JP3038391B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material containing a pyrazolone oxonol dye, and more specifically, a specific layer is dyed with the above dye. The present invention relates to a silver halide photographic light-sensitive material having less fog and less desensitization over time.

[Conventional technology]

Silver halide photographic materials are required to have high image quality characteristics such as excellent sharpness and color reproducibility.

In recent years, further reduction in processing time, that is, ultra-rapid processing suitability has been required in order to counter the immediateness of competing electrophotographic materials. In order to realize the high image quality characteristics and ultra-rapid processing suitability required for such photographic light-sensitive materials, efforts in the industry to further reduce the thickness of photographic light-sensitive materials and optimize silver halide and additive compound materials have been made. It has been done.

By the way, it is well known that a dye is contained in a silver halide photographic material for the purpose of improving image quality or adjusting the sensitivity of a silver halide emulsion, and is used, for example, for preventing halation, preventing irradiation, and using a light absorption filter. Have been.

Recently, dyes intended to replace yellow colloidal silver in color photographic light-sensitive materials (hereinafter referred to as "YC dyes")
The use of dyes for dyeing crossover cut layers in X-ray photographic materials and dyes for dyeing non-photosensitive emulsion layers in printed photographic materials has been widespread.

The dye used for these purposes depends on the purpose of use. 1. It must have a good absorption spectrum. 2. It must not diffuse from the colored layer to other layers. No effect 4. Stable in silver halide photographic light-sensitive material 5. Easily added 6. Stable in emulsion coating solution and do not affect solution viscosity 7. After processing It is required that the color does not remain.

Numerous dyes have been proposed for the purpose of satisfying these required properties. For example, US Pat. No. 3,540,887
No. 3,544,325, No. 3,560,214, Mochisho 31-10578
No. 51-3623, etc., benzylidene dyes, British Patent No. 506,385 and Oxonol dyes in Japanese Patent No. 39-2269, U.S. Pat.No. 2,493,747, merocyanine dyes, U.S. Pat.No. 1,845,404, styryl dyes Etc. have been proposed.

It is a general method to dissolve these dyes in water or an organic solvent miscible with water and to add them to a photographic component layer.
If the dye is water-soluble, it will diffuse into all layers instead of staying in the layer to be dyed. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye for the diffusion of the other layer, and undesired phenomena such as a decrease in sensitivity, gradation fluctuation and fog abnormality are caused in both the own layer and the other layer. It will appear. In particular, when the photographic material is stored over time, fogging and desensitization are remarkable, and if the amount used is reduced to avoid these, the original light absorption effect cannot be sufficiently obtained. Dyes with reduced diffusivity such as dyeing a specific layer for such a problem are known, and as diffusion-resistant dyes, for example, U.S. Pat.No. 2,538,008, 2,539,009, 4,420,
No. 555, JP-A Nos. 61-204630, 61-205934, 62-3
No. 2460, No. 62-56958, No. 62-92949, No. 62-222248
Nos. 63-40143, 63-184749 and 63-316852 describe YC dyes. Also, these dyes are commonly used in color photographic elements by Carey Lea Silver
Yellow colloidal silver, which is not only in the blue light region but also absorbs longer wavelengths in part, thereby lowering green sensitivity, improving the drawback of increasing fog in adjacent layers, and saving valuable silver resources. Many have been proposed for.

These diffusion-resistant dyes can alleviate the above-mentioned drawbacks to some extent, but on the other hand, they deteriorate storage stability, cause desensitization with time, and have insufficient bleaching properties, causing problems such as color contamination. Newly occurred. In order to solve these problems, a new diffusion-resistant dye is required.

[Object of the invention]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which meets the above-mentioned requirements for a dye which has been made resistant to diffusion and has improved image quality and stability over time.

[Configuration of the invention]

The present inventors have conducted intensive studies in view of the above problems, and as a result, the object of the present invention is to provide a photograph containing a solid fine particle dispersion of a compound represented by the following general formula [I] on a support: It has been found that this can be achieved by a silver halide photographic material having at least one constituent layer.

