JPH04147249A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic emulsion with the sensitivity capable of being increased without increasing fogging by incorporating a specified compd. into the emulsion. CONSTITUTION:A compd. expressed by formula I is incorporated to form a silver halide photographic emulsion layer. In the formula, R<1> and R<2> are hydrogen atom and the alkyl, alkenyl, cycloalkyl, aryl and heterocyclic groups which can be substituted, X is oxygen atom, nitrogen atom and sulfur atom, Z is an atomic group necessary to form 5 or 6-membered heterocycle, A is proton acid, n1 is an integer of 1, 2 and 3, and n2 is an integer of 0 or 1, 2 and 3. R1 and R2 are capable of forming a 6-membered ring.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chemically sensitized silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion chemically sensitized with a sulfur-containing compound or the like. The present invention relates to a silver halide photographic material characterized by having a layer.

[Background of the invention]

Photographic silver halide emulsions inherently have low sensitivity, and various methods are used to increase their photographic sensitivity.

For example, U.S. Patent Nos. 2,410,689 and 3,5
01.313, West German Patent No. 1,422,869, Japanese Patent Publication No. 49-20533, etc., sulfur sensitization methods are described.

This is an attempt to achieve high sensitivity by adding a small amount of a sulfur-containing compound (for example, sodium thiosulfate) to a silver halide emulsion to form silver sulfide nuclei.

Also, U.S. Patent Nos. 2,399,083 and 3,297
．． It is also common to sensitize a silver halide emulsion by adding a reducing agent (reduction sensitization) or an alloy compound (gold sensitization) as described in No. 446.

Furthermore, 7. “The Theory of the Photographic Process” 4th edition (Ma
(Cwiillan Co., 1977) describes a sensitization method that combines these methods.

Hydrogen sensitization using hydrogen gas is also a generally well-known sensitization method.

In recent years, X3200 Professional (
As shown in Konica's products, the trend is to increase the sensitivity of silver halide photographic materials, and we are in a situation where even higher sensitivity is required.

In general, technology for increasing sensitivity is important from the perspective of photographic image quality. For example, if the same sensitivity can be achieved with silver halide grains having a smaller grain size, graininess will be improved. Furthermore, by reducing the amount of silver used, thinner films can be achieved and sharpness can also be improved. Naturally, it is also advantageous in terms of cost. Therefore, various attempts have been made to achieve even higher sensitivity, but in the conventional sensitization method using a sensitizer, significant fogging occurs when the amount of sensitizer used increases. It had the disadvantage that it would cause problems.

Techniques using inhibitors and the like are known to suppress this, but it is difficult to completely suppress fog.

Furthermore, if the amount of inhibitor is increased by the amount of sensitizer, the sensitizing effect will be significantly reduced.

In order to solve these problems, the special public
No. 8, JP-A-58-80,634, JP-A-1-114
．． Publications such as No. 839 and No. 1-227,140 disclose chemical sensitization methods using thiourea derivatives.

However, it cannot be said that these compounds have sufficiently achieved the target, and further improvements in the layer have been desired.

[Purpose of the invention]

The first object of the present invention is to provide a silver halide photographic emulsion that can increase sensitivity without increasing fog, which is harmful to photographic properties.

The second is an increase in fogging even when stored under high temperature and high humidity conditions.
Another object of the present invention is to provide a silver halide photographic emulsion with little decrease in sensitivity.

[Means to achieve the goal]

The above object has been achieved by a silver halide photographic emulsion characterized by containing a compound represented by the following general formula CI).

General formula CI) [In the formula, R1 and R1 represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and X is an oxygen atom, a nitrogen atom, or a sulfur atom. represents. Z represents an atomic group necessary to form a 5-membered or 61L heterocycle, and A represents a protonic acid. n represents l, an integer of 2.3; n represents an integer of 0 or 1, 2.3;

R1 and R3 can form a 5- or 6-membered ring. ] Hereinafter, the present invention will be explained in more detail.

In the general formula (1), RIRl represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and examples of the optionally substituted alkyl group include, for example. Methyl group, ethyl group, D-propyl group, isopropyl group, t-butyl group, n-hexyl group,
Examples include D-octyl group, 2-ethyloxy group, n-dodenyl group, n-bentadenyl group, and eicosyl group.

