JPH09106040A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material with excellent safe-light safety, high sensitivity and excellent conservation stability. SOLUTION: A silver halide photosensitive material has a silver halide emulsion layer and a hydrophilic colloid layer on a support, either the silver halide emulsion layer or the hydrophilic colloid layer containing dye shown in a general formula. (In the formula, R<1> represents a branched alkyl group and R<2> represents a hydrogen atom or a substitutional group. R<3> and R<4> represent hydrogen atoms, aliphatic hydrocarbon groups, acyl groups or sulfonyl groups. R<2> , R<3> and R<4> can be connected one another to form five or six circles. (m) represents 0, 1 or 2. If (m) is 2, R<2> can be the same or different. L<1> , L<2> and L<3> represent methine groups which can be substituted one another. (n) represents 0 or 1 but has at least one sulfo group or its salt in molecules).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material having a dyed layer, and more particularly to a silver halide photographic light-sensitive material having a filter layer.

[0002]

2. Description of the Related Art In a silver halide photographic material, a photographic emulsion layer and other hydrophilic colloid layers are often colored in order to absorb light in a specific wavelength range. When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, the filter layer may be located between them. An image based on light scattered when passing through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the photosensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. For the purpose of preventing blurring or halation, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an antihalation layer may be provided between the layers. The photographic emulsion layer is also colored in order to prevent a reduction in image sharpness (this phenomenon is generally called irradiation) due to light scattering in the photographic emulsion layer. For example, in the photoengraving process in the field of print reproduction, particularly in the work processes of plate collection and reversal, work efficiency and work environment have been improved by performing work in a brighter environment. For this reason, there is provided a silver halide photographic light-sensitive material for plate making that can be handled under an environment that can be called a bright room under safelight light. A coloring layer is provided by adding a filter dye such as a yellow dye or an ultraviolet absorbing dye into the photosensitive material.

It is natural that the dyes used in these layers do not adversely affect the photographic properties such as fog or rapidly decolorize in the developing process, but they have a proper spectral absorption according to the purpose of use. Must, in addition,
It is necessary for the photographic material to have good stability over time and not discolor or fade.

Until now, much effort has been made to find dyes satisfying the above conditions. For example, Japanese Patent Publication No. 5-54098 and Japanese Patent Laid-Open No. 2-165.
The arylidene dyes described in JP-A No. 135 and JP-A No. 1-196040 are proposed.

[0005]

However, the specific dyes disclosed in these publications still do not provide satisfactory spectral absorption. That is, when the safe light property is attempted to be satisfied because the bottom of the absorption spectrum at the wavelength end is not sufficient, the sensitivity at the appropriate exposure wavelength in the light-sensitive material is decreased, and sufficient sensitivity should be provided. Then, there is a problem that the safety of the safelight is lowered. On the other hand, the arylidene dyes containing isoxazolone as an acidic nucleus, which are described in U.S. Pat. No. 3,0028,37, JP-A-58-83841, JP-A-58-38950, etc., have a preferable absorption spectrum at the end of wavelength. However, there was a problem with the storage stability in the light-sensitive material, and the density decreased with time. An object of the present invention is to provide a light-sensitive material containing a novel dye having an appropriate spectral absorption property as a filter dye, having high sensitivity, excellent safety in safelight, and good storage stability.

[0006]

The above object of the present invention has been attained by the following means. (1) A silver halide emulsion layer and a hydrophilic colloid layer are provided on a support, and any one of the silver halide emulsion layer and the hydrophilic colloid layer contains a dye represented by the following general formula (I). Silver halide photographic light-sensitive material.

[0007]

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In the formula, R ¹ represents a branched alkyl group,
R ² represents a hydrogen atom or a substituent. R ³ and R ⁴ represent a hydrogen atom, an aliphatic hydrocarbon group, an acyl group or a sulfonyl group. R ² , R ³ and R ⁴ may be connected to each other to form a 5- or 6-membered ring. m represents 0, 1 or 2. When m = 2, R ² may be the same as or different from each other. L ¹ , L ² and L ³ each represent an optionally substituted methine group, and n represents 0 or 1. However, it has at least one sulfo group or a salt thereof in the molecule. (2) The silver halide photographic light-sensitive material according to the above (1), wherein in the general formula (I), R ¹ is a secondary or tertiary alkyl group. (3) The silver halide emulsion layer is Ir, Ru, Rh, R
The silver halide according to (1) above, which contains at least 1 × 10 ⁻⁶ mol of a heavy metal selected from e and Cr per mol of silver halide and contains silver halide grains having a silver chloride content of 95 mol% or more. Photographic material.

