JPH0792614A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the storage stability of a photosensitive material and to enable decoloration of dye dispersed in a state of fine solid particles contained in a hydrophilic colloidal layer by incorporating a fine slid particle dispersion of a specified dye in this layer. CONSTITUTION:This hydrophilic colloidal layer contains the fine solid particle dispersion of at least one kind of dye represented by the formula in which each of R1 and R2 is an alkyl; preferably, a 1-8 C alkyl optionally substituted; each of L1-L5 is a methine group and at least one of them has a substituent and each may combine with each other to form a 5- or 6-membered ring; and each of R1 and R2 and L1-L5 has no group having an ionizable proton or its salt.

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 hydrophilic colloid layer, which is a dye which is photochemically inert and is easily decolorized and / or eluted in the course of photographic processing. The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material, a photographic emulsion layer and other hydrophilic colloid layers are often colored for the purpose of absorbing light of a specific wavelength.
When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring 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. If there are multiple photographic emulsion layers, the filter layer may be located in between.

Light scattered during or after passing through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. A colored layer called an antihalation layer is provided for the purpose of preventing blurring of images, that is, halation. When there are a plurality of photographic emulsion layers, an antihalation layer may be placed between the layers. In order to prevent deterioration of image sharpness (this phenomenon is generally called irradiation) due to light scattering in the photographic emulsion layer, the photographic emulsion layer is also colored.

Dyes are usually contained in these hydrophilic colloid layers to be colored. This dye needs to satisfy the following conditions. (1) It has 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, for example, reduction of sensitivity, latent image regression, or fog. (3) It should not be decolorized during the photographic processing, or be dissolved in the processing solution or washed with water to leave no harmful coloring on the photographic light-sensitive material after processing. (4) Do not diffuse from the dyed layer to other layers. (5) It has excellent stability over time in a solution or photographic material and should not discolor.

Particularly when the colored layer is a filter layer,
Alternatively, in the case of an antihalation layer which is placed on the same side of the support as the photographic emulsion layer, it is preferable that those layers are selectively colored so that the other layers are not substantially colored. Often needed. This is because otherwise, not only the detrimental spectroscopic effect is exerted on other layers, but also the effect as a filter layer or an antihalation layer is diminished. Also, even when preventing irradiation, selective dyeing of only the target emulsion layer is necessary in order to exert the desired function sufficiently without causing the same adverse effect on other layers. Becomes However, wet contact between the dyed layer and other hydrophilic colloid layers often causes some of the dye to diffuse from the former to the latter. Many efforts have been made to prevent the diffusion of such dyes.

For example, a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye is allowed to coexist in a layer as a mordant and the dye is localized in a specific layer by interaction with a dye molecule is described in US Pat. No. 548,564, No. 4,124,386, No. 3,625,694 and the like. In addition, a method of dyeing a specific layer by using metal salt fine particles to which a dye is adsorbed is disclosed in US Pat. No. 2,719,08.
No. 8, No. 2,496,841 and No. 2,496,843
And JP-A-60-45237. Further, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-55-120030 and JP-A-56-12639.
No. 55-155350, No. 55-155351
No. 63, No. 63-27838, No. 63-197943,
52-92716, European Patent 15601, 32
No. 3729, No. 274723, No. 276566, No. 299435, and World Patent No. 88/04794.

However, even when these improved methods are used, the problem of the diffusion of the dye in the dye fixing layer, the decolorization rate during the development processing is slow, the processing speed is increased, and the processing solution composition is improved. Alternatively, when various factors such as improvement of photographic emulsion composition are changed, there is a problem that the decolorizing function cannot be sufficiently exhibited.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to preserve a photographic material such that a specific hydrophilic colloid layer in a photographic light-sensitive material is dyed and the dye does not diffuse to other layers during storage. Another object of the present invention is to provide a photographic light-sensitive material containing a solid fine-particle-dispersed dye which is designed to be rapidly decolorized during development processing.

[0009]

The object of the present invention is achieved by a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one solid fine particle-dispersed dye represented by the following general formula (I). It General formula (I)

[0010]

[Chemical 2]

In the formula, R ₁ and R ₂ represent an alkyl group,
L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group. However, at least one of the methine groups represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ has a substituent.
Also, R ₁ , R ₂ , L ₁ , L ₂ , L ₃ , L ₄ and L ₅
Is not a group having an ionizable proton or a salt thereof.

Next, the dye represented by formula (I) will be described in detail. The alkyl group represented by R ₁ or R ₂ is an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, n
-Propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclohexyl,
2-ethylhexyl, 3-methylbutyl, cyclopentyl, 2-ethylbutyl) is preferable, and a substituent [for example,
Halogen atom, cyano group, nitro group, hydroxyl group, carbon number 0
~ 6 amino group (for example, unsubstituted amino group, dimethylamino, diethylamino), C1-8 alkoxy group (for example, methoxy, ethoxy, phenoxy, p-methylphenoxy), C6-10 aryl Group (eg phenyl, 2-chlorophenyl), ester group having 2 to 8 carbon atoms (eg methoxycarbonyl, ethoxycarbonyl), acylamino group having 1 to 8 carbon atoms (eg,
Acetylamino group, benzoylamino group)]. An unsubstituted alkyl group is more preferable, and an alkyl group having 1 to 5 carbon atoms is still more preferable.

