JPH0534858A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain the tone of a blackened image from yellowing material by using an emulsion layer having a covering power of >=60 and an electron- attractive or condensed ring anthraquinone dye so as to raise an unexposed part transmitted density after development processing by <=0.06. CONSTITUTION:The dye represented by formula I having a covering power of <=60 is contained in the emulsion layer so as to raise the unexposed part transmitted density after development processing by 0.06 due to addition of the dye. In formula I, each of R11-R18 is, independently, H, halogen, or the like, or each of (R11 and R12), (R12 and R13), (R13 and R14), (R15 and R16), (R16 and R17), or (R17 and R18) may combine with each other to form a 5-or 6-membered ring, but one of R11-R18 is cyano or aryl, or one of the above mentioned 6 couples forms one ring and are non-metal atom groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material in which the yellowing of the color tone of image silver is reduced.

[0002]

The covering power of silver halide emulsions is of great interest to emulsion manufacturers. This is because the use of high covering power emulsions saves the amount of silver needed to maintain a constant optical density. However, the color tone of developed silver of the emulsion grains giving a high covering power depends on the grain size and the grain thickness, but is yellowish and gives an image viewer an unpleasant feeling. The yellowish tint is due to the fact that the size and thickness of developed silver also decreases due to the phenomenon of grain size and grain thickness, the scattering of blue light components increases, and the light becomes strongly yellowish. Therefore, as seen in JP-A-60-154251 and JP-A-61-285445, it has been attempted to control the color tone and suppress the yellow tint by using a substantially water-insoluble dye. .. However, when a dye having a conventionally used structure is used, the dye has a sub-absorption at a light wavelength shorter than the main absorption, so that the sub-absorption makes the image yellowish. was there.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material which eliminates the above-mentioned drawbacks and suppresses the yellow tint of images.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention provide 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 emulsion layer is 60 or more, and the dye represented by the following general formula (I) is contained in the silver halide emulsion layer and / or other layers, depending on the content of the dye in the unexposed portion transmission density after development processing. It has been found that the above problems can be solved by a silver halide photographic light-sensitive material characterized by containing an increase in density of 0.06 or less. General formula (I)

[0005]

[Chemical 2]

In the formula, each group of R _{11 to} R ₁₈ may be the same or different and is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group or a sulfonic acid. Group, carboxylic acid group, OR ₂₁ , NR ₁₉ R ₂₀ , CO
OR ₂₁ , COR ₂₁ , SO ₂ R ₂₁ , NR ₂₀ COR ₂₁ , NR
₂₀ SO ₂ R ₂₁ , NR ₂₀ COOR ₂₁ , NR ₁₉ CONR ₁₉ R
₂₀ , CONR ₁₉ R ₂₀ , SO ₂ NR ₁₉ R ₂₀ , OCOR ₂₁ or R ₁₁ and R ₁₂ or R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₆ and R ₁₇ Alternatively, R ₁₇ and R ₁₈ represent a group of non-metal atoms necessary for connecting to each other to form a 5- or 6-membered ring. However, at least one of the groups R _{11 to} R ₁₈ is a cyano group, an aryl group, a heterocyclic group, a carboxylic acid group, or COOR.
₂₁ , SO ₂ R ₂₁ , NR ₂₀ COR ₂₁ , NR ₂₀ SO ₂ R ₂₁ ,
NR ₂₀ COOR ₂₁ , NR ₁₉ CONR ₁₉ R ₂₀ , CONR ₁₉
Represents one of groups selected from R ₂₀ , SO ₂ NR ₁₉ R ₂₀ , and OCOR ₂₁ , or represents R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R
_At least one group of ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₆ and R ₁₇ , R ₁₇ and R ₁₈ represents a non-metallic atomic group necessary for forming a 5- or 6-membered ring. And Here, R ₁₉ and R ₂₀ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₂₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₉ and R ₂₀ or R ₂₀ and R ₂₁ represent They may be linked to form a 5- or 6-membered ring.

