JPH0711683B2 - Silver halide photographic emulsion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion using an organic thioether compound.

(Prior Art) It has long been known to use an organic thioether compound as a silver halide solvent, a chemical sensitizer, or the like in the production of a silver halide photographic emulsion.

For example, U.S. Patent Nos. 3271157, 3531289, and 3574628.
No. 4057429, the silver halide photographic emulsion (hereinafter simply referred to as "emulsion") is made uniform by the presence of an organic thioether compound during the precipitation step and physical ripening. A technique for producing a so-called monodisperse emulsion is disclosed.

Also, US Patent Nos. 2521926, 3021215, and 3038805.
No. 3506443, No. 3057724, No. 3062646, No. 35747
No. 09, No. 3622329, No. 3625697 and the like disclose a technique for increasing the photographic sensitivity of an emulsion by allowing an organic thioether compound to be present during chemical ripening during emulsion production or immediately before coating.

(Problems to be Solved by the Invention) However, when an organic thioether compound is present during emulsion production, fog tends to increase.

In order to prevent the fog caused by the organic thioether compound, for example, a technique of precipitating the organic thioether compound at a pH value of 4 or less and ultrapurifying the organic thioether compound are known, but the effect is insufficient, There are drawbacks such as not being practical on a physical scale.

Further, as described in JP-B-58-27489, it may be used in combination with a specific antifoggant, or JP-B-58-30
Although thioether compounds such as those described in No. 571 have been developed, it has been desired to develop a compound with less fog and high sensitivity.

Therefore, an object of the present invention is to provide an emulsion in which fog does not increase even when the photographic sensitivity is increased by using an ether compound in the production of the emulsion.

(Means for Solving Problems) The object of the present invention was achieved by a silver halide photographic emulsion using a compound represented by the following general formula (I).

General formula (I) (R ₁₎ mN _{[-J 1 -XJ 2 a (Y)} bJ 3 c (Z) d
w] n In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group. The alkyl group represents an aryl-substituted or unsubstituted alkyl group. X, Y and Z
Is sulfur atom, oxygen atom Represents Preferably, X, Y and Z are sulfur atoms. X, Y and Z may be the same or different. W
Is a substituted alkyl group having 1 to 10 carbon atoms, the substituent is -OR
₂ , -COOM, -SO ₃ M, And a heterocyclic group. Examples of heterocycles include pyridyl,
Examples thereof include imidazolyl, thiasolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyrrolidinyl, piperidyl, morpholinyl and the like. Preferably -OR
₂ , −COOM, A heterocyclic group can be mentioned.

J ₁ J ₂ and J ₃ are alkylene groups having 1 to 5 carbon atoms,
J ₁ , J ₂ and J ₃ may be the same or different.

a, b, c, d and m are 0 or 1. n is 2 or 3. However, m + n is 3. Where R ₅ , R ₆
And R ₇ are aryl-substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, which may be the same or different. Specifically, it is methyl, ethyl, n-propyl, benzyl or the like.

R ₂ , R ₃ , R ₄ and R ₈ are hydrogen atoms or have 1 to 10 carbon atoms.
Of alkyl groups, which may be the same or different. M represents a hydrogen atom, an alkali metal, or a quaternary ammonium. Q represents an anion. Further, the amino group or heterocyclic group of the compound of the present invention may form a salt. Examples of salts include hydrochloride, hydrobromide p-toluenesulfonate, oxalate and the like.

Specific examples of the compounds preferably used in the present invention are shown below. Of course, it is not limited to these.

3.N (CH ₂ CH ₂ SCH ₂ CH ₂ OH) ₃ 4.N (CH ₂ CH ₂ SCH ₂ CO ₂ Na) ₃ 5.N (CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ CO ₂ K) ₃ 6 .N (CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ SO ₂ Na) ₃ 8.N (CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH) ₃ 9.N (CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₃ CO ₃ K) ₃ 10.N (CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ K) ₃ 24.CH ₃ N (CH ₂ CH ₂ SCH ₂ CH ₂ OH) ₂ 25.C ₂ H ₅ N (CH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ H) ₂ 26.CH ₃ N (CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ H) ₂ As the method for synthesizing the compound used in the present invention, a general method can be used, and for example, the description in Journal of the Amelin Chemical Society, Vol. 73, pages 3635 to 3641 (1951), etc. It can be synthesized by referring to it.

