JPH07311436A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having high sensitivity in which the increase of fog is hardly caused even when stored for a long time and such a dye is used that can be effectively spectrally sensitized in 540-550nm spectrum range and shows good color remaining in the photographic material after processed, by allowing a specified dye to adsorb to silver halide particles and incorporating a specified compd. into the photosensitive material. CONSTITUTION:A benzoimidazolo carbocyanine dye expressed by formula I is made to adsorb to silver halide particles in an emulsion layer. The photosensitive material contains a compd. expressed by formula II, where R11-R14 are alkyl groups, one of R11 and R12 is an alkoxyalkyl group, one of R13 and R14 is a sulfoalkyl group, X11-X14 are hydrogen atoms, cyano groups, or the like, Z is an ion necessary to balance charges, and n is 1 or 2, Q is a group of atoms to complete a five-member heteroring directly or indirectly having -SO3M or the like, M is a hydrogen atom, or alkali metal atom, R2 is a hydrogen atom or alkali metal atom, R3 is a hydrogen atom, or 1-6C alkyl group, and R4 is a hydrogen atom or aliphatic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a green light-sensitive silver halide photographic light-sensitive material, which uses a novel sensitizing dye to have high sensitivity and little residual color, and has good storability. Is provided. Especially, it is applied to medical X-ray sensitive materials.

[0002]

BACKGROUND OF THE INVENTION Silver halide photography usually involves the exposure of silver halide to light to form a latent image, which latent image is developed during photographic processing to form a visible image. Silver halide is inherently sensitive only to light in the blue region of the spectrum. Therefore, a spectral sensitizing dye is necessary in order to extend the photosensitive wavelength range of silver halide to the longer wavelength side.

During processing of color photographic materials, silver halide is removed from the photographic material. In black-and-white photographic materials, unexposed silver halide is removed. In either case, it is desirable that the sensitizing dye be removed as well. Sensitizing dyes that are not removed tend to cause residual color and adversely affect the image recorded on the photographic material. The problem of residual color is
It is exacerbated with increasing use of tabular grain emulsions and high silver chloride emulsions. The tabular grain emulsion has a large surface area per 1 mol of silver and a large amount of sensitizing dye is added, so that the residual color is relatively large. High chloride emulsions require the use of sensitizing dyes with enhanced adsorption to silver halide and are often used for rapid processing, which can exacerbate the residual color problem.

Most photographic films that require green sensitivity have the mid-green wavelengths of the spectrum (540-555 nm, for sufficient sensitivity, color separation and color reproduction).
It requires a high degree of sensitivity in the highest sensitivity range for the human eye). Benzimidazolocarbocyanine, oxacarbocyanine and benzimidazolooxacarbocyanine dyes are all known spectral sensitizing dyes that absorb light in the green region of the spectrum. These dyes are described, for example, in Abott et al., US Pat. Nos. 4,425,425 and 4,425,4.
No. 26 (reexamination certificate 907), Ukai et al., US Pat.
U.S. Pat. No. 4,801,801 to Yoshida et al.
526 and Ikeda et al., U.S. Pat. No. 4,837,14.
No. 0 is disclosed.

Benzimidazolocarbocyanine dyes are extremely effective in utilizing light energy, and because of their high basicity, they can be protonated and removed by treatment with an acidic solution, resulting in low residual stains. .
These dyes perform best as J-aggregates on the surface of silver halide grains. However, such benzimidazolocarbocyanine aggregates generally have 560 to 590 n
m, absorbs light in the long green region of the spectrum. To that end, another group of dyes, conventionally oxacarbocyanines or benzimidazolooxacarbocyanines,
It was necessary to use it for sensitization in the mid-green range. These dyes, however, are less basic and tend to leave unacceptably high levels of residual dye after processing.

In general, when such a benzimidazolocarbocyanine is used as a spectral sensitizer in a photographic light-sensitive material, high spectral sensitivity can be obtained, but fog is not observed when the photographic light-sensitive material is stored for a long period of time. It also has the drawback that it tends to rise, and improvements have been desired.

[0007]

The object of the present invention is therefore to use dyes which are spectrally sensitized effectively in the 540-555 nm region of the spectrum and which have very good residual color in the photographic material after processing, It is an object of the present invention to provide a photographic light-sensitive material which has high sensitivity and is less likely to cause fog during storage for a long time.

[0008]

The objects of the present invention have been achieved by the following means. (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the emulsion layer have benzimidazolocarbocyanine represented by the general formula (I). A silver halide photographic light-sensitive material, wherein at least one kind of dye is adsorbed, and the light-sensitive material contains at least one kind of the compound represented by the general formula (II). General formula (I)

[0009]

[Chemical 5]

General formula (II)

[0011]

[Chemical 6]

R in the general formula (I)₁₁, R₁₂Is replaced or nothing
Represents a substituted alkyl group, R₁₁, R ₁₂At least one of
Represents an alkoxyalkyl group. R₁₃, R₁₄Is replaced or
Represents an unsubstituted alkyl group, R₁₃, R₁₄At least
One represents a sulfoalkyl group. X₁₁, X₁₂, X₁₃, X
₁₄Each may be the same or different and the hydrogen source
Child, cyano group, halogen-substituted alkyl group, or
Represents a halogen atom, X₁₁, X₁₃At least one of which is water
Represents an elementary atom. Z is necessary to balance the charge
Represents an ion, and n is 1 or 2. Form an inner salt
It is 1 when it does. In general formula (II), Q is -SO₃M,-
COOR₂, -OH, -NHR₃At least one of directly or between
Represents an atomic group that completes a 5-membered heterocyclic ring, and M is water
Elemental atom, alkali metal atom, or quaternary ammonium group
Or represents a quaternary phosphonium group, R ₂Is a hydrogen atom,
Lucari metal atom, or alkyl group having 1 to 6 carbon atoms, R
₃Is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -COR_Four,-
COOR_FourOr SO₂R_FourRepresents R _FourIs a hydrogen atom, an aliphatic group
Alternatively, it represents an aromatic group.

