JPH03206442A - 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 an alkenyl group, cycloalkyl group, aryl group, heterocyclic group, etc.; L1 to L5 denote a methine group; n1, n2 denote 0 or 1. The silver halide photogrpahic sensitive material which provides less fogging, is improved in preservable stabil ity with age and has excellent photographic characteristics 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, it 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, suitability for ultra-rapid 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. It is used.

Recently, dyes (hereinafter referred to as rYC 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 No. 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 the extent that it will diffuse into other layers, resulting in undesirable phenomena such as decreased sensitivity, gradation fluctuations, and fog abnormalities in both the white layer and other layers. appears. 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 U.S. Patent Nos. 2.538.008 and 2,539.00.
No. 9, No. 4,420.555, JP-A-61-2046
No. 30, No. 61-205934, No. 62-32460
No. 6256958, No. 62-92949, No. 6
No. 2-222248, No. 63-40l43, No. 63-
YC dyes are described in No. 184749 and No. 63-316852. These dyes are also commonly used in color photographic elements such as Carey LeaSilv.
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]

Accordingly, an object of the present invention is to provide a silver halide photographic material that meets the above-mentioned requirements for dyes with increased resistance to extended exposure and has improved image quality and storage stability.

[Structure of the invention]

The present inventors conducted intensive studies in view of the above-mentioned problems, and as a result, the above-mentioned object of the present invention is to provide a compound containing the following general formula (I) on a support.
This is achieved by a silver halide photographic light-sensitive material having at least one photographic structure layer containing a solid fine particle dispersion of a compound represented by the general formula [I], where Rl and R2 are an alkenyl group or a cycloalkyl group. basis,
Aryl group, heterocyclic group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulf7ynyl group, carbamoyl group, sulfamoyl group, represents a cyano group, an amino group, a sulfonamide group, an amide group, a ureido group, a thiourido group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxyl group, or a hydroxyl group; ,L. ,L ,,L
Lee L. represents a methine group, nl, n! represents 0 or l.

The present invention will be explained in more detail below.

Examples of the alkenyl group represented by R+ and Rz include a vinyl group, an allyl group, a l-probenyl group, a 1,3-butadienyl group, and a 2-pentenyl group.

The alkenyl 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.), sulfinic acid group, carboxyl group,
Nitro group, hydroxyl group, mercapto group, amino group (
For example, amine group, diethylamino group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, octyloxy group, i-proboxy group, etc.), aryloxy group (phenoxy group, natyloxy group, etc.), carbamoyl group ( For example, aminocarponyl group, methylcarbamoyl group, pentylcarbamoyl group, morpholinocarponyl group,
7-enylcarbamoyl group, etc.), amide group (e.g. methylamide group, penzamide group, octylamide group, etc.), sulfamoyl group (e.g. sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, morpholinosulfonyl group, butylsulfamoyl group) groups), sulfonamide groups (e.g., methanesulfonamide groups, heptanesulfonamide groups, benzenesulfonamide groups, etc.), sulfinyl groups (e.g., methylsulfinyl groups, ethylsulfonyl groups, phenylsulfinyl groups, octylsulfinyl groups, etc.) 7ynyl group, arylsulfinyl group such as phenylsulfinyl group), alkoxylponyl group (e.g. methoxycarponyl group, ethoxyluponyl group, 2-hydroxyethoxyluponyl group,
octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., 7enocyrponyl group, naphthyloxyrponyl 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. benzoyl group, p-
methanesulfonamide benzoyl group, p-carpoxybenzoyl group, na7toyl group, etc.), cyano group, ureido group (e.g. methylureido group, phenylureido group, etc.),
Examples include thioureido groups (eg, methylthioureido group, phenylthioureido group, etc.).

R. Examples of the aryl group represented by , R include a phenyl group and a na7thyl group. The aryl group includes those having a substituent, and examples of the substituent include an alkyl group, the above-mentioned R. , R, or an alkenyl group represented by R, ,R. The above-mentioned groups can be mentioned as substituents for the alkenyl group represented by.

