JPH1083041A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material capable of coloring a specified hydrophilic colloidal layer of the photographic sensitive material and rapidly decoloring it in the cource of development processing by incorporating a molecularly dispersed specified compound. SOLUTION: The photographic sensitive material contains the molecularly dispersed compound represented by the formula in which each of L1 -L3 is an optionally substituted methine group; R1 is H atom or a substituent including a substituted atom; R2 is a substituent including a substituted atom; (m) is 1, 2, 3, or 4; R3 is H atom or a -CHR3 ' group; R3 ' is H atom or a subtituent including a substituted atom; X is an electron withdrawing group having a Hammett's substituent constant σm of 0.3-1.5; R4 is a -COOR10 , -COR11 , -CONR11 R12 , or -CN group; R5 is H atom or an alkyl or aryl or heterocyclic group; R10 is an alkyl or aryl group; each of R11 and R12 is H atom or an alkyl or aryl group; and (n) is 1 or 2.

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 having a dyed layer, and more particularly to a hydrophilic material containing a dye which is photochemically inert and which is easily decolorized and / or eluted by photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer.

[0002]

2. Description of the Related Art In a silver halide photographic material, a photographic emulsion layer and other hydrophilic colloid layers are often colored in order to absorb light in a specific wavelength range. When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, the filter layer may be located between them.

Light scattered when passing through or after transmission through a photographic emulsion layer is reflected at the interface between the emulsion layer and the support or on the surface of the photosensitive material on the side opposite to the emulsion layer and reenters the photographic emulsion layer. In order to prevent blurring or halation of an image based on the photographic emulsion layer, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an antihalation layer may be provided between the layers. In order to prevent a decrease in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation), the photographic emulsion layer is also colored.

These hydrophilic colloid layers to be colored usually contain a dye. This dye must satisfy the following conditions. (1) To have appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a decrease in sensitivity, regression of a latent image, or fog. (3) No decolorization during the photographic processing or elution into the processing solution or washing water, leaving no harmful coloring on the processed photographic light-sensitive material. (4) Do not diffuse from the dyed layer to other layers. (5) It is excellent in stability over time in a solution or a photographic material and does not discolor.

[0005] In particular, when the coloring layer is a filter layer,
Alternatively, in the case of an antihalation layer on the same side of the support as the photographic emulsion layer, it is preferred that those layers are selectively colored and that the other layers are not substantially colored. Often needed. Otherwise, not only would it have a detrimental spectral effect on the other layers, but it would also destroy its effect as a filter layer or antihalation layer. However, when the layer containing the dye and another hydrophilic colloid layer come into contact with each other in a wet state,
It often occurs that some of the dye diffuses from the former to the latter. More efforts have been made in the past to prevent such dye diffusion.

For example, a method of dyeing a specific layer using solid fine dye particles insoluble in water is disclosed in JP-A-56-12363.
9, No. 63-197943, European Patent No. 15601
Nos. 274723 and 299435, and U.S. Pat. No. 4,950,586.

Particularly, a method using a solid fine particle dispersion of a dye in which an acidic nucleus and a 5-membered heterocyclic ring are bonded by a methine chain is disclosed in JP-A-55-155351, JP-A-3-144438, and JP-B-48-42175. , European Patent No. 524594A
And U.S. Pat. No. 4,923,788.

Further, in order to achieve the above object, a method of using a solid fine particle dispersion of a dye comprising a pyrazolone nucleus and an indole nucleus as a photographic dye is disclosed in JP-A-8-50345.
JP-A-5-86056, JP-A-3-167546
And European Patent No. 434026A. JP-A-5-53241 discloses an example in which the dye is used by dispersing it in oil and / or polymer latex. Most of these dyes are used as yellow photographic dyes. In recent years, dyes that absorb light of a longer wavelength and decolorize by processing or the like have been desired.

[0009]

In the case of a dye comprising a pyrazolone nucleus and an indole nucleus, for example, when used as a magenta dye, three or more methine chains are required. Compounds having such a structure are disclosed in JP-A-8-50345,
Although these are described slightly in, for example, JP-A-167546, the use of these solid fine particle dispersions results in a low decolorization rate during development processing, thereby speeding up the processing and improving the composition of the processing solution (particularly, a reduction in the amount of sodium sulfite added). ), Or when there are changes in various factors for improvement such as the composition of the photographic emulsion, there has been a problem that the decolorizing function cannot always be sufficiently exhibited. When the solid fine particle dispersion is used as a filter, it may have unnecessary absorption and thus lower the sensitivity of the lower layer in some cases. When the above-mentioned dyes are dispersed in an oil and / or a polymer latex for use, emulsification is difficult, and although the decolorizing property is good, the dyes diffuse to other layers during storage and the sensitivity is lowered. There is a problem that the photographic performance is adversely affected. That is, there has been a demand for a compound capable of achieving both decolorization and diffusion resistance, exhibiting absorption characteristics superior to long wavelengths than yellow, and not adversely affecting photographic properties.

It is an object of the present invention to provide a photographic emulsion which has no adverse chemical effects, dyes only a specific layer in a photographic light-sensitive material, and does not diffuse to other layers. An object of the present invention is to provide a silver halide photographic material which contains a dye compound which is eluted and has excellent absorption characteristics.

[0011]

As a result of various studies, the present inventors have found that the object of the present invention can be achieved by the following silver halide light-sensitive materials. (1) A silver halide photographic material comprising at least one kind of a compound represented by the following general formula (I) in a molecular dispersion.

[0012]

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In the formula, L ₁ , L ₂ and L ₃ each represent an optionally substituted methine group. R ₁ and R ₃ represent a hydrogen atom or a substituent (including a substituent atom). R ₂ represents a substituent (including a substituent atom). m is 0 or 1 to 4
Represents an integer up to, and when m is an integer of 2 to 4, R ₂
May be the same or different. R ₃ represents a hydrogen atom or a -CHR ₃ 'X. R ₃ ′ represents a hydrogen atom or a substituent (including a substituent), and X represents an electron-withdrawing group having a Hammett's substituent constant σ _m of 0.3 or more and 1.5 or less. R ₄ is -COOR ₁₀ , -COR ₁₁ , -CON
R ₁₁ represents R ₁₂ , or —CN, and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₁₀ represents an alkyl group or an aryl group, and R ₁₁ and R ₁₂ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 1 or 2. However, the compound represented by the general formula (I) must not have a sulfo group, a salt of a sulfo group, a carboxyl group or a salt of a carboxyl group as a substituent.

Preferred embodiments include the following (2) to (4). (2) The halogenation according to the above (1), further comprising a hydrophilic colloid layer containing at least one compound represented by the general formula (I) as an oil composition and / or a polymer latex composition. Silver photographic photosensitive material. (3) The halogenation according to the above (1) or (2), wherein X is an alkoxycarbonyl group or a cyano group, R ₄ is —COOR ₁₀ or a cyano group, and n = 1. Silver photographic photosensitive material. (4) The silver halide photographic material as described in (2) above, wherein the compound represented by the general formula (I) is fixed in a layer containing the composition.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The dye used in the present invention does not have a sulfo group, a salt of a sulfo group, a carboxyl group, or a salt of a carboxyl group as a substituent to be fixed to a specific hydrophilic colloid layer. Organic solvents having a boiling point of about 30 ° C. to about 150 ° C., for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and water It preferably has high solubility in a solvent that is easily soluble in water, for example, alcohols such as methanol and ethanol.