A specific synthesis example will be described below.

Synthesis Example 1 Synthesis of Exemplified Compound (1) Tri (chloroethyl) amine hydrochloride 6.8 g under nitrogen atmosphere
38.2 g of sodium methylate (28% methanol solution) was added dropwise to a solution of dimethylaminoethanetool hydrochloride in ethanol (150 ml), and the mixture was heated under reflux for 3 hours.

The NaCl generated after cooling was removed by filtration, and the filtrate was concentrated under reduced pressure. 200 ml of acetone was added to the concentrate, 20 ml of hydrogen chloride (25% ethanol solution) was added, and the resulting crystals were collected by filtration and recrystallized from 1000 ml of methanol and 700 ml of ethyl acetate to obtain the exemplified compound (1) as a hydrochloride salt.

The yield was 13.3 g (82%) and the m.p. was 267 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound (5) 20 g of tri (chloroethyl) amine hydrochloride under nitrogen atmosphere
And β-mecaptopropionic acid 26.4g are dissolved in a mixed solvent of ethanol 100ml and water 50ml, sodium hydroxide 23.3g
Aqueous solution (100 ml) was gradually added. After heating under reflux for 3 hours, 21.4 ml of concentrated hydrochloric acid was added, and the reaction solution was concentrated under reduced pressure.
300 ml of methanol was added and heated, NaCl was removed by filtration, 14 g of potassium hydroxide in methanol solution (150 ml) was added to the filtrate, the mixture was concentrated, acetone (250 ml) was added, and the precipitated crystals were collected by filtration. ) Got.

The yield was 41.3 g (94%) and the m.p. was 247 ° C.

In the present invention, the organic thioether compound is added in at least one step selected from the steps of precipitation formation of silver halide grains, subsequent physical ripening, chemical ripening and immediately before coating during emulsion production. It is preferable. In particular, it is preferably added at the time of precipitation formation, physical ripening, or chemical ripening.

In the present invention, a silver halide grain can be formed by a general method well known in the art, but a double jet method is particularly preferable.

The double jet method is a silver halide aqueous solution and an aqueous solution of one or more halides (for example, an alkali metal halide such as erium bromide) simultaneously in two separate jets to form a protective colloid of silver halide (eg gelatin or gelatin). It is a method of adding a derivative) to a stirred solution.

In the present invention, in order to add the organic thioether compound during the precipitation of silver halide and / or during the physical ripening, it is preferable to add it to the solution of the protective colloid before starting the precipitation. It is also possible to add into the protective colloidal solution via a jet for adding the halide and / or a jet for adding silver nitrate, or via another jet.

The pH, pAg, temperature and other conditions during silver halide grain formation in the present invention are not particularly limited, but the pH value is from about 1 to about 1.
0, especially 2 to 8, is preferable, and pAg value is about 5 to about 11,
Particularly, it is preferable to keep it at 7.8 to 10.5.

The silver halide grains can be formed at a temperature of about 30 to about 90 ° C, preferably 35 ° C to 80 ° C.

Of course, pH, pAg and temperature may be changed during the formation of silver halide grains.

The amount of the organic thioether compound of the present invention added during the formation of silver halide grains is preferably 0.01 to 100 g, and particularly preferably 0.1 to 10 g per silver halide / mole.

Further, at the same time as the thioether compound of the present invention, the above-mentioned known thioether compound, ammonia, thiocyanate (for example, rodancali, etc.), and JP-B-58-5125.
2, JP-A-55-77737, U.S. Pat.No. 4,221,863, JP-B-60
It may be used in combination with the compounds described in -11341 and the like.

Further, when the organic thioether compound of the present invention is used before chemical ripening (for example, during silver halide grain formation), it is deactivated as a silver halide solvent by the method described in JP-A-60-136736. You can also let it.

