JPH0429230A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is improved in sharpness, image quality and preservable stability by having at least one layer of photograph constituting layers contg. the solid fine particle dispersion of specific compds. CONSTITUTION:This photosensitive material has at least one layer of the photograph constituting layers contg. the solid fine particle dispersion of the compds. Expressed by formula I. In the formula I, X<1>, X<2> denote an oxygen atm, sulfur atom, etc.; R<1> to R<3> denote a hydrogen atom, alkyl group, etc.; R<1> to R<3> denote a group which may have a substituent and has at least one carboxyl group and/or sulfoneamide group as the substituent. Y<1> to Y<4> denote an oxygen atom or sulfur atom; L1 to L5 respectively denote a methine group; n<1> and n<2> respectively denote 0, 1 or 2. The silver halide photographic sensitive material which fogs less, is improved in the age stability n preservation and has the excellent photographic characteristics, such as sharpness, is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material containing an oxonol dye having thiohydantoin and/or rhodanine core. This invention relates to a dyed silver halide photographic material with excellent image quality and storage stability.

[Conventional technology]

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

Further, in recent years, in order to compete with the immediacy of competing electrophotographic materials, there has been a demand for further reduction in processing time, that is, ultra-rapid processing capability. In order to achieve the high image quality characteristics and ultra-rapid processing suitability required of such photographic materials, the industry is making efforts to further reduce the film thickness of photographic materials and to optimize silver halide and additive compound materials. It has been done.

Incidentally, it is well known that dyes are incorporated into silver halide photographic materials for the purpose of improving image quality or adjusting the sensitivity of silver halide emulsions. used in

Recently, dyes (hereinafter referred to as "YC dyes") have been developed to replace yellow colloidal silver in color photographic materials.
Its uses are expanding, such as dyes for dyeing cross-over cut layers in X-ray photographic materials, and dyes for dyeing dark-sensitive emulsion layers in printed photographic materials.

Depending on the purpose of use, the dyes used for these purposes must: (1) have a good absorption spectrum, (2) not diffuse from the colored layer to other layers, and (3) have a photographic effect on the light-sensitive silver halide emulsion. 4. Stable in silver halide photographic materials 5. Easy to add 6. Stable in emulsion coating solution and does not affect solution viscosity 7. After processing The properties required include that no color remains.

A large number of YC dyes have been proposed in the past for the purpose of satisfying these desired properties, for example, in U.S. Pat.
No. 0,887, No. 3,544,325, No. 3,560,
No. 214, Japanese Patent Publication No. 31-10578 and Japanese Patent Publication No. 51
-3623 etc. include hengelidene dye, British patent 506
．． No. 385 and Japanese Patent Publication No. 39-22069 propose oxonol dyes, U.S. Pat. No. 2.493.747 proposes merocyanine dyes, and U.S. Pat. No. 1.845.404 proposes styryl dyes.

The general method is to dissolve these YC dyes in water or an organic solvent that is miscible with water and add them to the photographic constituent layers, but if the dye is water-soluble, it will not remain in the layer you want to dye. It spreads to all layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to the extent that it will diffuse into other layers, and undesirable phenomena such as decreased sensitivity, gradation fluctuations, and abnormal fogging may occur in both the white layer and other layers. It will appear. In particular, when a photosensitive material is stored over time, cuffing and desensitization occur significantly, and if the amount used is reduced to avoid these problems, the original light absorption effect cannot be obtained sufficiently. To solve this problem, YC dyes with suppressed diffusion properties that dye specific layers are known, and as diffusion-resistant dyes, for example, U.S. Pat.
No. 9.009, No. 4,420,555, JP-A No. 1983-
No. 204630, No. 61-205934, No. 62-3
No. 2460, No. 62-56958, No. 62-9294
No. 9, No. 62222248, No. 63-40143,
Y in No. 63-184749, No. 63316852, etc.
C dye is listed. These dyes are also commonly used in color photographic elements, such as Carey Lea 5.
Yellow colloidal silver called ilver absorbs not only the blue light region but also some long wavelengths, which reduces green sensitivity and increases fogging of adjacent layers, and saves valuable silver resources. Many have been proposed for.

