JPH03206441A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which is excellent in image quality and preservable stability by providing at least one layer of photograph constituting layers contg. specific solid fine particle dispersed bodies on a substrate. CONSTITUTION:At least one layer of the photograph constituting layers contg. the solid fine particle dispersed, bodies of the compd. expressed by following formula I are provided on the substrate. In the formula I, R1, R2 denote a substituent; R3, R4 denote a hydrogen atom, alkyl group, cycloalkyl group, etc.; L1 to L5 denote a methine group; n1, n2 denote 0 or 1. At least one of R1 to R4 contain a sulfone amide group and/or sulfamoyl group and contains at least two sulfone amide groups and/or sulfamoyl groups in the compd. The silver halide photographic sensitive material improved in image quality and preservable stability 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 a birazolone oxonol dye, and more particularly to a silver halide photographic material containing a birazolone oxonol dye. This invention relates to a silver halide photographic material with excellent storage stability.

[Conventional technology]

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

Furthermore, 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-quick processing. 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.

By the way, it is well known that dyes are incorporated into silver halide photographic materials for the purpose of improving image quality or adjusting silver halide emulsion sensitivity. 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 light-sensitive materials, and dyes for dyeing non-light-sensitive emulsion layers in printed photographic light-sensitive materials.

The dyes used for these purposes vary depending on the purpose of use. 2. It has a good absorption spectrum. 3. Do not diffuse from the colored layer to other layers. 4. No photographic effect on the light-sensitive silver halide emulsion. 5. Stable in silver halide photographic materials. 6. Easy to add. 7. It is stable in the emulsion coating solution and does not affect the solution viscosity. The properties required include that no color remains after processing.

A large number of dyes have been proposed in the past for the purpose of satisfying these desired characteristics, such as U.S. patent No. 3,540,
No. 887, No. 3,544,325, No. 3,560.2
No. 14, Mochiko Sho 31-10578 and Mochikai Sho 51-3
No. 623 etc. include penzylidene dye, British patent 506.3.
No. 85 and No. 39-22069 propose oxonol dyes, US Pat. No. 2,493,747 proposes merocyanine dyes, and US Pat. No. 1.845.404 proposes styryl dyes.

The common method is to dissolve these dyes in water or an organic solvent that is miscible with water and add them to the photographic constituent layers. However, if the dye is water-soluble, it will not remain in the layer to be dyed but will be added to the entire layer. It will spread into layers. Therefore, in order to achieve the original purpose, it is necessary to add a large amount of dye to cover other layers, resulting in undesirable problems such as decreased sensitivity, gradation fluctuations, and fogging abnormalities in both the own layer and other layers. A phenomenon begins to appear. In particular, when a photosensitive material is stored over time, fogging 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, dyes with suppressed diffusion properties that dye specific layers are known. Examples of diffusion-resistant dyes include US Patent No. 2,538.008 and Patent No. 2,539.00.
No. 9, No. 4,420.555, JP-A-6120463
No. 0, No. 61-205934, No. 62-32460, No. 6256958, No. 62-92949, No. 62
No. -222248, No. 63-40143, No. 63-1
YC dyes are described in No. 84749 and No. 63-316852. These dyes are also commonly used in color photographic elements such as Carey Lea Silv.
The yellow colloidal silver called ER absorbs not only the blue light region but also some long wavelengths, which reduces green sensitivity and increases fogging of adjacent layers, and saves precious silver resources. Many have been proposed for.

Although these diffusion-resistant dyes improve the above 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. A new occurrence has 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 image quality and storage stability.

[Structure of the invention]

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

General formula [I] In the formula, R I and R x represent a substituent, R,, R4 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alganyl group, an aryl group, or a heterocyclic group, Ll, L2, L,
, L 4 SL s represents a methine group, and nl and n2 represent 〇 or l. However, at least one of R,, R2, R,, R, has a sulfonamide group and/or a sulfamoyl group, and the compound has at least two sulfonamide groups and/or sulfamoyl groups.

The present invention will be explained in more detail below.

In the above general formula (1), the substituents represented by 'Rr and R2 include alkyl groups, alganyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, alkylcarbonyl groups, arylcarbonyl groups, and alkoxy groups. , aryloxycanolebonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group, ureido group, thioureido group, Preferable examples include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carpoxyl group, and a hydroxyl group.

