JPH0432833A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To form the above emulsion having the sufficiently high spectral absorption max. at about 600nm by incorporating a specific sensitizing dye. CONSTITUTION:The compd. expressed by formula I is used for the silver halide photographic emulsion. In the formula I, Z denotes a hydrogen atom, methyl group or ethyl group; R to R2 denote an alkyl group; W denotes a hydrogen atom, alkyl group, halogen atom, etc.; W1 denotes a hydrogen atom, alkyl group, halogen atom, cyano group, etc.; X denotes a paired ion enough to neutralize the charge of the molecule; (n) denotes 0 or 1. The substituents expressed by W, W1 may be incorporated with >=2 pieces into the same molecule. The silver halide emulsion contg. the novel sensitizing dye which applies the sufficiently high spectral absorption max. at about 600nm is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic emulsion and a noanine dye. In particular, the present invention relates to a silver halide emulsion containing an isoxadurohenzimidadurocarbocyanine having a phenyl group at the 5-position and the above-mentioned n-anine dye.

(Prior art) Spectral sensitization technology in silver halide photography is known as a means of expanding the sensitive wavelength range of silver halide photographic emulsions from the inherent sensitivity range of silver halide to the longer wavelength side, and is an important technique. It has become a technology.

The sensitive wavelength range has been adjusted to the infrared range by selecting the structure of the sensitizing dye according to the required purpose.

However, very few silver halide photographic emulsions having a sufficiently high spectral absorption maximum around 600 nm have been found so far. Further, cyanine dyes are widely used as photographic sensitizing dyes, and among cyanine dyes, dyes having an isoxazole nucleus are described in US Patent No. 3.
No. 071 467, etc.

However, up to now, no isoxadurobenzimidaduroponeanine having a phenyl group at the 5-position has been disclosed.

(Problems to be Solved by the Invention) That is, the first objective of the present invention is to provide a novel sensitizing dye that provides a sufficiently high spectral absorption maximum around 600 nm, and the second objective is to An object of the present invention is to provide a silver halide photographic emulsion containing a sensitive dye.

(Means for solving the problem) As a result of intensive research efforts to achieve these objectives, the present researchers have discovered that a compound represented by the following general formula [I] can be used in a silver halide photographic emulsion. The inventors have discovered that the above object can be achieved, and have completed the present invention.

RR, (X).

(In the formula, Z represents a hydrogen atom, a methyl group, or an ethyl group. R, R, and R2 represent an alkyl group.

W is a hydrogen atom, an alkyl group, a halogen atom, a cyano group,
Represents an alkoxy group, an amide group, or an alkoxycarbonyl group. Two or more substituents represented by W may be contained in the same molecule, and Wl is a hydrogen atom, an alkyl group, a halogen atom, sia/i, an alkoxy group, an amide group, an alkoxycarbonyl group, a carboxyl group, a hydroxy group. ,
Or represents an aryl group. Two or more substituents represented by Wl may be contained in the same molecule. X represents a counterion sufficient to neutralize the charge of the molecule. n is 0 or 1, and is O when forming an inner salt. ) To explain in more detail, Z is a hydrogen atom, a methyl group, or an ethyl group, preferably a hydrogen atom.

The alkyl groups represented by R and R may be substituted, and examples thereof include alkyl groups having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms (unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups such as aralkyl groups (e.g. hensyl, 2-phenylethyl, etc.), hydroxyalkyl groups (e.g. 2-hydroxyethyl) , 3-hydroxypropyl, etc.), carboxyalkyl groups (e.g., 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl, etc.), alkoxyalkyl groups (e.g., 2-methoxyethyl, 2(2- methoxyethoxy)ethyl, etc.),
Sulfoalkyl! (For example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl,
1(3-sulfopropoxy)ethyl, 2-hydroxy-
3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.), sulfatoalkyl groups (e.g., 3-sulfatopropyl, 4-sulfatobutyl, etc.), heterocyclic-substituted alkyl groups (e.g., 2-(pyrrolidin-2-one-
(1yl) ethyl, tetrahydrofurfuryl, etc.), 2-
acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl) or an allyl group.

Either R or R is preferably a sulfoalkyl group or a carboxyalkyl group.