Hereinafter, the present invention will be described in detail. In the compound of the present invention, by selecting such an electron-withdrawing substituent as X in the general formula (I), the compound and a nucleophile (mainly hydroxyl ion and sulfite ion) in the processing solution during the photographic processing are selected. Reaction is promoted, and a remarkable effect on improvement of the decolorization property is exhibited. This effect is presumed to be due to the fact that the substitution of the electron-withdrawing group on the indole nitrogen atom at the conjugate position with the reaction point with the nucleophile lowers the electron density at the reaction point and facilitates the reaction.

First, the general formula (I) will be described in detail. Hammett's substituent constant σ _m represented by X (for example,
Chem. Rev., 91, 165 (1991))
Examples of the electron-withdrawing group having a size of 0.3 to 1.5 include, for example, a halogen atom (for example, a fluorine atom (σ _m value = 0.
34 or less), chlorine atom (0.37), bromine atom (0.39), iodine atom (0.35)), trifluoromethyl group (0.43), cyano group (0.56), formyl group (0.35), acyl group (eg, acetyl (0.38)), acyloxy group (eg, acetoxy (0.39)), carboxyl group (0.37), alkoxycarbonyl group (eg, methoxycarbonyl (0 .
37)), an aryloxycarbonyl group (eg, phenoxycarbonyl (0.37)), an alkylcarbamoyl group (eg, methylcarbamoyl (0.35)), a nitro group (0.71), an alkylsulfinyl group (eg, methyl Sulfinyl (0.52)), alkylsulfonyl group (for example, methylsulfonyl (0.60)),
And a sulfamoyl group (0.53). Preferably, it is an alkoxycarbonyl group or a cyano group. More preferably, it is an alkoxycarbonyl group.

The methine groups represented by L ₁ , L ₂ and L ₃ are
It may have a substituent (for example, a methyl group, an ethyl group, a cyano group, a chlorine atom), but is preferably unsubstituted, and n is preferably 1.

The substituent represented by R ₁ or R ₂ is, for example, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, t-butyl,
Cyclohexyl, methoxyethyl, ethoxyethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl,
Cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl, acetoxyethyl and the like, and a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (for example,
Benzyl, 2-carboxybenzyl and the like, and a substituted or unsubstituted aryl group having 6 to 18 carbon atoms (for example, phenyl, 4-methylphenyl, 4-methoxyphenyl,
-Carboxyphenyl, 3,5-dicarboxyphenyl, etc.), a substituted or unsubstituted acyl group having 2 to 6 carbon atoms (for example, acetyl, propionyl, butanoyl, chloroacetyl, etc.), a substituted or unsubstituted acyl group having 1 to 8 carbon atoms. Substituted sulfonyl groups (eg, methanesulfonyl, p-toluenesulfonyl, etc.), alkoxycarbonyl groups having 2 to 6 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, etc.), and aryloxycarbonyl groups having 7 to 12 carbon atoms (eg, phenoxy) Carbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, n-butoxy, methoxyethoxy, etc.), 6 to 10 carbon atoms Substituted or unsubstituted aryl Alkoxy group (e.g., phenoxy, 4-
Methoxyphenoxy, etc.), a substituted or unsubstituted acyloxy group having 2 to 8 carbon atoms (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy), substituted or unsubstituted having 1 to 6 carbon atoms. A carbamoyloxy group having 2 to 8 carbon atoms (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.), a substituted or unsubstituted amino group having 0 to 8 carbon atoms (eg, , Unsubstituted amino, methylamino, dimethylamino, diethylamino, phenylamino, methoxyphenylamino,
Chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino,
n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, phenylcarbamoylamino, acetylamino, ethylcarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino, etc.); An unsubstituted carbamoyl group (for example, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl,
t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc., a substituted or unsubstituted sulfonamide group having 1 to 8 carbon atoms (eg, methanesulfonamide, p-toluenesulfonamide, etc.), halogen atom (eg, , Fluorine, chlorine,
Bromine), a hydroxyl group, a nitro group, a cyano group and the like.

R ₁ is preferably a hydrogen atom or a substituent selected from an alkyl group, an aryl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Particularly preferred is a hydrogen atom or a methyl group. m is 0, 1
Or 2 is preferable. When m = 1 or 2, R
₂ is an alkyl group, an aryl group, an amino group, an alkoxy group, an acyloxy group, a carbamoyl group, a halogen atom,
It is preferably a substituent selected from a nitro group and a carboxyl group. More preferably, R ₃ ′ where m = 0 is a hydrogen atom or a substituent selected from an alkyl group and an aryl group. Particularly preferred is an alkyl group.

The alkyl group represented by R ₁₀ , R ₁₁ and R ₁₂ may have a substituent, and is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, octyl, cyclohexyl, Ethoxycarbonylmethyl, 2
-Hydroxyethyl, 2-ethoxyethyl, cyanoethyl and the like are preferred. The aryl group represented by R ₁₀ , R ₁₁ and R ₁₂ may have a substituent, and is preferably an aryl group having 6 to 12 carbon atoms, for example, phenyl, 4-methoxyphenyl, 3-methylphenyl, 4-Chlorophenyl and the like are preferred.

As R ₄ , —COOR ₁₀ and —CN are more preferred. The alkyl group represented by R ₅ may have a substituent, and is preferably an alkyl group having 1 to 18 carbon atoms, such as methyl, 2-phenylsulfamoylethyl, 2-methylsulfamoylethyl, -Acetylsulfamoylethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-ethoxycarbonylethyl and the like are preferred.

The aryl group represented by R ₅ may have a substituent, and is preferably an aryl group having 6 to 22 carbon atoms, for example, phenyl, 4-ethoxycarbonylphenyl, 4- (2-chlorophenylsulfur Moyl) phenyl, 4-phenylsulfamoylphenyl, 4-acetylsulfamoylphenyl, 4-isovalerylsulfamoylphenyl, 4-butanesulfonamidocarbonylphenyl, 4-methanesulfonamidophenyl, 4-phenylsulfonamidophenyl And a 4-ethoxycarbonylsulfamoylphenyl group and the like. Examples of the heterocyclic group represented by R ₅ include pyridyl and sulfolane-3-yl.

The compound represented by formula (I) preferably has a dissociable group in order to achieve both fixability in the light-sensitive material and decolorization during processing. Examples of preferred dissociable groups include a substituted sulfonylamino group (eg, CH ₃ SO ₂ NH—,
_{H 5 C 6 -SO 2 NH-)} , acyl sulfamoyl group, acylsulfamoyl group, a sulfonylcarbamoyl group, a carbamoyl sulfamoyl group. Hereinafter, specific examples of the compound used in the present invention are shown, but the present invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The compound of the general formula (I) used in the present invention is prepared by converting the compound of the general formula (II) and the compound of the general formula (III) into an organic solvent (for example, methanol, ethanol, isopropyl Alcohol, acetonitrile,
N, N-dimethylformamide, N, N-dimethylacetamide, acetic acid, pyridine) at room temperature to reflux. When the progress of the reaction is slow, it can be easily synthesized by adding an appropriate amount of acetic acid, acetic anhydride, p-toluenesulfonic acid, triethylamine, pyridine, ammonium acetate and the like.