General formula [I] In the formula, R ₁ and R ₂ represent a substituent, and R ₃ and R ₄ represent an m-carboxyphenyl group or an o-carboxyphenyl group.
L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group, and n ₁ and n ₂ represent 0 or 1. However, when n ₁ = n ₂ , R ₃ and R ₄ represent an m-carboxyphenyl group.

 Hereinafter, the present invention will be described in more detail.

In the general formula (I), the substituent represented by R ₁ and R ₂ includes an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkylcarbonyl group,
Arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfimoyl group,
Preferred are cyano, amino, sulfonamido, amide, ureido, thioureido, alkoxy, aryloxy, alkylthio, arylthio, carboxyl, and hydroxyl groups.

Examples of the alkyl group represented by R ₁ and R ₂ include a methyl group, an ethyl group, a propyl group, an i-propyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a dodecyl group Pentadecyl group, eicosyl group and the like. The alkyl group includes those having a substituent. Examples of the substituent include a halogen atom (eg, each atom of chlorine, bromine, iodine, fluorine, etc.), an aryl group (eg, a phenyl group, a naphthyl group, etc.), and a heterocyclic group. Group (for example, pyrrolidyl group, pyridyl group, etc.), sulfinic acid group,
Carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (eg, amino group, diethylamino group, etc.), alkoxy group (eg, methoxy group, ethoxy group,
Butoxy group, octyloxy group, i-propoxy group, etc.), aryloxy group (phenoxy group, naphthyloxy group, etc.), carbamoyl group (for example, aminocarbonyl group, methylcarbamoyl group, pentylcarbamoyl group,
Phenylcarbamoyl group, etc.), amide group (eg, methylamide group, benzamide group, octylamide group, etc.), sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, butylsulfamoyl group, etc.), sulfone Amido group (eg, methanesulfonamide group, heptanesulfonamide group, benzenesulfonamide group, etc.), sulfinyl group (eg, alkylsulfinyl group such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, octylsulfinyl group, etc.), phenylsulfinyl group, etc. Arylsulfinyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, 2-hydroxyethoxycarbonyl group, octyloxycarbonyl group, etc.), aryloxy group A cicarbonyl group (eg, phenosylcarbonyl group, naphthyloxycarbonyl group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, hexylthio group, etc.), an arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkylcarbonyl group (eg, acetyl Group, ethylcarbonyl group, butylcarbonyl group, octylcarbonyl group, etc.), arylcarbonyl group (eg, benzoyl group, p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group, naphthoyl group, etc.), cyano group, ureido group (eg, A methylureido group, a phenylureido group, etc.) and a thioureido group (eg, a methylthioureido group, a phenylthioureido group, etc.).

Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and examples of the substituent include those described above.
Alkyl group represented by R _1, R ₂ are, or the aforementioned groups mentioned as substituents for the alkyl group represented by R _1, R ₂ can be mentioned.

As the alkenyl group represented by R ₁ and R ₂ , a vinyl group,
Allyl group, 1-propenyl group, 1,3-butadienyl group,
Examples of the alkenyl group include those having a substituent, and examples of the substituent include those exemplified as the substituent of the alkyl group represented by R ₁ and R ₂ .

Examples of the heterocyclic group represented by R ₁ and R ₂ include a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-carboxy-2-pyridyl group, 3,5-dichloro-2 -Pyridyl group, 4,6-dimethyl-2-pyridyl group,
6-hydroxy-2-pyridyl group, 2,3,5,6-tetrafluoro-4-pyridyl group, 3-nitro-2-pyridyl group, etc., oxazolyl group (5-carboxy-2-benzoxazolyl group) , 2-benzoxazolyl group, 2-oxazolyl group, etc.). Thiazolyl group (5-sulfamoyl-2
-Benzothiazolyl group, 2-benzothiazolyl group, 2-
Thiazolyl group, etc.), imidazolyl group (1-methyl-2-
Imidazolyl group, 1-methyl-5-carboxy-2-benzimidazolyl group, etc., furyl group (3-furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.), thienyl group (2-thienyl group, etc.), pyrazinyl group (2-pyrazinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2-
Pyridazinyl group, etc., purinyl group (8-purinyl group, etc.), isoxazolyl group (3-isoxazolyl group, etc.), selenazolyl group (5-carboxy-2-selenazolyl group, etc.), sulfolanyl group (3-sulfolanyl group, etc.), piperidinyl Groups (such as a 1-methyl-3-piperidinyl group), a pyrazolyl group (such as a 3-pyrazolyl group), and a tetrazolyl group (such as a 1-methyl-5-tetopzolyl group), and the heterocyclic group has a substituent. And the substituents include the alkyl groups represented by R ₁ and R ₂ above and
Examples of the substituent of the alkyl group represented by R ₁ and R ₂ are given.