Examples of the alkyl group as a substituent represented by R, R, include methyl group, ethyl group, proyl group, i-7'
Examples include a biyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a pentadecyl group, and an eicosyl group. The alkyl group includes those having a substituent, and examples of the substituent include a halogen atom (for example, each atom such as chlorine, bromine, iodine, and fluorine), an aryl group (for example, a phenyl group, a naphthyl group, etc.), and a heterocycle. groups (e.g. pyrrolidyl group, pyridyl group, etc.)
Sulfinic acid group, carpoxyl group, nitro group, hydroxyl group, mercapto group, amino group (e.g. amino group, diethylamino group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, octyloxy group, i-propoxy group, etc.) ), aryloxy groups (phenoxy group, naphthyloxy group, etc.), carbamoyl group (e.g. aminocarbonyl group, methylcarbamoyl group, bentylcarbamoyl group, morpholinocarbonyl group, phenylcarbamoyl group, etc.), amide group (e.g. methylamide group, benzamide group) , octylamide group, etc.), sulfamoyl group (e.g. sulfamoyl group, tylsulfamoyl group, phenylsulfamoyl group, morpholinosulfonyl group, butylsulfamoyl group, etc.), sulfonamide group (e.g. methanesulfonamide group, heptanesulfone) (amito group, benzenesulfonamido group, etc.), sulf7ynyl group (e.g., methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, noalkylsulfinyl group such as octylsulf7ynyl group, arylsulfinyl group such as phenylsulfinyl group, etc.), Alkoxycarponyl groups (e.g. methoxycarbonyl group, ethoxycarponyl group, 2-hydroxyethoxycarbonyl group, octyloxycarponyl group, etc.), aryloxycarponyl groups (e.g. phenoxycarbonyl group, naphthyloxycarponyl group, etc.) etc)
, alkylthio groups (e.g. methylthio group, ethylthio group, hexylthio group, etc.), arylthio groups (e.g. phenylthio group, naphthylthio group, etc.), alkylcarbonyl groups (e.g. acetyl group, ethylcarbonyl group, butylcarbonyl group, octylcarbonyl group, etc.) ), arylcarbonyl groups (e.g. benzoyl group, p-methanesulfonamidobenzoyl group, p-carpoxybenzoyl group, naphthoyl group, etc.), cyanogen groups, ureido groups (e.g. methylureido group, phenylureido group, etc.), thioureido groups (e.g. methylthioureido group, 7enylthioureido group, etc.)
etc.

Examples of the aryl group as a substituent represented by R1 and R include a 7-enyl group and a naphthyl group. The aryl group includes those having a substituent, and examples of the substituent include the above-mentioned R. , the alkyl group as a substituent represented by R2, or the above-mentioned groups as a substituent of the alkyl group as a substituent represented by R1 and R2.

R. , R, as a substituent include vinyl group, allyl group, l-propenyl group, l,3
-butadienyl group, 2-pentenyl group, etc., and the alkenyl group includes those having a substituent, and the substituent includes the substituent of the alkyl group as the substituent represented by R, R2, etc. The ones listed above are listed.

Examples of the heterocyclic group as a substituent represented by R1 and R2 include a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-carpoxy-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
-carpoxy 2-penzoxazolyl group, 2-penzoxazolyl group, 2-year-old xazolyl group, etc.), thiazolyl,! (5-sul7amoy-2-bezothiazolyl group,
2-penzothiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (l-methyl-2-imidazolyl group, ■-methyl-5-carpoxy-2-bezoimidazolyl group, etc.)
, furyl group (3-furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.), chenyl group (2-chenyl 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.), bulinyl group (8-purinyl group, etc.), inoxazolyl group (3-inoxazolyl group, etc.), selenazolyl group (5-carpoxy-2-selenazolyl group, etc.), sulfolanyl group (3-sulfolanyl group, etc.) etc.), piperidyl groups (l-methyl-3-piperidyl groups, etc.), pyrazolyl groups (3-birazolyl groups, etc.), tetrazolyl groups (l-methyl-5-tetopzolyl groups, etc.), and the heterocyclic groups include Including those having a substituent, such substituents include those exemplified as substituents for the alkyl group as a substituent represented by R, R2 and the alkyl group as a substituent represented by R1 and R2. can be mentioned.

