JPH0731383B2 - Silver halide photographic emulsion - Google Patents

Description

The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion containing a thioether pyridine 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 in 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, or superpurifying the organic thioether compound is known, but the effect is insufficient, There are drawbacks such as the practical scale is not practical.

Further, as described in JP-B-58-27489, it may be used in combination with a specific antifoggant, or JP-B-58-30571.
Nos. 4,695,534 and U.S. Pat. No. 4,695,534 have been developed. However, it has been desired to develop a compound having less fog and high sensitivity.

Therefore, an object of the present invention is to provide a first novel thioether pyridine compound having an excellent silver halide crystal growth rate, and secondly to use the novel thioether pyridine compound in the production of an emulsion. An object of the present invention is to provide an emulsion in which fog does not increase even when the photographic speed is increased.

(Techniques for Solving Problems) The object of the present invention has been achieved by a silver halide photographic emulsion using a novel thioether compound represented by the following general formula [I].

General formula [I] In the formula, L ₁ , L ₂ , L ₃ and L ₄ are alkylene groups having 1 to 5 carbon atoms, and specific examples thereof include methylene group, dimethylene group, trimethylene group, tetramethylene group and methylethylene group. And X is (R ₁ represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.), and Y represents (Wherein R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 7, such as a methyl group, an ethyl group, a butyl group, a benzyl group, etc.), and are substituted with an alkyl group. R ₂ , R ₃ and R ₄ may be linked to form a heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring, imidazole ring, pyrazole ring, etc.).

m ₁ , m ₂ , m ₃ , l and n are 0 or 1, p is an integer of 1 to 5, preferably 2, and particularly 2,6 of the pyridine ring.
Those substituted at the position are preferred.

Z is an anion (eg, a halogen atom (eg, fluorine ion, chlorine ion, bromine ion, etc.)) various acids (sulfuric acid,
Acid radicals of organic or inorganic acids such as nitric acid, phosphoric acid, p-toluenesulfonic acid, acetic acid, etc. may be mentioned.

q is an integer that neutralizes the charge of the molecule.

Specific examples of the thioether-based pyridine compound preferably used in the present invention are shown below. Of course, it is not limited to this.

Next, the method for synthesizing the thioether-based pyridine compound used in the present invention is not particularly limited, and a very general method can be used. For example, British Patent No. 950,089, U.S. Patent No. 3,021,215, and Japanese Patent Laid-Open No. 62- 14,646, U.S. Pat.No. 4,695,53
It can be synthesized by using the method described in No. 4 or the like. Among them, it is general to synthesize a thioether compound by reacting a thiol compound with a halogen compound.

Specific synthetic examples will be described below, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplified Compound 2 2-chloromethylpyridine hydrochloride 12.3 g (0.075 mol) and 2-dimethylaminoethylthiol hydrochloride 10.6 g (0.075
Mol) in 100 ml of methanol and under a nitrogen atmosphere, 28%
After adding 52.5 ml (0.26 mol) of sodium methylate, the mixture was reacted at room temperature for 3 hours. The reaction solution was filtered, the filtrate was evaporated under reduced pressure to remove the solvent, the remaining concentrate was dissolved in ethyl acetate, and the ethyl acetate-dissolved portion was again evaporated under reduced pressure. To 13.3 g of this concentrate, 12.2 g (0.136 mol) of oxalic acid dissolved in 100 ml of acetone was added, and the precipitated crystals were separated by filtration. Recrystallized from acetone and exemplified compound (2) 11.8g
Obtained. The melting point was 87-88 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound 3 25 g (0.18 mol) of 2,6-dihydroxymethylpyridine was dissolved in 200 ml of chloroform and thionyl chloride was added in an amount of 31.5 ml under cooling with water.
(0.43 mol) was slowly added dropwise. The precipitated crystals were filtered to obtain 31.3 g of 2,6-dichloromethylpyridine hydrochloride. Next, 8.8 g of this 2,6-dichloromethylpyridine hydrochloride (0.0
5 mol) and 2-dimethylaminoethylthiol hydrochloride 14.
2 g (0.1 mol) was dissolved in 100 ml of methanol, 60 ml (0.3 mol) of 28% sodium methylate was added under a nitrogen atmosphere, and the mixture was heated to 60 ° C. with stirring for 3 hours. After the reaction solution was filtered, the filtrate was evaporated under reduced pressure to remove the solvent, the remaining concentrate was dissolved in ethyl acetate, and the ethyl acetate-dissolved portion was again evaporated under reduced pressure. 100m methanol to this concentrate
14.8 g (0.86 mol) of p-toluenesulfonic acid dissolved in 1
The precipitated crystals were filtered off. 22.7 g of the exemplified compound recrystallized from methanol was obtained. The melting point was 165-166 ° C.

In the present invention, the thioether-based pyridine 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 just 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, the method for forming silver halide grains may be a general method well known in the art, but the double jet method is particularly preferable.

The double jet method is a silver halide protective colloid (eg gelatin or gelatin) prepared by simultaneously treating an aqueous solution of silver nitrate and an aqueous solution of one or more halides (eg, an alkali metal halide such as potassium bromide) with two separate jets. It is a method of adding a derivative) to a stirring solution.

In the present invention, in order to add the thioether pyridine 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, but during the precipitation, Into the protective colloid solution,
It can also be added via a jet for adding the halide and / or a jet for adding silver nitrate, or via another jet.

The conditions such as pH, pAg, and temperature at the time of silver halide grain formation in the present invention are not particularly limited, but the pH value is about 1 to about.
10, especially 2 to 8 is preferable, and pAg value is about 5 to about 1.
It is preferable to keep it at 1, especially 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, the pH, pAg and temperature may be changed during the formation of silver halide grains.