R ₁ , as a cycloalkyl group represented by R ₂ , for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like, R ₁ , as an alkylcarbonyl group represented by R ₂ , for example, a methylcarbonyl group, Ethyl carbonyl group, i-propyl carbonyl group, t-butyl carbonyl group, octyl carbonyl group, dodecyl carbonyl group, etc.R ₁ , As the arylcarbonyl group represented by R ₂ , for example, phenyl carbonyl group, naphthyl carbonyl group, etc. As the alkoxycarbonyl group represented by R ₁ and R ₂ ,
For example, an ethoxycarbonyl group, an i-propoxycarbonyl group, a t-butoxycarbonyl group, a pentyloxycarbonyl group, a dodecyloxycarbonyl group, and the like, examples of the aryloxycarbonyl group represented by R ₁ and R ₂ include a phenyloxycarbonyl group, Examples of the alkylsulfonyl group such as a naphthyloxycarbonyl group include a methylsulfonyl group, an ethylsulfonyl group, an i-propylsulfonyl group, a t-butylsulfonyl group, an octylsulfonyl group,
Octadecylsulfonyl group and the like; arylsulfonyl groups such as phenylsulfonyl group and naphthylsulfonyl group; alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, i-propylsulfinyl group, t-butylsulfinyl group and octyl Examples of the arylsulfinyl group include a phenylsulfinyl group and a naphthylsulfinyl group. Examples of the carbamoyl group include an aminocarbonyl group, a methylcarbamoyl group, and an ethylcarbamoyl group.
Sulfamoyl groups such as -propylcarbamoyl group, t-butylcarbamoyl group, dodecylcarbamoyl group, phenylcarbamoyl group, 2-pyridylcarbamoyl group, 4-pyridylcarbamoyl group, benzylcarbamoyl group, morpholinocarbamoyl group, piperazinocarbamoyl group, etc. For example, aminosulfonyl, methylsulfamoyl, i-propylsulfamoyl, t-butylsulfamoyl, dodecylsulfamoyl, phenylsulfamoyl, 2-pyridylsulfamoyl, 4- Pyridylsulfamoyl group, morpholinosulfamoyl group, piperazinosulfamoyl group, etc. As the amino group, for example, amino group, methylamino group, ethylamino group, i-propylamino group, t-butylamino group, octylamino Group, de Shiruamino group,
Examples of sulfonamide groups such as dimethylamino group, anilino group, naphthylamino group, morpholino group, and piperazino group include, for example, methylsulfonamide group, ethylsulfonamide group, i-propylsulfonamide group, t-butylsulfonamide group, dodecyl Amide groups such as a sulfonamide group, a phenylsulfonamide group, and a naphthylsulfonamide group, such as a methylcarbonylamino group, an ethylcarbonylamino group, an i-propylcarbonylamino group, a t-butylcarbonylamino group, a dodecylcarbonylamino group, Examples of the ureido group such as a phenylcarbonylamino group and a naphthylcarbonylamino group include a methylureide group, an ethylureide group, an i-propylureide group, a t-butylureide group, a dodecylureide group, and a phenylureide. ,
Examples of thioureido groups such as 2-pyridylureido group and thiazolylureido group include methylthioureido group, i-propylthioureido group, t-butylthioureido group, dodecylthioureido group, phenylthioureido group, and 2-pyridyl. An alkoxy group such as a methoxy group, an ethoxy group, an i-propoxy group, a t-butyloxy group or a dodecyloxy group; an aryloxy group such as a phenoxy group or a naphthyloxy group; Examples of the alkylthio group include a methylthio group, an ethylthio group, an i-propylthio group, a t-butylthio group, and a dodecylthio group. Examples of the arylthio group include a phenylthio group and a naphthylthio group. Each group represented by these R _1, R ₂ includes those having a substituent, as the substituent of the alkyl group as the substituent represented by an alkyl group and R _1, represented by the aforementioned R ₁ Examples are given.