At least one of the methine groups represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ has a substituent, and the methine groups are linked to each other to form a 5- or 6-membered ring ( For example, a cyclopentene ring, a cyclohexene ring, a 1-chlorocyclohexene ring, a 1-dimethylaminocyclopentene ring, a 1-morpholinocyclopentene ring, etc.) may be formed. The number of substituents is preferably 1 to 3, and more preferably 1. The substitution position may be any of L _{1 to} L ₅ , but L ₂ , L ₃ and L ₄ are preferable. Among them, those in which L ₃ is a substituted methine group and L ₁ , L ₂ , L ₄ and L ₅ are unsubstituted methine groups are particularly preferable. L ₁ , L ₂ , L ₃ , L ₄ , L
Preferred substituents that ₅ has are an alkyl group (eg, methyl, ethyl, isopropyl, hydroxyethyl, etc.), an aryl group (eg, phenyl, 4-methylphenyl, etc.), an aralkyl group (benzyl, phenethyl, etc.), a halogen atom (chlorine). , Fluorine, bromine, etc.), alkoxy groups (methoxy, ethoxy groups, etc.), aryloxy groups (phenoxy, 4-chlorophenoxy, etc.), amino groups (amino, monomethylamino, dimethylamino, phenylamino, etc.), alkylthio groups (methylthio, Ethylthio, etc.), arylthio groups (phenylthio, 4-acetylaminophenylthio, etc.), hydroxyl groups, cyano groups,
Heterocyclic groups (morpholino, piperidino, imidazolyl, etc.) are mentioned, and alkyl groups and halogen atoms are more preferable examples. The sum of carbon numbers of the substituents on L _{1 to} L ₅ is preferably 0-10, more preferably 0-6. Further, the sum of the carbon numbers of L _{1 to} L _{5 and} the carbon numbers of R ₁ and R ₂ is preferably 2 or more and 16 or less, and particularly preferably 2 or more and 10 or less.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

The dye represented by the general formula (I) can be synthesized by a method known to those skilled in the art (for example, a condensation reaction between a corresponding pyrazolone compound and a substituted pentamethine source), and specifically, Kaisho 52-92716
No. 63-168385, No. 64-40827,
It can be synthesized according to JP-B-58-35544 and the following synthesis examples.

Synthesis Example 1 (Synthesis of I-1) 20 ml of triethylamine was added to a mixed suspension of 5.9 g of 3-methyl-5-pyrazolone, 7.5 g of a substituted pentamethine source a and 100 ml of ethanol, and then at room temperature for 2 hours. It was stirred. Next, 40 ml of water and 25 ml of a concentrated aqueous solution of concentrated hydrochloric acid were poured into the reaction mixture at 40 ° C., and after cooling, the dye was suction filtered and washed with water. After drying, 5.0 g of dye (I-1) was obtained. λ max = 676 nm ε = 1.01 × 10 ⁵ (dimethylformamide)

[0022]

[Chemical 8]

Synthesis Example 2 (Synthesis of I-3) Synthesis Example 1 except that 7.6 g of 3-n-propyl-5-pyrazolone was used in place of 3-methyl-5-pyrazolone in Synthesis Example 1. In the same manner, 7.1 g of Dye 4 was obtained. λ max = 678 nm ε = 9.95 × 10 ⁴ (dimethylformamide)

Synthesis Example 3 (Synthesis of I-6) To a mixed solution of 5.9 g of 3-methyl-5-pyrazolone, a substituted pentamethine source b of 8.3 g and 100 ml of dimethylformamide, 20 ml of triethylamine was added at 0 ° C. Stir at temperature for 2 hours. After stirring at room temperature for 1 hour,
40 ml of water and 25 ml of a concentrated aqueous solution of concentrated hydrochloric acid were poured into the reaction mixture at 40 ° C. After cooling, the dye was suction filtered, washed with water and dried to obtain 2.5 g of dye 6. λ max = 680 nm ε = 9.21 × 10 ⁴ (dimethylformamide)

[0025]

[Chemical 9]

In the present invention, dispersion of the dye is described in JP-A-52.
Dispersing machines such as ball mills, sand mills, colloid mills, vibration ball mills, planetary ball mills, jet mills, roll mills, Manton Gaulins, microfluidizers, disc impeller mills and the like, as described in No. 92716 and WO88 / 04794. Etc. can be arbitrarily selected, but a vertical or horizontal medium disperser is preferable. In any case, it is preferable to use a solvent (for example, water), and it is more preferable to use a dispersing surfactant. As a surfactant for dispersion, Japanese Patent Application Laid-Open No. Sho 5
It is also possible to use an anionic surfactant as described in 2-92716, WO 88/04794, etc., or an anionic polymer as in Japanese Patent Application No. 3-121749, and if necessary, nonionic. Although cationic or cationic surfactants can be used, anionic polymers or anionic surfactants are preferred.

Alternatively, the dye of the present invention may be dissolved in a suitable solvent and then a poor solvent for the dye of the present invention may be added to precipitate fine crystals. Agents may be used. Alternatively, the pH may be controlled in a solvent to be dissolved first, and then the pH may be changed to perform microcrystallization. The dye of the present invention in the dispersion has an average particle size of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm, more preferably 0.01 μm.
m to 0.5 μm, and in some cases 0.01 μm
To 0.1 μm is preferable. Further, the fine particles of the dye are preferably monodispersed.