In the present invention, as described above, the organic thioether compound may be added in the chemical aging step or the step immediately before coating.

In this case, the addition amount of the organic thioether compound of the present invention is 0.001 to 10 g, especially 0.01 to 2 g per mol of silver halide.
Is preferred.

Conditions of the chemical ripening step in the present invention, for example, pH, pAg,
The temperature, time, additives, etc. are not particularly limited, and the conditions generally used in the art can be used.

For example, the pH value is 3.0 to 8.5, particularly preferably 5.0 to 7.5, the pAg value is 7.0 to 9.5, particularly preferably 8.0 to 9.3, the temperature is 40 to 85 ° C, particularly 45 to 75 ° C, and the time is Is preferably 10 to 200 minutes, particularly preferably 30 to 120 minutes.

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

The particle size distribution may be narrow or wide.

The silver halide grains in photographic emulsions are cubic, octahedral, 14
It may have a regular crystal body such as a tetrahedron or an octahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape, or one of these crystal shapes. It may have a complex shape. It may consist of a mixture of particles of various crystal forms.

The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase.

Further, for example, a junction type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined,
Epitaxially grown silver halide crystals (for example, silver chloride, silver iodobromide, silver iodide, etc. are epitaxially grown on silver bromide) Hexagonal crystal form, regular hexahedral silver chloride is added to silver iodide. Crystals with overlapping orientations may be used. Further, tabular silver halide grains having an aspect ratio of 3 or more, preferably 5 to 20 can be used. More specifically, U.S. Pat.
No. 226, 4,439,520, European Patent 84,637A ₂ , JP Sho
No. 59-99433, Research Disclosure Volume 225 NO.2
2534 (January 1983).

The grain size distribution of silver halide grains in the photographic emulsion is arbitrary, but may be monodisperse. Here, monodisperse refers to a dispersion system in which 95% of particles fall within ± 60% of the number average particle size, preferably within 40%. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains.

In the present invention, the photographic emulsion is a P. Glaf
Kides) Chimie et Physique Photographique, published by Paul Montel (1967), GFDuffin, known as GFDuffin PhotographicEmulsion Chemistr
y), published by The Focal Press (1966), by Werz Erikmann et al. (VLZeli)
kman et al) Making and Coating P
hotographic Emulsion), The Focal Press (Th
e Fpcal Press) (1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
To keep constant, that is, so-called controlled
The double jet method can also be used.

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

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist. Further, the addition amount thereof may be a small amount or a large amount depending on the intended light-sensitive material.

In order to remove the soluble salts from the emulsion after formation of the precipitate or after physical ripening, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants and anionic polymers (for example, polystyrene) may be used. Sulfonic acid) or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used for the precipitation method (flosure method).

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Freezer (H.Friese)
r) "Die Grundlagen der Photographischen Prozesse (Die Grundlagen der Photographischen Prozesse
mit Silber-halogeniden) ”(Akademische Verlagsgesellschaft, 1968), pages 675-734.

That is, a compound containing sulfur capable of reacting with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method, the reduction sensitization method using a reducing substance, the noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rotanins and other compounds can be used.

Examples of the reduction sensitizer that can be used include primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, and silane compounds. For the sensitization of precious metals, platinum, iridium, palladium, etc. in addition to gold complex salts are used.
Group metal complex salts can be used.

In particular, a sensitization method using a noble metal such as a gold compound and a sensitization method using a sulfur compound can be preferably used.

Further, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its ether, astel, derivative such as amine, thioether compound, thiomorpholine, tetragonal ammonium salt compound,
Urethane derivative, urea derivative, imidazole derivative, 3
-Pyrazolidones may be included. For example, U.S. Patents 2,400,532, 2,423,549, 2,716,062 and 3,6
Those described in No. 17,280, No. 3,772,021 and No. 3,808,003 can be used.

Further, various compounds can be incorporated for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, crossbenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; for example, oxazoline thione Such thioketo compounds; azaindenes, for example, triazaindenes; tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes), pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers, such as benzenesulphonic acid, benzenesulphonic acid amide, benzenethiosulphonic acid, etc. can be added.