Of these groups represented by R ₁ and R ₂ , preferably an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group,
It is an amino group, an alkoxy group, a cyano group, or a carboxyl group, particularly preferably an alkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an alkoxy group, or a carboxyl group.

In the general formula [I], the o-carboxyphenyl group and the m-carboxyphenyl group represented by R ₃ and R ₄ include those having a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, an aryl group, a carboxyl group and the like.Specifically, the alkyl groups represented by R ₁ and R ₂ described above are exemplified. Examples of the substituent include those exemplified above.

Hereinafter, specific examples of the compound of the present invention are shown, but the present invention is not limited thereto.

Compounds of the present invention, for example, JP-A-48-62826, 49
No.-5125, No.51-77327, No.58-143342, No.59-111
In the same manner as in the synthesis methods described in JP-A Nos. 641 and 64-40827, the compound can be easily synthesized by reacting a pyrazolone derivative with a methine chain source. Hereinafter, specific synthesis examples of the present invention are shown, but other dyes can be similarly synthesized.

21.8 g of (1), 11.6 g of (2) and 100 ml of DMF were mixed to form a suspension, and 25.3 g of triethylamine was added dropwise at room temperature. After stirring at room temperature for one day, concentrated hydrochloric acid (200 ml) was added for acid precipitation.
22.6 g of the crude crystals obtained by filtration were dispersed in 200 ml of water, 5 g of sodium hydroxide was added to completely dissolve, and concentrated hydrochloric acid was added until pH = 2 to perform acid precipitation.

After repeating this operation three times, the obtained solid was dispersed by heating in 300 ml of dimethyl sulfoxide, 100 ml of concentrated hydrochloric acid was added thereto, and the product was obtained by acid precipitation, filtration and drying. Yield 1
4.6 g, 68.7% yield.

The parent compound peak was confirmed from the mass spectrum of the target compound.

The compound of the present invention is used in a silver halide photographic material so that the optical density is in the range of 0.05 to 3.0 depending on the purpose.

As a method for adding a dispersion of the solid fine particles of the compound of the present invention to a light-sensitive material, for example, a method disclosed in US Pat. No. 4,857,446 is mentioned as a specific example.

In the present invention, the photographic constituent layer includes, for example, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, an intermediate layer, a protective layer,
Shows a photosensitive layer or a non-photosensitive layer such as a filter layer, an antihalation layer and an irradiation prevention layer.

The compound of the present invention is preferably contained in a non-photosensitive layer, and particularly preferably contained in a filter layer.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used.

The emulsion can be chemically sensitized by a conventional method.
By using a sensitizing dye, it can be optically sensitized to a desired wavelength range.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or poorly water-soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material. Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, the hardener, by the coupling with the colored coupler having the effect of color correction, the competitive coupler and the oxidized form of the developing agent, Antifoggants, antifoggants,
Compounds that release photographically useful fragments, such as chemical sensitizers, spectral sensitizers, and sensitizers are used.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an anti-irradiation layer may be provided. In these layers and / or the emulsion layer, a dye which is discharged from the light-sensitive material or bleached during the development processing may be contained. .

To the light-sensitive material, a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder and a bleaching accelerator can be added.

As a support of the photosensitive material, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, or the like can be used.

In order to obtain an image using the light-sensitive material of the present invention, generally known photographic processing can be performed after exposure.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 In this example, a silver halide photographic material was prepared as follows.