When the dye of the general formula (I) is dispersed, the dye solid may be dispersed as it is without any pretreatment.
At this time, it is preferable to use a wet dye solid obtained in the process of synthesizing the dye for dispersion. If necessary, the heat treatment may be performed before and / or after the dispersion, and in order to perform the heat treatment more effectively, it is preferable to perform the heat treatment at least after the dispersion. The heating method is not particularly limited as long as heat is applied to the dye solid, and the temperature is preferably 40 ° C. or higher, and the upper limit is any number as long as the dye is not decomposed, and preferably 250 ° C. or lower. More preferably, it is 50 ° C to 150 ° C. The heating time is not particularly limited as long as the dye does not decompose, 15 minutes to 2
Weekly, preferably 1 hour to 8 days. In order to effectively carry out the heat treatment, it is preferable to carry out in a solvent, and the kind of the solvent is not limited as long as it does not substantially dissolve the dye of the general formula (I), and examples thereof include water and alcohols. (For example, methanol, ethanol, isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol, diethylene glycol, ethyl cellosolve), ketones (for example, acetone, methyl ethyl ketone), esters (for example, ethyl acetate,
Butyl acetate), alkyl carboxylic acids (eg, acetic acid,
Propionic acid), nitriles (eg acetonitrile), ethers (eg dimethoxyethane, dioxane, tetrahydrofuran) and the like can be mentioned.

The coexistence of organic carboxylic acids during the heat treatment can more effectively solve the problems of the present invention. Examples of the organic carboxylic acid include alkyl carboxylic acids (for example, acetic acid and propionic acid), carboxymethyl celluloses (CMC), aryl carboxylic acids (for example, benzoic acid and salicylic acid).
When used as a solvent, the amount of the organic carboxylic acids can be 0.5 to 100 times the weight of the dye of the general formula (I). When an organic carboxylic acid is added by using a solvent other than the organic carboxylic acids, the compound of the general formula (I)
It can be used in a weight ratio of 0.05 to 100% with respect to the dye.

The dye represented by the general formula (I) can be used in any effective amount, but is preferably used so that the optical density is in the range of 0.05 to 3.0. Preferably 0.5mg / m ² ~1000mg / m ² The addition amount,
More preferably ^{1mg / m 2 ~500mg / m 2} . The addition time may be any step before coating. The dye represented by the general formula (I) can be used in any of the emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, antihalation layer, filter layer, etc.) and is used in a single layer. It may be used or may be used in a plurality of layers. Above all, it is particularly preferable to use it for the antihalation layer.

Gelatin is a typical hydrophilic colloid, but any of the other conventionally known ones that can be used for photography can be used. The silver halide emulsion used in the present invention is preferably silver bromide, silver iodide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The silver halide grains used in the present invention are cubic,
It has a regular crystal form such as an octahedron, an irregular crystal form such as a sphere or a plate, or a compound form of these crystal forms. . It is also possible to use a mixture of grains having various crystal forms, but it is preferable to use a regular crystal form. Regarding silver halide grains, photographic emulsions, their manufacturing methods, binders or protective colloids, hardeners, sensitizing dyes, stabilizers, antifoggants, etc., JP-A-3-238447, page 18, lower left column, line 18 The contents described in page 17 of the same publication, page 20, lower left column, line 17 can be directly applied to the present invention.

The light-sensitive material of the present invention comprises a coating aid, an antistatic agent,
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic characteristics (for example, development acceleration, contrast enhancement, sensitization). The light-sensitive material produced by using the present invention may contain a dye other than the present invention as a filter dye or in a hydrophilic colloid layer for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanine dyes are also useful. . These dyes can be added by being dissolved in water when they are water-soluble, and can be added as solid fine particle dispersions when they are difficult to dissolve in water. The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

Regarding the multi-layered multicolor photographic light-sensitive material, the support, the method for coating the photographic emulsion layer, the means for exposing the light-sensitive material, the photographic processing of the light-sensitive material, etc., JP-A-3-238447 (20).
The contents described in line 14 in the lower right column of the page to line 2 in the upper right column of the same publication (27) can be applied.

[0034]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 A 125 μm-thick polyethylene terephthalate support having subbing layers on both sides was sequentially coated on one side with a conductive layer and a protective layer having the following formulations in the order of increasing distance from the support. (1) Conductive layer DULIMER ET410 (manufactured by Nippon Pure Chemicals KK) 38 mg / m ² (polyacrylic ester) SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 216 mg / m ² compound -1 5 mg / m ² compound ^{-2 5 mg / m 2 (2} ) protective layer Chemipearl S120 (Mitsui petrochemical K.K., Ltd.) 33 mg / m ² (polyolefin aqueous dispersion) Snowtex C (Nissan chemical KK) 17 mg / m ² compound-1 5 mg / m ² compound-35 mg / m ² sodium polystyrene sulfonate 2 mg / m ²

[0035]

[Chemical 10]

Further, a dyeing layer, an emulsion layer and a protective layer having the following formulations were simultaneously coated on the opposite surface of the support. (3) Dyeing layer Gelatin 1.4 g / m ^{2 *} Solid disperse dye See Table-1 Compound-4 7 mg / m ² Compound-5 41 mg / m ² Sodium polystyrene sulfonate 25 mg / m ² Sodium dodecylbenzene sulfonate 20 mg / m ² Phosphoric acid 15 mg / m ²

[0037]

[Chemical 11]