By using the light-sensitive material of the present invention, it was possible to improve the safelight property and increase the storage stability without lowering the photographic sensitivity.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION General formula (I) used in the present invention is as follows.
The compound will be described in detail. The branched alkyl group represented by R ¹ is preferably a branched alkyl group having 3 to 12 carbon atoms, and more preferably 3 to 8 carbon atoms. Particularly preferred is a secondary or tertiary alkyl group having 3 to 8 carbon atoms. Examples of branched alkyl groups include isopropyl, sec-butyl, isobutyl,
tert-butyl, 1-methylbutyl, neopentyl,
tert-pentyl, 2-ethylhexyl, tert-
Octyl, 1-ethylcyclopropyl, cyclohexyl and the like can be mentioned.

The substituent represented by R ² is, for example, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (for example,
Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl,
Diethylaminoethyl, hydroxyethyl, chloroethyl, acetoxyethyl, etc.), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, carboxybenzyl, etc.), a substituted or unsubstituted aryl group having 6 to 18 carbon atoms ( For example, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, etc.), a substituted or unsubstituted acyl group having 2 to 6 carbon atoms (eg, acetyl, propionyl, butanoyl). , Chloroacetyl, etc.),
A substituted or unsubstituted sulfonyl group having 1 to 8 carbon atoms (eg, methanesulfonyl, p-toluenesulfonyl, etc.), an alkoxycarbonyl group having 2 to 6 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, etc.), 7 carbon atoms 12 aryloxycarbonyl groups (eg, phenoxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenylcarbonyl, etc.), substituted or unsubstituted alkoxy groups having 1 to 4 carbon atoms (eg, methoxy, ethoxy, n-butoxy, Methoxyethoxy, etc.), substituted or unsubstituted aryloxy having 6 to 10 carbon atoms (eg, phenoxy, 4-methoxyphenoxy, etc.), substituted or unsubstituted acyloxy having 2 to 8 carbon atoms (eg, acetoxy, ethylcarbonyloxy). , Cyclohexyl Ruboniruokishi, benzoyloxy, chloro acetyloxy etc.), from 1 to 6 carbon atoms
A substituted or unsubstituted sulfonyloxy (eg, methanesulfonyloxy, etc.), a carbamoyloxy group having 2 to 8 carbon atoms (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), a substituted or unsubstituted group having 0 to 8 carbon atoms An amino group (for example, an unsubstituted amino,
Methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, phenylcarbamoylamino, acetylamino, Ethylcarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino, p-toluenesulfonylamino, etc.), a substituted or unsubstituted carbamoyl group having 1 to 8 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl) , Ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinoca Bamoiru pyrrolidinopyridine carbamoyl, etc.), a halogen atom (e.g., fluorine, chlorine, bromine), a hydroxyl group, a nitro group, a cyano group, a carboxy group.

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. Particularly preferably, it is a hydrogen atom or an alkyl group.

The aliphatic hydrocarbon group represented by R ³ and R ⁴ is, for example, an alkyl group having 1 to 6 carbon atoms (for example,
Methyl, ethyl, n-propyl, n-butyl, isopropyl, etc.), an aralkyl group having 7 to 15 carbon atoms (eg,
Benzyl, phenethyl, etc.), an alkenyl group having 1 to 6 carbon atoms (eg, allyl, 3-hexenyl, etc.) and the like are preferable, and these may have a substituent (eg, the aforementioned substituents and the like). An alkyl group is more preferable, and an unsubstituted alkyl group is still more preferable.

The acyl group represented by R ³ and R ⁴ preferably has 2 to 8 carbon atoms, and examples thereof include acetyl, propionyl, pivaloyl, hexanoyl, benzoyl and 2-methylpropionyl.

The sulfonyl group represented by R ³ and R ⁴ preferably has 1 to 8 carbon atoms, and examples thereof include methylsulfonyl, ethylsulfonyl, butylsulfonyl, phenylsulfonyl and p-toluenesulfonyl.

The 5- or 6-membered ring formed by linking R ² , R ³ or R ⁴ is a piperidine ring,
Examples thereof include a pyrrolidine ring.

The methine group represented by L ¹ , L ² and L ³ may have a substituent (for example, a methyl group, an ethyl group, a cyano group, a chlorine atom, etc.), but is unsubstituted. Preferably there is. It is preferable that n is 0.

It is preferable that m is 1 or 2. Particularly preferably, m = 1.

As a preferred combination, R ¹ is a branched alkyl group having 3 to 8 carbon atoms, R ² is a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, and R ³ and R ⁴ are hydrogen atoms. Alternatively, it is an alkyl group, n = 0, and m = 1. Particularly preferably, R ¹ is secondary or tertiary having 3 to 8 carbon atoms.
Primary alkyl group, R ² is a hydrogen atom or an alkyl group, R ³ and R ⁴ are alkyl groups, and n = 0.
And the combination of m = 1.

However, at least one dye molecule of the present invention is used.
It has one sulfo group or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, etc.).

Specific examples of the compound used in the present invention are shown below, but the present invention is not limited thereto.