Substituents for the above alkyl groups include halogen atoms (e.g. chlorine, bromine, iodine, fluorine, etc.), aryl groups (e.g. phenyl group, naphthyl group, etc.), heterocyclic groups (e.g. pyridyl group, thienyl group, thiazolyl group). , pyrrolidyl group,
imidazolyl group, etc.), carboxyl group, nitro group, hydroxyl group, mercapto group, amino group, alkylamino group (e.g. dimethylamino group, diethylamino group, hydroquinethylamino group, etc.), alkyloxy group (e.g. methyloxy group, ethyloxy group) , n-butyloxy group, isopropyloxy group, octyloxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenyloxy group, naphthyloxy group, etc.), carbamoyl group (e.g. aminocarbonyl group, methylcarbamoyl group, phenylcarbamoyl group) group, pyridylcarbamoyl group, etc.), amide group (e.g., methylamide group, benzamide group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, n-octylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonamide group ( For example, methanesulfonamide group, benzenesulfonamide group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl group (for example, methylsulfinyl group, phenylsulfinyl group, etc.), alkyloxycarbonyl group ( For example, methyloxycarbonyl group, ethyloxycarbonyl group, isopropyloxycarbonyl group,
octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (e.g., methylthio group, isopropylthio group, n-octylthio group, etc.), arylthio group (e.g., phenylthio group, naphthylthio group, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, isopropylcarbonyl group, n-octylcarbonyl group, etc.), arylcarbonyl group (e.g. phenylcarbonyl group, naphthylcarbonyl group QF), cyano group, ureido group (e.g. methylureido group) (eg, methylthioureido group, phenylthioureido group, etc.), and thioureido groups (for example, methylthioureido group, phenylthioureido group, etc.).

Examples of the optionally substituted alkenyl group include a vinyl group, an allyl group, a l-propenyl group, a 1+3-butadienyl group, and a 2-pentenyl group. Examples of substituents for the alkenyl group include the alkyl group and the six groups listed as substituents for the alkyl group.

Examples of the optionally substituted cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which can be substituted with an alkyl group and the six groups listed as substituents for the alkyl group.

Examples of the optionally substituted aryl group include a phenyl group and a naphthyl group, which can be substituted with an alkyl group and the six groups listed as substituents for the alkyl group.

Examples of the optionally substituted heterocyclic group include a pyridyl group, an oxacylyl group, a thiazolyl group, an imidazolyl group, a thienyl group, a furyl group, a pyrrolyl group, a pyrimidinyl group, a pyrazinyl group, a purinyl group, a pyridazinyl group, and an inoxazolidinyl group. Examples include a selenazolyl group, a sulfolanyl group, a piperidinyl group, a pyrazolyl group, a morpholyl group, a tetrazolyl group, etc., and can be substituted with an alkyl group and the six groups listed as substituents for the alkyl group.

As the protonic acid represented by A, a wide range of organic acids and inorganic acids can be used, such as hydrochloric acid, hydrobromic acid, 'fi
Preferred examples include L#, carbonic acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid, pyromellitic acid, and trinitrophenol.

Examples of the 5- or 6-membered ring formed by R1 and R1 include a virole ring, an imidazole ring, a pyrazole ring, an isoindole ring, an indole ring, an indazole ring, a purine ring, a carbazole ring, an intiazole ring, an inoxazole ring, Phenoxazine ring, pyrroline ring, imidazolidine ring, pyrazolidine ring, pyrazoline ring, morpholine ring,
Examples include a piperazine ring, an indoline ring, etc., and the 6 listed as substituents for the alkyl group and the substituent for the alkyl group.
can be substituted with groups.

Next, specific examples of compounds represented by general formula [I] will be shown, and the compounds used in the present invention are CH3 OCR.

CH.

CH.

Compounds of the invention may be used, for example, in Chem, Ber., 63.
208 (1930), J,org,ches+,,36
3895(197), J.Chem.Soc.

It can be easily synthesized by the method described in 1957.2999 and the like.

The compound of the present invention may be added to a silver halide photographic emulsion at any time during the emulsion manufacturing process, but generally,
It is desirable to add it at the beginning of chemical ripening after washing the emulsion with water.

The amount of the compound of the present invention to be used varies depending on the type of silver halide photographic emulsion, the type of compound used, etc., but is usually 3 x 10-' mol to I x 10-' mol per mol of silver halide. Preferably it is in moles.

The value of pAg (logarithm of the reciprocal of silver ion concentration) during chemical ripening is preferably 8.0 to 11.0.