^* Preparation Method of Solid Disperse Dye The preparation method in the present invention is based on the method of JP-A-63-197943. That is, 434 ml of water and TritonX-2
53g of a 6.7% solution of 00R surfactant (TX-200R, sold by Rohm & Haas) was placed in a 1.5 liter screw cap bottle. Add 20 g of dye and 800 ml of zirconium oxide (ZrO ₂ ) beads (2 mm diameter), put the lid on the bottle tightly and place it in the mill.
The contents were ground for 4 days. The contents were added to 160 g of a 12.5% aqueous gelatin solution and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered and filtered with ZrO ₂
The beads were removed. If left as it is, the average particle size is 0.3 μm
However, since the particles still contained coarse particles, the particles were classified by a centrifugal separation method so that the maximum particle size was 1 μm or less. (4) Emulsion layer Preparation of emulsion While keeping the following solution A at 65 ° C and stirring, add solution B and solution C to 5
Added by the double jet method for minutes. Then 7 minutes 6
After physical aging was performed while maintaining the temperature at 5 ° C, the following D liquid and E
The solution was added over 40 minutes by the controlled double jet method while controlling the pAg to 7.2. The obtained grains were monodisperse cubic silver iodobromide grains having an average grain size of 0.25 μm and a silver iodide content of 1 mol% (variation coefficient: 9%). (Solution A) Gelatin 20 g Potassium bromide 3 g Benzenethiosulfonic acid 5 mg 1,3-Dimethylimidazolidin-2-thione 6 mg Water 900 ml (solution B) Silver nitrate 18.9 g Water 85 ml (C liquid) Potassium bromide 13.9 g Water was added to 60 ml (D liquid) Silver nitrate 151 g Water was added to 680 ml (E liquid) Potassium bromide 106 g Potassium iodide 1.5 g Water was added to 455 ml Washed with water by flocculation method according to the method, added 41 g of gelatin, pH 6.8, pAg 8.9
Adjusted to. (5) Protective layer Gelatin 0.5 g / m ² Polymethylmethacrylate fine particles (average particle size 0.9 μ) 30 mg / m ² compound-7 (gelatin dispersion) 35 mg / m ² compound-8 8 mg / m ² dodecyl Sodium benzenesulfonate 5 mg / m ² colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd.) 90 mg / m ² compound-9 5 mg / m ² L-ascorbic acid 10 mg / m ² 1,5-dihydroxy-2-benz Aldoxime 5 mg / m ² Sodium acetate 100 mg / m ² Sodium polystyrene sulfonate 15 mg / m ²

[0039]

[Chemical 12]

After dissolving and dispersing this emulsion at 35 ° C.,
After the following sensitizing dye was added at 5 × 10 ⁻⁴ mol per mol of silver, the temperature was raised to 65 ° C. over 15 minutes, and then 14 mg of sodium thiosulfate and 4 mg of N, N-dimethylselenourea per mol of silver were added. Chloroauric acid (5 mg) and benzenethiosulfonic acid (7 mg) were added and chemically sensitized for 60 minutes, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (100 mg) was added as a stabilizer, and phenoxyethanol was used as a preservative. 100 mg was added.

[0041]

[Chemical 13]

Further, 1-phenyl-5-mercaptotetrazole 15 mg / mol Ag, 3- (5-mercaptotetrazole) -sodium benzene sulfonate 100 mg
/ Mol Ag, 4-hydroxy-6-methyl-1,3,3
1.5 g of a, 7-tetrazaindene / mol Ag, 700 mg / mol Ag of potassium bromide and 150 mg / mol Ag of compound-6 were added.

[0043]

[Chemical 14]

Next, 20 mg of sodium polystyrene sulfonate was added as a thickener per 1 g of gelatin, and the pH was adjusted to 5.2 with phosphoric acid. Polyethyl acrylate latex as plasticizer (average particle size 0.05μm)
Was added to gelatin in an amount of 30% by weight, and 2-bis (vinylsulfonylacetamide) ethane was added as a hardening agent. The coating solution Ag1.4g / m ^2, gelatin 1.3 g / m ^2,
The hardener was applied at 100 mg / m ² .

<Evaluation of Sample> 1. Evaluation of Photographic Performance Exposure was carried out with tungsten light (1000 lux) having a color temperature of 2856K through a continuous wedge for 1/5 second. The processing was performed using an automatic processor Prostar II processor manufactured by Eastman Kodak Co. at a processing speed of 3 m / min. The developer and fixer used were Prostar Plus developer (38 ° C.) and Prostar Plus fixer manufactured by EK. The replenishment rate was 100 cc / m ² . The sensitivity at this time was expressed by the logarithm of the reciprocal of the exposure amount that gives a density of 1.0. The sensitivity of the sample was set to 100 and the relative value was shown. 2. Evaluation of residual color The sample was processed without being exposed. As processing conditions, the temperature of the developer / fixer used in the evaluation of photographic performance is 34 ° C.
The same conditions were used except that the temperature of the washing water was maintained at 10 ° C. or lower. Evaluation was performed visually by placing the above sample on a white paper, and was 5 (colorless), 4, 3 (with residual color), 2, 1
Five-level evaluation (large residual color) was performed. The acceptable level is 4 or higher. The results are shown in Table 1.

[0046]

[Table 1]

[0047]

[Chemical 15]

As is clear from Table 1, by adding the solid disperse dye of the present invention to the AH layer (dye layer), the residual color is improved while the superiority of sharpness is maintained.