Although these diffusion-resistant YC dyes improve the above-mentioned drawbacks to some extent, they also have problems such as poor storage stability, desensitization over time, and insufficient bleaching properties, which can cause color staining. has newly occurred. In order to solve these problems, new diffusion-resistant dyes are required.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide photographic material that meets the above-mentioned requirements for a diffusion-resistant dye and has improved sharpness, image quality, and storage stability.

[Structure of the invention]

The present inventors have conducted intensive studies in view of the above problems, and have found that the above object of the present invention is to provide a photographic constituent layer containing a solid fine particle dispersion of a compound represented by the following general 2N) on a support. It has been found that this can be achieved by using a silver halide photographic material having at least one layer.

General formula [1] [wherein x' and x2 represent an oxygen atom, a sulfur atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. In addition, these R1, R2,
R3 may have a substituent, and one of the substituents is a group having a carboxyl group and/or a sulfonamide group and/or a sulfamoyl group.Y'
, Y"Y3, Y' represents an oxygen atom or a sulfur atom, L
l, Lz = R3, La and R5 each represent a methine group, nl and R2 each represent 0.1 or 2. 〕below,
The present invention will be explained more specifically.

In the above general formula (1), examples of the alkyl group represented by R1, R2, and R3 include methyl group, ethyl group, propyl group, 1-propyl group, t-butyl group, pentyl group, hexyl group, and octyl group. , 2-ethylhexyl group, dodecyl group, pentadecyl group, eicosyl group and the like. The alkyl group includes those having a substituent, and the substituent includes, for example, a halogen atom (such as chlorine, bromine,
iodine, fluorine, etc.), aryl groups (e.g. phenyl group, naphthyl group, etc.), heterocyclic groups (e.g. pyrrolidyl group, pyridyl group, etc.), carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (e.g. amino group,
diethylamino group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, butoxy group, octyloxy group, i-
propoxy group, etc.), aryloxy group (phenoxy group,
naphthyloxy group, etc.), carbamoyl group (e.g., aminocarbonyl group, methylcarbamoyl group, pentylcarbamoyl group, morpholinocarbonyl group, phenylcarbamoyl group, etc.), amide group (e.g., methylamide group, benzamide group, octylamide group, etc.), sulfamoyl group (
For example, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, morpholinosulfonyl group, butylsulfamoyl group, etc.), sulfonamide group (for example, methanesulfonamide group, heptanesulfonamide group,
heptanesulfonamide group, etc.), sulfinyl! (For example, alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, octylsulfinyl group, arylsulfinyl group such as phenylsulfinyl group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group,
hydroxyethoxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, hexylthio group, etc.), arylthio group (e.g., phenylthio group, naphthylthio group, etc.), alkylcarbonyl group (e.g. acetyl group, ethylcarbonyl group, butylcarbonyl group, octylcarbonyl group, etc.), arylcarbonyl group (e.g. hendyl group, p-methanesulfonamide hendyl group, p-carpoxyhendz) yl group, naphthoyl group, etc.), cyan group, ureido group (eg, methylureido group, phenylureido group, etc.), thioureido group (eg, methylthioureido group, phenylthioureido group, etc.), carboxyl group, and the like.

Examples of the aryl group represented by R1, R2, R:I include a phenyl group and a naphthyl group.

The aryl group includes those having a substituent, and the substituent includes, for example, the alkyl group represented by R1, R2, and R3, or the substituent of the alkyl group represented by R1, R2, and R:l. Examples include the aforementioned groups listed as .

As the alkenyl group represented by R1, R2, R:l,
Examples include vinyl group, allyl group, 1-propenyl group, 1,3-butadienyl group, 2-pentenyl group, etc., and the alkenyl group includes those having a substituent, and the substituent includes the above-mentioned R1, R2, The substituents for the alkyl group represented by R:l include those listed above.