(2) General formula (I
The silver halide photographic light-sensitive material described in (1), wherein the compound of I) is represented by the general formula (III). General formula (III)

[0014]

[Chemical 7]

In the general formula (III), Y and W each independently represent a nitrogen atom or CR ₅ (R ₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). , R ₆ represents an alkyl group or an aryl group substituted with at least one selected from the group consisting of —SO ₃ M, —COOM, —OH, and —NHR ₃ , and M is a hydrogen atom, an alkali metal atom, or a tetravalent group. Represents a quaternary ammonium group or a quaternary phosphonium group, R ₃ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ₄ , —COOR ₄ or SO ₂ R ₄ , and R 3
₄ represents a hydrogen atom, an aliphatic group or an aromatic group.

(3) General formula (I) contained in the light-sensitive material
The silver halide photographic light-sensitive material described in (1), wherein the compound of I) is represented by the general formula (IV). General formula (IV)

[0017]

[Chemical 8]

In the general formula (IV), X ₂ is a sulfur atom or
Represents an oxygen atom, R ₆ is —SO ₃ M, —COOM, —OH, —
Represents an alkyl group or an aryl group substituted with at least one selected from the group consisting of NHR ₃ , M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, and R ₃ represents a hydrogen atom. Represents an alkyl group having 1 to 6 carbon atoms, —COR ₄ , —COOR ₄ or SO ₂ R ₄ , and L ₁ represents —CONR ₇ —, —NR ₇ CO —, —SO ₂ NR ₇ —, —
NR ₇ SO ₂ −, −OCO −, −OCOO −, −COO −, −S−, −C
O -, - SO -, - NR 7 -, - OCOO -, - NR 7 CONR 8 -, - N
_{R 7 COO -, - OCONR 7} -, - NR 7 SO 2 NR 8 - represents the selected linking groups from the group consisting of, R _7, R ₈ are each hydrogen atom,
It represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and n is 0 or 1.

(4) The silver halide photographic light-sensitive material according to (2), wherein the silver halide emulsion contained in the emulsion layer has a silver chloride content of 10 mol% or more based on silver. (5) The silver halide photographic light-sensitive material according to (3), wherein the silver halide emulsion contained in the emulsion layer has a silver chloride content of 10 mol% or more with respect to silver.

The benzimidazolocarbocyanine dye represented by formula (I) will be described in detail. In the formula, R ₁₁ and R
₁₂ represents a substituted or unsubstituted alkyl group. At least one of them is an alkoxyalkyl group (having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms. Specifically, a methoxymethyl group,
A methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group and the like. ), Preferably at least one is an ethoxyethyl group. The remaining one of R ₁₁ and R ₁₂ is preferably a methyl group or an ethyl group. R ₁₃ and R ₁₄ represent a substituted or unsubstituted alkyl group, at least one of which is a sulfo which is preferably substituted with an aromatic group having 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. It is an alkyl group. The remaining one of R ₁₃ and R ₁₄ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms (methyl, ethyl, propyl, butyl). , Isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.). Examples of the substituted alkyl group include a fluorine-substituted alkyl group (2,2-difluoroethyl group, 2,
2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, etc., hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group) , Hydroxypropyl group, etc.), aralkyl group (benzyl, 2-phenylethyl, etc.), carboxyalkyl group (carboxymethyl, 2-carboxyethyl, 3-carboxypropyl,
4-carboxybutyl, etc.), alkoxyalkyl group (2-methoxyethyl, 2- (2-methoxyethoxy))
Ethyl, etc.), sulfoalkyl groups (2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.) sulfatoalkyl group (3-sulfatopropyl) , 4-sulfatobutyl, etc.), hetero-substituted alkyl groups ((2-pyrrolodin-2-one-1-yl)
Ethyl, tetrahydrofurfuryl, 2-morpholinoethyl, etc.), 2-acetoxyethyl group, carboxymethoxymethyl group, 2-methanesulfonylaminoethyl group, and allyl group.