[0022]

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[0023]

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The compound of the present invention is obtained by converting the compound represented by the following general formula (II) and the following general formula (III) into an organic solvent (for example, methanol, ethanol, isopropyl alcohol, acetonitrile, N, N-dimethylformamide, N, N-
Dimethylacetamide, acetic acid, pyridine, etc.) at room temperature or under heating under reflux.

[0025]

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When the reaction proceeds slowly, it can be easily synthesized by adding an appropriate amount of acetic acid, acetic anhydride, p-toluenesulfonic acid, triethylamine, pyridine, ammonium acetate or the like. The compound represented by the general formula (II) can be synthesized by the condensation ring-closing reaction of the corresponding β-ketoester and hydroxylamine as shown in formula 1. Specifically, "The Chemistry of Heterocyclic Compounds
(Weissberg, A. Ed., John Wiley & Sons, Inc.), Volume 17, pages 117 to 124 (1962) and the like.

[0027]

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Next, a specific synthesis example of the dye will be described.

Synthesis Example 1 Synthesis of Dye I-1 3-tert-Butyl-5-isoxazolone 1.6 g
And [N-ethyl-N- (2-sulfoethyl)] amino-
35 ml of ethanol was added to 3.4 g of 2-methylbenzaldehyde sodium salt, and the mixture was heated under reflux for 3 hours. After cooling to room temperature, the precipitated crystals were filtered and washed with ethanol. After drying, 3.4 g of dye I-1 was obtained. λmax
= 498nm (H ₂ O).

Synthesis Example 2 Synthesis of Dye I-6 A similar method except that 1.5 g of 3-isopropyl-5-isoxazolone was used in place of 3-tert-butyl-5-isoxazolone in Synthesis Example 1. With dye I
3.1 g of -6 was obtained. λmax = 498 nm (H2
O).

Synthesis Example 3 Synthesis of Dye I-3 2.8 g of 3-tert-butyl-5-isoxazolone
And [N-methyl-N- (2-sulfoethyl)] aminobenzaldehyde sodium salt 5.2 g ethanol 50.
ml was added and the mixture was heated under reflux for 3 hours. After cooling to room temperature, the precipitated crystals were filtered and washed with ethanol. After drying,
5.1 g of dye I-3 was obtained. λmax = 485 nm
(H ₂ O).

Synthesis Example 4 Synthesis of Dye I-9 In Synthesis Example 3, 3-tert-butyl-5-isoo was prepared.
Instead of xazolone, 3- (1-ethylcyclopropyl
Same as above, except that 3.1 g of))-5-isoxazolone was used.
By a similar method, 1.8 g of Dye I-9 was obtained. λmax =
483 nm (H _TwoO).

The compound represented by the general formula (I) can be used in any effective amount, but the optical density is from 0.05 to
It is preferable to use it in the range of 3.0. The addition amount is 1 to 1000 mg per 1 m ² , preferably 20 to 800 mg, and more preferably 50 to 5 mg.
00 mg. The time of addition may be any step before coating. The compound represented by the general formula (I) is contained in the hydrophilic colloid layer. As the hydrophilic colloid layer, an emulsion layer and other hydrophilic colloid layers (filter layer,
(Protective layer, intermediate layer, antihalation layer, back layer, etc.)
It may be used in any of the above, and may be used in a plurality of layers.

It is also possible to use in combination with other dyes, and in this case, they may be used in the same layer or different layers. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . These dyes can be added by dissolving in water when they are water-soluble, and can be added as solid fine particle dispersions when they are hardly soluble in water. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer. As a hydrophilic colloid,
Gelatin is a typical one, but any of those conventionally known as those usable for photographic use can be used.

The silver halide emulsions used in the light-sensitive material of the present invention include silver bromide, silver iodide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodobromide and silver chloride. preferable. Particularly preferred are silver chlorobromide, silver chloroiodobromide and silver chloride in which 95 mol% or more, particularly 99% mol% or more, is composed of silver chloride.

The halide emulsion of the silver halide photographic light-sensitive material used in the present invention has an average grain size of 0.20 μm.
m or less is preferable. In particular, it is preferably 0.08 to 0.16 μm. In the present invention, silver halide grains are prepared by mixing at a reaction temperature of 50 ° C. or lower, preferably 40 ° C. or lower, and a silver potential of 70 mV or higher, preferably 30 at a sufficiently high stirring speed for uniform mixing.
0 mV to 400 mV or 5,6-cyclopentane-
Good results can be obtained by preparing at 80 mV to 120 mV in the presence of a stabilizer such as 4-hydroxy-1,3,3a, 7-tetrazaindene. The particle size distribution is basically not limited, but monodisperse particles are preferred. The term "monodisperse" as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within + -40% of the average particle size, and more preferably +-.
It is within 20%. The silver halide grains of the present invention are cubic, those having a regular crystal form such as octahedron, spherical,
It has an irregular crystal form such as a plate, or has a composite form of these crystal forms. Further, a mixture of particles having various crystal forms can be used, but those having a regular crystal form are preferable, and a cube is particularly preferable.

