JPH04247449A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain the tone of a silver image from becoming yellowish after development by using a specified dye for the photosensitive material of a silver halide emulsion layer having a covering power of >=60. CONSTITUTION:The silver halide emulsion layer contains a dye represented by formula I so as to control increase of transmission of density in a nonexposed part to <=0.06. In formula I, Z11 is a nonmetallic atomic group; each of R11 and R12 is H or an electron donor; each of R13 and R14 is H or a substituent group; each of R15, and R16 is H, alkyl, or aryl; and n is 0, 1, or 2.

Description

Description: [0001] The present invention relates to a silver halide photographic material in which the yellowing of the silver tone of an image is reduced. BACKGROUND OF THE INVENTION The covering power of silver halide emulsions is of great interest to emulsion manufacturers. This is because using a high covering power emulsion saves on the amount of silver needed to maintain a constant optical density. However, the color tone of the developed silver of the emulsion grains that provide this high covering power is yellowish and gives an unpleasant feeling to the image viewer, although it depends mostly on the grain size and grain thickness. This yellowish tinge is due to the fact that the developed silver also decreases in size and thickness as the particle size and thickness change, scattering of the blue light component increases, resulting in light with a strong yellowish tinge. For this reason, JP-A-60-1
As seen in No. 54251 and No. 61-285445, the color tone has been adjusted and yellowing has been suppressed by using substantially water-insoluble dyes. However, when dyes with conventional structures are used, the dye has sub-absorption at light wavelengths shorter than the main absorption, and this sub-absorption causes the image to take on a yellowish tinge. was there. SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks and to provide a silver halide photosensitive material in which images have a suppressed yellow tinge. Means for Solving the Problems The present inventors have proposed a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support. The covering power of the silver halide emulsion layer is 60 or more, and the transmission density of the unexposed area after developing the dye represented by the following general formula (I) in the silver halide emulsion layer and/or other layers. It has been found that the above-mentioned problems can be solved by a silver halide photographic material characterized in that the increase in density due to dye inclusion is 0.06 or less. General formula (I) ##STR2## In the formula, Z11 represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and R11 and R12 represent a hydrogen atom or an electron-donating group (provided that , R12 is bonded to a carbon atom of the heterocycle), R13 and R14 represent a hydrogen atom or a substituent, R15 and R16 represent a hydrogen atom, an alkyl group or an aryl group, and R15 and R16 are bonded to each other. to form a 5- or 6-membered ring, R13 and R1
5 or R14 and R16 may be linked to each other to form a 5- or 6-membered ring. n represents 0, 1 or 2. Each group in general formula (I) will be explained. Examples of the heterocycle formed from Z11 and a pyrazoline ring condensed with Z11 include pyrazolotriazole, pyrazolopyrazole, imidazopyrazole, pyrazolotetrazole, and pyrazolobenzimidazole. It is zolotriazole. R11,
The electron-donating group represented by R12 is not particularly limited as long as the value of Hammett's substituent constant σp is zero or negative. The electron-donating group represented by R11 and R12 includes an alkyl group having 1 to 32 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, n- octyl, isooctyl, tridecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl) aryl groups with 6 to 10 carbon atoms (e.g., phenyl, naphthyl), alkoxy groups with 1 to 32 carbon atoms (e.g., methoxy, ethoxy, 2 -dodecyl ethoxy), carbon number 6
~10 aryloxy groups (e.g., phenoxy, naphthoxy), acylamino groups (e.g., acetamide, benzamide, tetradecanamide, butyramide), amino groups (e.g., unsubstituted amino, methylamino, dimethylamino, anilino), ureido groups (e.g. methylureido, ethylureido, phenylureido), alkylthio groups (e.g. methylthio, octylthio, tetradecylthio, isobutylthio), arylthio groups (e.g. phenylthio, naphthylthio), alkoxycarbonylamino groups (e.g. methoxycarbonylamino) ,