Examples of the cycloalkyl group as a substituent represented by R1 and R2 include a cyclopropyl group, a cyclobutyl group,
Examples of the alkyl group include cyclopentyl group, cyclohexyl group, etc., and examples of the alkyl group include methyl group, ethyl group, i-propyl group, t-butyl carbonyl group, octyl carbonyl group, dodecyl group, and aryl group. Examples of carponyl groups include phenylcarbonyl group and naphthylcarbonyl group; examples of alkoxycarponyl groups include ethoxycarponyl group, i-propoxycarponyl group, t-butoxycarponyl group, pentyloxycarponyl group, and dodecyloxycarponyl group. Aryloxycarbonyl groups include, for example, phenyloxyluponyl groups, na7thyloxyluponyl groups, etc. Alkylsulfonyl groups include, for example, methylsulfonyl groups, ethylsulfonyl groups, i-probylsulfonyl groups, and t-butyl groups. Sulfonyl group, octylsulfonyl group, octadecylsulfonyl group, etc. Arylsulfonyl group includes, for example, 7enylsulfonyl group, na7tylsulfonyl group, etc. Alkylsulf7ynyl group includes, for example, methylsulfinyl group, ethylsulfinyl group, l- Arylsulfinyl groups include, for example, phenylsulfinyl, na-7tylsulfinyl, etc.; carbamoyl groups include, for example, aminocarponyl; group, methyl-rubamoyl group, ethyl-rubamoyl group, i-propylcarbamoyl group, t-butylcarbamoyl group, dodecyl-rubamoyl group, phenylcarbamoyl group, 2-pyridyl-rubamoyl group, 4-pyridyl-rubamoyl group, pen Examples of the sulfamoyl group include a dicarbamoyl group, a morpholinocarponyl group, a piperazinocarponyl group, and an aminosulfonyl group, a methylsulfamoyl group, an i-probylsulfamoyl group, a t-butylsulfamoyl group, and the like. , dodecylsulfamoyl group, phenylsulfamoyl group, 2-pyridylsulfamoyl group, 4-pyridylsulfamoyl group, morpholinosulfonyl group, piperazinosulfonyl group, etc. Examples of the amino group include amine group, methylamino group, etc. basis,
Examples of sulfonamide groups include ethylamino group, i-propylamino group, t-butylamino group, octylamino group, dodecylamino group, dimethylamino group, anilino group, naphthylamino group, morpholino group, biperazino group, etc.
For example, amide groups such as methylsulfonamide group, ethylsulfonamide group, i-probylsnorefonamide group, t-butinolesnorefonamide group, dodecylsulfonamide group, phenylsulfonamide group, naphthylsulfonamide group, etc. Examples of ureido groups include methyl carbonylamino group, ethyl carbonylamino group, i-propylic carbonylamino group, 1-/thyl carbonylamino group, dodecyl carbonylamino group, phenylcarbonylamino group, naphthyl carbonylamino group, etc. , for example, methylureido group, ethylureido group, i-probylureido group, t-butylureido group, dodecylureido group,
A phenyl ureido group, a 2-pyridyl ureido group, a thiazolyl ureido group, etc.; Examples of the thioureido group include a methyl thioureido group, an i-propyl thioureido group, a t-butyl thioureido group, a dodecyl thioureido group, a phenyl thioureido group, 2-Biridylthioureido group, thiazolylthioureido group, etc. Alkoxy groups include, for example, methoxy group, ethoxy group, l-proboxy group, t-butyloxy group, dodecyloxy group, etc. Aryloxy group includes, for example, phenoxy base, na7
Examples of alkylthio groups such as thyloxy group include methylthio group, ethylthio group, j-propylthio group, t-butylthio group, and dodecylthio group. Examples of arylthio groups include phenylthio group and naphthylthio group. Each group preferable as R1 and R2 includes those having a substituent, and the substituents include the alkyl group as the substituent represented by R1 and the alkyl group as the substituent represented by R1. Examples of the group include those listed above.

Among these groups represented by R1 and R2, preferred are an alkyl group, an aryl group, an alkyl group, an aryl carbonyl group, an alkoxy group, a carbamoyl group, an amino group, an alkoxy group, a cyano group, and a carpoxyl group. Particularly preferred are an alkyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group, an alkoxy group, and a carpoxyl group.

In general formula (I), the groups represented by R3 and R4 and their substituents include the above-mentioned R. , R, and those exemplified as the substituents thereof.