R. Examples of the heterocyclic group represented by , 4,6-dimethyl-2-pyridyl group, 6-hydroxy-2-pyridyl group, 2,3.5.6
-tetrafluoro-4-biridyl group, 3-nitro-2-
pyridyl group, etc.), oxazolyl group (5-carboxy-2
-penzoxazolyl group, 2-benzoxazolyl group,
2-oxazolyl group, etc.), thiazolyl group (5-sul7amoyl-2-penzothiazolyl group, 2-benzothiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (l-methyl-2-imidazolyl group, l-methyl- 5-carpoxy-2-penzimidazolyl group, etc.), furyl group (3-
Furyl group, etc.), pyrrolyl group (3-pyrrolyl group, etc.), chenyl group (2-chenyl group, etc.), birazinyl group (2-virazinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group,
4-chloro-2-pyrimidinyl group, etc.), pyridazinyl group (2-pyridazinyl group, etc.), purinyl group (8-burinyl group, etc.), isooxazolyl group (3-isooxazolyl group, etc.), selenazolyl group (5-carpoxy 2- Selenazolyl group, etc.), sulfolanyl group (3-sulfolanyl group, etc.)
, biveridyl group (l-methyl-3-piperidyl group, etc.),
Examples include pyrazolyl group (3-virazolyl group, etc.), tetrazolyl group (1-methyl-5-tetopzolyl group, etc.),
The heterocyclic group includes those having a substituent, and examples of the substituent include an alkyl group, an alkenyl group represented by R2, and an R. , R, as examples of the substituents for the alkenyl group represented by R.

R. , R. Examples of the cycloalkyl group represented by R+ and Rz include cyclopyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.; examples of the alkylcarbonyl group represented by R+ and Rz include methyl group, ethyl group, etc. Rubonyl group, i-propylene carbonyl group, t
Arylcarbonyl groups represented by R+ and Rz include -butylcarbonyl group, octylcarbonyl group, dodecylcarbonyl group, etc.
For example, phenylcarbonyl group, na7thylcarbonyl group, etc. Rl1R! Examples of the alkoxycarponyl group represented by R,, R2 include ethoxycarponyl group, i-proboxycarponyl group, t-butoxycarbonyl group, benzyloxycarbonyl group, dodecyloxycarbonyl group, etc. Examples of the aryloxycarbonyl group include phenyloxycarbonyl group and naphthyloxycarbonyl group. Examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, i-probylsulfonyl group, t-butylsulfonyl group, and octyl group. Examples of arylsulfonyl groups such as sulfonyl group and octadecylsulfonyl group include phenylsulfonyl group and naphthylsulfonyl group; examples of alkylsulfinyl groups include methylsulfinyl group, ethylsulf7ynyl group, i-probylsulf7ynyl group, and t-butyl group. Sulfinyl group, octylsulfinyl group, dodecylsulfinyl group, etc. Arylsulf7ynyl group includes, for example, 7enylsulfinyl group, naphthylsulfinyl group, etc. Carbamoyl group includes, for example, aminocarbonyl group, methylrubamoyl group, ethylrubamoyl group, i-propyrubamoyl group, t-butylcarbamoyl group, dodecylrubamoyl group, phenylcarpamoyl group, 2-biridylrubamoyl group, 4-pyridylrupamoyl group, penzylcarbamoyl group, morpholinocarponyl group, piperazinocarponyl group Examples of the sulfamoyl group include an aminosulfonyl group, a methylsulfamoyl group, an i-globilsulfamoyl group, a t1'thylsulfamoyl group, a dodecylsulfamoyl group, a phenylsulfamoyl group, and a 2-pyridylsulfamoyl group. Famoyl group, 4-pyridylsulfamoyl group, morpholinosulfonyl group, piperazinosulfonyl group, etc. Amino groups include, for example, amino group, methylamino group,
Examples of the sulfonamide group include ethylamino group, i-propylamino group, t-butylamino group, octylamino group, dodecylamino group, dimethylamino group, anilino group, naphthylamino group, morpholino group, piperazino group, etc. Amide group, ethylsulfonamide group, i-probylsulfonamide group, L-butylsulfonamide group, dodecylsulfonamide group, 7-enylsulfonamide group, naphthylsulfonamide group, etc. As the amide group, for example, methyl luponylamino group , ethyl power luponylamino, i-propyl carbonylamino group, L
Examples of ureido groups include methylureido group, ethylureido group, i-propylureido group, L- Examples of thioureido groups include methylthioureido group, i-propylthioureido group, t-butylthioureido group, dodecylthioureido group, etc. Ureido group, 7enylthioureido group, 2-pyridylthioureido group, thiazolylthioureido group, etc.; Examples of alkoxy groups include methoxy group, ethoxy group, i-propoxy group, L-butyloxy group, dodecyloxy group, etc. Aryloxy groups include, for example, 7-enoxy and naphthyloxy groups; alkylthio groups include, for example, methylthio, ethylthio, i-propylthio, t-butylthio, and dodecylthio; and arylthio groups include, for example, 7-enylthio. group, naphthylthio group, etc. These R. S.R. Each group represented by includes those having a substituent, and examples of the substituent include those exemplified as the alkyl group, the alkenyl group represented by Rl described above, and the substituent of the alkenyl group represented by R1. It will be done.