Tetradecyloxycarbonylamino), etc., and these groups can further include substituents (e.g., alkyl groups, alkoxy groups, aryl groups, aryloxy groups, halogen atoms, sulfonamide groups, acylamino groups, alkoxycarbonyl groups, aryl groups, etc.). Examples of these groups include a roxycarbonyl group, an acyl group, a cyano group, a ureido group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an amino group, an imide group, and a heterocyclic group. (described in No. 186567/1983). The substituents represented by R13 and R14 are alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl,
n-propyl, n-butyl, isobutyl, dodecyl, benzyl, phenethyl, 2-methanesulfonamidoethyl, 2-hydroxyethyl), alkoxy groups having 1 to 20 carbon atoms (e.g. methoxy, ethoxy), 2 to 20 carbon atoms
alkoxycarbonylamino groups (e.g. methoxycarbonylamino, ethoxycarbonylamino, isopropoxycarbonylamino), acylamino groups having 2 to 20 carbon atoms (e.g. acetamido, propanoylamino, benzoylamino), halogen atoms (e.g. fluorine , chlorine, bromine, iodine) are preferred. The alkyl group represented by R15 and R16 is preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl,
n-butyl, isobutyl, n-hexyl, dodecyl, octadecyl, 2-hydroxyethyl, 2-methanesulfonamidoethyl, 4-carbamoylbutyl, 2-carbamoylethyl, 2-sulfamoylethyl, 2-methoxyethyl, 3- hydroxyethyl, 2-carboxyethyl). The aryl group represented by R15 and R16 is preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-tolyl, 4-chlorophenyl, 4-methoxyphenyl). The 5- or 6-membered ring formed by connecting R15 and R16 to each other includes a piperidine ring,
Examples include a pyrrolidine ring and a morpholine ring. Examples of the 5- or 6-membered ring formed by linking R13 and R15 or R14 and R16 include a julolidine ring, a tetrahydroquinoline ring, and an indoline ring. Specific examples of the dye represented by general formula (I) are shown below, but the present invention is not limited thereto. [Formula 3] [Formula 3] [Formula 4] [Formula 4] [Formula 5] [Formula 5] [Formula 6] [Formula 7] ##STR10## The dye represented by the general formula (I) can be synthesized by the method described in JP-A-60-186567. As the dye used in the present invention, a dye represented by the general formula (I) is used. In addition, dyes represented by general formula (I) and 570 to 700n
Preferably, the dye is used in combination with another dye having a maximum absorption wavelength between 580 and 650 nm. Here, the maximum absorption wavelength exhibited by another dye in the present invention means the maximum absorption wavelength when the dye is present in the light-sensitive material. The dye having a maximum absorption wavelength of 570 to 700 nm used in the present invention is selected from among, for example, anthraquinone dyes, azo dyes, azomethine dyes, indoaniline dyes, oxonol dyes, cyanine dyes, styryl dyes, triphenylmethane dyes, etc. The one with the maximum wavelength is selected. Stability to development processing, light fastness, desensitization,
Considering the effects on photographic performance such as fog and stain, anthraquinone dyes, azo dyes, azomethine dyes,
and indoaniline dyes are preferably used. More preferably, the following general formula (II) or (II
I) is used. General formula (II) ##STR12## In the formula, R20 represents an alkyl group, an aryl group or a heterocyclic group, R21 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R22 represents Represents a hydrogen atom, an alkyl group, an acylamino group, an alkoxy group, or a ureido group, and R23 and R24 each represent the general formula (I)
R25, R2 are synonymous with R13 and R14 in
6 has the same meaning as R15 and R16 in general formula (I). Z21 is -CONH-, -NHCO- or -N
Represents HCONH-. Furthermore, R21 and R22 may be linked to form a 5- to 7-membered ring. General formula (III) ##STR13## In the formula, R31 represents a hydrogen atom or a substituent, and Za, Zb, and Zc are =CH-, =CR32-(R3
2 represents a hydrogen atom or a substituent. ) or =N-. If Zc=Zb is a carbon-carbon double bond, it may form part of another aromatic ring. However, R31 and R32
is the value of Hammett's substituent constant σp of either of them is 0
．． 6 or more, or the sum of the values of Hammett's substituent constant σp of these groups is 0.6 or more. R33
, R34 and R35 represent a hydrogen atom or a substituent. n
represents 0, 1 or 2. In addition, it may be a dimer or a multimer of more than one compound that is bonded to each other via a divalent or more polyvalent group at R31 or Za, Zb or Zc. Each group of general formula (II) will be explained. The alkyl group represented by R20, R21, and R22 is an alkyl group having 1 to 32 carbon atoms (for example, methyl, ethyl,