Each group of the general formula (I) will be described. R
_The alkyl group represented by _{11 to} R ₂₁ is preferably an alkyl group having 1 to 30 carbon atoms and has a substituent (for example, a hydroxyl group, a carboxylic acid group, a cyano group, an alkoxy group, an aryloxy group,
Halogen atom, sulfamoyl group, sulfonamide group,
It may have an alkoxycarbonyl group, an acyl group, a sulfonyl group, a carbamoyl group, an amino group, an aryl group). Specifically, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, cyclohexyl, 2-ethylhexyl, 2-carboxyethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-dimethyl. Aminoethyl, carboxymethyl, isopropyloxycarbonylmethyl, butoxycarbonylmethyl, 2-methanesulfonamidoethyl, 2-methoxyethyl, benzyl, 2-acetoxyethyl, 5-carboxypentyl, 2- (2-carboxybenzoyloxy) ethyl, Each group such as chloromethyl may be mentioned.

The aryl group represented by R _{11 to} R ₂₁ is preferably an aryl group having 6 to 14 carbon atoms and has a substituent (for example,
Carboxylic acid group, sulfonic acid group, alkyl group, sulfonamide group, sulfamoyl group, acyl group, amide group, carbamoyl group, alkoxycarbonyl group, alkoxy group,
Cyano group, hydroxyl group, nitro group, alkoxycarbonyl group, halogen atom, amino group). Specifically, phenyl, naphthyl, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, p-tolyl, 4-methoxyphenyl, 2
Each group such as -chlorophenyl, 4-methanesulfonamidophenyl, 2-hydroxy-5-carboxyphenyl, 2-methoxy-5-carboxyphenyl, 4-nitrophenyl, 4-dimethylaminophenyl and the like can be mentioned.

The heterocyclic group represented by R _{11 to} R ₂₁ is preferably a 5- or 6-membered heterocyclic ring, and may be a condensed ring. Specific examples thereof include 2-pyridyl, 3-pyrrolyl, 5-carboxybenzoxazol-2-yl, 3-pyrazolyl, 1-indolyl and the like, which may have a substituent. Examples of the substituent include an alkyl group and a substituent which the above-mentioned alkyl group may have.

Examples of the halogen atom represented by R _{11 to} R ₁₈ include fluorine, base, bromine, iodine and the like.

R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ , R
_The 5- or 6-membered ring formed by connecting ₁₅ and R ₁₆ , R ₁₆ and R ₁₇ , or R ₁₇ and R ₁₈ is a succinimide ring together with a double bond of an anthraquinone ring to which each group is bonded. , Benzene ring, naphthalene ring, indole ring, pyridine ring and the like.

Examples of the 5- or 6-membered ring formed by connecting R ₁₉ and R ₂₀ or R ₂₀ and R ₂₁ include a pyrrolidine ring, a piperidine ring, morpholinic acid and a pyrrolidone ring. Preferred in the general formula (I) is that at least one of R _{11 to} R ₁₈ represents COOR ₂₁ (R ₂₁ has the same meaning as defined above), or R ₁₁ and R ₁₂ or R _12. And R ₁₃
Are linked to each other to form a 5- or 6-membered ring. Specific examples of the dye represented by formula (I) are shown below, but the invention is not limited thereto.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

[0016]

[Chemical 6]

The dyes represented by the general formula (I) are those described in M.
Matsuoka, M. Kisimoto, tea. Kitao, Journal of the Society of Dears and Colorists, 94, 435, 1978 (M. Matsu
oka, M. Kishimoto, T. Kitao, J. Soc. Dyers and Colo
urists, 94, 435 (1978)) and Yutaka Hosoda "Dye Kagaku", pp. 673-741, Gihodo (1957).

The dye used in the present invention can be dispersed in the emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods. A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or a solvent and then using it in the emulsion layer or the hydrophilic colloid layer. Suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, US Pat.
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc. described in No. 6,830, or a mixed solvent thereof. A method in which a compound is dissolved in an oil, that is, a liquid having a high boiling point of substantially insoluble in water and having a boiling point of about 160 ° C. or more, is added to a hydrophilic colloidal solution and dispersed. Examples of the high boiling point solvent include, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate) as described in US Pat. No. 2,322,027. , Tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyllaurylamide), fatty acid ester (eg dibutoxy) Ethyl succinate, diethyl azelate), trimesic acid esters (for example, tributyl trimesic acid) and the like can be used. Also, the boiling point is about 30 ° C to about 150 ° C.
Organic solvents, for example, 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 water-soluble solvents such as methanol. It is also possible to use alcohol such as or ethanol.