[0038]

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The synthesis examples are shown below. Synthesis of compound D-10. (1) Synthesis of pyrazolone moiety

[0040]

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3-ethoxycarbonyl-1- (4-sulfophenyl) -5-pyrazolone sodium salt 150 g
(0.45 mol) was added to 500 ml of 25% aqueous ammonia and heated at 35 ° C. for 2 days for a total of 9 hours.
After the solvent was distilled off under reduced pressure, 300 ml of concentrated hydrochloric acid was added and the mixture was stirred. After suction filtration, the obtained crystals were washed with acetonitrile and dried under reduced pressure to obtain 148 g of 3-carbamoyl-1- (4-sulfophenyl) -5-pyrazolone (compound a).

133 g (0.47 mol) of compound a was added to 1000 ml of acetonitrile, and cooled to -8 ° C. in a methanol-ice bath. 157 ml of the ethylamine (1.1
After addition of 9 mol of tosyl chloride (0.1 mol).
52 mol) were added in small portions. After removing the cooling bath, the mixture was stirred for 1.5 hours, filtered, washed with acetonitrile, dried under reduced pressure, and dried under reduced pressure to give 3-carbamoyl-1- (4-sulfophenyl) -5-p-toluenesulfonyloxypyrazole. 221 g of triethylamine salt (compound b) (containing 1.5 times mol of triethylamine hydrochloride) (content 7
2%).

Compound b, 157 g (corresponding to 0.21 mol)
Was suspended in 800 ml of acetonitrile and cooled to -5 ° C in a methanol-ice bath. 92 g of phosphorus oxychloride
(0.60 mol) was added dropwise, and 70 ml (0.90 mol) of N, N-dimethylformamide was added dropwise. After stirring at 0 ° C. or lower for 2 hours, the reaction solution was poured into 2 liters of ice water, extracted with 1.5 liters of ethyl acetate, and the ethyl acetate phase was washed three times with brine and dried over sodium sulfate. After the desiccant was removed by filtration, the solvent was distilled off under reduced pressure. The obtained solid was dissolved by heating in ethyl acetate, and hexane was added to precipitate crystals. After filtration and drying under reduced pressure, 59.5 g (0.14 g) of 3-cyano-1- (4-chlorosulfonylphenyl) -5-p-toluenesulfonyloxypyrazole (compound c) was obtained.
mol).

17.5 g (40 mmol) of compound c was added to 150 ml of chloroform. To this was added 40 ml of 25% aqueous ammonia, and the mixture was vigorously stirred at room temperature for 20 minutes. Water 50
When 0 ml was added, crystals precipitated. The crystals were collected by filtration, dried under reduced pressure, and dried under reduced pressure to give 3-cyano-1- (4-sulfamoylphenyl) -5-p-toluenesulfonyloxypyrazole (compound d). 3 g (25 mmol) were obtained.

Compound d, 2.9 g (7 mmol) and chloride 2
2.4 g (15 mmol) of -ethylhexanoyl were added to 15 ml of acetonitrile. To this, 0.13 g (0.7 mmol) of p-toluenesulfonic acid monohydrate was added, and the mixture was heated under reflux for 4 hours. The reaction solution was diluted with 200 ml of dilute hydrochloric acid / 200 ethyl acetate.
It was poured into ml and separated. The ethyl acetate phase was washed twice with brine and dried over magnesium sulfate. The drying agent was removed by filtration, and the solvent was distilled off under reduced pressure to obtain an oily substance. This was subjected to flash column chromatography (hexane:
Purified by ethyl acetate = 2: 1) to give 3-cyano-1-
2.7 g (5 mmol) of (4- (2-ethylhexanoyl) sulfamoylphenyl) -5-p-toluenesulfonyloxypyrazole (compound e) were obtained.

2.6 g (4.8 mmol) of compound e was dissolved in 15 ml of methanol, and 1.38 g (10%) of potassium carbonate was dissolved.
mmol) and stirred at room temperature for 30 minutes. 200 water
After confirming that the pH was 10 or more by adding ml, the mixture was extracted with ethyl acetate. The aqueous phase was adjusted to pH <2 with 1N hydrochloric acid and extracted again with ethyl acetate. The ethyl acetate phase was washed once with a saline solution and dried over magnesium sulfate. The drying agent was removed by filtration, and the solvent was distilled off under reduced pressure to give 3-cyano-1- (4- (2-ethylhexanoyl) sulfamoylphenyl) -5-pyrazolone (compound f) 1.7.
g (91%).

(2) Synthesis of indole moiety

[0048]

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3-dimethylaminoacrylaldehyde 5
2.0 g (0.52 mol) was dissolved in 250 ml of acetonitrile, and cooled to -5 ° C in a methanol-ice bath. To this, 84.3 g (0.55 mol) of phosphorus oxychloride was added at an internal temperature of 15%.
The solution was added dropwise while keeping the temperature at not more than ° C and stirred for 30 minutes. Further, a solution of 65.6 g (0.5 mol) of 2-methylindole dissolved in 150 ml of acetonitrile was added dropwise while keeping the internal temperature at 5 ° C. or lower, and a cooling bath was taken and stirred for 1 hour. After the reaction solution was poured into 1 liter of cold water and stirred for 1 hour, a solution of 100 g of sodium hydroxide dissolved in 500 ml of water was added, and the mixture was extracted with 1.5 liter of ethyl acetate. The ethyl acetate phase was washed twice with brine and dried over sodium sulfate. The drying agent was removed by filtration, and the solvent was evaporated under reduced pressure to solidify. This was purified by recrystallization from methanol, and 3- (2-methyl-3-
Indolyl) acrylaldehyde (compound g) 45.0
g (0.24 mol) were obtained.

Compound g, 18.5 g (0.1 mol) was added to N,
Dissolve in 100 ml of N-dimethylformamide, add 27.6 g (0.2 mol) of potassium carbonate, and further add 2-bromo-
18.4 g (0.11 mol) of methyl propionate was added dropwise. The mixture was heated to 100 ° C. in an oil bath and stirred for 40 minutes. The reaction mixture was cooled, poured into 400 ml of 1N hydrochloric acid and extracted with 400 ml of ethyl acetate. The ethyl acetate phase was washed twice with brine and dried over magnesium sulfate. The drying agent was removed by filtration, and the solvent was distilled off under reduced pressure to obtain an oily substance. When methanol was added thereto, crystals were precipitated. The crystals were filtered and dried under reduced pressure to obtain 2- (3- (2
-Formylvinyl) -2-methyl-1-indolyl) methyl propionate (compound h) 15.0 g (55 mmol)
I got

(3) Synthesis of Dye 1.17 g (3 mmol) of compound f and 0.81 of compound h
g (3 mmol) was added to 15 ml of methanol and heated under reflux for 20 minutes. When the reaction mixture was cooled, crystals precipitated. The crystals were filtered and purified by flash column chromatography (hexane: ethyl acetate = 1: 1 to 2: 3) to obtain 1.2 g of Compound D-10 (1. 8 mmol).
λmax 533 nm (in ethyl acetate).

When the compound of the formula (I) is used as a filter dye or an antihalation dye, any effective amount can be used, but the optical density should be in the range of 0.05 to 3.5. It is preferred to use.
The timing of addition may be any step before coating.

The compound of the general formula (I) according to the present invention can be used in any of an emulsion layer and other hydrophilic colloid layers. The dispersion of the oil and / or polymer latex composition of the dye used in the present invention can be performed by the following method.