n-propyl, isopropyl, t-butyl, n-octyl, dodecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl) are preferred, and substituents (e.g. aryl group, cyano group, halogen atom, alkyl or arylcarbonyl group, alkyl or (Aryloxy group, alkyl or aryloxycarbonyl group, amino group, sulfonyl group, acyl group, acylamino group, carbamoyl group, sulfamoyl group, sulfonamide group, ureido group, hydroxy group, carboxy group, alkyl group, etc.)
It may have. The aryl group represented by R20 is preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl), and may have the substituents listed for the alkyl group. Examples of the heterocyclic group represented by R20 include a pyridyl group, a quinolyl group, a furyl group, a benzoxazolyl group, a benzothiazolyl group, an imidazolyl group, and a pyrazolyl group. You may do so. [0024] Examples of the halogen atom represented by R21 include fluorine, chlorine, bromine and iodine. The alkoxy group represented by R21 and R22 has 1 carbon number.
~32 alkoxy groups (e.g. methoxy, ethoxy,
(n-hexyloxy, n-dodecyloxy, n-pentadecyloxy, isobutyloxy) are preferred, and may have the substituents listed for the alkyl group. The acylamino group represented by R22 has 1 to 32 carbon atoms.
Preferred are acylamino groups (e.g., acetamido, propanoylamino, butanoylamino, pentanoylamino, hexanoylamino, benzamide, octanoylamino, dodecanoylamino) having the substituents listed above for the alkyl groups. It's okay. The ureido group represented by R22 is a ureido group having 1 to 32 carbon atoms (for example, an unsubstituted ureido group,
Methylureido, ethylureido, n-hexylureido, phenylureido, heptylureido) are preferable, and they may have the substituents listed for the alkyl group. The 5- to 7-membered ring formed by connecting R21 and R22 includes a benzene ring to which R21 and R22 are bonded, a naphthalene ring, an oxindole ring,
Examples include those in which a 2-oxobenzimidazoline ring, a carbostyryl ring, etc. are formed. Specific examples of the dye represented by general formula (II) are shown below, but the present invention is not limited thereto. [0026] [Chemical 14] [Chemical 15] [Chemical 16] [Chemical 17] [Chemical 16] [Chemical 17] The dye represented by the general formula (II) is described in JP-A-61-48854; It can be synthesized by the method described in JP-A No. 60-32851. Next, general formula (III) will be explained. General formula (III) is JP-A-63-1
It has the same meaning as the general formula (I) described in No. 45281. Specific examples of the dye represented by general formula (III) are shown below. Other specific examples of dyes represented by formula (III) are described in JP-A-63-145281. There is. The dye used in the present invention can be dispersed in the emulsion layer and other hydrophilic colloid layers (interlayer, protective layer, antihalation layer, filter layer, etc.) by various known methods. (2) A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye of the present invention is dissolved or dispersed in an aqueous solution or solvent and then used in an emulsion layer or a hydrophilic colloid layer. Suitable solvents, such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, halogenated alcohols described in JP-A-48-9715 and US Pat. No. 3,756,830, acetone, water, pyridine, etc.; It can also be dissolved in a mixed solvent of these and added to the emulsion in the form of a solution. (2) A method in which a solution of a compound dissolved in an oil, that is, a substantially water-insoluble high-boiling solvent with a boiling point of about 160° C. or higher, is added to a hydrophilic colloid solution and dispersed. Examples of the high boiling point solvent include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, etc.), as described in U.S. Pat. No. 2,322,027. , tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxy (ethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate), etc. can be used. Also, the boiling point is about 30℃
to about 150°C, such as lower alkyl acelates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and solvents that are easily soluble in water. For example, alcohols such as methanol and ethanol can also be used. The ratio of the dye to the high boiling point solvent used here is preferably 10 to 1/10 (weight ratio). (2) A method of incorporating the dyes and other additives of the present invention into a polymer latex composition filling a photographic emulsion layer or other hydrophilic colloid layer. Examples of the polymer latex include:
Polyurethane polymers, polymers polymerized from vinyl monomers (suitable vinyl monomers include acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, glycidyl acrylate, etc.), α-substituted acrylic esters) (methyl methacrylate, butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butylacrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl acetate, vinyl butyrate, etc.) , vinyl halides (vinyl chloride, etc.), vinylidene halides (vinylidene chloride, etc.)
, vinyl ethers (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-
methylstyrene, etc.), substituted styrenes (hydroxystyrene, chlorostyrene, methylstyrene, etc.), ethylene, propylene, butylene, butadiene, acrylonitrile, and the like. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomers as a minor component. Other vinyl monomers include itaconic acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, and the like. ]
etc. can be used. These filled polymer latexes are disclosed in Japanese Patent Publication Nos. 51-39853, 59943/1983, and 5/1989.
No. 3-137131, No. 54-32552, No. 54-
No. 107941, No. 55-133465, No. 56-1
No. 9043, No. 56-19047, No. 56-1268
It can be produced according to the method described in No. 30 and No. 58-149038. Here, the usage ratio of dye and polymer latex is 10 to 1/10 (preferably weight ratio). ■ A method of dissolving the compound using a surfactant. Useful surfactants include oligomers or polymers. For details of this polymer, see JP-A-53-138726 and JP-A-60-20025.
No. 1, No. 60-203935, Patent Application No. 1976-1276
It is stated in No. 6. (2) A method in which a hydrophilic polymer is used in place of the high-boiling point solvent or in combination with the high-boiling point solvent in (1) above. This method is described, for example, in U.S. Pat.
, No. 195 and West German Patent No. 1,957,467. (2) Microcapsule method using a polymer having carboxyl group, sulfonic acid group, etc. in the side chain as described in JP-A-59-113434. In addition, in the hydrophilic colloid dispersion obtained above, for example,
Hydrosols of lipophilic polymers as described in No. 39835 may also be added. Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be used for photography can be used. In the present invention, the dye-containing layer is an emulsion layer, a protective layer, a back layer, an antihalation layer, and an intermediate layer, and may be added separately. Preferred containing layers are emulsion layers and back layers. In the present invention, the content of the dye is preferably 0.06 to 0.01, more preferably 0.03 to 0.01 in order to increase the concentration by adding the dye. If the transmission density exceeds 0.06, the apparent fogging density will appear to have increased, resulting in poor visibility, and the silver tone will be strongly influenced by the tone modifier, making it impossible to obtain a desired silver tone. On the contrary, 0.01
If it is less than that, the degree of color tone improvement will be poor. The optimum amount of dye to be added depends on the support concentration, the extinction coefficient of the dye, the maximum absorption wavelength of the dye, and the color tone of the developed silver, but it is 1 x 10-7 mol/m2.
It is preferable to use 1×10 −4 mol/m 2 from 1×10 −4 mol/m 2 . More preferably from 2 x 10-7 mol/m2 to 2 x 10-5
mol/m2, most preferably from 5x10-7 mol/m2 to 1.5x10-5 mol/m2. The emulsion grains used in the present invention are preferably tabular grains. The tabular photosensitive silver halide emulsion used in the present invention includes silver chloride, silver chlorobromide,
Silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but silver bromide or silver iodobromide is preferable from the viewpoint of high sensitivity, and in particular, the iodine content is 0 mol% to 3.5 mol%. is preferred. The projected area diameter of the tabular emulsion of the present invention is 0.3 to
It is preferably 2.0 μm, particularly 0.5 to 1.5 μm. Also, the distance between parallel planes (particle thickness) is 0.
05 μm to 0.5 μm, particularly preferably 0.1 to 0.25 μm. The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are disclosed in JP-A-58-12
7,921, JP-A-58-113,927, JP-A-58
-113,928, and the method described in US Pat. No. 4,439,520. Also, p
