JP2002268172A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material without adversely affecting the photographic characteristics (sensitivity, fog, tone, etc.), of a photosensitive silver halide emulsion in processes for preparing and preserving the emulsion. SOLUTION: The silver halide photographic sensitive material is characterized by incorporating dehydroacetic acid or its salt, salicylic acid or its salt and sorbic acid or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having little fluctuation in performance during production and excellent stability.

[0002]

2. Description of the Related Art In general, a light-sensitive material is provided with at least one light-sensitive silver halide emulsion layer on a support and, if necessary, a photographic material such as an undercoat layer, an intermediate layer, an antihalation layer and a protective layer. It has a constituent layer. These photographic constituent layers include a silver halide in a hydrophilic binder, a stabilizer, an inhibitor, a filter dye,
It has various additives such as an antihalation dye, a matting agent, a surfactant, and a coupler. These additives are usually dissolved or dispersed in a water-soluble solvent (for example, a mixed solution of water and alcohol water) or dissolved in a high-boiling-point water-insoluble or poorly water-soluble solvent and dispersed as fine droplets. To be contained. One or more additive solutions or dispersions are stored and, when appropriate, uniformly mixed with the hydrophilic colloid solution or emulsion to produce a photographic aqueous composition for coating. As the hydrophilic colloid, gelatin useful as a photosensitive material is widely used because of its protective colloid strength, versatility, and productivity. Others, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-
Various kinds of synthetic water-soluble polymer materials such as homo- or copolymers such as N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and polyvinylimidazole are used.

[0003] The water-soluble polymer used for these hydrophilic colloids is easily affected by bacteria, yeasts, and molds, and is significantly affected by microorganisms in either a gel state or a sol state. For example, when a hydrophilic colloid is spoiled or decomposed by microorganisms, its ability as a protective colloid is reduced, and dispersed substances such as photosensitive silver halide emulsion particles and matting agent particles are aggregated and precipitated, and the metabolism of microorganisms is reduced. The material may adversely affect the photograph (fluctuation in sensitivity, increase in fog, fluctuation in tone, etc.), and the viscosity of the coating liquid, which is a liquid state of the coating composition, may be reduced or colored. In the production process of a silver halide photographic light-sensitive material, considering the efficiency in mass production, it is essential for the production of a silver halide emulsion to have stability over time in a solution state of a finished emulsion. Furthermore, if the long-term storage stability in a gel state after the production of a silver halide emulsion is stable, the efficiency of mass production will further increase. During long-term storage of a silver halide emulsion in a solution state or in a gel state, the protective colloid is spoiled or decomposed by microorganisms to cause the above-mentioned change in properties. This can result in stability.

It is known that a preservative or an antifungal agent is contained in a light-sensitive material as a method for suppressing the propagation of microorganisms generated in the light-sensitive material.

In general, preservatives or fungicides for such purposes include, for example, phenol, thymol,
Trichlorophenol, tetrachlorophenol, pentachlorophenol, cresol, p-chloro-m-cresol, o-phenylphenol, benzylphenol, 2-benzyl-4-chlorophenol, chlorophen, dichlorophen, bromochlorophen, 2, 2'-
Aromatic hydroxy compounds such as dihydroxy-5,5'-dichlorodiphenyl monosulfide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 3,4,5-tribromosalicylanilide, 4-n-hexylresorcinol Or a salt thereof, or formaldehyde, paraformaldehyde, chloroacetaldehyde,
Compounds having a carbonyl group such as glutaraldehyde, chloroacetamide, methylol chloroacetamide, or benzoic acid, monobromoacetate, p-
Carboxylic acids or esters thereof such as hydroxybenzoic acid esters and p-oxybenzoic acid esters, or amines such as hexamethylenetetramine, alkylguanidine and nitromethylbenzylethylenediamine;
Disulfides such as tetramethylthiuram disulfide, 2-mercaptobenzthiazole, 2-methoxy-
Nitrogen-containing heterocyclic compounds such as carbonylaminobenzimidazole, or organic mercury compounds such as mercury phenylacetate, mercury phenylpropionate, and mercury phenyloleate; and antibiotics such as neomycin, kanamycin, polymycin, streptomycin, and furamycin are common. Is known as an antiseptic and a fungicide. In addition, Research Disuc
No.18751, No.20526, JP-A-54-27424, JP-A-58-166343, JP-A-59-226343, JP-A-59-226344. JP-A-60-263938, JP-A-61-107343, JP-A-62-231955, JP-A-58-105145, etc., each of the compounds described therein And the like.
Some of these are also known to be used for photography.