A method of dispersing the compound by dissolving the compound in an oil, that is, a solvent substantially insoluble in water and having a boiling point of about 160 ° C. or higher, in a hydrophilic colloid solution. Examples of the high boiling point solvent include alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate) and phosphates (such as diphenyl phosphate and triphenyl phosphate) as described in US Pat. No. 2,322,027. , Tricresyl phosphate, dioctyl butyl phosphate), citrate esters (eg, tributyl acetyl citrate), benzoate esters (eg, octyl benzoate), alkylamides (eg, diethyl lauramide), fatty acid esters (eg, dibutoxy) Ethyl succinate, diethyl azelate), trimesic esters (eg, tributyl trimesate) and the like can be used. The boiling point is about 30 ° C
An organic solvent at about 150 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, or a solvent which is easily soluble in water, For example, alcohols such as methanol and ethanol can be used. Here, the use ratio of the dye to the high boiling point solvent is 10 to 1
/ 10 (weight ratio) is preferred.

A method of incorporating the dye and other additives of the present invention as a polymer latex composition filled with a photographic emulsion layer or other hydrophilic colloid layer. Examples of the polymer latex include polyurethane polymers and polymers polymerized from vinyl monomers [suitable vinyl monomers include acrylates (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, glycidyl acrylate, etc.) , Α-substituted acrylates (methyl methacrylate, butyl methacrylate, octyl methacrylate, glycidyl methacrylate, etc.), acrylamide (butyl acrylamide, hexyl acrylamide, etc.), α-substituted acrylamides (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl esters ( 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-methyl styrene, etc.), nucleus substituted styrene (hydroxy Styrene, chlorostyrene, methylstyrene, etc.), ethylene, propylene, butylene,
Butadiene, acrylonitrile and the like can be mentioned. These may be used alone or in combination of two or more, or other vinyl monomers may be mixed as a minor component. Examples of other vinyl monomers include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, and styrene sulfonic acid. ] Etc. can be used.

These filled polymer latexes are described in JP-B-51-39853, JP-A-51-59943, and
No. 3-137131, No. 54-32552, No. 54-
No. 107941, No. 55-133465, No. 56-1
No. 9043, No. 56-19047, No. 56-1268
No. 30, 58-149038. Here, the use ratio of the dye to the polymer latex is preferably 10 to 1/10 (weight ratio).

A method in which a hydrophilic polymer is used in place of the high boiling point solvent described above or in combination with the high boiling point solvent. Regarding this method, for example, US Pat. No. 3,619,195,
It is described in West German Patent 1,957,467.

A method of dissolving a compound using a surfactant. Useful surfactants are preferably oligomers or polymers. Details of this polymer are described in JP-A-60-158439, pages 19 to 27. In addition, for example, a hydrosol of a hydrophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above. As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.

The silver halide emulsion used in the present invention comprises:
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.

The silver halide emulsion used in the present invention may have any grain size distribution, but has a maximum grain size (average).
The weight of silver halide contained within a grain size range of ± 20% with respect to r is preferably 60% or more, more preferably 80% or more, of the total silver halide grain weight. The grain size of the silver halide may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm. The silver halide used in the present invention is silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2μm
The following fine particles may be large-sized particles having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion that can be used in the present invention includes:
For example, Research Disclosure (RD) No. 1
7643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", ibid.
8716 (November 1979), p. 648, ibid.
7105 (November 1989), pp. 863-865, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P.Glafkides. Chemie et Phisique Photographique, P.
aul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emuls
ion Chemistry, Focal Press, 1966), and Zerikman et al., "Manufacture and Coating of Photographic Emulsions", published by Focal Press (VLZelikman et al., Making and Coating Photogra
phic Emulsion, Focal Press, 1964).

US Pat. Nos. 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred. The aspect ratio (equivalent circle diameter of AgX particles / particle thickness) is about 3
Emulsions in which the above AgX grains are present in 50% or more (area) of all AgX grains in the emulsion can be used in the present invention. Tabular grains are described in Gatoff, Photographic Sunence and Engineering (Gutoff, Photographic Scien
ce and Engineering), Vol. 14, pp. 248-257 (1
970), U.S. Pat.
414,310, 4,433,048, 4,4
It can be easily prepared by the methods described in JP 39,520 and British Patent 2,112,157.

The silver halide emulsion composed of regular grains can be formed to a desired size by forming nuclei and growing grains while maintaining pAg at a constant level and a supersaturation degree that does not cause renucleation by the double jet method. Particles can be obtained. Further, the method described in JP-A-54-48521 can be applied. In a preferred embodiment of the method, a potassium iodide-gelatin aqueous solution and an ammonium silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide grains while changing the addition rate as a function of time. At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate, pH, pAg, temperature and the like. For details, see, for example, Photographic Science and Engineering, Volume 6,
159-165 (1962); Journal of Photograp
hic Science), 12, 242-251 (196)
4), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

The crystal structure may be uniform, the inside and the outside may have different halogen compositions, or may have a layered structure. These emulsion grains are described in GB 1,027,146 and GB 3,505,068.
No. 4,444,877 and Japanese Patent Application No. 58-248.
649 etc. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. The silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. Typical examples are JP-B-43-13162 and JP-A-61-215.
No. 540, JP-A-60-222845, JP-A-61-221
No. 75337, etc. are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions. Also, instead of a mere double structure, a triple structure as disclosed in JP-A-60-222844 or a multilayer structure more than that,
A silver halide having a different composition can be thinly applied to the surface of a core-shell double structure grain.

In order to give a structure inside the particle, not only the above-mentioned wrapping structure but also a particle having a so-called bonding structure can be produced. These examples are disclosed in
JP-133540, JP-A-58-108526, EP
199290A2, JP-B-58-24772, and JP-A-59-16254. The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure. In the case of a junction structure, a combination of silver halides is naturally possible, but a silver salt compound having no rock salt structure, such as silver rhodanate or silver carbonate, can be combined with silver halide to form a junction structure. A non-silver salt compound such as PbO may be used as long as it can form a junction structure.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, Alternatively, grains having a low silver iodide content in the core portion and a high shell portion may be used. Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. In addition, the boundary portion having a different halogen composition of the grains having these structures may be a clear boundary, or may be an unclear boundary formed by a mixed crystal due to a composition difference. It may have a structural change. The silver halide emulsion used in the present invention is EP-
No. 0096727B1, EP-0064412B1, etc., to give roundness to particles, or DE-2306647C2, JP-A-60-2213.
The surface may be modified as disclosed in No. 20.

The silver halide emulsion for use in the present invention is preferably of the surface latent image type. However, as disclosed in JP-A-59-133542, an internal latent image type emulsion can be prepared by selecting a developing solution or conditions for development. Can also be used. Also, a shallow internal latent image type emulsion covered with a thin shell described in JP-A-63-264740 is preferably used. Silver halide solvents are useful to promote ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. In the present invention, it is extremely important to perform chemical sensitization represented by sulfur sensitization and gold sensitization. The photographic properties of the particles doped with polyvalent metal ions of 1 × 10 ⁻⁴ mol / mol Ag or more have no characteristics in the unripened state, and have a remarkable effect when chemically sensitized. The location of chemical sensitization depends on the composition, structure,
It depends on the form and on the application for which the emulsion is used. There is a case where a chemical sensitizing nucleus is embedded in the inside of a grain, a case where the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, or a case where a chemical sensitizing nucleus is formed on the surface. The effect of the present invention is effective in any case, but particularly preferred is the case where a chemical sensitizing nucleus is formed near the surface. That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is described in TH James,
The Photographic Process, 4th Edition, Macmillan, 1977 (THJames, The Theory of the P
hotographic Process, 4th ed, Macmillan, 1977) 67
Can be carried out using active gelatin as described on page 76, and
20, April 1974, 12008; Research Disclosure, 34, June 1975, 1345
2, U.S. Pat. Nos. 2,642,361 and 3,297,
446, 3,772,031, 3,857,7
No. 11, 3,901,714, 4,266,01
8 and 3,904,415 and British Patent No. 1,315,755.
It can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers at pH 10, pH 5 to 8 and temperature 30 to 80 ° C. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, and in US Pat.
No. 11, 4,266,018 and 4,054
457, a sulfur-containing compound or hypo,
The reaction is performed in the presence of a sulfur-containing compound such as a thiourea compound or a rhodanine compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. As the chemical sensitization aid to be used, compounds such as azaindene, azapyrididine and azapyrimidine which are known to suppress fog and increase sensitivity in the course of chemical sensitization are used. Examples of chemical sensitization aid improvers are described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and "Photographs by Duffin". Emulsion Chemistry ", pp. 138-143.