Seed crystals containing 40% or more of tabular grains by weight are formed in an atmosphere with a relatively low pBr value of Br1.3 or less, and the seed crystals are grown while simultaneously adding silver and halogen solutions while keeping the pBr value at the same level. Obtained by growing . During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei. The size of the tabular silver halide grains is determined by the selection of the type and amount of temperature regulating solvent, the silver salt used during grain growth,
It can be adjusted by controlling the rate of addition of the halide and the like. Further, among tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The structure and manufacturing method of the monodispersed hexagonal tabular grains referred to in the present invention are as described in JP-A-63-151618. For the present invention, so-called halogen conversion type particles, such as those described in British Patent No. 635,841 and US Pat. No. 3,622,318, can be particularly effectively used. The degree of halogen conversion is 0.2 mol% to 2 mol%, especially 0.2 mol% to 0, based on the amount of silver.
．． 4 mol% is good. For silver iodobromide, grains having a structure having a high iodine layer inside and/or on the surface are particularly preferred. By converting the surface of the tabular silver halide grains of the present invention, a silver halide emulsion with higher sensitivity can be obtained. As a method for halogen conversion, an aqueous halogen solution having a solubility product with silver that is smaller than the halogen composition of the particle surface before halogen conversion is usually added. For example, for silver chloride and silver chlorobromide tabular grains, an aqueous solution of potassium bromide and/or potassium iodide is added, and for silver bromide and silver iodobromide tabular grains, an aqueous solution of potassium iodide is added. to cause conversion. The concentration of the aqueous solution to be added is preferably dilute, and is preferably 30% or less, more preferably 10% or less. Furthermore, 1 mole of silver halide per minute before halogen conversion
Preferably, the converted halogen solution is added at a rate of less than mol %. Further, during halogen conversion, part or all of the sensitizing dye and/or silver halide adsorbing substance of the present invention may be present, and silver bromide, silver iodobromide, etc. may be present in place of the aqueous conversion halogen solution. , silver halide fine grains of silver iodide may be added. The size of these fine particles is 0.
2 μm or less, preferably 0.1 μm or less, especially 0.05 μm
It is desirable that it be less than m. The halogen conversion method of the present invention is not limited to any one of the above methods, but can be used in combination depending on the purpose. The silver halide composition on the grain surface before halogen conversion is as follows:
Preferably, the iodine content is 3 mol% or less. In particular, it is preferably 1.0 mol% or less. When performing halogen conversion using the above method, a method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and tetrasubstituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and it is preferable to use 0.5 g to 5 g of thiocyanate and 0.2 g to 3 g of thioether per mole of silver halide. In the present invention, the tabular silver halide emulsion may be a mixture of two or more types of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. For example, a spherical or potato-shaped photosensitive emulsion or a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 3 times or more the grain thickness may be placed in the same layer or in different layers as described in JP-A-58-127921. May be used for layers. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or, conversely, on the side farther away. Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. coexist in the process of silver halide grain formation or physical ripening during silver halide production. You may let them. Further, during grain formation, a so-called silver halide solvent such as a thiocyanate, a thioether compound, a thiazolidine ethione, or a tetrasubstituted thiourea may be present. Among them, thiocyanates, tetrasubstituted thioureas and thioethers are preferred solvents for the present invention. There are no particular restrictions on the emulsion sensitization method or various additives used in the photosensitive material of the present invention.
Those described in the following relevant sections of Publication No. 68539 can be used. Item
Applicable pieces
Part 1 Chemical sensitization method
JP-A-2-68539, page 10, upper right column 1