In the general formula CI), the methine groups represented by L1 to L include those having substituents, such as alkyl groups (e.g. methyl group, ethyl group, l-propyl group, t-butyl group). 3-hydroxypropyl group, benzyl group, etc.), aryl group (e.g. phenyl group), halogen atom (e.g. chlorine, bromine, iodine, fluorine atom, etc.), alkoxy group (e.g. methoxy group, ethoxy group, etc.), acyloxy groups (eg, methylcarponyloxy group, 7enylcarponyloxy group, etc.), and the like.

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

The compound of the present invention is disclosed in, for example, JP-A No. 48-62826,
No. 49-5125, No. 51-77327, No. 58-
No. 143342, No. 59-111641, No. 64-4
Similar to the synthesis method shown in No. 0827, etc., synthesis can be easily carried out by reacting a virazolone derivative with a methine chain source. Specific examples of the present invention will be shown below, but other dyes may also be used.

Combination example 1 (combination of compound example 1) (1) (2) (1) 25.3g, (2) 8.4g and dimethylformamide 100+11 (2) were mixed, and 25.3g of triethylamine was slowly added at room temperature. After stirring at room temperature for 12 hours, 200 ffl (2) of concentrated hydrochloric acid was added to precipitate the mixture, yielding I; Acid precipitation was performed again.

After repeating this purification operation four times, the desired product was obtained by drying. Yield 16.3g% Yield 70%.

Confirm the parent peak of the target product using a mass spectrum.

Combination example 2 (combination of compound example 46) (3). (4) (3) 28.1g, (4) 11.6g
After mixing 25.3 g of triethylamine and 25.3 g of triethylamine, the mixture was heated under reflux for 8 hours, and then the reaction solution was cooled to room temperature and 200 mff of concentrated hydrochloric acid was added for acid precipitation. The crude crystals obtained by filtration were dispersed in 150 mQ of water,
15 g of sodium hydroxide was added and dissolved. After filtering to remove insoluble matter, adjust the pH of the aqueous solution to 2 or less using concentrated hydrochloric acid and perform acid precipitation.

The solid obtained by repeating this operation three times was heated and dispersed in dimethyl sulfoxide 300IIQ, and concentrated hydrochloric acid 200t
AQ was added to perform acid precipitation. The desired product was obtained by drying the obtained solid. Yield 16.2g, yield 6o%.

Confirm the parent peak of the target product by mass spectrometry.

The compound of the present invention is used in silver halide photographic materials 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 solid fine particle dispersion of the compound of the present invention into a light-sensitive material, for example, US Patent No. 4,857,44
Specific examples include the method shown in No. 6.

In the present invention, photographic constituent layers include, for example, a blue-sensitive 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.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

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

Anticapri agents, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

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

Couplers are used in the emulsion layer of light-sensitive materials for color photography. A colored coupler that also has the effect of color correction,
Development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectroscopy by coupling with competing couplers and oxidized forms of developing agents. Sensitizers and compounds that release photographically useful 7-ragments, such as sensitizers, are used.

Light-sensitive materials must be provided with auxiliary layers such as filter layers, anti-halation layers, and anti-irradiation layers, but these layers and/or emulsion layers contain substances that may flow out of the light-sensitive material during development. Alternatively, a bleaching dye may be included.

Photosensitive materials include formalin scavengers, optical brighteners, matting agents, lubricants, image stabilizers, surfactants, and color strength. Anti-blur agents, development accelerators, development retardants and bleach accelerators can be added.

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

To obtain an image using the photosensitive 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: r(A) monodisperse emulsion was prepared under the reaction vessel conditions of 60°C! 1pAg=8, and p
By the double jet method while keeping H=2, the average particle size is 0.
．． A monodisperse cubic emulsion of silver iodobromide having a diameter of 3 μm and containing 2 mol % of silver iodide was obtained. 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 elongated as follows.

Keep the gelatin aqueous solution at 40°C in the reaction vessel, add the above seed crystals, and then add ammonia water and acetic acid to pH = 9.
．． Adjusted to 5.

After adjusting pAg to 7.3 with ammoniacal silver ion solution, p
While keeping H and [)Ag constant, a solution containing ammoniacal silver ions, potassium iodide, and potassium bromide was added using a double jet method to form a silver iodobromide layer containing 30 mol% of silver iodide. Ta.

pH=9, pAg-9.0 using acetic acid and silver bromide
After adjusting the ammoniacal silver ion solution and potassium bromide at the same time, the grains were lengthened to 90% of the lengthened grain size. At this time, the pH was gradually lowered from 9.0 to 8.2o.