The alkyl group represented by R2 may be substituted,
Examples thereof include 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms.
, particularly preferably 1 to 4 alkyl groups (unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups, such as aralkyl groups (e.g., benzyl) , 2-phenylethyl, etc.),
Hydroxyalkyl groups (e.g., 2-hydroxyethyl, 3-hydroxypropyl, etc.), heterocyclic-substituted alkyl groups (e.g., 2-(pyrrolidin-2-one-1-yl))
ethyl, tetrahydrofurfuryl, etc.), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl) or an allyl group, preferably a methyl group or an ethyl group.

W is a hydrogen atom, an alkyl group (having 1 to 8 carbon atoms, e.g. methyl group, ethyl group, propyl group, butyl group, etc.), a halogen atom (e.g. chlorine atom, bromine atom, etc.), a cyano group, an alkoxy group ( 1 to 8 carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, etc.), amide group (2 to 8 carbon atoms)
8. W represents an acetamide group, propionamide group, benzamide group, etc.) or an alkoxycarbonyl group (carbon number 2 to 8, e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), W is 2 or more in the same molecule. May be included.

Wl is a hydrogen atom, an alkyl group (carbon number 1 to 8, e.g. methyl group, ethyl group, propyl group, butyl group, etc.), a halogen atom (e.g. chlorine atom, bromine atom, etc.), a cyano group, an alkoxy group (carbon number 1 to 8, such as methoxy group, ethoxy group, propoxy group, etc.), amide group (carbon number 2 to
8, for example, acetamido group, propionamide group, benzamide group, etc.), alkoxycarbonyl group (carbon number 2
-8, for example, a metquine carbonyl group, a hydroxyl group, a carboxyl group, a hydroxyl group, or an aryl group (e.g., a phenyl group, a tolyl group).

Two or more Wl's may be contained in the same molecule, and are preferably a trifluoromethyl group, a chlorine atom, an alkoxycarbonyl group, or a cyano group.

X9 represents a counterion sufficient to neutralize the charge of the molecule,
Examples of cations include hydrogen ions, sodium ions, potassium ions, triethylammonium ions,
and pyridinium ions, and examples of anions include chloride, bromide, iosito, p-)luenesulfonate, p-nitrobenzenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate, 1 .5-naphthalenedisulfonate and the like.

n is 1 or O, and when forming an inner salt, n=
It is 0.

Specific examples of the sensitizing dye represented by the general formula [I] used in the present invention are shown in Table 1 below, but the present invention is not limited thereto.

-C The compound shown in formula [1] is F, M, Hamer (F,
M. Haser), Heterocyclic Compounds, Cyanine Soybean and Related Compounds.
dsCyanine Dyes and Relate
d Compounds)'' Chapter 4, Chapter 5, Chapter 6, pp. 86-119, published by John Wiley & Sons (1964), D. M. Starmer (D. ,?I.

Heterocyclic Comp Bounds Special Topics in Heterocyclic Chemistry
oundsSpecial Topics in ) I
eterocyclic Chei+1stry)”,
It can be synthesized based on the method described in Chapter 8, pp. 482-515, published by John Wiley and Sons (1977).

Next, synthesis examples of representative compounds among the compounds represented by general 2N) will be described.

Compound (a) 4. in DMF50aff. 6 g (1
0 m +noffi) and acetic anhydride 1.4 d (15
s won) was added thereto, and the mixture was heated and stirred for 10 minutes while maintaining the reaction temperature at 100°C. Next, compound (b) 3.2(1
0 moj2) and triethylamine 4 m (29 m
mol2) was added, and the mixture was heated and stirred for an additional 30 minutes while maintaining the reaction temperature at 100°C. After the reaction was completed, the reaction solution was cooled to room temperature, 500 d of ethyl acetate was added, and the resulting crude crystals were filtered and subjected to silica gel column chromatography (eluent chloroform/methanol = 9°510.
5) and Sephadex column chromatography (
Purification was performed using methanol (eluent).

Yield 2.4 g (yield 43%) λ": 2 g' = 506 nm Melting point 95 °C (decomposition) 3.8 g (10 mol 1 on) of compound (c) and 1.4 d (15 m 5 o) of acetic anhydride in 1 d of DMFSC
f) and heated for 10 minutes while maintaining the reaction temperature at 100”C.
The mixture was heated and stirred for a minute. Next, compound (d) 4.2 (10 mog-
of) and triethylamine 4d (29m mol
) was added thereto, and the mixture was further heated and stirred for 30 minutes while maintaining the reaction temperature at 100°C. After the reaction was completed, the reaction solution was cooled to room temperature, 500 d of ethyl acetate was added, and the resulting crude crystals were filtered and subjected to silica gel column chromatography (eluent chloroform/methanol -9°510.5) and Sephadex column chromatography. (eluent: methanol).