From the 3rd line to the 16th line in the lower left column. 2 Antifoggant/Stabilizer From line 17 in the lower left column on page 10 to upper left on page 11
Column line 7 and page 3, lower left column line 2 to page 4
Bottom left column of the page. 3 Spectral sensitizing dye From line 4 of the lower right column on page 4 to page 8, lower right column 4 Surfactant/antistatic agent From line 14 of the upper left column on page 11 to upper left of page 12
Column 9th line 5 Matting agent/slip agent/plasticizer Page 12, top left column line 10 to top right column line 10
eye. Page 14, lower left column, line 10 to lower right column 1
Row 6 Hydrophilic colloid
Page 12, top right column, line 11 to bottom left column, line 16
eye. 7 Hardener
From the 17th line of the lower left column of page 12 to the upper right of page 13

Column 6th line. 8 Support
Page 13, upper right column, lines 7 to 20. 9 Dyes and mordants From page 13, lower left column, line 1 to page 14, lower left column
9
Row number. 10 Development processing method JP-A-2-103037, page 16, upper right column

From line 7 to line 15 in the lower left column of page 19. and special

Kaihei 2-115837 Publication, page 3, lower right column, line 5

From the top, page 6, top right column, line 10. EXAMPLES Next, the present invention will be explained in detail based on examples. Example 1 Preparation of Support A A biaxially stretched blue-dyed polyethylene terephthalate film (*) with a thickness of 175 μm was subjected to corona discharge treatment, and coated on both sides with a wire bar coater to the following coating amount. It was dried at ℃ for 1 minute.・Butadiene-styrene copolymer latex Butadiene/0.32g/m2 Styrene weight ratio = 31
/69・2,4-dichloro-6-hydroxy-s-triazinato 4.2 mg/m2 Lium salt *In the latex solution, as an emulsifying dispersant, [0045] Contains 0.4wt% per minute. (*) Polyethylene terephthalate film is 1,4
-Bis(2,6-diethylanilino)anthraquinone. Next, both sides were coated using a wire bar coater so that the coating amount was as shown below, and dried at 150° C. for 1 minute. ·gelatin

80mg/m2・Dye A (solid dispersion)