The silver halide emulsion of the present invention comprises Ir, R
A heavy metal selected from u, Rh and Re may be contained. Preferred as these heavy metals are metal coordination complexes, and hexacoordination complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (In the formula, M is a heavy metal selected from Ir, Ru, Rh, and Re. L is a bridging ligand. Y is oxygen or sulfur. M = 0, 1, 2 and n = 0, -1, -2,-
3. ) Preferred examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyan Nate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands. Specific examples of the metal coordination complex are shown below. M-1. [Rh (H ₂ O) Cl ₅ ] ^-2 M-2. [RhCl ₆ ] ^-3 M-3. [Ru (NO) Cl ₅ ] ^-2 M-4. [RhCl ₆ ] ^-3 M-5. [Rh (H ₂ O) Cl _5] ^-2 M-6. _{[Ru (NO) (H 2 O} ) Cl 4 ] ^-1 M-7. [Re (NO) Cl ₅ ] ^-2 M-8. [Ir (NO) Cl _5] ^-2 M-9. [Ir (H ₂ O) Cl _5] ^-2 M-10. _{[Re (H 2 O) 5 Cl} 5 ] ^-2 M-11. [RhBr ₆ ] ^-3 M-12. [ReCl ₆ ] ^-3 M-13. [IrCl ₆ ] ^-3 M-14. (Re (NS) Cl ₄ (SeCN)) ^-2

The metal complex can be added to the silver halide during grain preparation. The content of the heavy metal in the silver halide grains of the present invention is from 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide. It is preferably 10 ^{−6 to} 3 × 10 ⁻⁴ mol. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grain is not particularly limited, but it is preferable that the heavy metal is more present outside the grain.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, known methods can be used. For example, sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known, and any of these may be used alone or in combination for chemical sensitization. Of these, gold and sulfur sensitization with gold sensitization and sulfur sensitizers,
Gold sulfur selenium sensitization and gold selenium sensitization, which are combinations of these with a selenium sensitizer, are preferable, and gold sulfur selenium sensitization is particularly preferable.

As the selenium sensitizer used in the present invention, 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.
JP-A-4-25832 and JP-A-4-109240.
It is preferable to use the compounds described in Japanese Patent Application No. 3-92929 and Japanese Patent Application No. 3-92929. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropion, 2-
(Selenobutyric acid), selenoesters, diacylselenides, (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. The non-unstable selenium compound used in the present invention is Japanese Patent Publication No. 46-45.
No. 53, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 52-
The compound described in 34491 is 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. General formula (A)

[0041]

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In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents 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 (eg, a pyridyl group, a thienyl group, a furyl group, an imidazolyl group), -NR ₁ (R ₂ ),-
Represent OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, 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. Where R
₁ and R ₂ represent a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) ). In formula (A), Z ₁ is preferably an alkyl group, an aryl group or —NR
₁ (R ₁ ) and Z ₂ represents —NR ₅ (R ₆ ). R ₁ ,
R ₂ , R ₅ and R _{6, which} may be the same or different, 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-
Represents an alkyl-N-aryl-arylselenoamide. General formula (B)

[0043]

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Where Z_Three, Z_FourAnd Z_FiveAre the same
May be different, aliphatic group, aromatic group, heterocyclic group,
-OR₇, -NR₈(R₉), -SR_Ten, -SeR₁₁, X,
Represents a hydrogen atom. R₇, R_TenAnd R₁₁Is an aliphatic group,
Represents an aromatic group, heterocyclic group, hydrogen atom or cation
Then R₈And R₉Is an aliphatic group, aromatic group, or heterocyclic group.
Or a hydrogen atom, and X represents a halogen atom. one
In general formula (B), Z _Three, Z_Four, Z_Five, R₇, R₈,
R₉, R_TenAnd R₁₁The aliphatic group represented by
Branched or cyclic alkyl group, alkenyl group, alkynyl
Group, aralkyl group (for example, methyl group, ethyl group, n-
Propyl group, isopropyl group, t-butyl group, n-butyl
Group, n-octyl group, n-decyl group, n-hexadecyl
, Cyclopentyl, cyclohexyl, allyl
Group, 2-butenyl group, 3-pentenyl group, propargyl
Group, 3-pentynyl group, benzyl group, phenethyl group)
Express. In the general formula (B), Z_Three, Z_Four, Z_Five, R
₇, R₈, R₉, R_TenAnd R ₁₁Aromatic group represented by
Is a monocyclic or condensed aryl group (for example, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphen
Represents a nyl group). In the general formula (B), Z_Three,
Z_Four, Z_Five, R₇, R₈, R₉, R_TenAnd R₁₁Represented by
The heterocyclic group is a nitrogen atom, oxygen atom or sulfur atom.
A saturated 3- to 10-membered ring containing at least one of them, or
Unsaturated heterocyclic groups (eg, pyridyl group, thienyl group,
Furyl group, thiazolyl group, imidazolyl group, benzimi
Dazolyl group). In the general formula (B), R₇,
R_TenAnd R₁₁The cation represented by
Halogen represented by X, which represents a child or ammonium
For example, fluorine atom, chlorine atom, bromine atom or
Represents an iodine atom. In general formula (B), preferably
Z_Three, Z_FourOr Z_FiveIs an aliphatic group, an aromatic group or -O
R₇And R₇Represents an aliphatic group or an aromatic group
You. In formula (B), more preferably trialkylphosphine
Fin selenide, triarylphosphine selenide,
Lialkylselenophosphate or triarylselele
Represents nophosphate. In the general formulas (A) and (B)
Specific examples of the represented compounds are described in Japanese Patent Application No. 6-250156.
Described compound examples I-1 to I-20 and II-21 to II-4
3 can be mentioned.