X ₁₁ , X ₁₂ , X ₁₃ , and X ₁₄ may be the same or different and each is a hydrogen atom, a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, an alkyl group having 6 or less carbon atoms (methyl, Ethyl, propyl, butyl, cyclohexyl, etc.), acyl groups having 6 or less carbon atoms (acetyl, propionyl, benzoyl, etc.), acyloxy groups having 3 or less carbon atoms (acetoxy, etc.), and alkoxy groups having 8 or less carbon atoms (methoxycarbonyl). , Ethoxycarbonyl,
Phenoxycarbonyl, etc.), carivamoyl group having 8 or less carbon atoms (carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, etc.), sulfamoyl group having 8 or less carbon atoms (sulfamoyl, N, N-dimethylsulfamoyl) , Piperidinosulfamoyl, etc.), hydroxy group, haloalkyl group (trifluoromethyl, 2,2-difluoroethyl, 2,
2,2, -trifluoroethyl, 2,2,3,3-tetrafluoroethyl, etc.), and X ₁₁ , X
_At least one of ₁₃ is preferably a hydrogen atom, and each of X ₁₂ and X ₁₄ is preferably a cyano group, a haloalkyl group or a halogen atom. Z
Represents an ion necessary for neutralizing the charge, and n is 1 or 2. When forming an intramolecular salt, n is 1
Is. Specific examples of the substituents in the compound of the general formula (I) are shown in Table 1, but the present invention is not limited to these compounds.

[0022]

[Table 1]

The compound of formula (I) of the present invention may be added at any time before the coating step. Specifically, it is added at the time of preparing a photosensitive emulsion layer coating solution, at the time of forming silver halide grains, at the silver halide emulsion desalting step, immediately before the silver halide emulsion chemical ripening step. And a method of adding during silver halide emulsion chemical ripening. It is also possible to uniformly add the compound of the general formula (I) to each silver halide grain by adding it at a temperature of 25 ° C. or higher and lower than 55 ° C. and then raising the temperature to above the addition temperature for chemical ripening. The preferable addition timing is at the time of preparing the photosensitive emulsion layer coating solution,
Immediately before the silver halide emulsion chemical ripening step, during the silver halide emulsion chemical ripening step, and before the desalting step. Examples of the method of adding the compound of the general formula (I) of the present invention include a method of adding it as a solution of water or an organic solvent, a method of adding it as a gelatin dispersion, or a method of dissolving the gelatin dispersion by heating and adding it. . The addition amount of the compound of the general formula (I) of the present invention is 0.1 mmol or more and 10 mm per 1 mol of silver.
It is preferably less than ol, more preferably 0.2 mmol or more and less than 2.0 mmol. Further, it is also preferable to use two or more compounds of the general formula (I) together or to combine them with a sensitizing dye having another structure depending on the purpose.

Next, the compound of the present invention represented by the general formula (II) will be explained. Q in the general formula (II) is -SO
_At least 1 selected from ₃ M, -COOR ₂ , -OH or -NHR ₃
Completing a 5-membered heterocycle having a species directly or indirectly, for example, an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pentazole ring, a pyrimidine ring, A thiazine ring, a triazine ring and a thiodiazine ring. Of these, preferred are imidazole ring, triazole ring, tetrazole ring, thiadiazole ring and oxadiazole ring.

The general formulas (III) and (IV) are compounds completely contained in the general formula (II). Preferred as general formula (III) are imidazoles, triazoles and tetrazoles. Preferred as general formula (IV) are thiadiazoles and oxadiazoles. In the present invention, it is preferable to use a plurality of compounds represented by the general formula (II) in combination. In particular, it is preferable to use the compound represented by the general formula (III) and the compound represented by the general formula (IV) together. The thiadiazoles represented by the general formula (IV) in the present invention are the most preferred compounds,
It is preferably used in combination with a compound of tetrazole represented by (III). Preferred specific examples of the compounds represented by the general formulas (II), (III) and (IV) used in the present invention are shown below.

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

The compounds represented by the general formula (II) are known and can be synthesized by the methods described in the following documents. U.S. Pat. Nos. 2,585,388 and 2,541,924, Japanese Patent Publication No. 42-21,842,
JP-A-53-50,169, British Patent No. 1,275,
701, DA Burgess et al., “Journal of Heterocyclic Chemistry” (DA Berges et.al.,
"Journal of Heterocyclic Chemistry") Volume 15 981
Issue (1978), "The Chemistry of Heterocyclic Chemistry," Imidazole and Derivatives, Part I ("The Chemistry of Heterocylic C").
hemistry "Imidazole and Derivatives part I), 33
Pages 6-9, Chemical Abstracts
ct), 58, 7921 (1963), p. 394, E. Hogarth, "Journal of Chemical Society.
(E. Hoggarth "Journal of Chemical Society") 1160
~ P. 7 (1949), and SR Saudler W. Caro,
“Organic Functional Grape Preparation”, Academic Press (SR Saudler,
W.Karo, “Organic FanctionalGroup Preparation” Ac
ademic Press, pages 312-5 (1968), M. Chamdon, et.al., Bourtan de la Societe Simique de France (Bulletin de la Socie)
te Chimique de France), 723 (1954), DA Shirley, DW Array, Journal of the American Chemical Society (DAShirley, DWAlle
y, j. Amer. Chem. Soc.), 79, 4922 (1954).
A. Ball, W. Marchwald, Berichte (A. Wohl, W. Ma
rchwald, Ber.) (German Chemistry), vol. 22, p. 568 (1
889) Journal of American Chemical Society (J. Amer. Chem. Soc.), 44, 1502-10.
Page, U.S. Pat. No. 3,017,270, British Patent No. 94.
No. 0,169, Japanese Patent Publication No. 49-8,334, JP-A-55.
-59,463, Advanced in Heterocyclic Chem
istry), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives (The Chemistry o
f Heterocyclic Compounds Imidazole and Derivative
s) Vol. 1, p. 385, Organic Synthesis (Org.
Synth) IV., 569 (1963), Beritzhite (Ber.)
9, 465 (1976), Journal of American Chemical Society (J. Amer. Chem. Soc.) 4
5, 2390 (1923), JP-A-50-89034.
No. 53-28426, No. 55-21007, and Japanese Patent Publication No. 40-28496.