16mg/m2 00
Preparation of Dye A Solid Dispersion Water (434 ml) and Triton X-200 surfactant (TX-200) (53 g) (Rohm &
1.5 liters of 6.7% solution (sold by Haas)
I put it in a screw cap jar. To this, 20 g of dye and zirconium oxide (ZrO) beads (800 ml) (2 mm diameter) were added, the bottle was capped tightly and placed in a mill, and the contents were ground for 4 days. 12.5% content
was added to an aqueous gelatin solution (160 g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove ZrO beads. If this continues, the particle size will be 3
It is not preferable because it contains particles larger than μm. Therefore, 1
Particles larger than μm were removed by centrifuging at 5000 rpm for 5 min. Preparation of dye emulsion dispersions Using dyes 1 to 8 in Table 1, dye emulsions 1 to 8 were obtained in the following manner. 0.2 g of dye 1 and 0.01 g of the oligomer surfactant [Chemical formula 23] were dissolved in 3 cc of ethyl acetate, added to 15 cc of gelatin aqueous solution (15 wt%), and stirred at high speed at 15,000 rpm with a homogenizer. Emulsion 1
I got it. Dye emulsion 2 was prepared in the same manner for dyes 2 to 8.
-8 was obtained. Preparation of Emulsion A 4.5 g of potassium bromide and 20.6 g of gelatin in 1 liter of water
g, thioether HO(CH2)2S(CH2)2S(
Add 2.5 cc of a 5% aqueous solution of CH2)2OH,
Add an aqueous solution of 3.43 g of silver nitrate, 2.97 g of potassium bromide, and 0.363 g of potassium iodide into the solution kept at ℃ while stirring.
was added in 37 seconds using a double jet method. Subsequently, 0.9 g of potassium bromide was added, and then an aqueous solution containing 4.92 g of silver nitrate was added over 13 minutes. After that, the temperature was raised to 70℃, and 18cc of 25% ammonia solution was added.
After addition, 17 cc of 100% acetic acid was added to neutralize.
Subsequently, an aqueous solution of 133.49 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by a controlled double jet method while maintaining the potential at pAg 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was 2.6 times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 38.5 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After that, the temperature was lowered to 35°C, soluble salts were removed by the precipitation method, and then the temperature was raised to 40°C, 68 g of gelatin and 2.35 g of phenoxyethanol were added, and the pA
g was adjusted to 8.20. The prepared silver halide grains were tabular and had an average projected area circle equivalent diameter of 1.4 μm.
The average particle thickness was 0.20 μm. Next, add 56 emulsion
The temperature was raised to 0.degree. C., the pH was adjusted to 5.9, and 4-hydroxy-6-methyl-1,3,3a,7tetrazaindene and sensitizing dye 1 were added. After a further 10 minutes, sodium thiosulfate, potassium thiocyanate, and chloroauric acid were added to perform chemical sensitization, and emulsion A was obtained. Preparation of Emulsion Coating Solution The following chemicals were added to emulsion A per mole of silver halide to prepare a coating solution.・Dye emulsion

Table 2 - Polymer latex (poly(ethyl acrylate/methacrylic acid) = 97/3) 20.0g - Hardener 1,2-bis(vinylsulfonylacetamido)ethane 2.4g -2,6-
Bis(hydroxyamino)-4-diethylamino-1
,3,5-triazine

76mg ・Sodium polyacrylate (
Average molecular weight 41,000) 2
．． 1g ・Sodium polystyrene sulfonate (average molecular weight 600,000) 1.0g ・Dextran (molecular weight 39,000)
23.6g ・Trimethylolpropane
9.8
g ・Potassium hydroquinone monosulfonate
9.7g
Preparation of Photographic Material The above coating solution was coated on both sides of the support A at the same time as the hardener side protective layer solution.The amount of coated silver was 2 g/m2 per side. . The surface protective layer was prepared so that each component was coated in the following amounts to obtain Samples I-1 to I-10. Contents of surface protective layer

Application amount ・Gelatin

1.138g/m2 ・Dextran (
Average molecular weight 39,000)
0.228g/m2 ・4-hydroxy-6-
Methyl-1,3,3a,7-tetrazaindene
0.0155g/m2 ・Sodium polyacrylate (average molecular weight 41,000)
0.023g/m2 [Chemical formula 26] - Polymethyl methacrylate (average particle size 3.7
μm) 0.088g/m2 ・Proxel

