mol% were prepared by adding to a gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione by a double jet method while stirring.

Then, 1 × 10 ⁻³ mol of KI solution per mol of silver was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method.
After adding 40 g of gelatin per mol of silver and further adding 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid per mol of silver, pH 6.0, pAg
Adjusted to 7.8, added 3 mg sodium thiosulfate and 4 mg chloroauric acid per 1 mol of silver, chemically sensitized at 65 ° C. to obtain optimum sensitivity, and used 4-hydroxy-6-methyl as a stabilizer. 150 mg of -1,3,3a, 7-tetrazaindene was added, and proxel 100 was added as a preservative.
mg was added. The obtained grains were cubic grains of silver iodochlorobromide having an average grain size of 0.25 μm and a silver chloride content of 69.9 mol%. (Variation coefficient 10%)

<Preparation of coating sample> To the above emulsion, a sensitizing dye was added as shown in Table 1, and 3 × 10 ⁻⁴ mol of the mercapto compound represented by the following (a) per mol of silver, 4 × 10 4
^-4 mol of the mercapto compound represented by (b), 4 × 10
^-4 mol of the triazine compound represented by (c), 2 × 10
^-3 mol of 5-chloro-8-hydroxyquinoline, III-
The hydrazine derivative represented by 33 is 5 × per mol of silver.
10 ⁻⁴ mol, 1 × 10 1 of the nucleation accelerator represented by A-52.
^-3 mol was added. Further, N-oleyl-N-methyltaurine sodium salt was added so as to be coated at 30 mg / m ² , and the water-soluble latex shown in (d) was added at 200 mg / m ^2.
m ² , 200 mg / m ^{2 of} polyethyl acrylate dispersion,
200 mg / m ² of a latex copolymer of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7), and 1,3 as a hardener. -Divinylsulfonyl-2-propanol 20
0 mg / m ² was added. The pH of the solution was adjusted to 6.0. They were coated on a polyethylene terephthalate film having a moistureproof layer undercoating containing vinylidene chloride on both sides so that the coating silver amount was 3.0 g / m ² .

On these emulsion layers, as a protective layer, 1.0 g / m ² of gelatin, 40 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm, methanol silica of 0.1.
1 g / m ² , polyacrylamide 100 mg / m ² , sodium ethylsulfonate 5 mg / m ² , hydroquinone 200 mg
/ M ² , silicone oil 20 mg / m ^2, and a fluorosurfactant represented by the following structural formula (e) as a coating aid 5 mg /
m ² and sodium dodecylbenzene sulfonate 100mg /
m ² was applied. The back layer and the back protective layer were applied by the following formulation.

[0091]

[Chemical 30]

[Back Layer Formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0093]

[Chemical 31]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b] and dye [c] dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0095]

[Chemical 32]

[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-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

<Exposure and Development> The above sample was exposed to tungsten light through a step wedge, developed with a developer having the following composition for 30 seconds at 35 ° C., and then fixed, washed with water and dried. went. GR as fixer
-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used, and an FG-680A automatic processor (manufactured by Fuji Photo Film Co., Ltd.) was used for this development processing. The sensitivity was shown by the relative value of the reciprocal of the exposure amount that gives a density of 1.5. The value of Sample A was set to 100, and the higher the value, the higher the feeling. As an index (γ) that represents the contrast of the image, fog of the characteristic curve
The point of + density 0.3 to the point of fog + density 3.0 was connected by a straight line, and the slope of this straight line was expressed as a γ value. That is, γ
= (3.0-0.3) / [log (exposure amount that gives a density of 3.0) -log (exposure amount that gives a density of 0.3)], and the larger the γ value, the harder the photographic characteristics. It is shown that.
The black spots were evaluated by microscopically observing the actual spots, and "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. For the residual color, the actual portion when developed at 20 ° C. at 35 ° C. was observed with the naked eye and evaluated in 5 grades, with “5” being the best and “1” being the worst quality. "5" or "4" can be used practically, and "3" is poor, but can be managed practically,
"2" or "1" is impractical.