Example 2 (Preparation of Emulsion A) 0.13 M silver nitrate aqueous solution and 0.0
(NH ₄ ) ₃ RhCl ₆ and K ₃ IrCl ₆ were added to an aqueous solution of a halogen salt containing 33M potassium bromide and 0.11M sodium chloride to contain sodium chloride and 1,3-dimethylimidazolidine-2-thione. Nucleation was carried out by adding to the aqueous gelatin solution for 12 minutes with a double jet method at 43 ° C. with stirring to obtain silver chlorobromide grains having an average grain size of 0.16 μm and a silver chloride content of 75 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a halogen salt aqueous solution containing 0.22 M potassium bromide and 0.69 M sodium chloride were added over 20 minutes by the double jet method. After that, it was washed with water by the flocculation method according to a conventional method, 40 g of gelatin was added, and the pH was adjusted to 6.5 and pAg.
Adjusted to 7.5, and then added 20 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver, heated at 60 ° C. for 75 minutes, chemically sensitized, and added as a stabilizer. -Hydroxy-6-
Methyl-1,3,3a, 7-tetraazaindene 150
mg was added. The obtained particles have an average size of 0.26μ.
m, 75 mol% silver chloride content, per mol of silver Rh compound 1 × 10 ^-7 mol, Ir compound 5 × 10 ^-7 mol to obtain the content to silver chlorobromide cubic grains (coefficient of variation 10%).

Preparation of Dye Dispersion 2.5 g of dye, surfactant (trade name: Demol SNB,
Kao Corporation's 10% aqueous solution 4.4 g and water 56.
4g is mixed by stirring beforehand and the diameter is 0.8mm-1.2mm
Was placed in an Eiger motor mill (M-50, manufactured by Eiger Japan) containing 40 cc of zirconia beads, and dispersed at a rotation speed of 4500 rpm to obtain a fine crystal dispersion of a dye having a particle size of 1 μm or less. 50 g of the obtained crystal dispersion of dye, 1.8 g of gelatin and 13.3 g of water were added to 4
The mixture was stirred and mixed at 0 ° C. and used for preparation of the photographic light-sensitive material of the present invention.

(Preparation of photographic light-sensitive material) Emulsion layer coating solution To emulsion A, a 0.2% methanol solution of the following sensitizing dye was added at 85 mg per mol of silver. Further, for supersensitization and stabilization, 4,4-bis (4,6-dinaphthoxypyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allylbenzothiazole are used. 100 mg of iodine salt for each mol of silver
And 150 mg were added.

[0052]

[Chemical 16]

Dye layer Gelatin 0.5 g / m ² Solid disperse dye Type and amount are listed in Table 2 Sodium dodecylbenzene sulfonate 20 mg / m ² Sodium polystyrene sulfonate 50 mg / m ² 2-bis (vinylsulfonylacetamide) ethane 30 mg / m ²

Emulsion layer Gelatin 1.6 g / m ² Coating amount of silver 3.4 g / m ² Hydroquinone 0.1 g / m ² Polyethylene acrylate latex 0.5 g / m ² 2-bis (vinylsulfonylacetamide) ethane 90 mg / m ²

Protective layer Gelatin 0.7 g / m ² Polymethylmethacrylate 60 mg / m ^{2 having a} particle size of 2.5 μm Colloidal silica 80 mg / m ² sodium dodecylbenzenesulfonate having a particle size of 10 μm 40 mg / m ²

Photosensitive materials 7 to 12 were prepared by simultaneously coating multiple layers on the support in the order of the dye layer, the emulsion layer and the protective layer (from the support side) with the above coating amounts.

The base used in this example has a back layer and a back protective layer having the following compositions. [Back layer] Gelatin 2.1 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² 1,3-divinylsulfone-2-propanol 60 mg / m ² [Back protective layer] Gelatin 0.5 g / m ² Particle size 4. 7 μm polymethylmethacrylate 30 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² Fluorine-containing surfactant 3 mg / m ² Silicone oil 90 mg / m ²

Evaluation of Photographic Performance The obtained sample was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through an interference filter having a peak at 633 nm and a continuous wedge, and was then exposed by Fuji Photo Film Co., Ltd.
Using an automatic processor FG-710NH manufactured by KK, sensitometry was performed at the temperature and time shown below.

Photographic performance evaluation Residual color test Current image 38 ℃ 14 seconds 9 seconds Fixing 37 ℃ 9.7 seconds 6.2 seconds Water washing 26 ℃ 9 seconds (10 ℃) 5.8 seconds Squeeze 2.4 seconds 1.5 seconds Dry 55 ℃ 8.3 seconds 5.3 seconds 43.4 seconds in total 27.8 seconds The composition of the developer and fixer used is as follows. [Developer formulation] Hydroquinone 25.0 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g potassium sulfite 90.0 g diethylenetriaminepentaacetic acid 2.0 g potassium bromide 5.0 g 5-methylbenzotriazole 0.2 g 2-mercapto Benzimidazole-5-sulfonic acid 0.3 g Sodium carbonate 20 g Water added 1 liter (sodium hydroxide is added to adjust pH = 10.6) [Fixer formulation] Ammonium thiosulfate 210 g Sodium sulfite (anhydrous) 20 g Diethylenetriamine pentaacetic acid 0.1 g Glacial acetic acid 15 g Water was added to 1 liter (pH adjusted to 4.8 with ammonia water)

The logarithm of the exposure dose giving a density of 1.5 was taken as the sensitivity, and shown as the relative sensitivity. Evaluation of residual color The sample was processed without being exposed. Regarding processing conditions, the line speed was adjusted so that the development time was 9 seconds, and the processing was carried out in the same procedure as in the evaluation of photographic performance except that the temperature of the washing bath was lowered to 10 ° C. or lower, and three sheets were stacked. The residual color was evaluated. The results are shown in Table 2.