Among these groups represented by R, R, preferably aryl group, alkylcarbonyl group, arylcarbonyl group,
Alkoxy carbonyl group, carbamoyl group, amino group,
These include an alkoxy group, a cyano group, and a carpoxyl group, and particularly preferred are an alkylcarbonyl group, an alkoxyl group, a carbamoyl group, an amino group, an alkoxy group, and a carpoxyl group.

In the general formula CI), the methine groups represented by LI to L include those having substituents, such as alkyl groups (e.g. methyl group, ethyl group, i-probyl 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.), Examples include acyloxy groups (eg, methylalponyloxy group, phenylcarbonyloxy group, etc.).

Specific examples of the compounds of the present invention are shown below, and the compounds of the present invention are, for example, JP-A-48-62826, JP-A-49-1999,
No. 5125, No. 51-77327, No. 58-1433
No. 42, No. 59-111641, No. 64-40827
The combination can be easily carried out by reacting a pyrazolone derivative with a methine chain source, similar to the method shown in No. 1, etc. Specific examples of combinations according to the present invention will be shown below, but other dyes can also be combined in the same manner.

Combination Example 1 (combination of compound 2) COOH (1) (2) (1) 28g, (2) 8.4g and HD
After preparing a suspension of 100 mQ of MF, 25.3 g of triethylamine was added dropwise at room temperature. After stirring at room temperature for 5 hours, 2 oomQ of concentrated hydrochloric acid was added to perform acid precipitation. The crude crystals obtained by filtration were heated and dispersed in 300 ml of dimethyl sulfoxide, and 100 ml of concentrated hydrochloric acid was added to perform acid precipitation.

After repeating this operation three times, the desired product was obtained by drying. Yield 18.5g, yield 69%.

The parent ion peak of the target product was confirmed by mass spectrometry.

Combination example 2 (combination of compound 56) COOH (3) (4) (3) 23.4g, (4) 11.6g
1 ethanol 150mQ, triethylamine 25.3g
were mixed and heated under reflux for 9 hours. After cooling the reaction solution to room temperature, 200 mff of concentrated hydrochloric acid was added to precipitate the reaction solution, and the resulting solid was dispersed in 150 mQ of water, and 10 mQ of sodium hydroxide was added.
g was added to dissolve the solution, filtered to remove insoluble matter, and concentrated hydrochloric acid was added until the pH became 2 or less for acid precipitation. This purification operation was performed three times, and the resulting solid was purified with dimethyl sulfoxide 3
The desired product was obtained by heating and dispersing the mixture at 00+J, adding concentrated hydrochloric acid for acid precipitation, and drying the obtained solid.

Yield: 15.3 g, yield: 72%.

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

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 compound of the invention is preferably contained in the non-photosensitive layer,
Ru.

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 coated by chemical sensitization by a conventional method, or can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, 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. Colored covlar 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 fragments, 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.