The compound represented by the general formula (II) is contained in the silver halide emulsion layer and the hydrophilic colloid layer (intermediate layer, surface protective layer, yellow filter layer, antihalation layer, etc.). It is preferably contained in the silver halide emulsion layer or a layer adjacent thereto. The addition amount thereof is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ g / m ² , more preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻² g / m ² , and particularly preferably 1 × 10 5. ^{-4 to} 5 x 10 ^-3 g / m ² . The method of adding this compound to the emulsion may be in accordance with the usual method of adding photographic emulsion additives. For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water or a mixed solvent thereof, and added as a solution.

The compound represented by the general formula (II) can be added and used at any step of the process for producing a photographic emulsion, or can be added and used at any stage after the production of an emulsion and immediately before coating. it can. The compound represented by the general formula (II) is usually 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, per 1 mol of silver halide sensitized by selenium, sulfur, gold and reduction. Preferably 1 × 10 ⁻⁵ mol to 8
It is used in the range of × 10 ^-3 mol.

The silver halide grains of the present invention may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, it may be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion), or a grain such that a latent image is mainly formed inside the grain (for example, an internal latent image type emulsion, a pre-fogged direct inversion type emulsion). ) May be sufficient. Preferably, the particles are such that a latent image is mainly formed on the surface. Further, in order to control the growth of grains during the formation of the silver halide grains, as a silver halide solvent, for example, ammonia, rodancali, rhodammone, and a thioether compound (for example, US Pat. No. 3,271,157,
No. 3,574,628 and No. 3,704,130
No. 4,297,439, No. 4,276,37
4), thione compounds (for example, JP-A-53-14431).
No. 9, No. 53-82408, No. 55-77737.
No.), amine compounds (for example, JP-A-54-100717).
No.) can be used.

Cadmium salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt and the like may be present together in the process of silver halide grain formation or physical ripening.

The silver halide that can be used in the silver halide emulsion may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide, but it contains iodine. The amount is preferably 0.003 mol or less per mol of silver. The AgI distribution may be a high internal concentration or an external high concentration. In the present invention, it is preferable to use silver chlorobromide or silver chloride emulsion. In particular, the silver chloride content is preferably 10 mol% or more with respect to 1 mol of silver.

The form of silver halide grains that can be used in the silver halide emulsion is preferably tabular in the majority. The proportion of tabular grains contained in the emulsion layer is 5 in terms of the projected area of the silver halide grains.
It is 0% or more, and preferably 70% or more. The aspect ratio of a tabular grain is given by the average value of the ratio of the diameter of a circle having an area equal to the grain projected area of each tabular grain and the grain thickness of each tabular grain. The particle morphology in the present invention has an aspect ratio of 3 or more and less than 20, preferably 4
It is 10 or more and less than 10. Furthermore, the particle thickness is 0.3 μm.
The following is preferable, and 0.2 μm or less is particularly preferable.

Tabular silver halide emulsions of silver bromide or silver iodobromide are disclosed in JP-A-58-127927 and JP-A-58-127927.
It can be easily prepared by referring to the methods described in JP-A-113927 and JP-A-58-113928. Also, pB
A seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere of a relatively low pBr value of r1.3 or less, and a seed crystal is added while simultaneously adding a silver and halogen solution while maintaining a similar pBr value. Can also be obtained by growing. In this growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The size of tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of solvent, and controlling the addition rate of silver salt and halide used during grain growth. Further, tabular silver halide emulsions having a silver chloride content of 10 mol% or more based on silver are disclosed in JP-B-64-832.
No. 4, JP-B-64-8325, JP-B-64-8326
It can be prepared by utilizing the method described in Japanese Patent Publication No. 3-14328.

The emulsion layer of the present invention contains 1.
It is preferable to contain a thiocyanic acid compound in an amount of 0 × 10 ⁻³ mol or more and less than 2.0 × 10 ⁻² mol. The thiocyanate compound may be added in any process of grain formation, physical ripening, grain growth, chemical sensitization and coating, but addition before chemical sensitization is preferable. As the thiocyanic acid compound used during the preparation of the silver halide emulsion in the present invention, a water-soluble salt such as a metal thiocyanate or an ammonium salt can be generally used, but in the case of a metal salt, the photographic performance is adversely affected. Care should be taken to use metal elements that do not exceed the range, with potassium and sodium salts being preferred. Also, Ag
A sparingly soluble salt such as SCN may be added in the form of fine particles. In this case, the size of the AgSCN fine particles is preferably 0.2 μm or less in diameter, and particularly preferably 0.05 μm or less.

The silver halide emulsion used in the present invention can be chemically sensitized. Chemical sensitization methods include sulfur sensitization, selenium sensitization, complex salts, reduction sensitization with polyamines, gold sensitization with gold compounds, or sensitization with metals such as iridium, platinum, rhodium and palladium. Known methods such as can be used. These may be used in combination as necessary. Particularly, it is preferable to carry out the sulfur sensitization method using a sulfur-containing compound and / or the selenium sensitization method using a selenium-containing compound in the presence of a compound capable of adsorbing to silver halide. The compound adsorbed on silver halide as used herein means a class of spectral sensitizing dyes or photographic stabilizers, and is disclosed in JP-A-63-305343.
The compounds disclosed in JP-A No. 1-77047 and the like can be used. Further, it is preferable to adsorb the compound of the formula (I) of the present invention to silver halide.