 First, an emulsion was prepared as follows.

(A) Preparation of Monodisperse Emulsion Silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm was prepared by the double jet method while maintaining the reaction vessel conditions at 60 ° C., pAg = 8, and pH = 2. Was obtained. According to electron microscope observation, the twin generation rate is 1
% Or less. This emulsion was used as a seed crystal and further grown as follows.

The aqueous solution of gelatin was kept at 40 ° C. in the reaction vessel, and the seed crystal was added. The pH was adjusted to 9.5 by adding aqueous ammonia and acetic acid.

After adjusting to pAg7.3 with ammoniacal silver ion solution, pH and
While maintaining the pAg constant, a solution containing ammoniacal silver ion, potassium iodide and potassium bromide was added by a double jet method to form a silver iodobromide layer containing 30 mol of silver iodide.

After adjusting the pH to 9 and the pAg to 9.0 using acetic acid and silver bromide, an ammoniacal silver ion solution and potassium bromide were added at the same time, and grown to 90% of the grain size after growth. At this time
The pH was gradually lowered from 9.0 to 8.20.

After adding potassium bromide solution to make pAg = 11, further add ammoniacal silver ion solution and potassium bromide to gradually adjust pH.
The emulsion was grown while lowering to 8 to obtain a silver iodobromide emulsion having an average grain size of 0.7 μm and containing 2 mol% of silver iodide.

In the preparation of the emulsion, the following sensitizing dye (A) was added in an amount of 300 mg per mole of silver in the emulsion and 15 mg of the sensitizing dye (B) to obtain an emulsion. Sensitizing dye (B) Next, as shown below, a desalting step for removing excess salts was performed.

The silver halide emulsion solution was kept at 40 ° C., and the following compound (a) (exemplified compound II shown in JP-A-58-140322) was used.
-I) was added to sediment the silver halide grains, and after discharging the supernatant, pure water at 40 ° C was further added. Then, magnesium sulfate is added to precipitate the silver halide grains again, and the supernatant is removed. Do this again and add gelatin to pH 6.
An emulsion with 0 and pAg 8.5 was obtained.

Compound (a) The emulsion obtained above was kept at 55 ° C., and sensitized by adding chloroauric acid and hypo to give 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene was added to obtain a photosensitive emulsion. This is designated as emulsion (A).

Per mole of silver halide as an additive to the photosensitive emulsion of (A), Were added to obtain an emulsion coating solution.

Further, the following coating liquid was prepared as a protective layer liquid. That is, the following compounds were added in the following amounts per 1 g of gelatin,
A coating solution for a protective layer was used.

The following sample 1-1 was prepared using each of the above coating solutions.

Sample 1-1 As the undercoat liquid, glycidyl methacrylate 50 wt%,
Methyl methacrylate 10wt%, butyl methacrylate 40
An aqueous dispersion of a copolymer prepared by diluting a wt% copolymer so as to have a concentration of 10 wt% was used and applied to both surfaces to obtain an undercoated support. Next, the emulsion layer was coated on the support so that the amount of silver on one side was 3.2 g / m ^2, and the protective layer was coated so that the amount of gelatin on one side was 0.98 g / m ² at a coating speed of 140 m / min. .

Sample 1-2 Sample 1-1 was placed between the emulsion layer and the undercoat layer with respect to Sample 1-1.
The coating was carried out so as to insert a crossover cut layer containing the dye shown in (1).

The dye can be added by dissolving the dye in methanol containing a small amount of triethylamine,
Was adjusted to 6.0 to obtain a coating solution.

Samples 1-3 to 1-32 Coating was performed so as to insert a crossover cut layer in the same manner as in Sample 1-2. However, the method of adding the dye was such that the dye used in each case was dispersed in a ball mill solid fine particle according to the following procedure.

Water and a surfactant alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were placed in a ball mill container, the respective dyes were added, zirconium oxide beads were added, and the container was sealed and dispersed in a ball mill for 4 days.

Thereafter, an aqueous gelatin solution was added and mixed for 10 minutes to remove the beads, thereby obtaining a coating solution.