After adding potassium bromide solution to bring the pAg to -11, ammoniacal silver ion solution and potassium bromide were further added to gradually lower the pH to pH 8, and the average particle size was 0.7μ.
A silver iodobromide emulsion containing 2 mol % of m1 silver iodide was obtained.

In addition, when preparing the emulsion, the following sensitizing dye (A) was added in an amount of 300 mg per mole of silver in the emulsion, and the sensitizing dye (B) was added in an amount of 15 mg.
An emulsion was obtained.

Sensitizing dye (A) Sensitizing dye (B) (CHz)4503- (CH2),SO3Na Next, as shown below, a desalting step for removing excess salt was performed.

The silver halide emulsion solution was kept at 40°C, and the following compound (a) (exemplified compound II-1 shown in JP-A-58-140322) was added to precipitate silver halide grains,
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 a pH of 6.0 and a pAg of 8.5.

Compound (a) 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 7-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 400mg polyvinylpyrrolidone (molecular weight 10,000) 1.0
g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane IOg Diethylene glycol 5 g Nitrophenyl triphenylphosphonium chloride 50 mg 1.3
-dihydroxybenzene-4 ammonium sulfonate 4g 2-mercaptobenzimidazole-5 monosulfonate sodium. 5 mg of OH 1.1 dimethylol--PROMU 1 10 mg of nitromethane 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 Ig of gelatin to prepare a protective layer coating solution.

Na03S (;HCOO(;sH++(jノ..A
Matting agent made of polymethyl methacrylate with an average particle size of 7 μm 7mg Colloidal silica with an average particle size of 0.013 μm 70mg2-
Hydroxy-4,6-dichloroS triazine sodium 30mg using each of the above coating solutions,
The following samples were prepared.

Sample 1-1 As the subtracting liquid, glycidylme, tacrylate 5 owt
%, methyl methacrylate IOwt%, butyl methacrylate h 40wt% copolymer at a concentration of 10vt
A copolymer aqueous separation solution diluted to 10% was applied to both sides to obtain a subbed support. Then, a silver amount of 3.2 g/m on one side was deposited on the support.
”, the emulsion layer is adjusted to have gelatin content on one side of 0.9
Coat the protective layer at a speed of 140+ so that it is 8g/m''
Both sides were coated simultaneously at a rate of 0/min.

Sample 1-2 For sample 1-1, Table 1 was added between the emulsion layer and the subbing layer.
The coating was performed so that a crossover cut layer containing the dye shown in was inserted.

The method of adding the dye is to dissolve the dye in methanol containing a small amount of triethylamine, then add it to an aqueous gelatin solution and adjust the pH.
was set to 6.0 and used as a coating solution.

Samples 1-3 to 1-32 Coating was performed in the same manner as Sample 1-2, with a crossover cut layer inserted. However, regarding the method of adding the dye, the dye used in each case was dispersed in solid fine particles using a Pall Mill according to the following procedure.

Water and a surfactant Alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were placed in a Pall Mill container, each dye was added, zirconium oxide beads were added, the container was sealed, and Pall Mill dispersion was carried out 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 dye added to each sample was 50 mg/m on both sides.
It was made to be z.

The following evaluations were performed on the obtained samples.

Sensitometry measurement〉 Standard light B described in the “New Edition, Lighting Data Book” was used as the light source, exposure time was 0.1 seconds, 3. Exposure was performed using 2CIllS without a filter so that both sides of the 7-ilm were exposed to the same amount of light. The above sample was prepared using an SRX-501 automatic processor (
(manufactured by Konica Corp.) and processed with an XD-SD developer for 45 seconds, then fixed and dried, and then the sensitivity of each sample was determined. The sensitivity was determined by calculating the reciprocal of the amount of light necessary for the blackening density to increase by 1.0, and was expressed as a relative sensitivity, with the sensitivity of sample 1-1 (7) in Table 1 set as 100.

<Evaluation of MTF> M with lead square wave of 0.5 to IO line/mm
TF chart on fluorescent screen KO-250 (Konica)
Co., Ltd.), and irradiated with X-rays so that the density of the portion of the film surface not shielded by the lead chart was approximately 1.0 on both sides.

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 of the spatial frequency comparison dye l. 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 using the forward mixing method.

Pour solution B and solution C into a reaction vessel for emulsion preparation and rotate at 3 rotations.
The reaction temperature was maintained at 55°C by stirring with a Grobela type stirrer at 00 rpm.