Other chemical sensitizers can also be used in combination during chemical ripening. Examples of chemical sensitizers that can be used in combination include gold compounds described in U.S. Patent No. 2.399.083, U.S. Pat. No. 2.487.850, No. 2.51
No. 8.698, No. 2,521.925, No. 2.5
No. 21.926, No. 2,419°973, No. 2.
Reducing substances such as amines and tin salts described in US Pat. No. 694,637 and US Pat. No. 2.983.610, US Pat.
Examples include salts of noble metals such as platinum, palladium, iridium, and rhodium, which are described in No. 5, No. 2,566,263, and the like.

Sulfur sensitization using the compound of the present invention is performed using a silver halide solvent such as thiocyanate (ammonium thiocyanate, etc.).
Alternatively, the reaction may be carried out in the presence of a tetrasubstituted thiourea (tetramethylurea, etc.).

In the present invention, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used in combination. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. No. 2,518.698, No. 2,983.609, 2,
No. 983.610 and No. 2,694.637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used.
No. 083, No. 2.448.060, British Patent No. 618.
It is described in No. 061, etc.

In the photographic emulsion of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide.

The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the ridge length in the case of cubic grains, expressed as an average based on the projected area) is not particularly restricted. is preferably 3μ or less.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have a crystalline form (gular) or a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

The photographic emulsion of the present invention is P, Chi by Glafkides.
mie etPhysigue Photography
ique (published by Paul Monte1).

(1967), Photo by G.F. Duffin
graphic Emulsion Chemistry
(Published by The Focal Press, 1
966).

By V. L., Zelikman et al. Mak
ing and coatingPhotogra
Phic Emulsion (The Focal
Published by Press.

(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver decagenide emulsions formed separately may be used as a mixture.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobolane dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the basic basic ring nuclei commonly used for cyanine dyes can be applied to these dyes.

Namely, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei:
and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, Benzimidazole nuclei, quinoline nuclei, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl ring nucleus, etc. can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929,080;
U.S. Patent No. 2,231,658, U.S. Patent No. 2,493.748
No. 2,503゜776, No. 2,519.001, No. 2,912.329, No. 3,655゜394,
It is described in Japanese Patent No. 3,656,959, No. 3,672.897, No. 3,694°217, British Patent No. 1,242,588, and Japanese Patent Publication No. 14030/1983.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
, No. 688,545, No. 2,977.229, No. 3,
No. 397,060, No. 3,522.052, No. 3,5
No. 27,641, No. 3,617.293, No. 3,62
No. 8.964, No. 3,666.480, No. 3,679
, No. 428, No. 3,703,377, No. 3,769.
No. 301, No. 3,814,609, No. 3,837,8
No. 62, British Patent No. 1,344゜281, Special Publication No. 1973-
It is described in No. 4936, etc.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing standard ring groups (e.g., U.S. Pat. Nos. 2.933.390 and 3,63
5,721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like.

U.S. Patent No. 3,615.613, U.S. Patent No. 3,615.641
Particularly useful are the combinations described in No. 3,617.295 and No. 3,635.721.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-olins, quaternary ammonium salt compounds, and urethane. It may also include derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent Nos. 2,400.532 and 2,423.
, No. 549, No. 2,716,062, No. 3,617.
No. 280, No. 3,772.021, No. 3,808.0
03, etc. can be used.

The silver halide emulsion of the present invention contains an antifoggant (An-ti).
It may contain a foggant or a stabilizer.

As a compound, rAntifoggant of Protect Licensing Index, Vol. 92, P107
Those described in the section s and stabilizers J can be used.

The silver halide emulsion may contain a developing agent. As a developing agent, Product Licensing Index, Volume 92, P107-108 r Developinga
Those described in the section of GELLLTSJ can be used.

Silver halide can be dispersed in colloids that can be hardened by various organic or inorganic hardeners.

As a hardening agent, Product Licensing Index, Volume 92, P108 r Hardeners J
The one described in the section shall be used.

Silver halide emulsions may contain coating aids. As the coating aid, those described in the section of rcoating aids J in Product Licensing Index, Vol. 92, P108 can be used.

The silver halide emulsions of the invention can contain so-called color couplers. As a color coupler, Product Licensing Index, Volume 92 PI
Those described in Section 10 of Rcolor Materials J can be used.

The photographic material produced according to the present invention may contain a dye in the photographic emulsion layer or other hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include rAb in Product Licensing Index, Vol. 92, P109.
The sorbing and filter dyes described in the section ``Sorbing and filter dies'' are used.