The silver halide emulsion prepared according to the present invention can be used for both color photographic materials and black-and-white photographic materials. Examples of the color photographic light-sensitive material include color paper, color photographic film and color reversal film, and examples of the black-and-white photographic light-sensitive material include X-ray film, general photographic film, and printing photographic material. There are no particular restrictions on the additives of the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 1
Volume 76 Item 17643 (RD17643) and 1
87, Item 18716 (RD18716) can be referred to. RD17643 and RD18
The places where various additives are described in 716 are listed below.

[0071]

[Table 1]

The development processing when the light-sensitive material of the present invention is processed by an automatic developing machine is described in JP-A-3-1393720.
-21, 25, 30-33, 40, 45-46
Pp. 52-53, JP-A-3-171136, pp. 18-
Any of the processing methods such as the processing method described on page 19 and page 27 of JP-A-6-43583 can be applied.

In the preferred processing method of the photographic material of the present invention, the replenishment amounts of the developing solution and the fixing solution are from 25 ml to 200 ml per m ^{2 of the} photographic material, and more preferably from 30 ml to 200 ml.
It is at least 180 ml and most preferably at least 60 ml and at most 150 ml.

In the method for processing a light-sensitive material of the present invention, the development processing time is preferably from 5 seconds to 10 minutes. It is more preferably from 5 seconds to 60 seconds, and most preferably from 5 seconds to 30 seconds.

The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

[0076]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but it should not be construed that the invention is limited thereto. Example 1 Preparation of Sample 101 On a 205 μm-thick cellulose triacetate film support having an undercoat on both sides of a film, a multi-layer color photographic material having the following layers was prepared to prepare Sample 101. The coating amount of each composition was a value per 1 m ² of the sample.
For silver halide and colloidal silver, the weight was expressed in terms of equivalent silver.

First layer: Antihalation layer Black colloidal silver 0.25 g Gelatin 1.90 g UV absorber U-1 0.20 g UV absorber U-3 0.10 g UV absorber U-4 0.20 g High boiling organic solvent Oil-1 0.10 g

Second layer: Intermediate layer Non-photosensitive fine grain silver iodobromide emulsion (average grain size: 0.1 μm, AgI content: 1 mol%) Silver amount: 0.15 g Fine grain silver iodobromide emulsion whose surface and inside are fogged ( Average particle size 0.06 μm, Coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.050 g Compound Cpd-A 0.10 g Compound Cpd-G 0.050 g Gelatin 0.40 g

Third layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 4.0 mg High boiling organic solvent Oil-3 40 mg

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.30 g Emulsion B silver amount 0.40 g gelatin 0.80 g Coupler C-1 0.090 g Coupler C-2 0.050 g Coupler C-3 0.020 g Compound Cpd-C 1.0 mg Compound Cpd-F 0.050 g High boiling organic solvent Oil-2 0.10 g Latex dispersion of ethyl acrylate 0.50 g

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C Silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling organic solvent Oil-2 0.10 g Ethyl acrylate latex dispersion 0.050 g

Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.10 g Additive P-1 0.020 g Ethyl acrylate Latex dispersion 0.10 g

Seventh layer: Intermediate layer Gelatin 1.00 g Compound Cpd-E 0.28 g Additive P-1 0.050 g

Eighth layer: Intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average grain size: 0,1).
(06 μm, coefficient of variation 16%, AgI content 0.3 mol%)
Silver amount 0.02 g Gelatin 0.40 g Compound Cpd-A 0.10 g Compound Cpd-G 0.050 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with the inside of the grains fogged (average particle size 0.1 μm, AgI content 0.1 mol%) Silver content 0.15 g Emulsion E Silver content 0.30 g Emulsion F Silver content 0.10 g Emulsion G Silver content 0.10 g Gelatin 2.00 g Coupler C-4 0.21 g Coupler C-5 0.040 g Coupler C-6 0.041 g Compound Cpd-B 0.03 g Compound Cpd-G 0.010 g High boiling organic solvent Oil -2 0.2 g

Tenth layer: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.28 g Coupler C-5 0.053 g Coupler C-6 0.055 g Compound Cpd-B 0.030 g Compound Cpd-G 0.010 g Additive F-5 0.08 mg High boiling organic solvent Oil-2 0.010 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with the inside of the grains fogged (average grain size 0.2 μm, AgI content 0.1 mol%) Silver amount 0.050 g Emulsion I Silver amount 0.50 g Gelatin 1.10 g Coupler C-4 0.18 g Coupler C-5 0.18 g Coupler C-6 0.20 g Compound Cpd-B 0.08 g Compound Cpd-G 0.010 g High boiling organic solvent Oil-2 0.040 g

Twelfth layer: Intermediate layer Gelatin 0.40 g Ethyl acrylate latex dispersion 0.15 g

13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.10 g Gelatin 1.0 g Compound Cpd-A 0.040 g High boiling organic solvent Oil-1 0.010 g

Fourteenth layer: Intermediate layer Gelatin 0.60 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion with the inside of the grains fogged (average grain size 0.2 μm, AgI content 0.1 mol%) Silver content 0.10 g Emulsion J Silver content 0.40 g Emulsion K Silver content 0.10 g Emulsion L Silver content 0.10 g Gelatin 1.0 g Coupler C-7 0.50 g Coupler C-8 0.10 g Coupler C-9 0.10 g Compound Cpd-F 0.10 g

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.10 g Emulsion M silver amount 0.10 g gelatin 0.60 g Coupler C-7 0.020 g Coupler C-8 0.0020 g Coupler C-9 0.020 g

17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.60 g Gelatin 1.40 g Coupler C-7 0.050 g Coupler C-8 0.080 g Coupler C-9 0.80 g

18th layer: 1st protective layer Gelatin 0.90 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g High boiling organic solvent Oil-1 0.02 g Formalin scavenger Cpd -D 0.50 g Latex dispersion of ethyl acrylate 0.050 g Dye D-1 0.050 g Compound Cpd-A 0.020 g Compound Cpd-E 0.20 g

Nineteenth layer: Second protective layer Colloidal silver amount of silver 0.050 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.050 g Gelatin 0.30 g

Twentieth layer: Third protective layer Colloidal silver silver content 0.050 mg Fine grain silver iodobromide emulsion (average particle size 0.07 μm, AgI content 1 mol%) Silver content 0.050 g gelatin 0.60 g polymethyl methacrylate (average particle size) (Diameter 1.5 μm) 0.10 g 4: 6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5 μm) 0.10 g Silicone oil 0.030 g Surfactant W-1 3.0 mg Surfactant W-2 0.030 g

Additives F-1 to F-9 were added to each silver halide emulsion layer and intermediate layer. In addition, in each layer, in addition to the above composition, gelatin hardener H-1 and coating surfactants W-3, W-4 and W-5 were added, and emulsifying surfactant W
-6 was added. Phenol as an antiseptic and fungicide,
1,2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenyl isothiocyanate, and phenethyl alcohol were added.