The use ratio of the dye and the high boiling point solvent is preferably 10 to 1/10 (weight ratio). A method of incorporating the dye of the present invention and other additives as a polymer latex composition filled with 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 acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
Dodecyl acrylate, glycidyl acrylate, etc.),
α-substituted acrylic ester (methyl methacrylate,
Butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butyl acrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl acetate, vinyl butyrate, etc.), vinyl halide (Vinyl chloride, etc.), vinylidene halide (vinylidene chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-methylstyrene, etc.), substituted styrene (hydroxystyrene, chlorostyrene, etc.) , Methylstyrene, etc.), ethylene, propylene, butylene, butadiene, acrylonitrile and the like. These may be used alone or in combination of two or more kinds, or may be mixed with other vinyl monomer as a minor component. Other vinyl monomers include itaconic acid 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 JP-B-51-39853, JP-A-51-59943 and JP-A-51-59943.
No. 3-137131, No. 54-32552, No. 54-
107941, 55-133465, 56-1
9043, 56-19047, 56-1268.
It can be manufactured according to the method described in No. 30 and No. 58-149038. Here, the use ratio of the dye and the polymer latex is preferably 10 to 1/10 (weight ratio).

A method of dissolving a compound using a surfactant. The useful surfactant may be an oligomer or a polymer. Details of this polymer are described in JP-A Nos. 53-138726, 60-200251, 60-203935, and Japanese Patent Application No. 59-12766. The method of using a hydrophilic polymer in place of the high boiling point solvent or in combination with the high boiling point solvent. Regarding this method, for example, US Pat. No. 3,619,195 and West German Patent 1,
957,467. A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group or the like in its side chain as described in JP-A-59-113434. In addition, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

Gelatin is a typical hydrophilic colloid, but any of the other conventionally known ones that can be used for photography can be used. In the present invention, the content of the dye is an emulsion layer, a protective layer, a back layer, an antihalation layer or an intermediate layer, and may be added in divided portions. Preferred contained layers are an emulsion layer and a back layer. In the present invention, the content of the dye is preferably 0.06 to 0.01, more preferably 0.03 to 0.01, as the concentration is increased by adding the dye. Here, if the transmission density exceeds 0.06, it is apparent that the fog density has increased, and it is difficult to see through, and the silver tone is strongly influenced by the color tone adjusting agent, and the desired silver tone cannot be obtained. Conversely, 0.01
When the amount is below, the degree of color tone improvement is poor. The optimum amount of dye added depends on the concentration of the support, 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 × 10 ^-7 mol / m ² to 1 × 10 ^-4 mol / m ² Is preferably used. More preferably 2 × 10 ⁻⁷ mol / m ² to 2 × 10 ⁻⁵ mol / m ² , and most preferably 5 × 10 ⁻⁷ mol / m ² to 1.5 ×.
It is 10 ^-5 mol / m ² . The covering power referred to in the present invention is a value obtained by dividing the transmission density of a uniformly blackened light-sensitive material by the amount of developed silver (mg / dm ² ) in that portion and multiplying it by 10,000, and covering the silver halide emulsion. Ring power is of great interest to emulsion manufacturers. This is because the use of high covering power emulsions saves the amount of silver needed to maintain a constant transmission density. The covering power in the present invention is 60 or more, preferably 70 or more.