Specific examples of selenium sensitizers which are particularly preferable for exhibiting the effects of the present invention are shown below, but the present invention is not limited thereto.

[0046]

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[0047]

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[0048]

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[0049]

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The addition amount of the selenium sensitizer varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but is 1 × 10 ⁻ per mol of silver halide. ^It is preferably ⁷ mol or more and 5 × 10 ⁻⁴ mol or less.

As the gold sensitizer, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is preferably 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.
Known sulfur sensitizers can be used.
For example, thiosulfates, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like can be mentioned. Other US Patent No. 1,57
No. 4,944, No. 2,410,689, No. 2,2
No. 78,947, No. 2,728,668, No. 3,
Nos. 501,313 and 3,656,955, German Patent 1,422,869, JP-B-56-2
The sulfur sensitizers described in Japanese Patent No. 4937, JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains, but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide. 5x
It is preferably 10 ^-4 mol or less. Chemical sensitization with these sensitizers is performed by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain period of time after the addition of the sensitizer.

In addition to these sensitizers, noble metals such as platinum and palladium, primary tin salts, amines, reduction sensitizers such as formamidinesulfinic acid and silane compounds may be used in combination.

In the present invention, a hydrazine nucleating agent and a nucleating accelerator may be contained in the silver halide emulsion layer or other hydrophilic colloid layer. Preferred hydrazine nucleating agents are Japanese Patent Application Nos. 7-37814 and 7-27.
No. 845, a hydrazine derivative having a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine or an anionic group not forming an intramolecular hydrogen bond in the vicinity of the hydrazine group. The hydrazine nucleating agent is dissolved in a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Can be used. Also, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, hydrazine derivative powder is ball milled in water,
It can be dispersed and used by a colloid mill or an ultrasonic wave.

The hydrazine nucleating agent 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 layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol, and further preferably 5 ×, to 1 mol of silver halide.
Most preferably, it is 10 ⁻⁵ to 1 × 10 ⁻³ mol. Examples of the hydrazine-based nucleating agent used in the present invention include, in addition to those described above, RESEARCH DISCLOSURE Item 23516 (November 1983, P.346) and documents cited therein, and US Pat. No. 207, 4,269,
929, 4,276,364, 4,278,7
No. 48, No. 4, 385, 108, No. 4, 459, 34
No. 7, No. 4,478, 928, No. 4, 560, 638
Nos. 4,686,167 and 4,912,016
No. 4,988,604 and 4,994,365
No. 5,041,355, No. 5,104,769
No., British Patent No. 2,011,391B, European Patent No. 2
No. 17,310, No. 301,799, No. 356,89
No. 8, JP-A-60-179734 and JP-A-61-1707.
No. 33, No. 61-270744, No. 62-17824.
No. 6, No. 62-270948, No. 63-29751.
No. 63-32538, No. 63-104047,
63-121838, 63-129337, 63-223744, 63-234244, 6
3-234245, 63-234246, 63
-294552, 63-306438, 64-
10233, JP-A-1-90439, 1-100
No. 530, No. 1-105941, No. 1-105943
No. 1, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-283549, No. 1-2.
No. 85940, No. 2-2541, No. 2-77057.
No. 2, No. 2-139538, No. 2-196234, No. 2-196235, No. 2-198440, No. 2-1.
No. 98441, No. 2-198442, No. 2-2200.
42, 2-221953, 2-221954.
No. 2-285342, 2-285343, 2-289843, 2-302750, 2-3.
04550, 3-37642, 3-54549.
No. 3, No. 3-125134, No. 3-184039, No. 3-240036, No. 3-240037, No. 3-2.
59240, 3-280038, 3-2825.
No. 36, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230233, No. 4-96.
053, 4-216544, 5-45761.
No. 5, No. 5-45762, No. 5-45763, No. 5-
455764, 5-45765, and Japanese Patent Application No. 5-949.
Those described in No. 25 can be used in combination.