The amount of the thioether-based pyridine compound of the present invention added during the formation of silver halide grains is 1
The amount is preferably 0.01 to 100 g and particularly preferably 0.1 to 10 g per mol.

Further, at the same time as the thioether-based pyridine compound of the present invention, the above-mentioned known thioether compound, ammonia, thiocyanate (for example, rodancali, etc.), and JP-B-58.
-51252, JP-A-55-77737, U.S. Pat. No. 4,221,863, and JP-B-60-11341 may be used in combination.

When the thioether-based pyridine compound of the present invention is used before chemical ripening (for example, during formation of silver halide grains), it loses its function as a silver halide solvent by the method described in JP-A-60-136736. It can also be activated.

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

In this case, the addition amount of the thioether-based pyridine compound of the present invention is 0.001 to 10 g per mol of silver halide,
0.01 to 2 g is preferable.

Conditions for the chemical ripening step in the present invention, such as 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
Those with regular (regular) crystals such as tetrahedrons and rhombic dodecahedrons, and those with irregular (irregular) crystal forms such as spheres and plates, or those of these crystal forms 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, silver iodide and tetragonal silver chloride. A crystal in which the orientations are overlapped 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, it is described in U.S. Pat. Nos. 4,434,226, 4,439,520, European Patent 84,637A ₂ , JP-A-59-99433, Research Disclosure Vol. 225, No. 22534 (January 1983) and the like.

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 pea. Graf Kiddes (P.Glaf
Kides) Shimmy Physique Photographic (C
himie et Physique Photographique, published by Paul Montel in 1967, by GFDuffin Photographic Emulsion Chemistr
y), published by The Focal Press (1966), by Wiel Zelikmann et al. (VLZeli)
kman et al) Making and Coating Photographic Emulsion (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. Alternatively, a precipitation method (flocculation method) using a sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used.

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

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

Examples of the reduction sensitizer that can be used include primary tin salts, amines, hydrazine derivatives, formamidinesulfinic 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.

In order to increase sensitivity, increase contrast, or accelerate development, for example, polyalkylene oxide or its ether, ester, derivative such as amine, thioether compound, thiomorpholine, quaternary ammonium salt compound,
Urethane derivative, urea derivative, imidazole derivative, 3
-Pyrazolidones may be included. For example, US Patent 2,
400,532, 2,423,549, 2,716,062, 3,617,2
Those described in No. 80, No. 3,772,021, No. 3,808,003 and the like 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, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; for example, oxazoline thione Thioketo compounds such as; azaindenes such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes), pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers such as benzenesulfinic acid, benzenesulphonic acid amide, benzenethiosulphonic acid and the like 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 also 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 basic 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 Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, benzimidazole 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 emulsion of the present invention may contain a dye-forming coupler, that is, a compound (hereinafter abbreviated as coupler) which reacts with an oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. 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 baroylacetanilide 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. Patents 3,297,445, 3,379,529, 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 Vol. 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 comprises a black and white silver halide photographic light-sensitive material (for example, X-ray sensitive material, squirrel-sensitive material, negative film for black and white photography) and color photographic light-sensitive material (for example, color negative film, color reversal film) , Color paper, etc.). Further, it can be used as a light-sensitive material for diffusion transfer (for example, a color diffusion transfer element, a silver salt diffusion transfer element), a photothermographic material (black and white, color).

The photographic emulsion of the present invention is applied to a rigid support such as a plastic film, paper or other flexible support or glass generally used for photographic light-sensitive materials, dip coating method, roller coating method, curtain coating method, 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 baryter 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 Vol. 176, No. 17
The development processing can be carried out by the method described in pages 28 to 29 of 643 and page 651 of the same volume, No. 18716, left column, right column.

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

After removing unnecessary salts from this emulsion by flocculation method, the pH was adjusted to 6.3 pAg to 8.4 and divided into 8 parts, and sodium thiosulfate (addition amount 2 mg / mol AgX) was added to each of the compounds shown in Table 1. 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 and coated on a cellulose triacetate film support by the simultaneous extrusion method together with a surface protective layer and dried to obtain Samples 1 to 8.

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 seconds and 10 seconds), and the RD-III developer for an automatic processor (manufactured by Fuji Photo Film Co., Ltd.) at 35 ° C. 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 fogging value + 0.2, and 100 is the value when Sample 1 was exposed for 1/100 seconds.

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 forming grains of a silver iodobromide emulsion and chemically ripened with only sodium thiosulfate, the low illuminance reciprocity law failure is remarkably improved, and the compound of the present invention is added to the grains. It was found to be effective even when used during formation. (Sample No. 9 in Table 1) At this time, the particle size is about 0.
It was 90 μm, and the effect of promoting grain growth was also clear.

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

The obtained emulsion was divided into 5 parts, and a spectral sensitizing dye; anhydro-5-phenyl-5'-chloro-9-ethyl-3,3'-
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 10 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 sensitivity in Table 2 is the same as in Example 1 for the sample 10
It was set to 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. Constant cleaning 6 minutes 30 seconds 5. Water washing 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-Methyl-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 containing a compound represented by the following general formula [I]. General formula [I] In the formula, L ₁ , L ₂ , L ₃ and L ₄ are alkylene groups having 1 to 5 carbon atoms, and X is —S—, —O—, — (R ₁ represents a hydrogen atom or a lower alkyl group)
Y is (R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl group), and R ₂ , R ₃ and R ₄ may combine to form a heterocycle. _{m 1, m 2, m 3} , l and n is 0 or 1 p is an integer from 1 to 5 Z represents an anion, q is an integer to align the charged molecule neutral.