The silver content of the light-sensitive material of the present invention is preferably 0.5 to 5 g / m ² (per surface), more preferably 0.8 g / m ^{2 to} 2.0 g / m ² (per surface). is there.

Various additives and the like used in the photographic light-sensitive material of the present invention are not particularly limited in addition to the above, and for example, those described in the following relevant parts can be used. Item Relevant part 1) Silver halide emulsion and its production method JP-A-2-68539, page 8, lower right column, line 6 to page 10, upper right column, line 12 and 3-24537, JP 2 Page 10, right lower column, line 10 to page 6, right upper column, line 1; page 10, left upper column, line 16 to page 11 left lower column, line 19; Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. From line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 3) Color tone improving agent JP-A No. 62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; Tokukaihei 3-94249, page 6, lower left column, line 15 to 11 Top right column, line 19 4) Surfactants and antistatic agents JP-A-2-68539, page 11, upper left column, line 14 to page 12, upper left column, line 9 5) Matting agent, slip agent, plasticizer JP-A-2-68539, page 12, upper left column, line 10 to same upper right column, line 10, page 14 lower left column 10 line to lower right column 1 line. 6) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 7) Hardener JP-A-2-68539, page 12, upper right column, line 17 to page 13, upper right column, line 6 8) Supports JP-A-2-68539, page 13, upper right column, lines 7 to 20. 9) Crossover cut method JP-A-2-264944, page 4, upper right column, line 20 to page 14, upper right column. 10) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24539, page 14, lower left column, to page 16, lower right column. 11) Polyhydroxybenzenes JP-A-3-39948, page 11, upper left column to page 12, lower left column, EP Patent No. 452772A. 12) Layer structure JP-A-3-198041. 13) Development method From JP-A-2-103037, page 16, upper right, column 7, line 7 to page 19, left, lower column, line 15, and JP-A-2-115837, page 3, lower right column, line 5 Page 10, upper right column, line 10

[0043]

【Example】

Example 1 (Preparation of photographic light-sensitive material) (1) Preparation of high-sensitivity tabular emulsion T-1 6.9 g of potassium bromide and 1 of average molecular weight in 1 liter of water.
6.05 g of low molecular weight gelatin (5,000 g) was added, and while stirring in a container kept at 38 ° C, 37 cc of an aqueous solution of silver nitrate (2.4 g of silver nitrate) and an aqueous solution containing 5.9 g of potassium bromide 38
cc was added by the double jet method in 37 seconds. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 100 cc of silver nitrate aqueous solution (silver nitrate 11.2 g) was added over 22 minutes. Here, 8.5 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 8 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 145 g of silver nitrate and an aqueous solution of potassium bromide were added to pAg.
While accelerating the flow rate by the control double jet method while maintaining it at 8.5 (initial flow rate / final flow rate = 1 / 5.4)
Added over 35 minutes. Then, 35 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Pure silver bromide tabular grains having an average projected area diameter of 0.68 µm to a thickness of 0.123 µm and a variation coefficient of 23% were obtained.

After that, soluble salts were removed by the coagulation sedimentation method. The temperature was again raised to 40 ° C., 35 g of gelatin, 2.35 g of phenoxyethanol, and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 5.90 and pAg to 8.00 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, C ₂ H ₅ SO ₂ SNa is added at 1 × 10 ⁻⁵ mol /
Mol Ag was added, then 0.002 mol / mol Ag of AgI fine particles having a particle size of 0.03 μm was added, and then 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. Mol Ag and sensitizing dyes shown in Table-2, Comparison-1, Comparison-2 and Inventions I-1 and I-2 of 8 respectively.
× 10 ⁻⁴ mol / mol Ag was added.

[0046]

[Chemical 14]

Further, 0.83 g of calcium chloride was added, followed by sodium thiosulfate 2 mg / mol Ag, selenium compound C 2.5 mg / mol Ag and chloroauric acid 1.9 mg.
/ Mol Ag and 90 mg of potassium thiocyanate were added and after 40 minutes cooled to 35 ° C. Thus, preparation of tabular grain emulsion T1 was completed.

[0048]

[Chemical 15]

(2) Preparation of silver chlorobromide emulsion T2 The following solutions were prepared. Solution (1) Inert gelatin 10 g NaCl 2.2 g KBr 3.6 g H ₂ O 1750 cc

[0050]

[Chemical 16]

Solution (2) AgNO ₃ 34 g H ₂ O was added to 200 cc solution (3) NaCl 6.4 g KBr 11.9 g H ₂ O was added to 200 cc solution (4) AgNO ₃ 102 g H ₂ O was added to 600 cc Solution (5) NaCl 5.3 g KBr 65.5 g H ₂ O was added to 600 cc and the solution (1) kept at 35 ° C. was simultaneously added to the solution (2) and the solution (3) over 5 minutes while vigorously stirring. . After further raising the temperature to 45 ° C., the solution (4) and the solution (5) were simultaneously added over 30 minutes. Then, 35 cc of 2N potassium thiocyanate solution was added. Thereafter, emulsion T1
Soluble salts were removed and redispersed in the same manner as above to carry out chemical sensitization. The sensitizing dyes were added at 8 × 10 ⁻⁴ mol / mol Ag, respectively, as described in Table 2.