As the binder or protective colloid used for the light-sensitive material,
Although it is advantageous to use gelatin, hydrophilic synthetic polymers and the like can also be used. As the gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin and the like can be used.

Further, in the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , High contrast, sensitization), and various known surfactants may be included.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and the like. The dye used is a cyanine dye,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. It is a particularly useful dye, a merocyanine dye, and a composite merocyanine dye. Any of the nuclei normally used for cyanine dyes as a chlorinated heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

The photographic emulsions of the present invention may contain color image-forming couplers, ie compounds which react with the oxidation products of aromatic amine (usually primary amine) developing agents to form dyes (hereinafter abbreviated as couplers). The coupler is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. The coupler may be such that the product of the coupling reaction is colorless.

As the yellow color coupler, a known open chain ketomethylene type coupler can be used. Of these, benzoylacetanilide compounds and bivaloylacetanilide compounds are advantageous.

As the magenta coupler, a pyrazolone compound, an indazolone compound, a cyanoacetyl compound or the like can be used, and the pyrazolone compound is particularly advantageous.

As the cyan coupler, a phenol compound, a naphthol compound or the like can be used.

In addition to the DIR coupler, a compound which releases a development inhibitor upon development may be contained in the light-sensitive material. For example, U.S. Pat. Nos. 3,297,445, 3,379,529 and West German patent application (OL
S) Those described in No. 2,417,914 can be used.

Two or more of the above couplers can be contained in the same layer.
The same compound may be contained in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used.

The emulsion of the present invention is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure Volume 176, N
O.19643 (December 1978) and Vol. 187, NO.18716 (19
(November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in combination with the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

The silver halide emulsion of the present invention is a black-and-white silver halide photographic light-sensitive material (for example, X-ray sensitive material, squirrel-sensitive material, black-and-white photographic negative film, etc.) and a color photographic light-sensitive material (for example, color negative film, color reversal film). , Color paper, etc.). Further, a photosensitive material for diffusion transfer (for example, a color diffusion transfer element, a silver salt diffusion transfer element), a photothermographic material (black and white, color) and the like can be used.

The photographic emulsion of the present invention is applied to a rigid support such as a plastic film, a flexible support such as paper or a glass, which is usually used for a photographic light-sensitive material, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating. It is applied by a method or the like. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryta layer or an α-olefin polymer. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer).

Any known method can be used for photographic processing of a light-sensitive material produced by applying the present invention. A known treatment liquid can be used. The treatment temperature is usually chosen between 18 ° C and 50 ° C, but below 18 ° C or 50 ° C
The temperature may be higher than that. Depending on the purpose, either development processing for forming a silver image (black and white photographic processing) or color photographic processing including development processing for forming a dye image can be applied.

For more information, Research Disclosure Volume 176 NO.17
Development can be carried out according to the method described in pages 28 to 29 of 643, page 651, left column, right column, volume 187, NO.18716.

(Example) Hereinafter, the present application will be further described with reference to examples.

Example 1 While maintaining an aqueous solution containing gelatin and potassium bromide at 70 ° C. under vigorous stirring, an aqueous silver nitrate solution and a mixed aqueous solution of potassium bromide and potassium iodide were simultaneously added to give an aqueous solution of about 2 mol%. Average grain size including silver iodide is about 0.8
A monodisperse octahedral silver iodobromide emulsion of μ was prepared.

After removing unnecessary salts by flocculation method, this emulsion was divided into 9 parts by adjusting pH to 6.3 and pAg to 8.4, and sodium thiosulfate (addition amount 2 mg / mol AgX) was added to each and the results are shown in Table 1. The compound was added and chemically aged at 60 ° C. so as to show optimum sensitivity at 1/100 second exposure.

The following stabilizers, hardeners and coating aids were added to the emulsion thus obtained, together with the surface protective layer, by the simultaneous extrusion method,
Samples 1-9 were obtained by coating on a cellulose triacetate film support and drying.