Examples of the heterocyclic group represented by R1, R2, and R3 include a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group,
Pyridyl group, 5-carboxy-2=pyridyl group, 3,5
-dichloro-2-pyridyl group, 4,6-cymethyl-2-
Pyridyl group, 6-hydroxy 2-pyridyl group, 2,3,
5.6-tetrafluoro-4pyridyl group, 3-nitro-
2-pyridyl group, etc.), oxasilyl group (5-carboxy-2-hendioxazolyl group, 2-hendioxazolyl group, 2oxasilyl group, etc.), thiazolyl group (5-sulfamoyl-2-benzothiazolyl group, 2- benzothiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (l-
methyl-2-imidazolyl group, 1-methyl-5-carboxy-2-henzimidazolyl 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,
4chloro-2-pyrimidinyl group, etc.), pyridazinyl group (
2-pyridazinyl group, etc.), purinyl group (8-purinyl group, etc.), isoxasilyl group (3-isoxasilyl group, etc.)
, selenazolyl group (5-carboxy-2-selenazolyl group, etc.), sulfolanyl group (3-sulfolanyl group, etc.), piperidyl group (1-methyl-3-piperidyl group, etc.), pyrazolyl group (3-pyrazolyl group, etc.), tetrazolyl group Group (1
-methyl-5-tetrazolyl group, etc.), and the heterocyclic group includes those having a substituent, and the substituent includes the alkyl group represented by R1, RZ, and R3, and R1, R2. , and those exemplified as substituents for the alkyl group represented by R3.

The cycloalkyl group represented by R1, R2, R3 represents, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc., and these groups are
It may further have a substituent. Examples of this substituent include the alkyl group represented by R1, R2, and R3, and R'
, R'', and those exemplified as substituents for the alkyl group represented by R3.

In the general formula (1), the methine groups represented by LI, R2, R3, R4 and RI include those having substituents,
Examples of the substituent include alkyl groups (e.g., methyl group, ethyl group, i-propyl group, t-methyl group, 3-hydroxypropyl group, hensyl group, etc.), aryl groups (e.g., phenyl group, P-tolyl group, P-carboxyphenyl group, etc.), halogen atom (e.g., chlorine, bromine, iodine, fluorine atom, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), acyloxy group (e.g., methylcarbonyloxy group, etc.) group, phenylcarbonyloxy group, etc.), cyano group, etc.

Specific compound examples of the present invention are shown below, but the present invention is not limited thereto.

[Exemplary compounds] CH2CH□SO□N112 CH2CH2SO□NH.

0JHz SO□NH2 CH3 CH,C00H ChzCOOII (Fr1 SO□NHCl+3 SOzNlil;l'h 0JHBu 0JHBu Bu Ni Butyl group SO□NH2 CH2SO□NH2 SO□NH2 CHzSOzNHz Coo)I OOH CH2 OOH OOH 5 (hNH! 5OZNH2 SO□NIII N 5UzN11゜ CH.

H3 CHzCH20CH3 CHzcHzOcHz CHzCHzSO□NH□ CH2CH2SO□NH2 F3 0CCH:1 F3 Synthesis examples of the oxonol dye represented by the general formula [I] of the present invention will be shown below and specifically explained.

Synthesis Example 1 After dropping 7.7 g (0.11 mol) of compound (52) into 9.3 g (0.1 mol) of compound (51), the mixture was heated and stirred at 80° C. for 30 minutes. After cooling, the reaction solution was poured into water, adjusted to pH 119 with sodium hydrogen carbonate, and extracted with chloroform. After drying over magnesium sulfate and distilling off the solvent under reduced pressure, 12.9 g of compound (53) was obtained.
I got it. Yield 72% CH25O□N112 Compound (53) 19.3 g (0,108 mol)
and compound (54) 29 g (0.1 mol) in DM
The mixture was dissolved at F300d and heated at 120-130°C for 6 hours. After the reaction solution was distilled off under reduced pressure, it was purified by salting out to obtain 25 g of compound (55). Yield 70%CHZ
SOzNI(z Compound (55) 37 g (0.1 mol) in DMF
Compound (56) 8.8g (0,045mol
) and triethylamine 25.3 g (2.5 mol
) and stirred at room temperature for 4 hours. The reaction solution was poured into water and concentrated hydrochloric acid was added for acid precipitation, and the precipitate was collected to obtain 23 g of the target compound 02). Yield 60%. This compound was confirmed from the parent peak in the mass spectrum.

Synthesis Example 2 Compound (20) Compound (57) 27 g (0.1 mol) DMF
Compound (5B) 7.6 g (0.1 mol) in the solution
, and 10.1 g (0.1 mole) of triethylamine were added and stirred at room temperature for 1 hour. Dispersed in ethyl acetate to obtain 23 g of compound (59). Yield 50%.

Compound (59) 46 g (0.1 mol) in DMF
500ml! 11.6 g of compound (60) (
0.1 mol) was added thereto, and the mixture was stirred at room temperature for 3 hours. Purification was performed by acid precipitation to obtain 24 g of compound (61). Yield 5
8%.