[0052]

[Chemical 17]

The prepared emulsion having a silver chloride content of 15 mol% had a thickness of less than 0.3 μm, a diameter of 0.5 μm or more, and 80% of tabular grains having parallel (111) faces and an aspect ratio of 2 or more. The average projected area diameter of the tabular grains is 0.75 μm, the average thickness is 0.13 μm, and the average aspect ratio is 5.
It was 8.

(Preparation of Dye Dispersion A for Undercoat Layer) The following Dye-I was ball milled by the method described in JP-A-63-197943.

[0055]

[Chemical 18]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO ₂ ) beads 4
00 ml (2 mm diameter) was added and the contents were milled for 4 days.
After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion A was obtained.

(Preparation of support) Biaxially stretched thickness 17
Corona discharge treatment was performed on a 5 μm blue-colored polyethylene terephthalate film, and the first undercoat liquid having the following composition was applied by a wire bar coater so that the applied amount was 4.9 cc / m ^2, and the temperature was raised to 185 ° C. And dried for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface.・ Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31 to 69) 158cc ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc ・ Distilled water 300cc Above A second undercoat layer having the following composition on the first undercoat layer on both sides of each of the above, one side at a time so that the coating amount becomes the amount described below, and 165 ° C. on both sides by a wire bar coater method.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye Dispersion A (as dye solid content) 8 mg / m ²・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 1.8 mg / m ²・ Proxel 0.27 mg / m ² Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ^{2 In} this way, a support including a crossover cut layer was prepared.

(Preparation of Emulsion Coating Solution) The following chemicals were added to 1 mole of silver halide of each emulsion T1 and T2 to prepare a coating solution.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g -Gelatin For each coated sample, the addition amount was adjusted so that the coating amount of gelatin in the emulsion layer was 1.6 g / m ² . Hardener 1,2-bis (vinylsulfonylacetamide) ethane 3.2 g

[0059]

[Chemical 19]

Compounds A-1, A-2, A-3 of the present invention,
As shown in Table 2, A-4 and A-5 were added in an amount of 5 × 10 ^-4 mol per mol of silver halide in each emulsion.

[0061]

[Chemical 20]

The surface protective layer was prepared and prepared so that the amounts of the respective components were as follows. (Protective layer coating solution) Gelatin 800 g-dextran (average molecular weight _{39,000) 200g · C 16 H 33 O} (CH 2 CH 2 O) 10 H 39g · C 8 F 17 SO 2 N (C 3 H 7) (CH ₂ CH ₂ O) ₄ (CH ₂ ) SO ₃ Na 1.6 g ・ C ₈ F ₁₇ SO ₃ K 7 g ・ Polymethylmethacrylate particles (average particle size 3.7 μm) 91 g ・ Proxel 0.7 g ・ Polyacrylic acid Sodium (average molecular weight 41,000) 45 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 3 g ・ NaOH 1.6 g ・ C ₈ H ₁₇ C ₆ H ₄ (OCH ₂ CH ₂ ) ₃ SO ₃ Na 24 g ・ Distilled water Add 14 liters to complete

(Preparation of Photographic Material) The emulsion prepared above and the coating solution for the surface protective layer were sequentially coated on both sides of the above-mentioned support X under the same conditions by the simultaneous extrusion method. The amount of gelatin in the protective layer was 0.75 g / m ² . The coated silver amount was adjusted to be 1.2 g / m ² on one side of the support (2.4 g / m ^{2 on} both sides). Thus, the preparation of Samples 1 to 30 was completed. Regarding the obtained photographic material, JP-A-58-111
When the swelling ratio was measured according to the means and definition described in No. 93, it was 180%.

(Processing method and processing agent by automatic developing machine) As an automatic developing machine, FPM manufactured by Fuji Photo Film Co., Ltd.
-800A was modified so that the transport speed and the amount of developing / fixing replenisher were variable. In this experiment, the development temperature was 35 ℃, the fixing temperature was 34 ℃, and the processing time was Dry.
Processing was performed for 90 seconds. The developer has the following composition. In use, this composition was replenished as it was without dilution. The replenishment amount was 5 cc per 10 × 12 inch sheet, and the replenishment was once per 10 × 12 inch sheet.

Developer (1 liter formulation) Diethylenetriamine pentaacetic acid 4 g K ₂ CO ₃ 56 g Sodium sulfite 30 g Sodium erythorbate 54 g KBr 0.5 g 5-Methylbenztriazole 60 mg 4-Methyl-4-hydroxymethyl-1-phenyl-3 -Pyrazolidone 4g

[0066]

[Chemical 21]

The pH of the liquid was 9.50 with acetic acid and caustic soda.
Adjusted to. The fixing solution had the following composition. In use, this composition was replenished as it was without dilution.
The replenishment amount was 5 cc per 10 × 12 inch sheet, and the replenishment was once per 10 × 12 inch sheet. Fixer (1 liter formulation) Ethylenediaminetetraacetic acid 25 mg Sodium thiosulfate 290 g Sodium bisulfite 35 g NaOH 2.4 g The pH of the solution was adjusted to 5.4.