The nucleation accelerator used in the present invention includes
Examples thereof include amine derivatives, onium salts, disulfide derivatives, hydroxymethyl derivatives, acetylene derivatives, and urea derivatives. Particularly preferred are onium salts.

As the amine derivative, for example, JP-A-7-
Compounds represented by (Chemical formula 21), (Chemical formula 22) and (Chemical formula 23) described in No. 84331, and specifically, pages 6 to 8 of the publication.
Page, compounds represented by the general formula [Na] described in JP-A No. 7-104426, specifically, compounds Na-1 to Na-22 described on pages 16 to 20 of the publication. And compounds represented by the general formulas (1), (2), (3), (4), (5), (6), and (7) described in Japanese Patent Application No. 7-37817, Specifically, the compounds 1-1 to 1-19, the compounds 2-1 to 2-22, the compounds 3-1 to 3-36, and the compounds 4-1 to 4-5 described in the same specification. The compounds 5-1 to 5-41, the compounds 6-1 to 6-58, the compounds 7-1 to 7-38 and the like can be mentioned.

The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A Nos. 62-250439 and 62-250439.
The compounds described in Japanese Patent Application No. 280733 and Japanese Patent Application No. 7-27845 can be mentioned. Further, examples of preferable phosphonium salts are JP-A-61-167939.
The compounds described in JP-A No. 62-280733, Japanese Patent Application No. 7-27845 and the like can be mentioned.

Examples of the disulfide derivative include compounds described in JP-A-61-198147. As the hydroxy derivative, for example, US Pat.
698956, 4977118 and EP23185.
Examples thereof include compounds described in No. 0 and JP-A No. 62-50829, and more preferably a diarylmethacanol derivative. Examples of the acetylene derivative include compounds described in JP-A-3-168735, JP-A-2-271351 and the like. Examples of the urea derivative include compounds described in JP-A-3-168736.

Using the silver halide light-sensitive material of the present invention,
In order to obtain ultra-high contrast photographic characteristics, it has been used in printing materials.
It is not necessary to use the conventional infectious developer or the highly alkaline developer described in U.S. Pat. No. 2,419,975, which has a pH close to 13, and a stable developer can be used. That is, the silver halide light-sensitive material of the present invention contains sulfite ion as a preservative in an amount of 0.15 mol / liter or more and has a pH of 9.5.
A sufficiently high-contrast image can be obtained with a developing solution of about 11.0. As a specific example, Japanese Patent Application No. 7-2784.
No. 5 p-23-31.

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 This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectral sensitization described in JP-A Nos. 1-112235, 3-124560, 3-79928, 5-11389, and 4-330434. Pigment. 2) Surfactants, antistatic From JP-A-2-12236, page 9, upper right column, line 7 or the same, from antistatic agent, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 3) Antifoggant, Stability JP-A-2-103536, page 17, lower right column 19, agent line to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Compound having an acid group From 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 Page 11, upper left column, line 8. 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 7) Dye JP-A-2-103536, page 17, lower right column, line 1 to line 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 Dyes described in Kaihei 2-294638 and JP-A-63-296039. Further, solids described in WO88 / 04794, European Patent No. 456148, JP-A-5-11382, Japanese Patent Application No. 5-224717, Japanese Patent Application No. 6-117454, and the like. Disperse dye. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox compounds Compounds represented by formula (I) in JP-A-2-301743 (particularly compound examples 1 to 50), JP-A-3-174143, pages 3 to 20 Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 11) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to items, page 12, lower left column, and European Patent No. 452,772. 13) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. Further, in Japanese Patent Publication No. 46-22507, Japanese Patent Publication No. 50-73625, US Pat. Nos. 34 88708, 3939130, 392 9482, and Japanese Patent Application No. 5-300182, or in the specification. Polymer latices having active methylene groups as described. 14) Organic desensitizers Compounds described in Japanese Patent Publication No. 3-76450, JP-A No. 63-64039, Japanese Patent Application No. 6-117454, etc. or the description thereof.

[0061]

EXAMPLES The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto. Example 1 <Emulsion preparation> Emulsion A; sodium chloride kept at 40 ° C. and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per mol of silver, 5 × 10 ⁻³ mol of 4-hydroxy-6.
-Methyl-1,3,3a, 7-tetrazaindene in a 1.5% gelatin aqueous solution having a pH of 2.0 and an aqueous silver nitrate solution and 3.5 × 10 ^-6 mol of (NH ₄ ) per 1 mol of silver Rh (H ₂ O)
An aqueous solution of sodium chloride containing Cl ₅ was simultaneously added by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds so that half of the silver amount of the final particles was added to adjust 0.12 μm of particles in the core. After that, 10.5 per mol of silver nitrate aqueous solution and silver
A sodium chloride aqueous solution containing (× 10 ⁻⁶ ) mol of (NH ₄ ) Rh (H ₂ O) Cl ₅ was added in the same manner as above for 7 minutes to give an average particle size of 0.1
6 μm silver chloride cubic grains were prepared. (Coefficient of variation 12
%) Then, after washing with water by a flocculation method well known in the art to remove soluble salts, gelatin was added, pH was adjusted to 5.7 and pAg was 7.5, and further per mol of silver 4 × 10 ^-5 mol of chloroauric acid, 1 × 10 ^-5
After adding moles of sodium thiosulfate and heating at 60 ° C. for 60 minutes for chemical sensitization, compound-A and phenoxyethanol as preservatives were added at 60 mg per mol of silver and 4-hydroxy-6-methyl as stabilizer. -1, 3, 3a,
7-Tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver. (As final particles, pH = 5.7, pAg =
7.5, Rh = 7 × 10 ⁻⁶ mol / Ag mol. )