The amount of dye added to each sample was adjusted to 50 mg / m ² per 1 m ^{2 on} both sides.

 The following evaluation was performed on the obtained sample.

<Measurement of Sensitometry> The standard light B described in "New Edition, Lighting Data Book" was used as a light source, and exposure was performed on both sides of the film with a non-filter at an exposure time of 0.1 second and 3.2 cms so as to have the same light amount. . The samples were treated with an XD-SD developer for 45 seconds using an SRX-501 automatic developing machine (manufactured by Konica Corporation), then fixed and dried, and then the sensitivity of each sample was determined. The sensitivity was obtained by calculating the reciprocal of the amount of light required for increasing the blackening density by 1.0, and expressing the relative sensitivity with the sensitivity for sample 1-1 in Table 1 being 100.

<Evaluation of MTF> An MTF chart containing a square wave of 0.5 to 10 lines / mm made of lead was attached to the back side of the front side of the fluorescent screen KO-250 (manufactured by Konica Corporation), and a chart of lead on the film surface was obtained. X-rays were applied so that the density of the part not shielded by the method was about 1.0 on both sides.

After the sample irradiated with X-rays as described above is subjected to the same development processing as described above, the recorded rectangular wave pattern is converted into a Sakura microdensitometer M-5 (Konica Corporation)
Was used for the measurement. The aperture size at this time is 300 μm in the parallel direction of the rectangular wave and 25 μm in the perpendicular direction.
And the magnification was 20 times. The obtained MTF value is represented by a value of a spatial frequency of 2.0 lines / mm.

Comparative dye 1 As is evident from Table 1, the sample of the present invention has improved sharpness despite less decrease in sensitivity than the comparative sample.

On the other hand, the following polydisperse emulsion (B) and tabular grains (C) were prepared in place of the monodisperse emulsion (A).

(B) Preparation of polydisperse emulsion The following four kinds of solutions were prepared by a forward mixing method.

The solution B and the solution C were poured into a reaction vessel for preparing an emulsion, and stirred with a propeller-type stirrer at 300 rpm to keep the reaction temperature at 55 ° C.

Next, the solution A was divided into a ratio of 1 solution: 2 solutions, and 100 ml of one solution was added thereto over 1 minute. After stirring was continued for 10 minutes, the remaining two solutions of Solution A, 200 ml, were added over 10 minutes. Stirring was continued for another 30 minutes. Then, the solution D was added to adjust the pH of the solution in the reaction vessel to 6.0 to stop the reaction.

The average grain size of the silver halide grains was 0.65 μm, and the dispersity was 0.32. The silver iodide content was 1.2 mol%.

(C) Preparation of tabular grains 10.5 g of KBr in water 1 and a thioether compound [HO (CH)
₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH] 0.5 wt% aqueous solution (10 ml) and gelatin (30 g) were added and dissolved, and kept at 70 ° C. While stirring, 30 ml of an aqueous silver nitrate solution (0.88 mol /)
And 30 ml of an aqueous solution (0.88 mol /) of potassium iodide and potassium bromide (molar ratio: 3.5: 96.5) were added by a double jet method to obtain grains having an average grain size of 0.60 μm and a silver iodide content of 3.5 mol%. I got After the addition of the mixed solution was completed, the temperature was lowered to 40 ° C. To this, a condensate of sodium naphthalene sulfonate and formalin and magnesium sulfate, each 24.6 g /
1 mol of AgX was added, the pH was lowered to 4.9, and desalting was performed. Thereafter, 15 g of gelatin / 1 mol of AgX was added to prepare an emulsion.

The emulsions obtained in the above (B) and (C) were subjected to chemical sensitization. That is, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added to perform gold-sulfur sensitization.

After completion of chemical sensitization, 4-hydroxy-6-methyl-1,3,
3a, 7-Tetrazaindene was added. Thereafter, spectral sensitization was performed by adding 150 mg of potassium iodide / 1 mol of AgX and the same amount of the sensitizing dyes (A) and (B) as in the emulsion (A). The emulsions thus obtained are referred to as emulsions (B) and (C), respectively.