(Evaluation of Photographic Performance) The photographic material was manufactured by Fuji Photo Film Co., Ltd. X Ray Orthoscreen HG-M.
Was used for exposure for 0.05 seconds from both sides to evaluate the sensitivity. The sensitivity obtained by processing the sample 1 for sensitivity evaluation was taken as 100, and indicated by the reciprocal of the ratio of the exposure dose giving a density of 1.0.

(Evaluation of natural aging) 50 ° C. 68% inside
The coated sample was placed in a closed container kept at 10 ° C. for 5 days (forced aging). This sample and a sample for comparison (stored in a light-shielding container at room temperature) were subjected to the same treatment as used for evaluation of photographic properties, and the density of the fog portion was measured. The natural aging property was evaluated as a fogging rate. (Increased fog rate) = [(Increased fog over time) /
{(Maximum density)-(support density)} × 100 The lower the fog rate, the better the natural aging property.

(Evaluation of residual color) X-ray film Super-HRS30 manufactured by Fuji Photo Film Co., Ltd. was treated (blackening rate 3
0%) and running according to the above-mentioned replenishment method, then cutting each sample into 30.5 cm x 25.4 cm and rinsing with water at 5 ° C to perform the above treatment, and visually check the degree of residual color of the light-sensitive material. And evaluated according to the following criteria. ◎ …… Almost no color remains. ○ …… I don't feel like the color remains slightly. Δ: The color remains, but it is practically acceptable. ×: Many residual colors are not possible.

The results are shown in Table 2. It can be seen that the present invention is good in terms of sensitivity, natural aging, and residual color.

[0072]

[Table 2]

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[Procedure amendment]

[Submission date] January 25, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

The benzimidazolocarbocyanine dye represented by formula (I) will be described in detail. In the formula, R ₁₁ and R
₁₂ represents a substituted or unsubstituted alkyl group. At least one of them is an alkoxyalkyl group (having 2 to 20 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 5 carbon atoms. Specifically, a methoxymethyl group,
A methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group and the like. ), Preferably at least one is an ethoxyethyl group. The remaining one of R ₁₁ and R ₁₂ is preferably a methyl group or an ethyl group. R ₁₃ and R ₁₄ represent a substituted or unsubstituted alkyl group, at least one of which is a sulfo which is preferably substituted with an aromatic group having 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. It is an alkyl group. The remaining one of R ₁₃ and R ₁₄ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms (methyl, ethyl, propyl, butyl). , Isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.). Examples of the substituted alkyl group include a fluorine-substituted alkyl group (2,2-difluoroethyl group, 2,
2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, etc., hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group) , Hydroxypropyl group, etc.), aralkyl group (benzyl, 2-phenylethyl, etc.), carboxyalkyl group (carboxymethyl, 2-carboxyethyl, 3-carboxypropyl,
4-carboxybutyl, etc.), alkoxyalkyl group (2-methoxyethyl, 2- (2-methoxyethoxy))
Ethyl, etc.), sulfoalkyl groups (2-sulfoethyl,
3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.) sulfatoalkyl group (3-sulfatopropyl) , 4-sulfatobutyl, etc.), a hetero-substituted alkyl group ((2-pyrrolidin-2-one-1-yl)
Ethyl, tetrahydrofurfuryl, 2-morpholinoethyl, etc.), 2-acetoxyethyl group, carboxymethoxymethyl group, 2-methanesulfonylaminoethyl group, and allyl group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may be the same or different and each is a hydrogen atom, a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, a haloalkyl group (trifluoromethyl, 2,2). -Difluoroethyl, 2,2
2, -trifluoroethyl, 2,2,3,3-tetrafluoropropyl, etc.) and X ₁₁ , X ₁₃
It is preferable that at least one of them is a hydrogen atom, and it is preferable that X ₁₂ and X ₁₄ are any of a cyano group, a haloalkyl group and a halogen atom. Z
Represents an ion necessary for neutralizing the charge, and n is 1 or 2. When forming an intramolecular salt, n is 1
Is. Specific examples of the substituents in the compound of the general formula (I) are shown in Table 1, but the present invention is not limited to these compounds.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