40 g (0.1 mol) of the compound was dissolved in 400 d of acetic anhydride.
The mixture was heated and stirred at 100°C for 1 hour. After the reaction solution was distilled off under reduced pressure, it was purified by salting out to obtain 25 g of compound (62).
I got it. Yield 68%.

□ Compound (20) Compound (62) 40 g (0.1 mol) DMF
Compound (62) 10.0 g (0,
045 mol) and triethylamine 25.3 g (
2.5 mol) was added thereto, and the mixture was stirred at room temperature for 5 hours. Pour the reaction solution into water, add concentrated hydrochloric acid for acid precipitation, and collect the precipitate to obtain 28 g of the target compound (20).
I got it. Yield 65%.

This compound was confirmed from the parent peak in the mass spectrum.

Synthesis Example 3 F3 F3 F3 Compound (42) Compound (64) was obtained in the same manner as the synthesis of Compound (55) in Synthesis Example 1. 21 g of the compound (64) (
Compound (65) in a DMF 300m solution of 0.1 mol)
9.92 g (0.04 mol) and 25.2 g (0.25 mol) of triethylamine were added and stirred for 5 hours. The target compound (42
) was obtained. Yield 70%.

This compound was confirmed by the parent peak in the mass spectrum.

The solid fine particle dispersion in the compound shown in the above format [■] used in the present invention is water-insoluble at the pH of the silver halide photosensitive emulsion at the time of addition of the compound,
By dispersing a compound that becomes water-soluble in alkaline conditions, the particle diameter at this time is less than 1 μm, preferably 0.5 μm.
This refers to the state in which the solid state is added and dispersed with a diameter of less than 1 μm.

Specific examples of methods for adding this solid fine particle dispersion into photosensitive materials include the method shown in US Pat. No. 4,857,446.

In the present invention, photographic constituent layers include, for example, a blue emulsion layer,
Indicates photosensitive layers or non-photosensitive layers such as green-sensitive emulsion layers, red-sensitive emulsion layers, intermediate layers, protective layers, filter layers, antihalation layers, and antiirradiation layers.

The compounds of the invention are preferably contained in the non-photosensitive layer.

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

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Conventional antifoggants, stabilizers, etc. can be added to such silver halide emulsions. Although there are various binders for the emulsion, it is advantageous to use gelatin.

The emulsion layer formed by coating the pre-emulsion on the support and other hydrophilic colloid layers can be hardened, and can also be hardened, and can also be hardened, and can also be hardened, or a dispersion (latex) of a plasticizer, water-insoluble or poorly water-soluble synthetic polymer.
can be contained.

A coupler is added to the emulsion layer of the silver halide photographic light-sensitive material of the present invention as a color photographic light-sensitive material, and these emulsion layers further include a colored coupler having hardening for color correction, a competitive coupler, and a developer. By coupling with the oxidized form of the main agent, development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and compounds that release photographically useful fragments, such as sensitizers.

The silver halide photographic material of the present invention includes a filter layer,
Auxiliary layers such as an antihalation layer and an antiirradiation layer may be provided, but these layers and/or emulsion layers may contain dyes that will flow out of the light-sensitive material or be bleached during the development process. You may be forced to do so.

The silver halide photographic material of the present invention includes formalin scavenger-1 optical brightener, matting agent, lubricant, image stabilizer, surfactant, color fog preventive agent, development accelerator, development retardant and bleaching accelerator. can be added.

As the support for the silver halide photographic material of the present invention, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

The silver halide photographic light-sensitive material of the present invention is used for various purposes, but is preferably used as an XFFfA light-sensitive material.

To obtain an image using the silver halide photographic material of the present invention, commonly known photographic processing can be performed after exposure.

〔Example〕

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

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

First, an emulsion was prepared as follows.

(A) Creation of monodisperse emulsion The conditions of the reaction vessel were 60°C, pAge-8, and p
A monodisperse cubic crystal emulsion of silver iodobromide containing 2 mol % of silver iodide with an average grain size of 0.3 μm was obtained by a double jet method while maintaining the temperature at Hg-2. According to electron microscopic observation, the incidence of twins was 1% or less in number. Using this emulsion as a seed crystal,
It was further developed as follows.