Silver halide photographic emulsions may also contain antistatic agents, plasticizers, matting agents, lubricants, ultraviolet absorbers, optical brighteners, air anticapriants, and the like.

The silver halide emulsion used in the present invention has a vehicle as described in Product Licensing Index, Vol. 92, P.
10g r Vehicles section J (1971
(December 2013).

The silver halide emulsion is coated on a support along with other photographic layers if necessary. The application method is rcoati in Product Licensing Index, Volume 92, P109.
The methods described in OG procedures J can be used. The support is from Protect Licensing Index, Vol. 92, P108 (r 5ul)-
Those described in the section of portsJ can be used.

The silver halide photographic emulsion of the present invention is used for various purposes. For example, it is used for the following purposes.

Emulsions for color positives, emulsions for color paper, emulsions for color negatives, emulsions for color reversal (which may or may not contain couplers), emulsions for photosensitive materials for plate making (e.g. lithium film, etc.), and emulsions for cathode ray tube displays. Emulsions used in light-sensitive materials, emulsions used in light-sensitive materials for X-ray recording (especially materials for direct and indirect photography using screens), colloid transfer process (Col)
(e.g., as described in U.S. Pat. No. 2,716,059)
The emulsion used in the silver salt diffusion transfer process (Silve
r 5alt diffusion transfer
process) (e.g., U.S. Pat. No. 2,352
．． No. 014, No. 2,543.181, No. 3,020,
Emulsions used in color diffusion transfer processes (described in U.S. Pat. No. 3,087.817, U.S. Pat. No. 3,185.567, U.S. Pat.
, No. 983,606, No. 3,253.915, No. 3,
227゜550, 3,227.551, 3,2
27.552, 3,415゜644, 3,41
No. 5,645, No. 3,415.646, Research Disclosure Vol. 151 No. 15162, P75-8
7 (described in November 1976, etc.), the dye transfer process (imbibi
tion transfer process) (described in U.S. Pat. No. 2,882,156, etc.), silver dye bleaching method [Friedman's “Hi
Story of Co1or Photography
y″American Photographic P
publishers Co, 1944, especially Chapter 24)
and “Br1tish Journal of Photo
ogra-phy"Vo1.111, P2O3-309
Apr. 7.1964] and direct positive light-sensitive materials (e.g., U.S. Pat.
No. 7,875, No. 2,588.982, No. 3,367
．． No. 778, No. 3,501.306, No. 3,501.
No. 305, No. 3,672.900, No. 3,477.8
No. 52, No. 2,717.833, No. 3,023.10
No. 2, No. 3,050,395, No. 3,501゜307
Emulsions used in photosensitive materials for heat development (for example, U.S. Pat. No. 3,152,904, U.S. Pat. No. 3,
No. 312.550, No. 3,148.122, British Patent No. 1,110°046), emulsions used in physical development photosensitive materials (for example, British Patent No. 920,
No. 277, No. 1,131,238, etc.).

The emulsion of the present invention is particularly suitable for internal color in a multilayer structure, especially for reversal color and negative color, emulsion for black and white negative (black and white high-sensitivity negative, micro negative, etc.), emulsion for color diffusion transfer process, It is advantageously used as an emulsion for direct positive light-sensitive materials, and also as a core/shell internal latent image emulsion.

Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of a variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, etc. The exposure time is not only the 1/1000 second to 1 second exposure time normally used in cameras, but also the exposure time shorter than 1/1000 second,
For example, 1/10' using a xenon flash lamp or cathode ray tube.
Exposures longer than ~1/10' seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, σ-rays, or the like.

Any known method can be used for photographic processing of the light-sensitive material produced using the present invention.

For example, the photo processing described in Product Licensing Index, Volume 92, PIIO, Processing J may be used.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 The compounds shown in Table 1 were added to a silver iodide gelatin emulsion (average grain size 1.0 μm) containing 3 mol % of silver iodide, and the emulsion was heat-ripened at 60° C. for 60 minutes. Next, 4-hydroxy-6-methyl-1,3,
3a,7-titrazaindene (6,7X 10-' mol 1 mol Ag Thereafter, samples No. 1 to No. 21 were prepared by coating on a cellulose acetate film base (silver density: 5 g/+'') and drying.

Compound (A) c,H,0 HsC< CI CH20CCH5OsNaHs
C+ CHCH2OCCHz C2H,0 Compound CB) Compound (C) These samples were exposed to light (1/100 second exposure) through a wedge, and developed at 20° C. for 5 minutes using the following black and white developer.