The same additives as in (A) were added to the photosensitive emulsions (B) and (C) to obtain emulsion coating solutions.
Using these coating solutions and the above-described protective layer solution, solid fine particles were dispersed and added using the dye of the present invention in the same manner as described above, and coating was performed so as to insert a crossover cut layer. Similarly, a sample with a small decrease in sensitivity and improved sharpness was obtained.

Example 2 (Preparation of a cloth solution for use in an emulsion layer) Solution A water 9.7 sodium chloride 20 g gelatin 105 g solution B water 3.8 ml sodium chloride 365 g gelatin 94 g potassium bromide 450 g 0.01% aqueous solution of potassium hexachloroiridate 28 ml potassium hexabromodimate Aqueous solution of salt 0.01 ml 1.0 ml solution C water 3.8 silver nitrate 1,700 g The above solution B and solution C were functionally added simultaneously to the above solution A kept at 40 ° C. over 60 minutes while maintaining pH 3 and pAg 7.7. After stirring continuously for 5 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, 2% aqueous magnesium sulfate solution 2 and 2.5% aqueous solution of polynaphthalenesulfonic acid 2.55 were added, and the emulsion was flocculated at 40 ° C.
Decant and wash with water to remove excess aqueous salt. Then, water of 3.7 is added thereto to disperse, and 0.9% of a 20% aqueous magnesium sulfate solution is added again to remove excess salt of the aqueous solution in the same manner. And 3.7 water and 141
Add g of gelatin and disperse at 55 ° C. for 30 minutes. This gives 38 mol% of silver bromide, 62 mol% of silver chloride, and an average grain size of 0.
25 μm, particles with a monodispersity of 9 are obtained. 140 ml of a 1% aqueous solution of citric acid and 5% aqueous solution of potassium bromide are added to the particles.
After adding 7 ml, add 70 ml of 0.1% aqueous solution of sodium thiosulfate.
In addition, it was aged at 58 ° C for 70 minutes.

10 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer to the obtained emulsion,
After aging was stopped by adding 1,600 ml of 0% aqueous solution, 3.5 g of the following sensitizing dye (a), 1 g of (b), and 1 g of (c) were added, and 7 g of compound (d) was further added as a high contrast agent. And subsequently sodium p-dodecylbenzenesulfonate as spreading agent
10 g, saponin 30 g, butyl acrylate-acrylic acid-styrene copolymer as polymer latex 120 g, pA
A coating solution for an emulsion layer was prepared by adding 3 g of potassium bromide as a g regulator, 20 g of a styrene-maleic anhydride copolymer as a thickener, and adding formalin and glyoxal as hardeners.

Sensitizing dye (a) Sensitizing dye (b) Sensitizing dye (c) Compound (d) (Preparation of coating solution for protective layer) After dissolving 500 g of gelatin in water of 7.5, 15 g of the following compound (e) as a spreading agent, and an average particle size as a matting agent
10 g of 3.5 μm silica and formalin as a hardener were added to prepare a coating solution for a protective layer.

Compound (e) (Preparation of Coating Solution for Backing Lower Layer) After dissolving 650 g of gelatin in 10 parts of water, the compounds shown in Table 2 were dispersed in solid fine particles in the same manner as in Example 1 to obtain 0.2 g of the compound.
/ m ² and then saponin 3 as a spreading agent.
0 g, 30 g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex, 150 g of colloidal silica as a coating property improver, 3 g of a styrene-maleic anhydride copolymer as a thickener, and glyoxal as a hardener.
2.5 g was added to prepare a backing lower layer coating solution.

(Preparation of coating solution for backing upper layer) After dissolving 400 g of gelatin in 600 ml of water, 20 g of polymethyl methacrylate having an average particle size of 4 μm as a matting agent was prepared.
Bis (2-ethylhexyl) sulfosuccinate sodium salt (3 g) was added as a spreading agent, and glyoxal was added as a hardening agent to prepare a coating solution for the backing upper layer.