Keep the aqueous gelatin solution in the reaction vessel at 40°C, add the above seed crystals, and add ammonia water and acetic acid to pH = 9.5.
Adjusted to.

After adjusting pAg to 7.3 with ammoniacal silver ion solution, p
A solution containing ammoniacal silver ions, potassium iodide, and potassium bromide was added by a double jet method while keeping H and pag constant to form a silver iodobromide layer containing 30 mol % of silver iodide.

After adjusting the pH to 9 and 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 the particles were grown until they reached 90% of the grain size after growth. At this time, the pH was gradually lowered to 9.0 to 8.20.

After adding potassium bromide solution to set pAg to 11, ammoniacal silver ion solution and potassium bromide were further added to grow while gradually lowering the pH to pH 8, and the average particle size was 0.7μ.
A silver iodobromide emulsion containing 2 mol % of silver iodide was obtained.

Further, during the preparation of the emulsion, 300 .mu. of the following sensitizing dye (A) and 15 .mu. of the sensitizing dye (B) were added per mole of silver in the emulsion to obtain an emulsion.

Sensitizing dye (A) Sensitizing dye (B) C,)I.

C, H5 Next, a desalting step to remove excess salt was performed as shown below.

The silver halide emulsion solution was kept at 40°C, and the following compound (
(a) (Exemplary compound (1) shown in JP-A-58-140322) was added to precipitate silver halide grains, and after draining the supernatant, pure water at 40°C was added. Then, magnesium sulfate is added to precipitate the silver halide grains again, and the supernatant liquid is removed. This process was repeated once more and gelatin was added to obtain an emulsion with pH 6.0 and pAg 8.5.

Compound (A) (m indicates the degree of polymerization) The emulsion obtained above was kept at 55°C and chemically sensitized by adding chloroauric acid and hypo to 4-hydroxy-6
-Methyl-1,3,3a,? - A photosensitive emulsion was obtained by adding tetrazaindene. This is referred to as emulsion (A).

Silver halide 1 as an additive to the photosensitive emulsion of (A) above.
Per mole, t-butylcatechol 400 ■ vinylpyrrolidone (molecules 110,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyltriphenylphosphonium chloride 50 ■ dihydroxybenzene 4- Ammonium sulfonate 4g Mercaptobenzimidazole-5 Sodium sulfonate 5■C4H90
CH2CHCH2N (CH2COOH)zdimethylolbromo-tromethane (10 ml) and the like were added to prepare an emulsion coating solution.

Furthermore, the following coating solution was prepared as a protective layer solution.

That is, the following compounds were added in the following amounts per 1 g of gelatin to prepare a protective layer coating solution.

CJ+qO(CIhCHzO) r. C1hC) 120
8 3 ■ Matting agent made of polymethyl methacrylate with an average particle size of 7 μm 7 ■ Colloidal silica with an average particle size of 0.013 μm 70 ■ Sodium 2-hydroxy-4,6-dichloro-S-triazine
30 ■ The following samples 1-1 were prepared using each of the above coating solutions.

Trial Ero 221 As a subtraction liquid, glycidyl methacrylate 50wt%
, a copolymer of 10 wt% methyl methacrylate and 40 wt% butyl methacrylate at a concentration of 10 int%
A copolymer aqueous dispersion diluted to give a subbing process was obtained by coating both sides of the copolymer aqueous dispersion. Next, an emulsion layer was formed on the support so that the amount of silver on one side was 3.2 g/m2, and the amount of gelatin on one side was 0.98 g/m2.
Coat the protective layer at a speed of 140 m so that g/m2
Both sides were coated at the same time.

Samples 1-2 to 1-10 (comparative samples) Sample 1-1 was coated with a crossover cut layer containing the compounds shown in Table 1 inserted between the emulsion layer and the subbing layer. went.

The method of adding the compound was to dissolve the compound in methanol containing a small amount of triethylamine, and then add it to an aqueous gelatin solution to adjust the pl+ to 660 and prepare a coating solution.

-'1-1 to -20 (samples of the present invention) Coating was performed in the same manner as sample 1-2, with a crossover cut layer inserted. However, regarding the addition method of the compound, the compound used in each case was subjected to ball mill solid fine particle dispersion according to the following procedure.

Water and the surfactant Alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were placed in a ball mill container, each of the Somegetsu was added, zirconium oxide beads were added, the container was sealed, and ball mill dispersion was performed for 4 days.