Emulsion B; the metal species doped in grain formation is K ₂ Ru (NO) Cl ₅ , and the doping amount is 3.5 × 1.
Doping with an equal amount of particles of 0 ^-6 mol / Ag mol,
The chemical sensitization method uses 4 × 10 ⁻⁵ mol of chloroauric acid, 1 × 10 ⁻⁵ mol of sodium thiosulfate, and 1 mol of silver per mol of silver.
After adding 10 × ^-5 mol of selenium sensitizer SE-4, 60 ° C.
Preparation was made in the same manner as in Emulsion A except that the heating was performed for 60 minutes.

<Preparation of Coating Solution for Emulsion Layer and Coating Thereof> The following compounds were added to the emulsions shown in Table 1, and the coating amount of gelatin was 0.9 g / m ² on the following support including the subbing layer and the coating silver. Amount 2.
A silver halide emulsion layer was coated so as to have a weight of 7 g / m ² . Emulsion layer coating liquid 1-Phenyl-5-mercapto-tetrazole 1 mg / m ² compound-W (nucleating accelerator) 20 mg / m ² compound-Y (hydrazine-based nucleating agent) 20 mg / m ² N-oleyl-N- Methyltaurine sodium salt 10 mg / m ² compound-B 10 mg / m ² compound-C 10 mg / m ² compound-D 10 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl 760 mg / m ² methacrylate / acrylic acid copolymer (89/8/3) Compound-E (hardening agent) 105 mg / m ² sodium polystyrene sulfonate 57 mg / m ² (pH adjusted to 5.6)

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

<Preparation of Emulsion Protecting Lower Layer Coating Solution and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.6 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.6 g / m ² p-sodium dodecylbenzene sulfonate 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 2700ppm) 0.45g / m ² Amorphous silica matting agent 40mg / m ² (Average particle size 3.5μ, Pore diameter 25Å, Surface area 700m ² / g) Amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² p-sodium dodecylbenzenesulfonate 30 mg / m ² compound- A 1 mg / m ² liquid paraffin 40 mg / m ² water-soluble dye (coating amount shown in Table 1) 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 Liquid for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution so that the coating amount of gelatin was 0.
It was coated so as to be 06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 186 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 60 mg / m ² p-sodium dodecylbenzenesulfonate 13 mg / m ² dihexyl-α- Sulfosuccinate sodium 12 mg / m ² Polystyrene sodium 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 30ppm) 1.94mg / m ² Polymethyl methacrylate fine particles (average particle size 3.4μ) 15mg / 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 p-sodium dodecylbenzenesulfonate 7 mg / m ² dihexyl-α-sulfosuccinate sodium 29 mg / m ² compound-L 5 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine 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) Biaxially stretched polyethylene terephthalate supports (thickness: 100 μm) were coated with the first and second undercoat layers having the following compositions on both sides. <Undercoat 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 (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. The dry film thickness was 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 Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm. Sample 1
16 were produced.

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[0073]

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[0074]

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<Coating Method> On the support having the above-mentioned undercoat layer, first, from the side closer to the support as the emulsion surface side, the emulsion layer, the emulsion protection lower layer, and the emulsion protection upper layer were sequentially held at 35 ° C. in a slide hopper. Simultaneous multi-layer coating while adding a hardener solution according to the method and passing through a cold air set zone (5 ° C), and then the conductive layer and the back layer in this order from the side closer to the support on the side opposite to the emulsion side. Simultaneous multi-layer coating was performed by adding a hardener solution by a slide hopper method, and a cold air set zone (5 ° C.) was applied. At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time was 180 m / min.

<Drying conditions> After setting, the product was dried with a drying air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and 8
Dry 200 to 200% with dry air at 35 ° C and 30%, apply air as it is, and after 30 seconds from when the surface temperature reaches 34 ° C (assuming the end of drying), dry for 1 minute at 48 ° C and 2% air. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 35 from 800 to 200%.
Seconds, 5% from 200% to the end of drying. This sensitive material was wound up at 23 ° C and 40%, and then cut under the same environment, and 3
A barrier bag subjected to time humidity control was subjected to humidity control at 40 ° C. 10% for 8 hours, and then sealed with cardboard which had been humidity controlled at 23 ° C. 40% for 2 hours to prepare samples shown in Table 1.