Stabilizer; 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Hardener; 2,4-Dichloro-6-hydroxy-S-triazine sodium salt Coating aid; Sodium dodecylbenzene sulfonate The obtained sample was exposed through an optical wedge using a sensitometer (1/100 second and 10 second), and 35 ° C. with an RD-III developer for an automatic processor (manufactured by Fuji Photo Film Co., Ltd.). It was developed for 30 seconds, fixed, washed with water and dried by a conventional method, and the photographic sensitivity was measured.

The photographic sensitivity is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and the value at 100 / second exposure of Sample 1 was taken as 100.

As is clear from Table 1, the compounds of the present invention have higher arrival sensitivity than the comparative compounds, and the sensitivity is remarkably increased particularly after exposure for 10 seconds. That is, the reciprocity law failure of low illuminance in the photographic industry was remarkably improved.

Further, even when the compound ((3)) of the present invention is added at the time of grain formation of a silver iodobromide emulsion and then chemically ripened with sodium thiosulfate, the low illuminance reciprocity law failure is remarkably improved.
It has been found that the compounds of the present invention are also effective when used during grain formation. (Sample No. 10 in Table 1) At this time, the particle size was about 0.90 μm, and the particle growth promoting action was also clear.

Example 2 According to the double jet method, it has an internal high iodine type double structure with an average iodine content of 4 mol% and a core shell ratio of 1: 3, and has a plate-like shape with a sphere equivalent diameter of 0.7 μm and a diameter / thickness ratio of 5.0. A silver iodobromide emulsion composed of twinned grains was prepared, chloroauric acid, potassium thiocyanate and sodium thiosulfate were added, and the mixture was heated at 60 ° C. for 45 minutes for gold and sulfur sensitization.

The resulting emulsion was divided into 4 parts and a spectral sensitizing dye; anhydro-5-phenyl-5'-chloro-9-ethyl-3.3'- was used.
After adding di- (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt, the compounds shown in Table 2 were added. Further, the following additives were added, and coating and drying were performed together with the surface protective layer to obtain samples 11 to 14.

Additive Coupler: 1- (2,4,6-trichlorophenyl) -3-
[3- (2,4-di-t-amylphenoxy) -acetamido] benzamide-5-pyrazolone Antifoggant: 1- (m-sulfophenyl) -5-mercaptotetrazole mono Na salt Stabilizer: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Hardener: 2,4 -Dichloro-6-hydroxy-1,3,5-triazine sodium salt The sample is exposed under a light wedge through a yellow filter (1 /
After the color development processing described below, the photographic properties were measured and the results shown in Table 2 were obtained.

The sensitivities in Table 2 are the same as those of the first embodiment.
That of 100 was set as 100 and the other was expressed relatively.

1. Color development 2 minutes 45 seconds (38 ℃) 2. Bleaching 6 minutes 30 seconds 3. Washing water 3 minutes 15 seconds 4. Fixing 6 minutes 30 seconds 5. Washing water 3 minutes 15 seconds 6. Stability 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β hydroxyethylamino)-
2-Ethyl-aniline sulfate 4.5g Water added 1 Bleach Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt 130.0g Glacial acetic acid 14.0ml Water added 1 Fixer Tetra Sodium polyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 As is clear from Table 2, the compounds of the present invention can increase photographic sensitivity without increasing fog.

Claims (1)

[Claims] 1. A silver halide photographic emulsion comprising a compound represented by the following general formula (I). General formula (I) (R ₁₎ mN _{[-J 1 -XJ 2 a (Y)} bJ 3 c (Z) d
w] n (in the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, X, Y and Z are sulfur atoms,
Oxygen atom Represents X, Y and Z may be the same or different. W is a substituted alkyl group having 1 to 10 carbon atoms, the substituents _{-OR 2, -COOM, -SO 3 M} , And a heterocyclic group. J ₁ J ₂ and J ₃ have 1 to 5 carbon atoms
Is an alkylene group of, and J ₁ J ₂ and J ₃ may be the same or different. a, b, c, d and m are 0 or 1. n is 2 or 3. However, m + n is 3. Here, R ₅ , R ₆ and R ₇ are aryl-substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, and they may be the same or different.
R ₂ , R ₃ , R ₄ and R ₈ are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may be different from each other. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium. Q represents an anion. )