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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(Preparation of Organic Solid Dye Dispersion A) 10 g of Comparative Dye a shown below was mixed with KAO surfactant Demol T
2 g, 241 cc of water and 400 zirconium oxide beads
The mixture was placed in a pot together with the cc, and dispersed in a vibration ball mill manufactured by Chuo Koki Co., Ltd. for 4 days. After the dispersion, the contents were taken out, and the beads were removed by filtration, and gelatin was added to obtain an organic solid dye dispersion A.

[0116]

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(Preparation of Dye Emulsions BD) Dyes (described in Table 5) were emulsified and dispersed according to the following formulation to obtain dispersions. 1st liquid Dye (solid content) 150mg High boiling organic solvent-1 0.3g Ethyl acetate 4.5ml Sodium dodecylbenzenesulfonate 90mg 2nd liquid Gelatin (with Ca content of 30ppm) 1.2g Water 8.7ml Compound-1-3 Dissolve 0.12 ml of a 0.4% methanol solution at 60 ° C. Solution 2 is separately dissolved at 50 ° C. and added to solution 1. Using a high-speed stirrer (trade name: Homogenizer DX-11 (manufactured by Nippon Seiki Co., Ltd.)), the mixture was stirred at 12000 rpm for 5 minutes while keeping the temperature at 50 ° C. After completion, 16 ml of water was added and the temperature was lowered to 40 ° C. Then, ethyl acetate was removed under reduced pressure to obtain a dye emulsion having an average particle size of 0.22 μm.

[0118]

[Table 5]

[0119]

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The samples 102 to 105 correspond to the eighth sample of the sample 101.
Except that the organic solid dispersion A and the dye emulsions B to D were added to the layer so that the coating amount of the dye was 4.0 × 10 ⁻⁵ mol / m ² , the preparation was performed in exactly the same manner as in Sample 101. did.

Each of the obtained samples 101 to 105 was exposed to white light through an MTF pattern, subjected to development processing described later, and then measured for a magenta color image MTF value (5 cycles / mm) to compare sharpness. did. Evaluation is comparative sample 1.
The measurement was performed at a ratio (MTF ratio) when the MTF value of 01 was set to 1.

Each sample was subjected to wedge exposure with white light, and then subjected to the same processing as described above, followed by measuring magenta density to determine the minimum value (D ^G min). The difference (ΔD ^G min) from the comparative sample 101 was evaluated as the residual color caused by the dye.

The processing steps and the composition of the processing solution are shown below. Processing Step Time Temperature First development 6 minutes 38 ° C Rinse 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Pre-bleach 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ° C Rinse with water 4 minutes 38 ° C Final rinse 1 minute 25 ° C

The composition of each processing solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 22 g Hydroquinone potassium monosulfonate 20 g Potassium carbonate 15 g Sodium carbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.0 g Potassium iodide 2.0 mg Diethylene glycol 13 g Add water to 1000 mL pH 9.60 Adjusted with sulfuric acid or potassium hydroxide.

[Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 3.0 g Stannous chloride · dihydrate 1.0 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added and 1000 ml pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g Sodium sulfite 4.0 g Trisodium phosphate dodecahydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazinic acid 0.8 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 8.0 g 3,6-dithiaoctane- 1,8-diol 0.5 g Water was added to 1000 ml pH 11.65 pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g Sodium sulfite 4.0 g 1-thioglycerol 0.4 g Formaldehyde sodium bisulfite adduct 20 g Water was added to 1000 ml. Adjusted with sodium hydroxide.

[Bleaching Solution] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Milliliter pH 5.70 pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] Ammonium thiosulfate 70 g Sodium sulfite 3.0 g Sodium bisulfite 4.0 g Water was added, and the mixture was adjusted to 1000 ml with acetic acid or ammonia water.

[Final rinse liquid] 1,2-benzisothiazolin-3-one 0.02 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g polymaleic acid (average molecular weight: 2,000) 0.1 g Water was added. 1000 ml pH 7.0

Table 6 shows the evaluation results.

[0132]

[Table 6]

As is clear from Table 6, the dye emulsified dispersion of the present invention has a larger content than the organic solid dye dispersion.
It can be seen that it has a sharpness equal to or higher than that and has excellent decoloring performance with the processing solution.

Example 2 (Preparation of emulsion T1) 5.0 g of ammonium nitrate, 6.9 g of potassium bromide and 3.5 g of low-molecular-weight gelatin having an average molecular weight of 15,000 were added to 1 liter of water, and the mixture was kept at 50 ° C. While stirring, the silver nitrate aqueous solution 40 ml (silver nitrate 4.0
35 g of an aqueous solution containing g) and 0.85 g of potassium bromide were added over 40 seconds by the double jet method. Then 6
Raise the temperature to 0 ° C and use an aqueous solution of silver nitrate (4.0 g of silver nitrate).
40 ml were added in 10 minutes and potassium bromide 1.0
g and 18.4 g of gelatin were added.

Next, 15 ml of 1N caustic soda was added, the mixture was physically aged at 60 ° C. for 20 minutes, and 4 ml of 100% acetic acid was added. Subsequently, an aqueous solution of 162 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes while adding a flow rate by a control double jet method while maintaining the pAg at 8.6. Next, 35 ml of a 2N potassium thiocyanate solution was added, and the temperature was lowered to 35 ° C. after 5 minutes. The obtained silver halide grains are pure silver bromide tabular grains in which the sum of the projected areas of the tabular grains having an aspect ratio of 3 to 30 accounts for 96% of the total projected area of all grains. The average circle-equivalent diameter of the projected area was 0.7 μm, the average thickness was 0.12 μm, the variation coefficient of the diameter was 25%, and the average aspect ratio of each particle was 6.7.

Thereafter, soluble salts were removed by the coagulation sedimentation method. The temperature was raised again to 40 ° C., 35 g of gelatin, 0.1 g of phenoxyethanol and 0.4 g of polystyrene sodium sulfonate as a thickener were added, and the mixture was adjusted to pH 6.4 and pAg 8.2 with sodium hydroxide and an aqueous silver nitrate solution.

(Method of Chemical and Spectral Sensitization of Each Emulsion) These emulsions were subjected to chemical sensitization and spectral sensitization while being kept at 56 ° C. while stirring. Emulsion T-1 was added with 0.33 grams of potassium iodide per mole of silver halide, followed by 4-hydroxy-6-methyl-1,
0.2 g of 3,3a, 7-tetrazaindene was added, 2 × 10 ⁻⁴ mol of dye I-1 was added, followed by 3.5 mg of sodium ethylthiosulfinate.
Here, 1.2 × 10 ^-3 mol of sensitizing dye I-2 and 4 × 10 ^{-6 of} supersensitizing dye I-3 were added. Further, 4.6 mg of chloroauric acid and 60 mg of potassium thiocyanate were added. Subsequently, 5 × 1 sodium thiosulfate was added.
0 ^-6 mol of selenium compound A-1 were added 5 × 10 ^-6 mol. Seventy minutes later, 20 mg of Compound A-2 was added, and the mixture was cooled to 35 ° C.