The emulsion grains used in the present invention are preferably tabular grains. As the tabular photosensitive silver halide emulsion used in the present invention, silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide can be used, but the odor is high in view of high sensitivity. Silver iodide or silver iodobromide is preferred,
Particularly, the iodine content is preferably 0 mol% to 3.5 mol%. The projected area diameter of the tabular emulsion of the present invention is 0.3 to 2.0 μm.
m, particularly preferably 0.5 to 1.5 μm. The distance between parallel planes (particle thickness) is 0.05 μm.
.About.0.5 .mu.m, particularly preferably 0.1 to 0.25 .mu.m. The tabular silver halide grains can be produced by appropriately combining the methods known in the art.
The tabular silver halide emulsion is disclosed in JP-A-58-127,92.
1, JP-A-58-113, 927, JP-A-58-11
It can be easily prepared by referring to the method described in US Pat. No. 3,928, U.S. Pat. No. 4,439,520. Also, pBr
In an atmosphere having a relatively low pBr value of 1.3 or less, 40% or more by weight of tabular grains form a seed crystal, and the same p
It can be obtained by growing seed crystals while simultaneously adding a silver solution and a halogen solution while maintaining the Br value. During this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.

The size of the tabular silver halide grains is determined by selecting the kind and amount of the temperature controlling solvent, the silver salt used during grain growth,
It can be adjusted by controlling the addition rate of the halide and the like. Further, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grain according to the present invention are described in JP-A-63-151618.
For the present invention, so-called halogen conversion type (conversion type) particles as described in British Patent 635,841 and US Pat. No. 3,622,318 can be used particularly effectively. The degree of halogen conversion is 0.2 mol% to 2 mol%, especially 0.2 mol% to 0.4 mo with respect to the amount of silver.
l% is good. In silver iodobromide, grains having a structure having a high iodine layer inside and / or on the surface thereof are particularly preferable. By converting the surface of the tabular silver halide grains of the present invention, a silver halide emulsion having higher sensitivity can be obtained.

As a method for converting halogen, an aqueous halogen solution having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion is usually added. For example, potassium bromide and / or potassium iodide aqueous solution is added to silver chloride or silver chlorobromide tabular grains, and potassium iodide aqueous solution is added to silver bromide or silver iodobromide tabular grains. To convert.
The concentration of the aqueous solution to be added is preferably thin, 30% or less, and more preferably 10% or less. Furthermore, 1 per minute per mol of silver halide before halogen conversion
It is preferred to add the converted halogen solution at a rate of less than or equal to mol%. Further, during the halogen conversion, a part or all of the sensitizing dye and / or the silver halide adsorbing material of the present invention may be present, and instead of the converted halogen aqueous solution, silver bromide or silver iodobromide is used. Alternatively, fine silver halide grains of silver iodide may be added. The size of these particles is
0.2 μm or less, preferably 0.1 μm or less, particularly 0.0
It is preferably 5 μm or less. The halogen conversion method of the present invention is not limited to any one of the above methods and may be used in combination depending on the purpose. The silver halide composition on the grain surface before conversion to halogen is preferably an iodine content of 3 mol% or less.
In particular, it is preferably 1.0 mol% or less. When halogen conversion is carried out by the above method, the method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and tetra-substituted thioureas. Among them, the thioether compound and the thiocyanate are particularly effective, and it is preferable to use 0.5 g to 5 g of the thiocyanate and 0.2 g to 3 g of the thioether per mol of silver halide.

In the present invention, the tabular silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. The grain size, halogen composition, sensitivity, etc. of the emulsions to be mixed may be different. For example, a spherical or potato-shaped photosensitive emulsion or a photosensitive silver halide emulsion composed of tabular grains having a grain diameter of 3 times or more the grain thickness is used in the same layer or different as described in JP-A-58-127921. You may use it for a layer. 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 far side. Coexist with cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt in the process of silver halide grain formation or physical ripening during the production of silver halide. You may let me.
A so-called silver halide solvent such as thiocyanate, thioether compound, thiazolidineethione or tetra-substituted thiourea may be allowed to be present at the time of grain formation. Among them, thiocyanate, tetrasubstituted thiourea and thioether are preferred solvents for the present invention.