[0061]

[Table 2]

As is clear from the results shown in Table 2, by incorporating the solid disperse dye of the present invention into the dye layer, an image having high sharpness and less residual color can be obtained.

Example 3 Preparation of tabular grains 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and 37 cc of an aqueous solution of silver nitrate (4.00 g of silver nitrate) and potassium bromide were stirred in a container kept at 55 ° C. 38 cc of an aqueous solution containing 5.9 g was added by the double jet method in 37 seconds. Then, after adding 18.6 g of gelatin, 70
The temperature was raised to 0 ° C. and 89 cc of an aqueous silver nitrate solution (silver nitrate 9.8 g) was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added.
While maintaining Ag of 8.5, the mixture was added by the control double jet method over 35 minutes. Next, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Monodispersed pure silver bromide tabular grains having an average projected area diameter of 1.10 μm, a thickness of 0.165 μm and a diameter variation coefficient of 17.0% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C again, and 30 g of gelatin and 2.3 of phenoxyethanol were used.
0 g and 1.0 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted with caustic soda and silver nitrate solution.
It was adjusted to 5.90 and pAg 8.25. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.040 mg of thiourea dioxide was added, and the mixture was held for 22 minutes as it was for reduction sensitization. Then 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 20 mg
And sensitizing dye

[0064]

[Chemical 17]

380 mg of was added. Further, 0.83 g of calcium chloride was added. Subsequently, 1.3 mg of sodium thiosulfate, 3.0 mg of selenium compound-1, 2.5 mg of chloroauric acid and 90 mg of potassium thiocyanate were added.
After 0 minutes, it was cooled to 35 ° C. Thus tabular grains T-1
Was prepared.

[0066]

[Chemical 18]

Preparation of Coating Sample A coating sample was prepared by adding the following chemicals to 1 mol of silver halide of T-1 to prepare a coating solution.・ Gelatin (including Gel in emulsion) 65.6 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1,2 -Bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%.

[0068]

[Chemical 19]

The surface protective layer was prepared and prepared so that the coating amount of each component was as follows. Contents coating weight Gelatin 0.950 g / m ² · sodium polyacrylate surface protective layer (average molecular weight 400,000) 0.022 - 4-hydroxy-6-methyl-1,3,3a, 7- Tet Razainden 0.015

[0070]

[Chemical 20]

Polymethylmethacrylate (average particle diameter 3.7 μm) 0.090 Proxel (adjusted to pH 7.4 with NaOH) 0.0005 Preparation of support (1) Preparation of solid disperse dye for undercoat layer Same as in Example 2 The dye dispersion prepared by the method was filtered through a polypropylene non-woven fabric filter to remove particles having a size of 0.9 μm or more, and then used as the undercoat layer coating liquid. (2) Preparation of support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 183 μm that was biaxially stretched, and a first undercoat liquid having the following composition was applied to a coating amount of 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0072]

[Chemical 21]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc

[0074]

[Chemical formula 22]

2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc A second undercoat layer having the following composition is formed on the first undercoat layer on both sides. 150 ° C by wire / bar coater method on each side so that the coating amount is as shown below.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye dispersion

[0076]

[Chemical formula 23]

Matting Agent Preparation of Polymethyl Methacrylate 2.5 mg / m ² Photographic Material with Average Particle Diameter 2.5 μm The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method, and photographic material 13 -16.
The coated silver amount per one side was 1.75 g / m ² . <Evaluation of Photographic Performance> An X-ray sensitometry was carried out by using a photographic material, GRENEX Orthoscreen HR-4 wing cassette, from Fuji Photo Film Co., Ltd., which was closely attached to one side. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After the exposure, automatic developing machine processing was performed with the following developer and fixer.
The sensitivity is shown as a relative sensitivity with the photographic material being 100. <Measurement of sharpness (MTF)> Above (however, HR-4 on both sides
The MTF of the combination of the cassette (with the screen attached) and the automatic processor treatment was measured. 30 μm x 500 μm
The optical density was evaluated at the portion where the optical density was 1.0 using the MTF value with a spatial frequency of 1.0 cycle / mm.

<Measurement of Residual Color> The unexposed film was subjected to the above-mentioned automatic development treatment, and then the green transmission density was measured through a Macbeth Status A filter. On the other hand, the green transmission density of an unprimed blue dyed polyethylene terephthalate support was measured, and the net value obtained by subtracting this value was evaluated as the residual color density value.

The automatic developing machine used in this experiment was a modified automatic developing machine FPM-9000 manufactured by Fuji Photo Film Co., Ltd., and infrared drying was used in the drying section.
Is the street. The average processing amount of the photosensitive material per day is about 200 sheets in terms of the size of quarter cut.

[0080]

[Table 3]

The processing solution and its replenishment are as follows.

<Development Processing> Preparation of Concentrated Solution

(Developer) Parts Agent A Potassium hydroxide 330 g Potassium sulfite 630 g Sodium sulfite 255 g Potassium carbonate 90 g Boric acid 45 g Diethylene glycol 180 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamino) ethyl- 5-mercapto tetrazole 0.75 g hydroquinone 450 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 40 g Water added 4125 ml

Parts agent B Diethylene glycol 525 g 3-3'-dithiobishydrocinnamic acid 3 g Glacial acetic acid 102.6 g 5-Nitroindazole 3.75 g 1-Phenyl-3-pyrazolidone 65 g Water 750 ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water 750 ml

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-dimethylamino) -ethyl- 5-mercaptotetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water 600 ml pH 4.68

Preparation of Processing Solution The developer concentrate was filled in the following container for each parts agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself.