[Developer formulation] Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium metabisulfate 40.0 g Potassium carbonate 12.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.08 g 2,3 , 5,6,7,8-Hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 0.15 g hydroquinone 25.0 g 4-hydroxymethyl-4- Methyl-1-phenyl-3 pyrazolidone 0.45 g sodium erythorbate 3.0 g potassium hydroxide is added, water is added to make 1 liter and the pH is adjusted to 10.5. 1 liter

[0099]

[Table 1]

<Results> As shown in Table 1, it is understood that the samples of the present invention have high sensitivity and high γ, little residual color after processing, and few black spots.

Example 2 <Emulsion preparation> An emulsion was prepared in the same manner as in Example 1 except that the silver halide emulsion grains contained a dopant as shown in Table 2.

[0102]

[Table 2]

<Preparation of Coated Sample> A coated sample was prepared in the same manner as in Example 1 except that the sensitizing dye was added as shown in Table 3. <Exposure and development treatment> Exposure and development treatments were performed in exactly the same manner as in Example 1. <Results> The results are also shown in Table 3. It is understood that the samples of the present invention show good performance even when the type of metal dopant is changed.

Example 3 <Emulsion preparation> An emulsion was prepared in exactly the same manner as in Example 1 except that the silver halide emulsion grains were chemically sensitized under the following conditions. [CS-A] pH 6.0, adjusted to pAg 7.8, silver 1
3 mg of 1,3,3-triethyl-2-thiourea and 4 mg of chloroauric acid were added per mole, and chemical sensitization was performed at 65 ° C. for optimum sensitivity. [CS-B] pH 5.3, pAg 8.5 adjusted, silver 1
1 mg sodium thiosulfate and the following compound CS per mole
1 mg of -1 and 4 mg of chloroauric acid were added and chemically sensitized at 55 [deg.] C. to obtain the optimum sensitivity. [CS-C] pH 5.3, adjusted to pAg 8.5, silver 1
1 mg sodium thiosulfate and the following compound CS per mole
-2 and 1 mg of chloroauric acid were added and chemically sensitized at 55 [deg.] C. to obtain the optimum sensitivity.

[0105]

[Chemical 33]

<Preparation of Coated Sample> A coated sample was prepared in the same manner as in Example 1 except that the sensitizing dye was added as shown in Table 4. <Exposure and development processing> Exposure and development processing were performed in exactly the same manner as in Examples 1 and 2. <Results> The results are shown in Table 4. It is understood that the samples of the present invention show good performance even when the conditions of chemical sensitization are changed.

[0107]

[Table 3]

[0108]

[Table 4]

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one layer of the silver halide emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative, and the silver halide emulsion is spectrally sensitized with dyes of the following general formulas [I] and [II]. A silver halide photographic light-sensitive material characterized by the above. General formula [I] In the formula, X ₁ , X ₂ , X ₃ and X ₄ are a hydrogen atom, a cyano group,
It represents an alkyl group, a halogen atom, a halogen-substituted alkyl group, an alkylthio group, an alkoxycarbonyl group, or a carbamoyl group. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents a substituted or unsubstituted alkyl or alkenyl group, and R ₁ , R ₂ , R ₃ or R ₄
At least one of them is a group having a sulfo group or a carboxy group. Y ₁ represents a counter ion necessary for neutralizing the electric charge. n ₁ represents 0 or 1, and is 0 in the case of an inner salt. General formula [II] In the formula, Q represents an atom necessary for forming a substituted or unsubstituted benzoxazole or thiazoline nucleus, and R
₂₁ is an acid-substituted or acidic salt-substituted alkyl group, R ₂₂
And R ₂₃ are each an alkyl group, or R ₂₂ and R _23
23 together form an alkylene unit forming a heterocycle with the nitrogen atom to which they are attached, L ₂₁ , L
₂₂ , L ₂₃ and L ₂₄ are each a substituted or unsubstituted methine group. 2. An image forming method, wherein the silver halide photographic light-sensitive material according to claim 1 is developed with a developer having a pH of 9.6 or more and less than 11.0.