There are no particular restrictions on the emulsion sensitizing method and various additives used in the light-sensitive material of the present invention.
It is possible to use those described in the following relevant parts of Japanese Patent No. 68539. Item This section 1 Chemical sensitization method JP-A-2-68539, page 10, upper right column 13, line 3 to left lower column, line 16 2 Antifoggants / stabilizers, page 10, lower left column, 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 Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 4 Surfactants / antistatic agents, page 11, upper left column, line 14 to page 12, upper left column, line 9 5 Matting agents, slip agents, plasticizers, page 12, upper left column, line 10 to upper right column, line 10 Page 14, lower left column, line 10 to lower right column, line 1 of the same. 6 Hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16 7 Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 8 Supports, page 13, upper right column, lines 7 to 20. 9 Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9 10 Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, lower left column, line 15 And Japanese Patent Publication No. 2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10;

[0028]

EXAMPLES Next, the present invention will be described in detail based on examples. Example 1 Preparation of Support A Corona discharge treatment was performed on a biaxially stretched blue dyed polyethylene terephthalate film ^(*) having a thickness of 175 μm, and both surfaces were coated with a wire bar coater so that the coating amount was 175. It was dried at ° C for 1 minute. · Butadiene - styrene copolymer latex butadiene / 0.32 g / m ² Styrene weight ratio = 31/69 2,4-dichloro-6-hydroxy -s- triazine isocyanatomethyl 4.2 mg / m ² potassium salt ※ latex solution As an emulsifying dispersion

[0029]

[Chemical 7]

0.4 wt% of the solid content of latex. (*) The polyethylene terephthalate film contains 1,4-bis (2,6-diethylanilino) anthraquinone. Next, both sides were coated with a wire bar coater so as to have the following coating amount, and dried at 150 ° C. for 1 minute.・ Gelatin 80 mg / m ²・ Dye A (solid dispersion) 16 mg / m ²

[0031]

[Chemical 8]

Preparation of Dye A Solid Dispersion Water (434 ml) and Triton X-200 surfactant (T
X-200) (53 g) (sold by Rohm & Haas) and a 6.7% solution were placed in a 1.5 liter screw cap bottle. To this, 20 g of dye and zirconium oxide (Zr
O) beads (800 ml) (2 mm diameter) were added, the bottle was capped tightly, placed in a mill and the contents crushed for 4 days. 12.5% gelatin aqueous solution (1
60 g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove ZrO beads. If left as it is, particles having a particle size of 3 μm or more are contained, which is not preferable. Therefore, 50 particles of 1 μm or more
It was removed by centrifuging under the conditions of 00 rpm and 5 min.

Preparation of Dye Emulsion Dispersion Among the exemplified dyes, the dyes shown in Table 1 were emulsified and dispersed by the following dispersion method A or dispersion method B. Table 1 shows which dispersion method was used. Emulsion Dispersion Method A 2 g of dye and 0.2 g of the following oligomer surfactant A were dissolved in 30 cc of ethyl acetate to prepare a gelatin aqueous solution (15 wt.
%) 25 cc, and stirred at high speed with a homogenizer. After completion of stirring, 50 cc of water, 10 mg of proxel and 20 mg of phenoxyethanol were added. Emulsion Dispersion Method B 0.4 g of dye and 3.5 g of styrene polymer having an average degree of polymerization of 1700 were dissolved in 20 cc of ethyl acetate, and then 1.2 g of the following anionic surfactant A and gelatin aqueous solution (1
(5 wt%) 40 cc with a homogenizer at high speed. After completion of stirring, 35 cc of water and 40 mg of phenoxyethanol were added.

[0034]

[Chemical 9]