A formalin scavenger, an optical brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventer, a development accelerator, a development retardant, and a bleach accelerator can be added to the photosensitive material.

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 halogenide photographic light-sensitive material was prepared in the following manner.

First, an emulsion was prepared as follows.・(A) Preparation of monodispersed emulsion Reaction vessel conditions: 60°OSpAg=8, and l)
The average particle size was reduced to 0 using the double jet method while maintaining the temperature at H-2.
．． 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 grown 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 pA to 87.3 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 pAtg 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 mixture was lengthened until it reached 90% of the grain size. At this time, the pH was gradually lowered from 9.0 to 8.20.

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

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

Sensitizing dye (A) Sensitizing dye (B) (CHx)*SOs"'(shiH2ノ,"5U3Na) Next, as shown below, a desalting step for removing excess salt was performed.

The silver halide emulsion solution was kept at 40°C, the following compound (a) (exemplified compound n-1 shown in JP-A-58-140322) was added to precipitate the silver halide grains, and the supernatant liquid was discharged. Afterwards, 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 was repeated once more and gelatin was added to obtain an emulsion with pH 6-Ox pAg 8.5.

Compound (a) The emulsion obtained above was kept at 55°C and chemically sensitized by adding chlorauric 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 l as an additive to the photosensitive emulsion of (A) above.
Per mole: L-butylcatechol 400mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0
g Styrene-maleic anhydride copolymer 2.5g Trimethylolpropane lOg Diethylene glycol 5g Nitro7enyltri7enylphosphonium chloride 50mg1.3
-dihydroxybenzene-4-ammonium sulfonate 4g Sodium 2-mercaptobenzimidazole-5-sulfonate 5mgOH 1,1-dimethylol-1-bromo-1nitromethane 10mg 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 Ig of gelatin to prepare a protective layer coating solution.

Matting agent made of polymethyl methacrylate with an average particle size of 7 μm 7 mg Colloidal silicone strength with an average particle size of 0.013 μm 70 mg2-
Hydroxy-4,6-dichloroS triazine sodium 30mg using each of the above coating solutions,
Sample 1-l as shown below was prepared.

Sample 1-1 Lower i4+ 3? IF, l-: glycidyl methacrylate 50 wt%, methyl methacrylate 10 wt%
An aqueous copolymer dispersion prepared by diluting a copolymer containing 40 wt % of butyl methacrylate to a low concentration was used and was coated on both sides to obtain a subbed support. Then, on the support, an emulsion layer was coated on both sides at a coating speed of 140 m/min, and an emulsion layer was coated with a silver content of 3.2 g/m2 on one side, and a protective layer was coated with a gelatin content of 0.98 g/m2 on one side. did.

Sample 1-2 Sample 1-1 was coated so that a cross-over cut layer containing the dyes shown in Table 1 was inserted between the emulsion layer and the subbing layer.

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 1-26 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 into solid fine particles using a ball mill according to the following procedure.

Water and surfactant Alkanol XC (anolequinolenaphthalene snorephonate, manufactured by DuPont) in a Pall mill container.
Each dye was added, zirconium oxide beads were added, the container was sealed, and the container was dispersed in a Pall mill for 4 days; then, 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 per 1 m on both sides.
I set it to 2.

The following evaluations were performed on the obtained samples.

<Measurement of sensitometry> Using the standard light B described in the "New Edition, Lighting Data Book" as the light source, use an exposure time of 0.1 seconds, 3.2 cms, and use a non-filter to ensure that the same amount of light is applied to both sides of the film. exposed to light. The above sample was prepared using an SRX-501 automatic processor (Konica).
After processing with XD-SD developer for 45 seconds, fixing and drying, the sensitivity of each sample was determined. Sensitivity was determined by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0, and expressed as relative sensitivity, with the sensitivity for samples 1-1 in Table 1 set as 100.

<MTF evaluation> An MTF chart containing a lead square wave of 0.5 to lO line/mm was brought into close contact with the back side of the front side of a fluorescent screen KO-250 (manufactured by Konica Corporation), and the film surface was X-rays were irradiated so that the concentration of the part 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 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 even though the decrease in sensitivity is less than that of the comparative samples.