Next, solution A was divided into 1 solution: 2 solutions, and 100 ml of 1 solution was added over 1 minute.

After continuing stirring for 10 minutes, the remaining 2 solution of solution A, 20
0ml2 was injected over IO minutes. Stirring was continued for an additional 30 minutes. Then, Solution D was added to adjust the pH 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 0.5 g of KBrl, thioether compound [H
D(CH2)2S(CH2)2s(CHz)i0H)
O-5wt% aqueous solution 10tn (is and gelatin 30g
was added to dissolve and kept at 70°C. Add 30 m of silver nitrate aqueous solution (0.88 mol IQ) into this solution while stirring.
(l, potassium iodide and potassium bromide (molar ratio 3.5:
An aqueous solution (0.88 mol/03Qm4) of 96.5) was added by a double jet method to obtain particles with an average particle size of 0.60 μm and a silver iodide content of 3.5 mol%. After the addition was completed, the temperature was lowered to 40°C.

To this, a condensate of na7talenesnolephonate sodium and honoremarin and magnesium sulfate were added at 24.6% each.
g/AgX l mol was added and the pH was adjusted to 4.0+. : Desalting was performed by lowering the mixture, and then 15 g of gelatin/1 mole of AgX 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 chemical sensitization, 4-hydroxy-6-methyl-■,3
, 3a,7-tetrazaindene was added. After that, 150 mg of potassium iodide/1 mol of AgX and a sensitizing dye (A
) (B) was added in the same amount as in emulsion (A) to perform spectral sensitization. The emulsions obtained in this way were each emulsion (B
), (C).

(B). (C) The same additives as in (A) were added to each of the photosensitive emulsions to prepare an emulsion coating solution. Using these coating solutions and the above-mentioned protective layer solution, the dye of the present invention was added in a dispersed manner in the same manner as in the above-mentioned method, and the coating was carried out so as to insert a crossover cut layer. Similarly, samples with improved sharpness and little decrease in sensitivity were obtained.

Example 2 (Preparation of coating solution for emulsion layer) Solution A Water
9.7Q Sodium chloride 20g Gelatin 105g Solution B Water
3.8m Sodium chloride 3
65g Gelatin 94g Potassium Bromide 450g Hexachloroiridate Potassium Salt 0. Ol% aqueous solution 28m2 0.0% of potassium hexabromorodate salt. Ol% aqueous solution 1. OmQ solution C water
3.8Q silver nitrate
1. To 700g of the above solution A kept at 40°C, the above solution B and solution C were simultaneously added functionally over a period of 60 minutes while maintaining the pH at 3, I) Ag at 7.7, and further l
After stirring for 0 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and a 20% aqueous solution of magnesium sulfate (2.55%) and a 5% aqueous solution of polynaphthalene sulfonic acid (2.55%) were added.
2 was added, and the emulsion was loculated at 40° C., decanted and washed with water to remove excess aqueous salt. Next, 3.712 ml of water is added to disperse it, and 0.912 ml of a 20% aqueous magnesium sulfate solution is added again to remove the excess salt in the aqueous solution. And 3.
Add 712 g of water and 141 g of gelatin and heat at 55°C for 30 minutes.
Disperse for 0 minutes. 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. Add 1% aqueous solution of citric acid to these particles.
40mO. , after adding 57+nQ of a 5% aqueous solution of potassium bromide, a 0.1% aqueous solution of sodium thiosulfate was added to 701I
IQ was added and aged at 58°C for 70 minutes.

To the obtained emulsion were added 10 g of 4-hydroxy-6methyl-1.3.3a,7-tetrazaindene as a stabilizer and 1,600 mff of a 20% gelatin aqueous solution to stop ripening, and then the following sensitization was carried out. 3.5 g of dye (a), (
Ig of b) and Ig of (c) were added, and then 7g of compound (d) was added as a contrast enhancer, and then p was added as a spreading agent.
- 10g of sodium dodecylbenzenesulfonate, 30g of saponin, 120g of butyl acrylate-acrylic acid-styrene copolymer as polymer latex,
A coating solution for an emulsion layer was prepared by adding 3 g of potassium bromide as a pAg regulator, 20 g of styrene maleic anhydride copolymer as a thickener, and formalin and glyoxal as hardeners.