[Black and white developer composition]

Add water 1. After turning off, use KOH to pH 1.
Adjusted to 0.0.

Thereafter, it was fixed, washed with water, and dried according to a conventional method, and its photographic properties were measured. The results are shown in Table 1.

The sensitivity is expressed as the reciprocal of the exposure amount required to obtain an optical density of fog+0.1, and is expressed as a relative value ratio with the sensitivity of sample No. 1 set as 100.

* comparative compound NalSxOs'5H30 5-c-NH.

(Unexamined Japanese Patent Publication No. 1-227.140) From Table 1, the samples using the compounds of the present invention have lower fog than the samples using comparative compounds (1), (2), (3), and (4). It can be seen that high sensitivity has been achieved.

Example 2 A silver iodobromide gelatin emulsion (average grain size 0.8 μ■) containing 6 mol % of silver iodide was added with the compounds shown in Table 2 and 6 mg of potassium chloroaurate per 1 mol of silver halide. The mixture was then heated and aged at 50°C for 70 minutes. Further, during ripening, the following green-sensitive sensitizing dye (a) was added to each emulsion in an amount of 3.8 x 10-' mol per mol of silver halide, and color sensitization was carried out in accordance with a conventional method.

Green-sensitive sensitizing dye (a) The emulsion subjected to the above chemical sensitization and color sensitization contains 4-hydroxy-6-methyl-1,3,3m,7 as a stabilizer.
-Titrazaindene (7X 10-''mol 1 mole silver halide) was added.

To 1.8 g of the emulsion thus obtained, 1.9 g of gelatin was added.
g and the following magenta coupler [D] 00.20g
A dispersion of 0.06 g of ditanyalinonylphenol in which 0.05 g of colored magenta coupler [E] was dissolved, and the above compound [A] as a surfactant and the above compound [B] as a hardening agent were added and applied.・Dried sample N
o, 22 to No. 38 were produced.

In the above, the amount added is 1■ unless otherwise specified.
: The amount added per unit, and silver halide is expressed in terms of silver.

Some of the samples were stored at a temperature of 50°C and relative humidity of 80% for 3 days, and some were stored under normal indoor conditions for 3 days, then exposed to green light using a wedge, and then processed as described below. The photographic performance was evaluated.

Processing steps: Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds water
Washing 3 minutes 15 seconds Fixation 6 minutes 3
Wash with water for 0 seconds 3
Stabilization for 1 minute and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

[Color developer 4-amino-3-methyl-N-(β-hydroxyethyl)-aniline sulfate 4.57g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate
37.5 g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to make 112.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 mff Add water to make 1 g, and adjust to pH 6 using ammonia water. Adjust to 0.

[Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium vLite 8.6g Sodium metasulfite 2.3g Add water to make 112, and adjust to pH 6.0 using acetic acid.

[Stabilizing liquid coformin (37% aqueous solution) 1.5 m
Q Konidax (manufactured by Konica Corporation) 7.5mR
Add water to make B.

Table 2 shows the measurement results of photographic performance. As in Example 1, the sensitivity is expressed as a relative sensitivity, with the sensitivity when sample No. 22 was stored for 3 days under indoor conditions as 100.

Magenta Coupler [DJ Cuffed Magenta Coupler [E] As is clear from Table 2, when the color-sensitized emulsion was evaluated using a color development system, the sample using the compound according to the present invention exhibited poor fog-sensitivity characteristics. It turns out that it is excellent. In addition, the sample was stored under conditions of a temperature of 50° C. and a relative humidity of 80%. From the results of the sample, it can be seen that it has excellent storage stability under high temperature and high humidity conditions.

〔Effect of the invention〕

The present invention provides that by incorporating a compound represented by the general formula CI) into a silver halide photographic emulsion, the resulting silver halide emulsion can increase photosensitivity without increasing fog, and Even when stored under high temperature and high humidity conditions, there was little increase in fog or decrease in photosensitivity.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material characterized by having a silver halide photographic emulsion layer containing a compound represented by the general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a heterocyclic group, X is an oxygen atom,
Represents a nitrogen atom or a sulfur atom. Z represents an atomic group necessary to form a 5- or 6-membered heterocycle, and A represents a protonic acid. n_1 represents an integer of 1, 2, or 3, and n_2 represents an integer of 0 or 1, 2, or 3. R_1 and R_2 can form a 5- or 6-membered ring. ]