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.

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 1 solution, room+2, was added over a period of 1 minute.

After continuing stirring for 10 minutes, the remaining 2 solution of solution A, 20
0ml2 was added over 10 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 KBrlO. 5g, thioether compound [
HO(CHz)zS(CHz)2S(CHz)20H)
10m+2 of 0.5wt% aqueous solution and 30g of gelatin
was added to dissolve and maintained at 70'C. Add silver nitrate aqueous solution (0.88 mol/+2) into this solution while stirring.
30m (2, potassium iodide and potassium bromide (molar ratio 3)
．． 5:96.5) aqueous solution (0.88 mol 7030 ml
2 particles were added by double jet method, and the average particle size was 0.
Grains with a diameter of 60 μm and a silver iodide content of 3.5 mol % were obtained.

After the addition of the mixed solution was completed, the temperature was lowered to 40'O.

To this, 24.6 g/g of sodium naphthalene sulfonate, formalin condensate, and magnesium sulfate were added.
After adding 1 mol of AgX, the pH was lowered to 4.01 for desalting, and then 15 g of gelatin/1 mol 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-1.3
, 3a,7-tetrazaindene was added. After that, 150 mg of potassium iodide/1 mol of AgX and a sensitizing dye (
Spectral sensitization was carried out by adding the same amounts of A) and (B) as in emulsion (A). The emulsions thus obtained are 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 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
3.8mQ Sodium Chloride 36
5 g gelatin 94 g potassium bromide 450 g 0.01% aqueous solution of potassium hexapromorodate salt 28 ml 2 o. oi% aqueous solution 1.0ml2
Solution C water
3.8Q silver nitrate
1. The above solutions B and C were simultaneously added functionally over 60 minutes to 700g of the above solution A kept at 40°C while maintaining the pH at 3 and the pAg at 7.7, and
After stirring for a minute, the pH was adjusted to 6 with an aqueous sodium carbonate solution.
．． 0, add 2c of a 20% aqueous solution of magnesium sulfate and 2.55ml of a 5% aqueous solution of polynaphthalene sulfonic acid, loculate the emulsion at 40'C, decant and wash with water to remove the salt of excess aqueous solution. remove. Next, add 3.7Q of water to it and disperse it,
Again, 0.912 g of a 20% aqueous magnesium sulfate solution is added to remove excess salt in the aqueous solution in the same manner. And 3.7
Add Q water and 141g gelatin and heat at 55°C for 30 minutes.
Disperse for minutes. As a result, particles of 38 mol % of silver bromide, 62 mol % of silver chloride, and an average particle size of 0.25 μm and a monodispersity of 9 are obtained. A 1% aqueous solution of citric acid was added to the particles for 14 hours.
After adding 0 mQ of 5% aqueous solution of potassium bromide, 70 mQ of a 0.1% sodium thiosulfate aqueous solution was added, and the mixture was aged at 58°C for 70 minutes.

4-Hydroxy-6-methylenyl-1.3.3a. is added to the resulting emulsion as a stabilizer. log 7-tetrazaindene,
1. Add a 20% aqueous solution of gelatin. After adding 600 mQ and stopping ripening, add 3.5 g of the following sensitizing dye (a),
Added Ig of (b) and lg of (C), further added 7g of compound (d) as a contrast enhancer, and then added log of sodium p-dodecylbenzenesulfonate as a spreading agent.
30g of saponin 1 polymer latex, 120g of butyl acrylate-acrylic acid-styrene copolymer,
! ) 3gs of potassium bromide was added as an Ag regulator, 20g of styrene-maleic anhydride copolymer was added as a thickener,
A coating solution for an emulsion layer was prepared by adding formalin and glyoxal as hardeners.

Sensitizing dye (a) Sensitizing dye (b) Sensitizing dye (c) C,H. Compound (d) (Preparation of coating solution for protective layer) After dissolving 500 g of gelatin in 7.5 Q of water, 15 g of the following compound (e) as a spreading agent and 1 portion of silica having an average particle size of 3.5 μm as a matting agent were added. A protective layer coating solution was prepared by adding formalin as a hardening agent at 0 gs.