Thereafter, an aqueous gelatin solution was added and mixed for 10 minutes, and the beads were removed to obtain a coating solution.

The amount of compound added to each sample was 50 mg/m2 on both sides.

The following evaluations were performed on the obtained samples.

Sensitometry measurement〉 Use the standard light B described in the “New Edition, Lighting Data Book” as the light source, and use an exposure time of 0.1 seconds and 3.2 cm, with no filter, so that the same amount of light is applied to both sides of the film. It was exposed like this. The above samples were processed with XD-5D developer for 45 seconds using a 5RX-501 automatic processor (manufactured by Konica Corporation), then fixed and dried, and the sensitivity of each sample was determined. Sensitivity was determined by calculating the reciprocal of the amount of light necessary for the blackening density to increase by 1.0, and expressed as relative sensitivity with the sensitivity in the case of sample 1-1 in Table 1 set as 100.

<MTF evaluation> MT with lead square wave of 0.5 to 10 lines/mm
Place the F-chart in close contact with the back side of the front side of a fluorescent screen KO-250 (manufactured by Konica Corporation), and check that the density of the part of the lead chart on the film surface that has not been sown late is about 1 on both sides.
．． X-rays were irradiated so that it became 0.

After the sample irradiated with X-rays as described above was developed in the same manner as described above, the recorded rectangular wave pattern was measured using a Sakura Microdensitometer Model M-5 (manufactured by Konica Corporation).
It was measured using The aperture size at this time is 300 μm in the parallel direction of the rectangular wave and 25 μm in the perpendicular direction.
The magnification was 20 times. The obtained MTF values are representative and are shown as values at a spatial frequency of 2.0 lines/mm.

Table 1 Comparative Dye 1 As is clear from Table 1, the samples of the present invention have improved sharpness compared to the comparative samples despite less decrease in sensitivity.

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 solutions were prepared by the forward mixing method.

Solution B and solution C were poured into a reaction vessel for emulsion preparation and stirred with a propeller type stirrer at a rotation speed of 300 revolutions/minute, and the reaction temperature was maintained at 55°C.

Next, Solution A was divided into 1 solution: 2 solutions, and 100 mf of 1 solution was added over 1 minute. After continuing to stir for 10 minutes, add solution A to the remaining 2 solutions at 200 mI! ,
was added over a period of 10 minutes. Stirring was continued for an additional 30 minutes. Then, Solution D was added to adjust the pl+ of the solution in the reaction vessel to 6.0, and the reaction was stopped.

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

(C) Preparation of tabular grains In water If, 5 g of KBrlO, thioether compound (H
O(CH2)zS(CHz)2S(C1l□)20H)
0.5wt% water at 10mI! , , and 30 g of gelatin were added, melted, and kept at 70°C. Silver nitrate aqueous solution (0.88 mol/f) was added to this solution while stirring.
) 30 ml, potassium iodide and potassium bromide (molar ratio 3
．． 5:96.5) aqueous solution (0.88 mol/ffi) 3
0mffi was added by double jet method, and the average particle size was 0.60. ! /JTI silver iodide content is 3.5 mol%
particles were obtained. After the addition of the mixed solution was completed, the temperature was lowered to 40"C. To this was added a condensate of sodium naphthalene sulfonate and formalin, and 24% magna sulfate, respectively.
．． 6 g/1 mole of AgX was added, the pH was lowered to 4.0, and desalting was performed, and then 15 g/1 mole of gelatin was added to prepare an emulsion.

The emulsions obtained in (B) and (C) above 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 exacerbation, 4-hydroxy-6-methyl-1,3
,3a,7-chitrazaindene was added.

Thereafter, 150 mg of potassium iodide/1 mol of AgX and the same amounts of sensitizing dyes (A) and (B) as in emulsion (A) were added to carry out spectral sensitization. The emulsion obtained by this,
They will be referred to as emulsions (B) and (C), respectively.

Additives similar to those in (A) were added to each of the photosensitive emulsions (B) and (C) to prepare an emulsion coating solution. Using these coating solutions and the above-mentioned protective layer solution, the compound of the present invention is added as a dispersion of solid fine particles in the same manner as in the above-mentioned method to form a crossover cut layer between the emulsion layer and the subbing layer. When the coating was applied in an inserting manner, a sample with improved sharpness and little decrease in sensitivity was similarly obtained.