(Preparation of sample) A backing lower layer and an upper layer are simultaneously coated on a 100 μm-thick polyethylene terephthalate film base which has been subjected to an undercoating process, and then an emulsion layer and a protective layer are simultaneously coated on the surface opposite to the backing layer. Multi-layer coating was performed. The amount of silver applied is 4.
2 g / m ² , gelatin coverage 1.95 g / m ^{2 for} emulsion layer, 1.2 for protective layer
g / m ² , backing lower layer 2.7 g / m ² , backing upper layer 1.0
g / m ² .

The obtained sample was processed with an automatic developing machine GR-27 (manufactured by Konica Corporation) using a developing solution and a fixing solution having the following formulation, and the dot quality and storage stability were evaluated.
2 is shown.

<Dot Quality> After halftone exposure was performed so as to have a dot area of 90%, processing was performed and the dot quality was evaluated on a 10-point scale. The best halftone dot quality was 10, 1 was an extremely bad level, and 5 or more was a practical level.

<Storage stability> The obtained sample was conditioned at 23 ° C and 50% RH, and the emulsion side and the backing side were brought into contact with each other and sealed. This sample was stored under the conditions of 50 ° C. and 20% RH for 5 days, and the sensitivity of the sample after storage was determined by setting the sensitivity of the sample before storage to 100.

Here, the reciprocal of the exposure required for obtaining a density of 2.5 was used as the sensitivity.

Developing conditions (Process) (Temperature) (Time) Current image 28 ° C 30 seconds Fixed 28 ° C Approx. 20 seconds Rinse room temperature Approx. 20 seconds Drying 45 ° C 20 seconds Developing solution composition (Composition A) Pure water (ion exchange water) 150 ml disodium ethylenediaminetetraacetate 2 g diethylene glycol 50 g potassium sulfite (55% w / v aqueous solution) 100 ml potassium carbonate 50 g hydroquinone 15 g 5-methylbenzotriazole 200 mg 1-phenyl-5-mercaptotetrazole 30 mg potassium bromide 4.5 g potassium hydroxide used Amount to adjust the solution pH to 10.4 (Composition B) Pure water (ion-exchanged water) 3 mg Diethylene glycol 50 g Ethylenediaminetetraacetic acid 25 mg Disodium salt acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg Development When the solution was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 for use.

Fixer formulation (Composition A) Ammonium thiosulfate 240 ml (72.5% w / v aqueous solution) Sodium sulfite 17 g sodium acetate trihydrate 6.5 g nitric acid 6 g sodium citrate dihydrate 2 g acetic acid (90% w / v aqueous solution) 13.6 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% w / v aqueous solution) 4.7 g aluminum sulfate 26.5 g (AI ₂ O ₃ in terms of content of 8.1% w / v aqueous solution) water 500ml during use of the fixing solution The above composition A and composition B were dissolved in that order, and 1 was used after finishing.

 The pH of the fixing solution was about 4.3.

Comparative sample 2 Comparative dye 3 As is clear from Table 2, the sample of the present invention has good halftone dot quality and excellent storage stability.

Further, the following dye (e) was used in place of the sensitizing dyes (a), (b) and (c), and the compounds (3), (8), (20), (27), (45), (48),
When a sample was prepared using (52) and evaluated, the same effects as in Table 2 were obtained.

Spectral sensitizing dye (e) [Effects of the Invention] As described above in detail, by containing a solid fine particle dispersion of the compound of the present invention, a silver halide having less fog, improved storage stability over time, and excellent photographic properties A photographic light-sensitive material is provided.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-52-92716 (JP, A) JP-A-60-2188641 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one photographic constituent layer containing a solid fine particle dispersion of a compound represented by the following general formula [I] on a support. General formula [I] [Wherein, R ₁ and R ₂ represent a substituent, and R ₃ and R ₄ represent an m-carboxyphenyl group or an o-carboxyphenyl group.
L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group, and n ₁ and n ₂ represent 0 or 1. However, when n ₁ = n ₂ , R ₃ and R ₄ represent an m-carboxyphenyl group. ]