Compound (e) - So 3Na (Preparation of coating solution for packing lower layer) 650 g of gelatin was added to 1OQ. After dissolving in water, Table-2
The compound shown in Example 1 was dispersed in solid fine particles in the same manner as in Example 1, and added to give a concentration of 0.2 g/m'', followed by spreading agent 1, saponin 30z, polymer latex, butyl acrylate, and vinylidene chloride. A coating solution for the packing lower layer was prepared by adding 30 g of the copolymer of 1, 150 g of colloidal silica 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. Prepare it.

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

(Preparation of sample) A lower packing layer and an upper layer are simultaneously coated on a 100 μm thick polyethylene tere-7 tallate film base that has been subjected to an undercoating process, and then an emulsion layer and a protective layer are applied on the opposite side from the packing layer. The layers were coated simultaneously. The amount of silver applied is 4
-2g/m”, the amount of gelatin applied is 1.95g/m in the emulsion layer.
", protective layer 1.2g/m", packing lower layer 2.7
g/m'', and the upper packing layer was l.Og/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.

<Halt quality> After halftone exposure was carried out so that the halftone dot area was 90%, the sample was processed and the halftone dot quality was evaluated at the IO stage. Best halftone quality 1
0, l is considered to be an extremely bad level, and 5 or more is considered to be a practical level.

<Storage stability> After conditioning the obtained sample at 23°0, 50% RH,
The emulsion side and the packing side were brought into contact and overlapped and sealed.

This sample was stored for 5 days under conditions of 50° C. and 120% RH, 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) Development fixing Water application Washing and drying Drying developer composition (set A) Pure water (ion exchange water) 1 50m
(Disodium 2-ethylenediaminetetraacetate 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) 100ml potassium carbonate 50g hydroquinone 15g 5-methylbenzotriazole 200mg l-phenyl-5-mercaptotetrazole 30mg potassium bromide
4.5g potassium hydroxide Adjust the pH of the working solution to 1
Amount to make 0.4 (assembly B) Pure water (ion exchange water) 3 mg diethylene glycol 50 g (time) 30 seconds approx. 20 seconds approx. 20 seconds 20 seconds (temperature) 28°0 28°C Room temperature 45°C Ethylenediamine tetra vinegar rl1 2 5
mg disodium salt acetic acid (90% aqueous solution) 0.3 ml
25-nitroindazole 110mg
l-7enyl-3-pyrazolidone 500m
When using the g developer, the above-mentioned group A and group B were dissolved in 500 mQ of water in this order, and finished to 1Q before use.

Fixer formulation (composition A) Ammonium thiosulfate 240mg (
72.5% wi/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)
13.6mffi (assemble B) Pure water (ion exchange water) 1 7mQ sulfuric acid (50% w/v aqueous solution) 4.7g
Aluminum sulfate 26.5g (
A.I., O. When using a fixer (converted content: 8.1% w/v aqueous solution), the above compositions A1 and B were dissolved in the order of 500ml of water (2) and finished to 1Q.

Comparative Sample 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 place of the present invention compound (1) of sample 2-3, (48)
, (57), and (58), the above-mentioned effects were also observed.

In addition, the following dye (e) was used instead of the sensitizing dyes (a), (b), and (c), and the compound (4) of the present invention was prepared in the same manner as in Table 2.
). (8), (10). (13) (16) (22
)． (26). (32). (35).
(38). When samples were prepared and evaluated using (41), (47), (53), and (54), 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 photographic A silver halide photographic material with excellent properties 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] ▲ Numerical formulas, chemical formulas, tables, etc. Oxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, carbamoyl group, sulfamoyl group, cyano group, amino group, sulfonamide group, amide group,
Represents a ureido group, thioureido group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxyl group or hydroxyl group, L_1, L_2, L
_3, L_4, L_5 represent methine groups, n_1, n_
2 represents 0 or 1. ]