Example 2 (Preparation of coating liquid for emulsion layer) And water to ink 9.
7! 0.01% aqueous solution of potassium hexachloroiridate salt Sodium chloride gelatin 3.
81 Silver nitrate 1,700g4
p! in the above solution A kept at 0°C! 13.14g7
．． The above solution B and solution C were simultaneously added functionally over a period of 60 minutes while maintaining the pH at 7. After stirring was continued for an additional 10 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.
0% aqueous solution of magnesium sulfate at 2°C and 5% aqueous solution of polynaphthalene sulfonic acid 0g 1,0 m j2 8mf 05g 3,8 ml.

65g 4g 50g Add 2.55β, flocculate the emulsion at 40'C, decant and wash with water to remove excess water. 8
? Remove the salt of a. Next, 3.7! Add water to disperse, and then re-dissolve 20% magnesium sulfate in water. &
0.91 was added to remove excess salt from the aqueous solution in the same manner. And 3.7! Add water and 141g of gelatin,
Disperse for 30 minutes at 55°C.

As a result, particles having 38 mol % of silver bromide, 62 mol % of silver chloride, an average particle size of 0.25 μm, and a monodispersity of 9 are obtained. After adding 140 mj2 of a 1% citric acid aqueous solution and 57 mj2 of a 5% potassium bromide aqueous solution to the particles, 70 m1 of a 0.1% sodium thiosulfate aqueous solution was added, and the mixture was incubated at 58°C for 7 ml.
Aged for 0 minutes.

To the obtained emulsion, 4-hydroxy 6-methyl-1,3,3a,7-chitrazaindene was added as a stabilizer at a Log concentration of 1,600 rne and a 20% gelatin aqueous solution was added to stop the ripening, and then the following sensitizing dye (a ) 3.5g, (b) 1
g, 1 g of (C) was added, and further compound (
d) was added, followed by 10 g of sodium p-dodecylbenzenesulfonate as a spreading agent and 30 g of saponin.
g, 120 g of butyl acrylate-acrylic acid-styrene copolymer as a polymer latex, 3 g of potassium bromide as a pAg regulator, 20 g of styrene-maleic anhydride copolymer as a thickener, and formalin as a hardening agent. and glyoxal were added to prepare a coating solution for an emulsion layer.

Sensitizing dye (a) CII□Cl12CN Sensitizing dye (b) 2H5 C, I+.

Sensitizing dye (C) C2HS Compound (d) (Preparation of coating solution for protective layer) After dissolving 500 g of gelatin in 7.51 g of water, 15 g of the following compound (e) as a spreading agent and the average particle size as a matting agent. A coating solution for a protective layer was prepared by adding 10 g of 3.5 μm silica and formalin as a hardening agent.

Compound (e) CHzCOOC+ o) lz CHCOOCsll r + (i) 03Na (Preparation of coating solution for backing lower layer) Samples 2-1 to 2-8 (comparative sample) 650 g of gelatin was mixed with 10! After dissolving the compounds shown in Table 2 in a methanol solution containing a small amount of 1-ethylamine, this solution was added to the gelatin solution at a concentration of 0.2 g/m''. Then, 30 g of saponin was added as a spreading agent, and 30 g of a copolymer of butyl acrylate and vinylidene chloride was added as a polymer latex.
0 g, 150 g of colloidal silica as a film property improver.
g, 3 g of styrene-maleic anhydride copolymer as a thickener and 2.5 g of glyoxal as a hardening agent were added to prepare a coating solution for a backing lower layer.

Samples 2-9 to 2-24 (Samples of the present invention) Coating liquids were prepared in the same manner as Sample 2-1. However, regarding the addition method of the compounds shown in Table 2, the compounds used in each were subjected to ball mill solid fine particle dispersion according to the same procedure as in Example 1.

(Preparation of coating solution for backing upper layer) After dissolving 400 g of gelatin in 600 mL of water, 20 g of polymethyl methacrylate with an average particle size of 4 μm as a matting agent, 3 g of bis(2-edylhexyl)sulfosuccinate sodium salt as a spreading agent, A coating solution for the backing upper layer was prepared by adding glyoxal as a hardening agent.