Preparation of Emulsion A 4.5 g of potassium bromide and 20.6 gelatin in 1 liter of water.
g, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH ( _2.5 cc) was added to the solution kept at 65 ° C while stirring, and 3.43 g of silver nitrate was added. Aqueous solution and potassium bromide 2.97
g and an aqueous solution containing 0.363 g of potassium iodide were added by the double jet method in 37 seconds. Then, potassium bromide 0.
After adding 9 g, 1 part of an aqueous solution containing 4.92 g of silver nitrate was added.
Added over 3 minutes. After this, the temperature is raised to 70 ° C and the temperature is 25%.
After adding 18 cc of ammonia solution of 100% acetic acid 17
cc was added to neutralize, and subsequently 133.49 g of silver nitrate
And an aqueous solution of potassium bromide were added by the control double jet method for 35 minutes while keeping 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 completion of the addition, 15 cc of 2N potassium thiocyanate solution was added, and further 38.5 cc of 1% potassium iodide aqueous solution was added over 30 seconds. Then, the temperature was lowered to 35 ° C., the soluble salts were removed by the precipitation method, and the temperature was raised to 40 ° C. to obtain gelatin 6
8 g and 2.35 g of phenoxyethanol were added, and pAg was adjusted to 8.20 with potassium bromide. The prepared silver halide grains were tabular, the average projected area circle-equivalent diameter was 1.4 μm, and the average grain thickness was 0.20 μm. Next, the emulsion was heated to 56 ° C., adjusted to pH = 5.9, and 4-hydroxy-6-methyl-1,3,3a, 7 tetrazaindene and sensitizing dye (1) were added. 10 more
After a minute, sodium thiosulfate, potassium thiocyanate and chloroauric acid were added for chemical sensitization to obtain Emulsion A.

[0036]

[Chemical 10]

Preparation of Emulsion Coating Solution The following chemicals were added to Emulsion A per mol of silver halide to prepare a coating solution.・ Dye emulsion Table 2 ・ Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 20.0 g ・ Hardener 1,2-bis (vinylsulfonylacetamide) ethane 2.4 g ・ 2,6-bis (Hydroxyamino) -4-diethylamino-1,3,5-triazine 76 mg-Sodium polyacrylate (average molecular weight 410,000) 2.1 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.0 g-Dextran ( Molecular weight 39,000) 23.6 g-trimethylolpropane 9.8 g-potassium hydroquinone monosulfonate 9.7 g

[0038]

[Chemical 11]

Preparation of photographic material The coating solution was coated on both sides of the support A at the same time as the surface protective layer solution, and the coated silver amount was 2 g / m ² per side.
The surface protective layer was prepared so that each component had the following coating amount, and samples 1 to 13 were obtained. Contents of the surface protective layer Coating amount-Gelatin 1.138 g / m ² -Dextran (average molecular weight 39,000) 0.228 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaine Den 0.0155g / m ² · Sodium polyacrylate (average molecular weight 410,000) 0.023g / m ²

[0040]

[Chemical formula 12]

[0041] - at polymethyl methacrylate (average particle size 3.7μm) 0.088g / m ² · Proxel 0.0006 g / m ² green light having a peak evaluation 550nm performance, photographic materials 1 to 1
3 was exposed on both sides for 1/10 second. Next, Dry to Dry 90 seconds processing was performed using an automatic developing machine EPM-5000 manufactured by FUJIFILM, a developing solution RD3, and a fixing solution FUJI F. At that time, the developing solution temperature is 35 ° C., the fixing solution temperature is 30 ° C., and the washing water temperature is 2
Performed at 0 ° C. The density increase value Dv due to the addition of the dye was determined by the difference between the green density value obtained by subjecting the unexposed sample to the above-mentioned automatic processor processing and the green density value of the sample to which the dye was not added. The covering power is the same as the exposure,
Under the developing conditions, the amount of silver in the Dmax part was measured by the fluorescent X-ray method, and the value was divided by the amount of developed silver (mg / dm ² ) to obtain a value of 10,000.
It was calculated by multiplying by 0. Regarding the developed silver color tone, the color tone of the sample was observed by using the sample uniformly exposed over a relatively wide area so that the transmitted light blackening density was 1.0 under the above-mentioned developing conditions.

[0042]

[Table 1]

[0043]

[Table 2]

As can be seen from Table 1, compared with Comparative Examples 1, 2 and 4, the developed silver image was obtained by adding the color tone adjusting dye of the present invention in an amount such that ΔDv was 0.01 to 0.06. It can be seen that the yellowing of the color tone is reduced and there is an effect of improving the color tone. In addition, it can be seen from Example 2 that it is also effective in rapid processing. As can be seen from Table 2 of the results of Example 3, it is understood that the developed silver image tone is improved even when the dye of the present invention is added to the back layer. Example 2 Using the same sample as in Example 1, the same experiment was conducted under the developing conditions. Developed by Fujifilm's automatic processor FPM9
000, developer RD7, fixer Fuji F using Dry to D
ry Processed for 45 seconds. The treatment liquid temperature is the FPM of Example 1.
Same as 5000. The results obtained were the same as those of Example 1.