Further, the above fixing solution concentrate was also filled in the same kind of container.

First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was used as a starter in the developing tank.
Was added.

The processing agent-containing container is turned upside down and inserted into the perforating blade of the processing solution stock tank mounted on the side of the developing machine to break the sealing film of the cap and remove each processing agent in the container. The stock tank was filled.

The developing agent and the fixing tank of the developing machine were filled with the respective treating agents at the following ratios by operating the pumps installed in the developing machine.

In addition, every time 8 sheets of the photosensitive material were processed in terms of quarter size, the processing agent stock solution and water were mixed at this ratio and replenished in the processing tank of the developing machine.

Developer Part agent A 55 ml Part agent B 10 ml Part agent C 10 ml Water 125 ml pH 10.50

Fixer Concentrate 80 ml Water 120 ml pH 4.62

The washing tank was filled with tap water. The results are shown in Table 4.
It was shown to.

[0096]

[Table 4]

It can be seen that, by using the dye of the present invention, a photographic material having less deterioration in sensitivity, excellent sharpness and less residual color can be obtained as compared with the comparative dye.

Example 4 A silver halide emulsion was prepared as follows. The average volume of each silver halide grain was determined by the Coulter counter method.

(Preparation of silver chlorobromide emulsion B1) 1600 ml of a 3% aqueous solution of lime-processed gelatin was added with sodium chloride 17.6.
g, and an aqueous solution containing 0.094 mol of silver nitrate and an aqueous solution containing 0.12 mol of sodium chloride were added and mixed at 58 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.85 mol of silver nitrate and 1.15 of sodium chloride were added.
An aqueous solution containing a mole was added and mixed at 58 ° C. with vigorous stirring. After that, desalting was performed by washing with sedimentation water at 40 ° C. Further, 90.0 g of lime-processed gelatin was added. A silver bromide fine grain emulsion having a grain size of 0.07 μm was added to this emulsion in an amount equivalent to 0.005 mol in terms of silver amount to form a silver bromide-rich region on the surface of the silver chloride host grains, and then a sulfur sensitizer and a gold sensitizer were used. A sensitizer was added and optimum chemical sensitization was performed at 60 ° C. In the silver bromide fine particles, 0.8 mg of hexachloroiridium (IV) acid potassium was contained per 0.005 mol of the silver bromide fine particles during the grain formation. Thus silver chlorobromide emulsion B1 (cubic grains, average grain size 0.50
μm (diameter equivalent to the circle of the projected area), average volumetric volume of 0.13 μm ³ , and coefficient of variation of particle size distribution of 0.08 were prepared.

Next, after corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to prepare the following. A multilayer color photographic paper (101) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 15.8 g, ethyl acetate 180.0 ml, solvent (Solv-1) and (S
olv-2) 24.0 g of each was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate 6
Emulsified Dispersion A was prepared by dispersing in 560 ml of 18% gelatin aqueous solution containing 0.0 ml and 10 g of citric acid. The above-mentioned silver chlorobromide emulsion B1 and this emulsified dispersion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-15 and C are added to each layer.
The total amount of pd-16 is 25.0 mg / m ² and 50.0, respectively.
It was added to be mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0103]

[Table 5]

[0104]

[Table 6]

[0105]

[Table 7]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-mercaptotetrazole was added in an amount of 2.5 x 10 ^-4 mol, 7.7 x 10 ^-4 mol, and 1 mol of silver halide, respectively.
3.5 × 10 ⁻⁴ mol was added. Also, 4-hydroxy-6- for the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
Methyl-1,3,3a, 7-tetrazaindene was added to 1 × 10 ⁻⁴ mol and 2 × 10 ⁴ mol of silver halide per mol of silver halide, respectively.
^-4 mol and 1.5 × 10 ^-4 mol were added. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0107]

[Chemical formula 24]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper (Polyethylene on the first layer contains white pigment (TiO ₂ ; content 15% by weight) and bluish dye (ultraviolet))

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion B1 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilization Agent (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.30

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion (Cubic, 1: 3 Mixture of Large Size Emulsion G1 with Average Grain Size 0.45 μm and Small Size Emulsion G2 with 0.29 μm (silver mole ratio) (The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. Each emulsion consists of silver halide grains in which 0.8 mol% of silver bromide is locally contained on a part of the grain surface and the rest is silver chloride.) 0.13 Gelatin 1.50 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.15 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.02 colors Image stabilizer (Cpd-9) 0.07 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15 Fourth layer (color mixing prevention layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 colors Image stabilizer (Cpd-5) 0.02 Solvent (Sol -2) 0.18 solvent (Solv-3) 0.18 solvent (Solv-7) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 8: 2 mixture (molar ratio) of large size emulsion R1 with average grain size 0.5 μm and small size emulsion R2 with 0.4 μm grain size. The coefficient of variation of distribution is 0.09 and 0.10, respectively. For each size emulsion, 0.8 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is composed of silver halide grains containing silver chloride.) 0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-) 10) 0.16 color image stabilizer (Cpd-11) 0.14 color image stabilizer (Cpd-12) 0.01 solvent (Solv-1) 0.01 solvent (Solv-6) 0.22 sixth layer (ultraviolet absorbing layer) gelatin 0.55 ultraviolet absorber (UV-1) 0.38 stable color image (Cpd-13) 0.15 Color image stabilizer (Cpd-6) 0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-) 14) 0.01 The compounds used here are shown below.