(Preparation of sample) A lower backing layer and an upper layer were simultaneously coated on a 100 μm thick polyethylene terrestrial film base that had been subjected to an undercoat process, and then an emulsion layer and a protective layer were coated on the side opposite to the banking layer. Coated in multiple layers at the same time. The amount of silver applied is 4
．． 2g/m2, the amount of gelatin in the emulsion layer is 1.95g
7 m'', protective layer 2 g/m'', lower banking layer 2.7 g/m2, upper banking layer], 0 g7 m''.

The obtained sample was processed in an automatic processor GR-27 (manufactured by Konica Corporation) using a developer and fixer according to the following formulation, and the halftone quality and storage stability were evaluated, and the results are shown in the table below. 2
It was shown to.

Halftone dot quality> After exposure, the halftone dot quality was evaluated on a scale of 10 to 90%. Best halftone quality 1
0, 1 as extremely bad level, and 5 or more as practical level.

(Storage Stability) The obtained two-format preparation was incubated at 23°C and 150% R1+, and then the emulsion side and the banking side were brought into contact with each other and sealed together. This sample was stored for 5 days under the condition of 50° Cl2o% R1+, and the sensitivity of the sample after storage was determined by setting the sensitivity of the sample before storage as 100.

Here, the reciprocal of the exposure amount required to obtain a density of 2.5 was used as the sensitivity.

Development processing conditions (process) (temperature) (time) development
Fix at 28°C for 30 seconds Rinse at 28°C for about 20 seconds Dry at room temperature for about 20 seconds 45°C for 20 seconds 55Xw
/y aqueous solution) 100mj! potassium carbonate
50g hydroquinone
15g5-methylbenzotriazole 20
0mg 1-phenyB-5-methylcaptotetrazole
30mg potassium bromide
4.5g potassium hydroxide Amount to make the working solution PL+ 10.4 (composition) Pure water (ion-exchanged water) Diethylene glycol ethylenediaminetetraacetic acid disodium salt Acetic acid (90% aqueous solution) 5-nitroindazole 1-phenyl-3- Pyrazolidone 0,3 rni.

mg 0g 5mg 110mg 100mg 500mjl of water when using developer! The above-mentioned composition A was dissolved in the order of composition A and composition 11 was prepared and used.

How to reach feet (Composition A) Ammonium 1,000 sulfate 240m1! .

(72.5% w/v water? Volume w!i) Sodium sulfite 17g Sodium acetate trihydrate 6.5g Nitric acid
6g sodium citrate dihydrate 2g acetic acid (90% w/v aqueous solution) 1
3.6 ml (I) Pure water (ion exchange water) 17rr+1!
.

Sulfuric acid (50% w/v aqueous solution) 4.7 g Aluminum sulfate 26.5 g (Azz
o: + converted content is 8.1''Aw/ν aqueous solution) When using a fixer, the above composition A was dissolved in the order of composition A and composition in 500 mL of water, and the composition was finished to 1!.

The pH of this fixer was about 4.3.

Table 2 Comparative Dye 2 Comparative Dye 3 As is clear from Table 2, the samples of the present invention have good halftone dot quality and excellent storage stability.

In addition, the following dye (e) was used instead of the sensitizing dye (aL (b), (c)), and the compounds of the present invention (33), (35), (36), (37) were prepared in the same manner as in Table 2. ),
(38), (41L(44), (45), (46
), (47), (49), and (50) were used to prepare and evaluate samples, and the same effects as shown in Table 2 were observed.

Spectral sensitizing dye (e) [Effects of the invention] As explained in detail above, by containing the solid fine particle dispersion of the compound of the present invention, fogging is reduced, stability over time during storage is improved, and sharpness is improved. A silver halide photographic light-sensitive material having excellent photographic properties such as properties is provided.

applicant

Claims (1)

[Scope of Claims] 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 general formula [I] on a support. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X^1 and X^2 represent oxygen atoms, sulfur atoms, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1 ,R
^2, R^3 are hydrogen atoms, alkyl groups, alkenyl groups,
Represents a cycloalkyl group, an aryl group, or a heterocyclic group. Furthermore, these R^1, R^2, and R^3 may have a substituent, and at least one of the substituents is a group having a carboxyl group, a sulfonamide group, and/or a sulfamoyl group. It is. Y^1, Y^2, Y^
3, Y^4 represents an oxygen atom or a sulfur atom, L_1, L
_2, L_3, L_4 and L_5 each represent a methine group, and n^1 and n^2 each represent 0, 1 or 2. ]