Yield: 1.8 g (yield: 32%) λ':::'-506111 Melting point: 95°C (decomposition) The sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these are first dissolved in a suitable solvent such as evaporative methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. You can also do that. Ultrasonic waves can also be used for melting. In addition, the method of adding this sensitizing dye is as described in US Pat. A method of adding a dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion; Tokuko Showa 61-4521
As described in No. 7, a water-insoluble dye is placed in an aqueous solvent,
A method of mechanically crushing and dispersing and adding this dispersion to an emulsion; as described in U.S. Pat. No. 3,822,135, the dye is dissolved in a surfactant and the solution is added to the emulsion. Method: method described in JP-A No. 51-74624; method of dissolving using a compound that causes nodonof [.] and adding the solution into an emulsion; dye as described in JP-A-50-80826 A method may be used in which the compound is dissolved in a substantially water-free acid and the solution is added to the emulsion.

Other additions to emulsions include U.S. Patent No. 2.912343.
No. 3,342,605, No. 2996,28
No. 7, No. 3. Methods described in '429,835 and the like may also be used. The sensitizing dyes may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but can of course be dispersed at any stage of the preparation of the silver halide emulsion.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Silver halide preferred for photographic materials is silver iodobromide containing 15 mol % or less of silver iodide. Particularly preferred is 2 mol% to 12 mol%.
It is silver iodobromide containing silver iodide up to.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, and the edge length for cubic grains, expressed as the average calculated by the projected area) is Although not particularly limited, it is preferably 3μ or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particle.

The photographic emulsion used in the present invention includes P, Gelafuchides (P
, Glafkides), “Chimie et Phys Photographic”
iquePhotographique, etc., published by Paul Montel (1967)
, G.F. Duffin, “
Photographic ink emulsion chemistry (P
photographicEmulsion Chemi
stry)'', Focus J Press (Focal P
ress) Publishing (1966), V. L. Zelikman et al., “Making and Coating Photographic Emulsion”
It can be prepared using the method described in "Photographic Emulsion", published by Focal Press (1964), etc. In other words, any of the acid method, neutral method, ammonia method, etc. may be used, and soluble root salts and As a method for reacting the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. 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 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 halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be allowed to coexist. good.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H, Freezer (Hll:
rieser) &i, “Die Grundlagender Fotografischen Prozesse Mint Silverhalogennieden (Die Grundlag
enderPhotographjschen Pro
zesse sitSilberhalogenide
n)”, Akademische Verlagsgesgese+
1schaft) (1968) pp. 675-734
The method described on page can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as r5Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorohenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthion; azaindenes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, etc.; henzenethiosulfonic acid, henzenesulfinic acid, benzenesulfone Many compounds known as antifoggants or stabilizers can be added, such as acid amides and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, sheer properties, emulsification dispersion, adhesion prevention, and photographic property improvements (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-virapritones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glysodyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The photographic material of the present invention may contain sensitizing dyes other than those of the present invention.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, melonanine dyes, and complex melonanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxaprine nucleus, thiazole nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenadur nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a core with a ketomethylene structure, such as a birapurin-5-one core, a thiohydantoin core, and a 2-thioxazolidine-2 core.
, 4-dione nucleus, thiosilydine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used for the purpose of supersensitization.

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,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), aromatic organic formaldehyde condensates (such as those described in US Pat. No. 3,743.510), cadmium salts, azaindene compounds, and the like.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The silver halide emulsions of this invention may contain color couplers such as cyan couplers, magenta couplers, yellow couplers, and compounds that disperse the couplers.

That is, in color development processing, an aromatic primary amine developer (
For example, a compound that can develop color by oxidative coupling with a phenylenediamine derivative, an aminophenol derivative, etc.) may be used.