[0112]

[Chemical 25]

[0113]

[Chemical formula 26]

[0114]

[Chemical 27]

[0115]

[Chemical 28]

[0116]

[Chemical 29]

[0117]

[Chemical 30]

[0118]

[Chemical 31]

[0119]

[Chemical 32]

(Preparation of solid fine particle dispersion KB-1 of dye) Dye-a finely divided by a sand mill (as described above)
0.01 mol was dissolved in 5 ml of a 5% aqueous solution of the following surfactant (KK-1), and 1 g of citric acid was further dissolved.
After dispersing in 25 ml of 0% gelatin aqueous solution, the sand used was removed using a glass filter. The dye adsorbed on the sand on the glass filter was washed off with hot water and added, and solid fine particle dispersion KB-1 of the dye (gelatin concentration 7%,
The average particle size of the fine powder dye was 0.3 μm).

[0121]

[Chemical 33]

Sample 201 was prepared by adding a solid disperse dye layer having the following composition between the support and the first layer, and coating the sample 101 obtained above. (Solid disperse dye layer, numeral represents coating amount (g / m ² )) Gelatin 0.50 Solid fine particle dispersion KB-1 1.00 Next, for sample 201, the type of dye in the solid fine particle dispersion is shown in Table 8. Samples 202 to 203 which were different only in that

[0123]

[Table 8]

Samples 101 and 201 obtained as described above
The following evaluations were performed for ~ 203. (Evaluation of Sharpness) Exposure was performed through an optical wedge for measuring sharpness and a green filter, and processing was performed according to the processing steps shown below. The sharpness is expressed by the spatial frequency (lines / mm) that gives a CTF of 0.5. The larger the value, the higher the sharpness. (Evaluation of storability of photosensitive material) Each sample was tested at 25 ° C, 55% RH
After being stored for 2 days under the condition of 0 ° C. and 80% RH, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K) was used and 1/10 through a green filter.
Gradation exposure for sensitometry was given at 250 lux per second, and processing was performed according to the processing steps shown below. The reflection density of the processed sample thus prepared was measured to obtain a so-called characteristic curve, and the sensitivity was defined as the logarithm of the reciprocal of the exposure dose giving a density 0.5 higher than the fog density. 25 ° C 55% R
The sensitivity difference of the sample of 50 ° C. and 80% RH with respect to the sample of H was used as a measure of the storability of the light-sensitive material. The closer the value is to 0, the better the storage stability. The stain after treatment was also measured and used as a measure of whether the solid disperse dye was rapidly decolorized during treatment.

Color development processing (Processing step) (Temperature) (Time) (Replenisher) ^* (Tank capacity) Color development 35 ℃ 45 seconds 161 ml 17 liter Bleach fixing 30-35 ℃ 45 seconds 215 ml 17 liter Rinse (1 ) 30 to 35 ° C 20 seconds -10 liters Rinse (2) 30 to 35 ° C 20 seconds -10 liters Rinse (3) 30 to 35 ° C 20 seconds 315 ml 10 liters Dry 70 to 80 ° C 60 seconds * Per 1 m ^{2 of} material. (3 tank counter-current system from rinse (3) to rinse (1))

Color developing solution Tank solution Replenishing solution Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g- Potassium carbonate 25.0 g 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water is added 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g 1,000 ml pH (25 ° C) 6.0 rinse solution with water (tank solution and replenisher are the same) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less)

Table 8 shows the photosensitive materials thus obtained and the evaluation results.

From Table 8, when a dye having neither a group having an ionizable proton or a salt thereof nor having a substituent on the methine chain is used, the sensitivity is largely decreased by the storage of the light-sensitive material, and after the processing, While the stain is high,
It can be seen that when the dye of the present invention is used, the desensitization is small and the decolorizing property is excellent.

[0130]

EFFECT OF THE INVENTION By using the solid fine particle-dispersed dye represented by the general formula (I) in the hydrophilic colloid layer, a silver halide photographic light-sensitive material having excellent storability of the light-sensitive material and a small residual color can be obtained. To be

Claims (4)

[Claims] 1. A solid fine particle represented by the following general formula (I):
Hydrophilic colloid containing at least one child-dispersed dye
Silver halide photographic light-sensitive material characterized by having a transparent layer
Fee. General formula (I)Where R₁, R₂Represents an alkyl group, L₁,
L₂, L₃, L_FourAnd L _FiveRepresents a methine group. However
Then L₁, L₂, L₃, L_FourAnd L_FiveIs represented by
At least one of the tin groups has a substituent. Also,
R₁, R₂, L₁, L ₂, L₃, L_FourAnd L_FiveA
Having a group having a proton capable of being turned on or a salt thereof
Make it not exist. 2. The dye according to claim 1, wherein L ₃
Is a substituted methine group, and L ₁ , L ₂ , L ₄ , and L ₅ are unsubstituted methine groups. The silver halide photographic light-sensitive material according to claim 1, wherein 3. The silver halide photographic light-sensitive material according to claim 1, wherein the average particle diameter of the dye according to claim 1 is 0.005 to 10 μm or less. 4. The hydrophilic colloid layer according to claim 1, which is coated on the side having the emulsion layer closest to the support or on the side opposite to the support with respect to the support. The silver halide photographic light-sensitive material according to claim 1.