[0138]

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(Preparation of Coating Solution for Emulsion Layer) A coating solution for the emulsion layer was prepared such that the components to be added to the emulsion layer T1 were in the following coating amounts per one side of the support. 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 1.7 mg / m ² dextran 0.45 g / m ² sodium polystyrene sulfonate (average molecular weight 600,000) 33 mg / m ² (Including emulsion addition) Gelatin 1.1 g / m ² (Including emulsion addition) Compound A-3 0.11 g / m ² Dye emulsion b (as dye solid content) 6.8 mg / m ^2. Dye emulsion m (as dye solids) 0.4 mg / m ²

[0140]

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• 1,2-Bis (vinylsulfonylacetamido) ethane The amount was adjusted so that the melting time described in Table 1 was obtained, and added.

(Preparation of Dye Emulsion b) 60 g of Dye-1
62.8 g of 2,4-diamylphenol, 62.8 g of dicyclohexyl phthalate and ethyl acetate 3
33 g were melted at 60 ° C. Next, 65 ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate and gelatin 94
g and water (581 ml) were added, and the mixture was treated at 60 ° C. with a dissolver at 3 ° C.
Emulsified and dispersed for 0 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei ultrafiltration lab module ACP105
Using 0, the mixture was concentrated to a total amount of 2 kg, and 1 g of methyl p-hydroxybenzoate was added to obtain a dye emulsion b.

[0143]

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(Preparation of Dye Emulsion m) 10 g of Dye-2
A dye emulsion m was prepared by weighing out, dissolving in a solvent consisting of 10 ml of tricresyl phosphate and 20 ml of ethyl acetate, and emulsifying and dispersing in 100 ml of a 15% aqueous gelatin solution containing 750 mg of an anionic surfactant. .

[0145]

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(Preparation of Dye Dispersion i) Dye-3 was handled as a wet cake without drying, and weighed to a dry solid content of 6.3 g. The dispersing aid V was treated as a 25% by weight aqueous solution, and was added so that the dry solid content was 30% by weight based on the solid content of the dye. Add water and add 6
3.3 g, and mixed well to form a slurry. 100 cc of beads made of zirconia having an average diameter of 0.5 mm are prepared, put into a vessel together with the slurry, and dispersed with a dispersing machine (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) for 6 hours to give a dye concentration of 8% by weight. Water was added to obtain a dye dispersion. The resulting dispersant was mixed so that the solid content of the dye was 5% by weight and the photographic gelatin was equal to the solid content of the dye by weight.
An aqueous solution was added to a concentration of 000 ppm, refrigerated, and stored in a jelly form. Thus, a dye dispersion i was obtained as a non-elutable solid fine particle dispersion dye having a light absorption maximum at 915 nanometers. The average particle diameter of the solid fine particles of the dye dispersion i was 0.4 μm.

[0147]

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[0148]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for the surface protective layer was prepared such that each component of the surface protective layer was applied in the following amount per one side of the support.・ Gelatin As described in Table 1 ・ Additive D 1.4 mg / m ²・ Sodium polyacrylate (average molecular weight 41,000) 34 mg / m ²・ Additive-1 40 mg / m ²・ Additive-25 .4mg / m ² · additives -3 22.5mg / m ² · additives -4 0.5mg / m ² · matting agent-1 (average particle size 3.7 microns) 72.5 mg / m ²

[0150]

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Compound A-4 4.4 mg / m ² Compound A-5 1.3 mg / m ² Compound A-6 0.5 mg / m ²

[0152]

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(Preparation of Dye Layer Coating Solution) A coating solution was prepared so that each component of the dye layer had the following coating amount. Gelatin 0.25 g / m ² Additive D 1.4 mg / m ² Sodium polystyrene sulfonate (average molecular weight 600,000) 5.9 mg / m ² Dye dispersion i (as dye solids) 20 mg / m ²

(Preparation of Support) Biaxially stretched thickness 17
Corona discharge treatment was performed on a 5 μm blue-dyed polyethylene terephthalate film, and both surfaces were coated using a wire bar coater so that the hydrophobic polymer layer had the following coating amount, and dried at 185 ° C. for 1 minute.

[0155] (hydrophobic polymer layer) Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{= 31/69 0.32g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8. 4 mg / m ² * The latex solution contains 0.4 wt% of emulsifying dispersant-A based on the solid content of the latex.

[0156]

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Next, the hydrophilic colloid layer was coated on both sides with a wire bar coater so that the following coating amount was obtained.
A sample dried at 55 ° C. for 1 minute was designated as 201.

(Hydrophilic colloid layer) ・ Gelatin 80 mg / m ²・ Polyethyl acrylate 20 mg / m ²・ Coating aid-B 1.8 mg / m ²・ Dye-C 8 mg / m ²・ Additive-D 27mg / m ²

[0159]

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Preparation of Solid Fine Particle Dispersion of Dye-C 20 g of dye and 1% aqueous solution of carboxymethylcellulose 2
200 g, by mixing H ₂ O 287 g, and 8 hours at Eiger mill (Eiger Japan Co., Ltd.) at 5,000rpm conditions with beads of zirconium oxide having a diameter of 2 mm (ZrO _2). The resulting mixture is filtered and ZrO
_Two beads were removed.

Instead of dye C, comparative dye b, 18.3
g of Comparative Dye b, and Compounds D-4, D-9, D-16 and D-34 of the present invention prepared in the same manner as the solid fine particle dispersion of Dye C except that g was used. A dye emulsified dispersion emulsified in the same manner as in Example 1 was added in place of the solid fine particle dispersion of Dye C so that the coating amount of each dye was 1.6 × 10 ⁻⁵ mol / m ^2. Samples prepared in exactly the same manner as the sample 201 were referred to as samples 202, 203, 204, 205, and 206, respectively.

[0162]

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(Preparation of developer replenisher) A developer replenisher A having the following formulation and using sodium erythorbate as a developing agent was prepared. Diethylenetriaminepentaacetic acid 8.0 g Sodium sulfite 19.6 g Sodium bisulfite 2.8 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate 60.0 g 4-Hydroxymethyl-4-methyl-1-phenyl- 3-pyrazolidone 13.2 g 3,3'-diphenyl-3,3'-dithiopropionic acid 1.44 g diethylene glycol 50.0 g

[0164]

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Water is added to make up 1 liter. Adjust the pH to 10.1 with sodium hydroxide or acetic acid.

(Preparation of New Developing Solution) The above developing replenisher A 2
The liter was diluted to 4 liters with water, and a starter solution having the following composition was added to 200 ml per liter of the developing replenisher A and adjusted to pH 9.5 to obtain a new developing solution. Starter liquid Potassium bromide 11.1 g Acetic acid 10.8 g Add water to make 100 ml

(Preparation of Fixing Replenisher) A fixing replenisher having the following formulation was prepared. Water 0.5 L Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate pentahydrate 400 g Sodium bisulfite 98.0 g Sodium hydroxide 2.91 g Adjust pH to 5.4 with NaOH, add water, and add 1 L And

(Preparation of New Fixing Solution) 2 L of the above fixing replenisher was diluted with water to make 4 L. pH was 5.6.