Next, the compound of the present invention represented by the general formula (II) will be explained. Q in the general formula (II) is -SO
_At least 1 selected from ₃ M, -COOR ₂ , -OH or -NHR ₃
Completing a 5-membered heterocycle having a species directly or indirectly, for example, an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pyrimidine ring, a thiazine ring, A triazine ring and a thiodiazine ring. Of these, preferred are imidazole ring, triazole ring, tetrazole ring, thiadiazole ring and oxadiazole ring.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The compounds represented by the general formula (II) are known and can be synthesized by the methods described in the following documents. U.S. Pat. Nos. 2,585,388 and 2,541,924, Japanese Patent Publication No. 42-21,842,
JP-A-53-50,169, British Patent No. 1,275,
701, DA Burgess et al., “Journal of Heterocyclic Chemistry” (DA Berges et.al.,
"Journal of Heterocyclic Chemistry") Volume 15 981
Issue (1978), "The Chemistry of Heterocyclic Chemistry," Imidazole and Derivatives, Part I ("The Chemistry of Heterocylic C").
hemistry "Imidazole and Derivatives part I), 33
Pages 6-9, Chemical Abstracts
ct), 58, 7921 (1963), p. 394, E. Hogarth, "Journal of Chemical Society.
(E. Hoggarth "Journal of Chemical Society") 1160
~ P. 7 (1949), and SR Saudler W. Caro,
“Organic Functional Grape Preparation”, Academic Press (SR Saudler,
W.Karo, “Organic FanctionalGroup Preparation” Ac
ademic Press, pages 312-5 (1968), M. Chamdon, et.al.,), Bulletin de la Societe Simique de France (Bulletin de la Socie)
te Chimique de France), 723 (1954), DA Shirley, DW Array, Journal of the American Chemical Society (DAShirley, DWAlle
y, J. Amer. Chem. Soc.), 79, 4922 (1954).
A. Ball, W. Marchwald, Berichte (A. Wohl, W. Ma
rchwald, Ber.) (German Chemistry), vol. 22, p. 568 (1
889) Journal of American Chemical Society (J. Amer. Chem. Soc.), 44, 1502-10.
Page, U.S. Pat. No. 3,017,270, British Patent No. 94.
No. 0,169, Japanese Patent Publication No. 49-8,334, JP-A-55.
-59,463, Advances in Heterocyclic Chemistry
istry), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives (The Chemistry o
f Heterocyclic Compounds Imidazole and Derivative
s) Vol. 1, p. 385, Organic Synthesis (Org.
Synth) IV., 569 (1963), Beritzhite (Ber.)
9, 465 (1976), Journal of American Chemical Society (J. Amer. Chem. Soc.) 4
5, 2390 (1923), JP-A-50-89034.
No. 53-28426, No. 55-21007, and Japanese Patent Publication No. 40-28496.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

[0052]

[Chemical 17]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

[0061]

[Chemical 20]

Claims (5)

[Claims] 1. At least one layer of halogenation on a support.
In a silver halide photographic light-sensitive material having a silver emulsion layer,
The silver halide grains contained in the emulsion layer have the general formula (I)
Less represented by benzimidazolocarbocyanine dye
Both of them are adsorbed, and the photosensitive material has the general formula
Contains at least one of the compounds represented by (II)
A silver halide photographic light-sensitive material characterized by being processed. one
General formula (I)General formula (II)In the general formula (I), R₁₁, R₁₂Is a substituted or unsubstituted al
Represents a kill group, R₁₁, R₁₂At least one of the
Represents a cyalkyl group. R₁₃, R₁₄Is a substituted or unsubstituted
Represents an alkyl group, R₁₃, R₁₄At least one of the
Represents a alkyl group. X₁₁, X₁₂, X₁₃, X₁₄Are the same
Same or different, hydrogen atom, cyano
Groups, halogen-substituted alkyl groups, or halogen sources
Represents a child, X₁₁, X₁₃At least one of the
You Z represents the ions necessary to balance the charge.
However, n is 1 or 2. When forming an intramolecular salt
It is 1. In general formula (II), Q is -SO₃M, −COOR₂,-
OH, −NHR₃Directly or indirectly having at least one of
Represents a group of atoms that completes a 5-membered heterocycle, where M is a hydrogen atom,
Lucari metal atom or quaternary ammonium group or quaternary
Represents a phosphonium group, R ₂Is hydrogen atom, alkali metal
Atom or alkyl group having 1 to 6 carbon atoms, R₃Is hydrogen
Child, alkyl group having 1 to 6 carbon atoms, -COR_Four, -COOR_FourAlso
Is SO₂R_FourRepresents R _FourIs hydrogen atom, aliphatic group or aromatic
Represents a group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound of the general formula (II) contained in the light-sensitive material is represented by the general formula (III). General formula (II
I) [Chemical 3] In formula (III), Y and W are independently a nitrogen atom or CR.
₅ (R ₅ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Or represents a substituted or unsubstituted aryl group), R ₆ represents an alkyl group or aryl group substituted with at least one selected from the group consisting of —SO ₃ M, —COOM, —OH, and —NHR _3. Where M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ₃ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ₄ , —COOR ₄ or SO ₂ R ₄ , R ₄ represents a hydrogen atom, an aliphatic group or an aromatic group. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound of the general formula (II) contained in the light-sensitive material is represented by the general formula (IV). General formula (I
V) [Chemical 4] In general formula (IV), X ₂ represents a sulfur atom or an oxygen atom, and R ₆ is an alkyl substituted with at least one selected from the group consisting of —SO ₃ M, —COOM, —OH, and —NHR _3. Group or an aryl group, M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group, R ₃ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —COR ₄ , —COOR ₄ or SO ₂ R ₄ and L ₁ is-
CONR ₇ −, −NR ₇ CO −, −SO ₂ NR ₇ −, −NR ₇ SO ₂ −, −OC
O-, -OCOO-, -COO-, -S-, -CO-, -SO-,
_{-NR 7 -, - OCOO -,} - NR 7 CONR 8 -, - NR 7 COO -, - OC
ONR ₇ −, —NR ₇ SO ₂ NR ₈ — represents a linking group selected from the group consisting of R ₇ , R ₈ each being a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. And n is 0 or 1. 4. The silver halide photographic light-sensitive material according to claim 2, wherein the silver halide content of the silver halide emulsion contained in the emulsion layer is 10 mol% or more based on silver. 5. The silver halide photographic light-sensitive material according to claim 3, wherein the silver halide content of the silver halide emulsion contained in the emulsion layer is 10 mol% or more based on silver.