0.0006 Performance Evaluation Photographic material I in green light with a peak at 550 nm
-1 to I-10 were exposed for 1/10 seconds from both sides. Next, using a Fujifilm automatic processor FPM-5000, developer RD3, and fixer Fuji F, Dry to Dr.
y Processed for 90 seconds. The developer temperature at that time was 35℃
The fixing solution temperature was 30°C and the washing water temperature was 20°C. The density increase value Dv due to the addition of dye was determined from the difference between the green density value obtained by processing the unexposed sample in the automatic processor described above and the green density value of the sample to which no dye was added. Covering power is Dma under the above exposure and development conditions.
The amount of silver in x parts was measured using a fluorescent X-ray method, and the density was determined by the amount of developed silver (
mg/dm2) and multiplied by 1,000. The developed silver tone has a transmitted light blackening density of 1.
The color tone of the sample was observed using a sample that was uniformly exposed over a relatively wide area so that the light intensity was 0. [Table 1] [Table 2] [0059] As can be seen from Table 2, by adding the color tone adjusting dye of the present invention in an amount such that ΔDv is 0.01 to 0.06, It can be seen that, compared to Comparative Examples 1 to 3, the yellowing of the developed silver image tone was reduced, and there was a tone improving effect. Further, from Example 2, it can be seen that the present invention is also effective in rapid processing. As can be seen from Table 3 of the results of Example 3, it can be seen that even when the dye of the present invention is added to the back layer, the tone of the developed silver image is improved. Example 2 Using the same sample as in Example 1, the same experiment was conducted except for the development conditions. Developed using Fujifilm automatic developing machine FPM9.
Dry using 000, developer RD7, and fixer Fuji F.
to Dry for 45 seconds. The processing liquid temperature was the same as that of FPM5000 in Example 1. The results obtained are
The results were the same as in Example 1. Example 3 Contents of back dye layer - Dye emulsion

Table 3 Gelatin

3.4g/m2
embedded image Sodium polystyrene sulfonate (average molecular weight
600,000) 15mg/m2 1,2,bis(vinylsulfonylacetamido)ethane
68mg/m2 colloidal silica

0.4g/m2 Polymer latex (poly(ethyl acrylate/methacrylic acid) 2g/m2 acid) = 97/3
) Contents of back surface protective layer Gelatin

0.57g/m2 Polymethyl methacrylate (average particle size 3.7μm) 0.0
9 g/m2 Preparation of Photographic Material The above-mentioned back dye coating solution was coated simultaneously with the surface protective layer on one side of a 175 μm blue-colored polyethylene terephthalate transparent support to form a back. Next, an emulsion coating solution was prepared using the same emulsion A as in Example 1 and the same formulation as in Example 1. However, the dye emulsion in Example 1 was not added. Next, this emulsion coating solution was applied together with the surface protective layer of Example 1 to the opposite side of the back surface described above in a coating amount of 4 g/silver.
Samples III-1 to III-
Got 5. Evaluation of coated samples In the same manner as in Example 1, △Dv, covering power,
The developed silver tone was observed. However, single-sided exposure was used. [Table 3] [Effects of the Invention] By using the dye represented by the general formula (I) in a sensitive material having a silver halide emulsion layer with a covering power of 60 or more, the silver image after development can be improved. It was possible to suppress the color tone from becoming yellowish.

Claims (2)

[Claims] Claim 1. In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, the silver halide emulsion layer comprises:
A coating power of 60 or more, and an increase in the transmission density of the unexposed area after development treatment with a dye represented by the following general formula (I) in the silver halide emulsion layer and/or other layers due to the inclusion of the dye. A silver halide photographic light-sensitive material characterized by containing 0.06 or less of general formula (I) [Formula 1] In the formula, Z11 represents a nonmetallic atomic group necessary for forming a nitrogen-containing heterocycle; , R11 and R12 represent a hydrogen atom or an electron-donating group (provided that R12 is bonded to a carbon atom of the heterocycle), R13 and R14 represent a hydrogen atom or a substituent, and R15 and R16 represent a hydrogen atom or an electron-donating group. represents an atom, an alkyl group, or an aryl group, R15 and R16 may be linked to each other to form a 5- or 6-membered ring, and R13 and R15 or R14
and R16 may be linked to each other to form a 5- or 6-membered ring. n represents 0, 1 or 2. 2. In addition to the dye represented by the general formula (1), it also contains a dye having a maximum absorption wavelength between 570 and 700 nm, and the transmission density of the unexposed area after development processing increases due to the dye content. The silver halide photographic material according to claim 1, characterized in that the silver halide photographic material contains 0.06 or less.