(Processing Method of Photographic Material) The aperture ratio was set to 0.02.
Automatic processing machine F manufactured by Fuji Photo Film Co., Ltd.
In PM-1300, using the developing solution and the fixing solution,
The developer replenisher and the fixing replenisher photosensitive material 1 m ² per 32
Processing was performed while supplementing ml. When replenishing development and fixing, the same amount of water as each replenisher is simultaneously poured into each tank. The breakdown of each step when the operation is performed for 120 seconds from dry to dry is described. Process temperature Processing time Current image 35 ° C 25 seconds Fixed 35 ° C 25 seconds Rinse 25 ° C 30 seconds Dry 55 ° C 40 seconds Total (dry to dry) 120 seconds

(Preparation of photographic material) The coating solutions for the emulsion, surface protective layer and dye layer prepared above were successively applied to both surfaces of the support under the same conditions by a simultaneous extrusion method. Further, the amount of silver applied to each photographic material is set to be 1.25 g / m ² . In addition, as the hydrophilic colloid in this experiment, the total sum of the coating amounts of gelatin, dextran, and sodium polyacrylate was used.

(Evaluation of photographic performance) X-ray orthoscreen H sold by Fuji Medical System Co., Ltd.
Exposure was performed for 0.1 second from both sides using GM, and processing from development to drying was performed for 120 seconds (development time: 25 seconds) to evaluate sensitivity. The value of the relative sensitivity is the fog value (including the base density) +1.
The relative value is shown with the sensitivity of the sample 101 as 100 with respect to 0 as a reference point.

(Evaluation of Remaining Color) The absorption spectrum of the processed photographic material was measured and evaluated by ABS at 550 nm. Table 7 shows the results.

[0173]

[Table 7]

From the results shown in Table 7, it is understood that the dye of the present invention is suitable for obtaining a photosensitive material having low residual color and high sensitivity.

Example 3 The dyes shown in Table 8 were emulsified and dispersed in accordance with the emulsification formulation of Example 1 to prepare dye emulsions a-1 to a-4.

[0176]

[Table 8]

Preparation of Emulsion A 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 27 0.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridate (III) (0.001% aqueous solution) 6 ml

Solution 2 and solution 3 were added simultaneously to solution 1 maintained at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, sodium thiosulfate 1.0 mg, chloroauric acid 4.0 mg, triphenylphosphine selenide 1.5 mg, sodium benzenethiosulfonate 8
mg and sodium benzenethiosulfinate 2 mg, and 55
Chemical sensitization was carried out at ℃ to obtain the optimum sensitivity. Further, 4-hydroxy-6-methyl-1,3,3a,
100 mg of 7-tetrazaindene, phenoxyethanol as a preservative, and finally a silver chloroiodobromide cubic emulsion A containing 70 mol% of silver chloride and having an average grain size of 0.25 μm.
I got

Preparation of Coated Samples Emulsion A was added with 3.8 × 10 ^-4 mol / mol Ag of sensitizing dye and subjected to spectral sensitization. Furthermore, KBr 3.4 × 10 ^-4 mol / mol Ag, compound 3.2 × 10 ^-4 mol / mol A
g, compound 8.0 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0
× 10 ^-3 mol / mol Ag, compound 1.0 × 10 ^-4 mol / mol Ag, compound 6.0 × 10 ^-4 mol / mol A
g, 35 wt% polyethyl acrylate latex based on gelatin, 20 wt% colloidal silica having a particle size of 10 μm based on gelatin, 4 wt% based on gelatin
was added to wt% of the compound, Ag3.7g / m ² on a polyester support was coated to a gelatin 1.6 g / m ^2. On this, a protective layer upper layer and a protective layer lower layer of the following composition, and a UL layer of the following composition under this were applied.

Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² compound (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound 5 mg / m m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound 20 mg / m ² protective layer underlying gelatin 0.5 g / m ² compound 15 mg / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² of polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound 40 mg / m ² Compound CY-1 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound Y 40 mg / m ² Compound M 20 mg / m ² Compound CY-2 90 mg / m ² 1,3-Divinylsulfonyl-2-propanol 60 mg / m ² polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² compound 120 mg / m ² conductive layer gelatin 0.1 g / m ² sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight) Ratio, average particle size 0.25μ) 200mg / m ²

[0183]

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[0184]

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Except for the compound M in the back layer of the sample 301, the solid fine particle dispersion of the comparative dye b and the dye emulsions a-1 to a-4 prepared in Example 2 were added in an amount of 4. Samples 302 to 306 were prepared in exactly the same manner as Sample 301 except that they were added to the protective lower layer at 0 × 10 ⁻⁵ mol / m ² .

(Evaluation of photographic performance)
Exposure was performed with a xenon flash light having a light emission time of 10 ^-6 seconds through a step wedge through an interference filter having a peak at. Using FG-710NH automatic developing machine manufactured by Fuji Photo Film Co., Ltd., developing, fixing, washing,
A drying process was performed.

Photo Performance Evaluation Remaining Color Test Current Image 35 ° C. 14 seconds 9 seconds Fix 35 ° C. 9.7 seconds 6.2 seconds Rinse 25 ° C. 9 seconds 5.8 seconds (10 ° C.) Squeeze 2.4 seconds 1. 5 seconds Drying 55 ° C 8.3 seconds 5.3 seconds Total 43.4 seconds 27.8 seconds The developing solution and fixing solution used are as follows. <Developer composition> Diethylenetriamine-5 acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1-phenyl-5 -Mercaptotetrazole 0.02 g Sodium sulfite 2 g Add water to 1 liter and adjust pH to 9.7.

(Fixing solution) The formula per liter of the fixing solution concentrated solution is shown below. Ammonium thiosulfate 360 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8.7 g Sodium gluconate 5.1 g Aluminum sulfate 25.2 g pH 4.85 When used, 1 part of the above concentrated liquid is diluted with 2 parts of water. The pH of the working solution is 4.8.

The evaluation method of sensitivity and residual color was in accordance with Example 3. Table 9 shows the results.

[0190]

[Table 9]

From the results shown in Table 9, it was found that all of the dyes of the present invention can obtain a high-sensitivity light-sensitive material having a low residual color.

Claims (4)

[Claims] 1. A silver halide photographic material comprising at least one kind of a compound represented by the following general formula (I) in a molecular dispersion. Embedded image In the formula, L ₁ , L ₂ and L ₃ each represent an optionally substituted methine group. R ₁ represents a hydrogen atom or a substituent (including a substituent atom). R ₂ represents a substituent (including a substituent atom). m represents 0 or an integer from 1 to 4,
When m is an integer of 2 to 4, R ₂ may be the same or different. R ₃ is a hydrogen atom or —CH
Represents R ₃ 'X. R ₃ ′ represents a hydrogen atom or a substituent (including a substituent), and X represents an electron-withdrawing group having a Hammett's substituent constant σ _m of 0.3 or more and 1.5 or less. R ₄ is-
COOR ₁₀ , —COR ₁₁ , —CONR ₁₁ R ₁₂ , or —
Represents CN, and R ₅ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₁₀ represents an alkyl group or an aryl group, and R ₁₁ and R ₁₂ represent a hydrogen atom, an alkyl group, or an aryl group. n represents 1 or 2. However, the compound represented by the general formula (I) must not have a sulfo group, a salt of a sulfo group, a carboxyl group or a salt of a carboxyl group as a substituent. 2. The halogen according to claim 1, further comprising a hydrophilic colloid layer containing at least one of the compounds represented by the general formula (I) as an oil composition and / or a polymer latex composition. Silver halide photographic material. 3. The compound according to claim 1, wherein X in the general formula (I) is an alkoxycarbonyl group or a cyano group, R ₄ is —COOR ₁₀ or a cyano group, and n = 1. Item 3. A silver halide photographic material according to Item 2. 4. The silver halide photographic material according to claim 2, wherein the compound represented by the general formula (I) is fixed in a layer containing the composition.