Example 3 Contents of Back Dye Layer-Dye Emulsion Table 3 Gelatin 3.4 g / m ²

[0046]

[Chemical 13]

The sodium polystyrenesulfonate (average molecular weight 600,000) 15 mg / m ² 1, 2, bis (vinylsulfonyl acetamide) ethane 68 mg / m ² Colloidal silica 0.4 g / m ² latex polymer (poly (ethyl acrylate / methacrylic 2g / m ² le acid) = 97/3) back contents of the surface protective layer gelatin 0.57 g / m ² polymethyl methacrylate (average particle size 3.7 .mu.m) 0.09 g / m ²

[0048]

[Chemical 14]

Preparation of Photographic Material The back dye coating solution was applied to one surface of a 175 μm transparent polyethylene terephthalate transparent support which was colored blue at the same time as the surface protective layer to form a back. Next, using the same emulsion A as in Example 1, an emulsion coating solution was prepared with 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 on the side opposite to the above-mentioned back surface so that the coated silver amount was 4 g /
It was applied so as to be m ^2, and samples 14 to 21 were obtained. Evaluation of coated sample In the same manner as in Example 1, ΔDv, covering power,
The developed silver color tone was observed. However, single-sided exposure was used for the exposure. The results are shown in Table 2.

[0050]

[Table 3]

[0051]

The use of the dye represented by formula (I) in a light-sensitive material having a silver halide emulsion layer having a covering power of 60 or more suppresses the color tone of a silver image after development from becoming yellowish. I was able to.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, wherein the silver halide emulsion layer has a covering power of 60 or more. And the silver halide emulsion layer and / or
Alternatively, the dye represented by the following general formula (I) is contained in another layer so that the density increase of the transmission density of the unexposed portion after development processing due to the inclusion of the dye is 0.06 or less. Silver halide photographic light-sensitive material. General formula (I): In the formula, each group of R _{11 to} R ₁₈ may be the same or different,
Hydrogen atom, halogen atom, hydroxyl group, alkyl group, aryl group, heterocyclic group, cyano group, nitro group, sulfonic acid group,
Carboxylic acid group, OR ₂₁ , NR ₁₉ R ₂₀ , COOR ₂₁ , CO
R ₂₁ , SO ₂ R ₂₁ , NR ₂₀ COR ₂₁ , NR ₂₀ SO
₂ R ₂₁ , NR ₂₀ COOR ₂₁ , NR ₁₉ CONR ₁₉ R ₂₀ , C
ONR ₁₉ R ₂₀ , SO ₂ NR ₁₉ R ₂₀ , OCOR ₂₁ , or R ₁₁ and R ₁₂ or R ₁₂ and R ₁₃ , R ₁₃ and R ₁₄ ,
R ₁₅ and R _16, R ₁₆ and R ₁₇ or R ₁₇ and R ₁₈ represents a non-metallic atomic group necessary for forming a 5 or 6-membered ring. However, at least one of the groups R _{11 to} R ₁₈ is a cyano group, an aryl group, a heterocyclic group, a carboxylic acid group, or COO.
R ₂₁ , SO ₂ R ₂₁ , NR ₁₉ COR ₂₁ , NR ₁₉ SO
₂ R ₂₁ , NR ₁₉ COOR ₁₉ , NR ₁₉ CONR ₁₉ R ₂₀ , C
ONR ₁₉ R ₂₀ , SO ₂ NR ₁₉ R ₂₀ , represents one of groups selected from OCOR ₂₁ , or R ₁₁ and R ₁₂ , R ₁₂ and R
₁₃ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₆ and R ₁₇ , R ₁₇ and R ₁₈
At least one set of each of the above groups represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring. Where R ₁₉ ,
R ₂₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₂₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₁₉ and R ₂₀ or R ₂₀ and R ₂₁ are linked to each other, or A 6-membered ring may be formed.