For example, magenta couplers include 5-viladurone couplers, pyrazolobenzimidazole couplers, cyanoacetyl coumaron couplers, open-chain asolacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g. hendiylacetanilides, pivaloylacetanilides). cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler is 4 for silver ions.
Either equivalence or 2-equivalence may be used. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the coupling reaction product is colorless and releases a development inhibitor.
It may also contain a coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. Of course you can.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) , active vinyl compound (1,3,5-triacryloyl-hexahydro-5-)riazine, 1.3-
vinylsulfonyl-2-propanol), active halogen compounds (2,4-dichloro-6-hydroxy-8-
triazines, etc.), mucohalogenates (mucochloric acid,
mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, aryl group-substituted Henztriazole compounds (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., as described in U.S. Pat. Nos. 3,314,794 and 3,352,681) ), hendphenone compounds (e.g. those described in JP-A No. 46-2784),
Cinnamate ester compounds (e.g. U.S. Pat. No. 3,705)
No. 805, No. 3,707,357), butadiene compounds (such as those described in U.S. Pat. No. 4,045,229), or hendioxidol compounds (such as those described in U.S. Pat.
For example, those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based Noane dye-forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, soanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, P-oxophenol derivatives, and bisphenols.

For photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions as described, for example, in Research Disclosure No. 176, pages 28-30, can be applied. can do.

(Examples) Examples will be described below to more specifically explain the content of the present invention, but the present invention is not limited to these Examples.

Example-1 In a reaction vessel, 1000 d of water, 25 g of deionized bone gelatin, and 15 m of 50% NH,NO3 water solution! and 7.5 mf of a 25% NH3 aqueous solution were added, kept at 50 °C, stirred well, and 750 m of a lNA g N03 aqueous solution and an IN-KBr aqueous solution were added over 50 minutes to increase the silver potential during the reaction. was maintained at 150 mV with respect to the saturated Amagi electrode.

The silver bromide particles obtained were cubic, with a side length of 083±0.0.
It was 6 μm. Desalt the above emulsion, add 95 g of deionized bone gelatin and 430 mQ of water, and boil at 50°C.
After adjusting H = 6.5 and pAg = 83, add sodium thiosulfate to achieve optimal sensitivity and incubate at 55°C for 50 minutes.
I was left alone for 0 minutes. Emulsion 1 contained 0.76 mol of silver bromide per gram.

Collect 45g of each emulsion and add 1°4X of aggravating dye.
10-'mol/mol Ag, 1 potassium iodide
Add 1X 10-”mol/mol Ag, and then add 4-”
10 μl of hydroxy-6-methyl-1,3,3a,7-thitrazaindene, 15 g of 10% deionized gelatin gel, and 55 d of water were added and coated onto a polyethylene terephthalate film base as described below.

The amount of coating liquid is the amount of silver 2. 22g/rrf, gelatin amount 4
．． 3 g/rrr, and the upper layer contains 0.22 g/f of sodium dodecylbenzenesulfonate, 0.50 g/l of p-sulfostyrene sodium homopolymer, and 2.4 -Dichloro-6-hydroxy-135-triazine sodium3.
1g/1. , an aqueous solution containing 50 g/l of gelatin as a main component was simultaneously applied.

The magenta image density of the above samples was measured, and each relative sensitivity (the relative sensitivity of sample S-1 was characterized) was determined.The sensitivity was determined based on the exposure amount when the density increased by 0.2 from the fog density. .

Table 3 shows the maximum spectral absorption wavelength of the J-hand, and Table 4 shows the obtained sensitivity values.

Table 3 Compound Nα (Present invention) (Present invention) (Comparative example) From the results in Tables 3 and 4, the dye of the present invention is G.

It can be seen that the spectral absorption maximum is sufficiently high near Qnm.

(Effects of the Invention) As shown above, by using the sensitizing dye of the present invention, it was possible to provide a silver halide photographic emulsion having a sufficiently high spectral absorption maximum around 600 ns.

Claims (2)

[Claims] (1) A silver halide photographic emulsion characterized by containing a sensitizing dye represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, Z represents a hydrogen atom, methyl group, or ethyl group. R, R_1, and R_2 represent an alkyl group. W is a hydrogen atom, an alkyl group, or a halogen atom. , cyano group,
Represents an alkoxy group, an amide group, or an alkoxycarbonyl group. Two or more substituents represented by W may be contained in the same molecule. W^1 is a hydrogen atom, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an amide group, an alkoxycarbonyl group, a carboxyl group, a hydroxy group,
Or represents an aryl group. Two or more substituents represented by W^1 may be contained in the same molecule. X represents a counterion sufficient to neutralize the charge of the molecule. n is 0 or 1
It is. It is 0 when forming an inner salt. ) (2) A compound represented by the general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] In the formula, R and R_1 are C_2H_5, -(CH_2)_3
SO_3^-, (CH_2)_4SO_3^- is represented.