Sensitizing dye (a) Sensitizing dye (b) Sensitizing dye (c) C2H6 compound (d) (Preparation of coating solution for protective layer) After dissolving 500 g of gelatin in 7.54 g of water, add the following compound as a spreading agent. A coating solution for a protective layer was prepared by adding 15 g of (e) as a matting agent, 10 g of silica having an average particle size of 3.5 μm, and formalin as a hardening agent.

Compound (e) (Preparation of coating solution for packing lower layer) After dissolving 650 g of Seratin in 1012 of water, Table 2
The compound shown in is dispersed in solid fine particles in the same manner as in Example 1, and added at a concentration of 0.2 g/m2, followed by 30 g of saponin as a spreading agent and 30 g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex. A coating solution for the lower packing layer was prepared by adding 150 g of colloidal silicate as a film property improver, 3 g of styrene-maleic anhydride copolymer as a thickener, and 2.5 g of glyoxal as a hardening agent.

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

(Preparation of sample) A lower packing layer and an upper layer are simultaneously coated on a polyethylene terephthalate film base with a thickness of 100 μm that has been subjected to an undercoating process, and then an emulsion layer and a protective layer are simultaneously coated on the side opposite to the packing layer. Multilayer coating was applied. The amount of coated silver was 4.2g/7m, and the amount of gelatin applied was 1.95g/emulsion layer.
m", protective layer is 1.2g7m", packing lower layer is 2.
7g7m2, packing upper layer was 1.0g/m''.

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

Halftone dot quality> After halftone exposure was carried out so that the halftone dot area was 90%, it was processed and the halftone dot quality was evaluated on a scale of 10. The best halftone quality I
0, 1 was defined as an extremely bad level, and 5 or more was defined as a practical level.

<Storage stability> After conditioning the obtained sample at 23°C and 150% RH,
The emulsion side and the packing side were brought into contact and overlapped 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 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
28°0 30 seconds fixation 28°C
Wash with water for about 20 seconds, dry at room temperature for about 20 seconds, 45℃ 2
0 second developer set or (set 1!A) Pure water (ion exchange water) 150lI2 Disodium ethylenediaminetetraacetate 2g diethylene glycol 50g Potassium sulfite (5
5% W/V aqueous solution) 100mff potassium carbonate 50g hydroquinone
15g 5-methylbenzotriazole 200mgl-phenyl-5-mercabutotetrazole 30fflgpotassium bromide
4.5g hydroxide solution pl1 to 1
Amount to make 0.4 (Kumikai B) Pure water (ion exchange water) 3mg diethylene glycol 50g ethylenediaminetetraacetic acid 25mg disodium salt vinegar 1m (90% aqueous solution) 0.3m
l25-nitroindazole llO
mg1-phenyl-3-virazolidone 50
When using 0mg developer, add the above group A to 500mff of water.
One set was dissolved in the order of B, finished with lffi, and used.

Fixer formulation (composition A) Ammonium thiosulfate 240ml2 (
72.5% v/v aqueous solution) Sodium sulfite 17g Sodium acetate trihydrate 6.5g Nitric acid
6g sodium citrate dihydrate 2g acetic acid (90% w/v aqueous solution)
13.6mff (group B) Pure water (ion exchange water) 17mQ sulfuric acid (50% W aqueous solution) 4.7g aluminum sulfate 26.5g (A+
When using a fixer (aqueous solution with a 2ox equivalent content of 8.1% w/v), the above-mentioned Kumiaki A and Kumikai B were dissolved in 500 mff of water in that order, and the solution was made into N2.

Comparative Sample 2 Table 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.

(89) instead of compound (1) of the present invention in sample 2-3
, (92). The above-mentioned effects were also observed for each sample using (96).

Also, sensitizing dye (a). (b). The following dye (e) was used instead of (c), and the compound of the present invention (3
)． (5). (14). (24).
(30) , (35) . (40). (48)
, (50). (58). (67) When samples were prepared and evaluated using (80), the surface spectral photosensitizing dye (
e) As explained in detail above, a silver halide photographic light-sensitive material with less fog, improved stability over time during storage, and excellent photographic properties by containing the solid fine particle dispersion of the compound of the present invention. is provided.

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 following general formula [I] on a support. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 represent substituents, R_3 and R_
4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, L_1, L
_2, L_3, L_4, L_5 represent methine groups, n_
1 and n_2 represent 0 or 1. However, R_1, R_2
, R_3, and R_4 have a sulfonamide group and/or a sulfamoyl group, and the compound has at least two sulfonamide groups and/or sulfamoyl groups. ]