<Evaluation Method> Practical Skill Sensitivity In order to evaluate the practical skill sensitivity, a manuscript “transparent embedment base / line drawing positive image having the structure shown in FIG. 1 of Japanese Patent Publication No. 28856/1990 was formed. Film (line drawing original) / transparent embedment base / film on which a halftone image is formed (halftone original) "in this order, and bring this original and the emulsion side of each sample into close contact. Then, it was exposed with a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and it was treated with an automatic processor FG-680AG manufactured by Fuji Photo Film Co., Ltd. and a developer 1 at 38 ° C. for 20 seconds, fixed, washed with water and dried. The fixer used was fixer 1. In addition, DIA Rayon P-1 manufactured by Mitsubishi Rayon Co., Ltd. between the light source and the sample during exposure.
Exposure was performed with a 003 mm thick filter (having a transmittance of 50% at 393 nm, which absorbs light on the shorter wavelength side and transmits light on the longer wavelength side).

At this time, the halftone dot% of the halftone dot original is 50%,
The practical sensitivity refers to the exposure amount (exposure count number) at which the sample subjected to the exposure treatment forms 50% of the halftone dot, and the sensitivity of the sample 1 is 1
The other samples were represented by relative values with respect to Sample 1 (exposure count number of each sample / exposure count number of Sample 1).
The smaller the number, the higher the practical skill sensitivity.

Safelight Safety In order to evaluate the safelight safety of each sample, a white fluorescent lamp (FL40SW) manufactured by Toshiba Corp. covered with a sharp cut filter SC-42 manufactured by Fuji Photo Film Co., Ltd. was used. After being left under 400 Lux for 2 minutes to 60 minutes, development processing was performed in the same manner as described above, and the limit irradiation time at which the fogging value started to increase was determined.

Storage stability The sample was left under conditions of 50 ° C. and 70% for 10 days, exposed through an optical wedge by the above-mentioned P-627FM printer, and developed, fixed, washed with water and dried in the same manner as above.
The storability was evaluated by comparing this result with the sensitivity immediately after coating. As the change in sensitivity, the change in the logarithmic value (S _1.5 ) of the exposure amount giving a density of 1.5 S _1.5 (immediately after coating) -S
Evaluation was performed at _1.5 (50 ° C., 70%, 10 days). The larger this value is, the more sensitized the image is. Table 1 shows the results.

[0081]

[Table 1]

[0082]

Embedded image

<Developer 1> Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0. 08 g 4-hydroxymethyl-4-methyl-1 phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercapto Sodium benzimidazole-5-sulfonate 0.15 g Sodium erythorbate 3.0 g Potassium hydroxide is added and water is added to 1 liter to adjust the pH to 10.5. 1 liter

<Fixer 1> Ammonium thiosulfate 119.7 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.03 g Sodium thiosulfate pentahydrate 10.9 g Sodium sulfite 25.0 g NaOH (pure content) 12.4 g Glacial acetic acid 29. 1 g Tartaric acid 2.92 g Sodium gluconate 1.74 g Aluminum sulfate 8.4 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.8 g Water to add 1 liter

From the above results, it can be seen that the light-sensitive material of the present invention is excellent in sensitivity, safelight safety and storage stability.

[0086]

According to the present invention, there is provided a silver halide photographic light-sensitive material which is excellent in safelight safety in a bright room, has high sensitivity, and is excellent in storage stability.

Claims (3)

[Claims] 1. A dye having a silver halide emulsion layer and a hydrophilic colloid layer on a support, and any one of the silver halide emulsion layer and the hydrophilic colloid layer is represented by the following general formula (I). A silver halide photographic light-sensitive material comprising: Embedded image In the formula, R ¹ represents a branched alkyl group, and R ² represents a hydrogen atom or a substituent. R ³ and R ⁴ represent a hydrogen atom, an aliphatic hydrocarbon group, an acyl group or a sulfonyl group.
R ² , R ³ and R ⁴ may be connected to each other to form a 5- or 6-membered ring. m represents 0, 1 or 2. m = 2
In the case of, R ² may be the same as or different from each other. L ¹ ,
L ² and L ³ each represent an optionally substituted methine group, and n represents 0 or 1. However, it has at least one sulfo group or a salt thereof in the molecule. 2. The silver halide photographic light-sensitive material according to claim 1, wherein in the general formula (I), R ¹ is a secondary or tertiary alkyl group. 3. The silver halide emulsion layer comprises Ir, Ru, R
7. A silver halide grain containing a heavy metal selected from h, Re, and Cr in an amount of at least 1.times.10.sup.- ⁶ mol per mol of silver halide, and containing silver chloride grains having a silver chloride content of 95 mol% or more. 1. The silver halide photographic light-sensitive material described in 1.