However, many of these may adversely affect photographic properties. If it is not added in a large amount, its effect will not be exhibited, it will be harmful to living organisms, it will be effective only for specific bacteria, or it will have a bactericidal effect due to interaction with other photographic additives. Often insufficient. For example, unless phenols are added in a large proportion of 2% or more of the hydrophilic colloid, a sufficient antifungal effect is not exhibited. When formaldehyde or the like is used, the photosensitive material is liable to fog.
Benzthiazoles tend to give a desensitizing effect to the photosensitive material. Mercury compounds are harmful to living organisms and their use must be avoided. As described above, none of the conventional preservatives and antifungal agents have practically satisfactory characteristics when incorporated into a silver halide photographic material as a preservative.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for manufacturing and storing a silver halide photographic material.
It is an object of the present invention to provide a storage method for protecting an aqueous photographic coating composition from microorganisms such as bacteria and mold without adversely affecting the photographic characteristics (sensitivity, fog, tone, etc.) of the photosensitive silver halide emulsion. A second object is to provide a preservative method which allows long term storage of the photosensitive silver halide emulsion.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, contain at least one compound selected from the following group. It has been found that the above objective is achieved in the material. A: Dehydroacetic acid or its salt B: Salicylic acid or its salt C: Sorbic acid or its salt

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The dehydroacetic acid or a salt thereof, salicylic acid or a salt thereof and sorbic acid or a salt thereof used in the present invention are not only simple substances but also salts such as sodium, potassium, lithium and ammonium salts. Is shown. These compounds are used in pharmaceuticals and food additives and are extremely safe. It can be easily obtained as a commercial product.

The dehydroacetic acid, salicylic acid and sorbic acid used in the present invention are generally known as fungicides and antibacterial agents. For example, Japanese Patent Application Laid-Open No. 10-265678 discloses a method for polymer materials. Although antibacterial properties are obtained by using dehydroacetic acid, there is no mention of the effect on photosensitive silver halide emulsions.

The disinfection and fungicide of the photosensitive silver halide emulsion are disclosed in JP-A-59-226643 and the like, but the photosensitive silver halide emulsion of dehydroacetic acid, salicylic acid and sorbic acid used in the present invention is used. No mention is made of the effect on

The conditions which must be provided as a bactericidal and antifungal agent for the photosensitive silver halide emulsion are (1) not to affect photographic characteristics (sensitivity, fog, tone, etc.); (2)
Does not interact with photographic additives, (3) Does not affect photographic processing performance (developability, desilvering, multicoloring, etc.), (4) Has a large amount of bactericidal and antifungal action even in a small amount. (5) No impact on the environment and ecosystem,
(6) It is desired that there is no effect on the human body. Dehydroacetic acid or a salt thereof, salicylic acid or a salt thereof and sorbic acid or a salt thereof used in the present invention satisfy all of these requirements.

The dehydroacetic acid or a salt thereof, salicylic acid or a salt thereof and sorbic acid or a salt thereof used in the present invention can be used not only in a photosensitive silver halide emulsion,
In addition, it can be added to a photographic constituent layer. The amount of addition is 1 × 10 ⁻⁷ to the hydrophilic colloid contained in the photosensitive silver halide emulsion and the photographic constituent layer.
Good 1% by weight in the range, further 5 × 10 ^-5 ~5 × 10 ^-1 wt% range are preferred. However, the above range may be increased or decreased depending on the type of the photosensitive silver halide emulsion and other photographic constituent layers and the storage condition.

The dehydroacetic acid or a salt thereof, salicylic acid or a salt thereof and sorbic acid or a salt thereof used in the present invention may be used alone, or two or three of these may be used in combination. Good.

The dehydroacetic acid or a salt thereof, salicylic acid or a salt thereof and sorbic acid or a salt thereof used in the present invention may be directly dispersed in a photographic component layer coating solution, or may be water or methanol, ethanol, isopropanol, acetone, In the presence of a surfactant after dissolving or emulsifying and dispersing in a solvent that does not adversely affect photographic performance and physical properties among organic solvents such as ethylene glycol, or dissolving in a high boiling solvent, a low boiling solvent or a mixed solvent of both May be added to the coating solution of the photographic constituent layer, or may be coated on the surface of a gelled photosensitive silver halide emulsion or other photographic constituent layer coating solution, and the gelled photosensitive halogen may be added. The silver halide emulsion and other photographic constituent layer coating solutions are mixed with a dehydroacetic acid solution or a salt thereof, a salicylic acid or a salt thereof and a solution thereof. Bottle acids or may be immersed in a solution or emulsified dispersion of a salt thereof. Dehydroacetic acid or a salt thereof, salicylic acid or a salt thereof and sorbic acid or a salt thereof used in the present invention may be added during or after the production of a photosensitive silver halide emulsion or other coating solution for a photographic component layer.

The silver halide in the silver halide emulsion used in the light-sensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention is not particularly limited, and may be silver chloride, silver chlorobromide, silver chloroiodobromide, or iodoodor. Silver halide, silver bromide, or the like can be used.

The emulsion grains of the silver halide emulsion used in the light-sensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention may have a uniform inner or surface layer or different layers. When it is composed of different layers, it may have either a core-shell structure or an epitaxial structure.

The grain size distribution of the emulsion grains of the silver halide emulsion used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention is not limited, and the morphology and crystal habit of the emulsion grains are not particularly limited.

The method for preparing the silver halide emulsion used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention may be any of known methods such as forward mixing, reverse mixing, and simultaneous mixing.

In the course of formation or physical ripening of silver halide emulsion grains used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention, cadmium salts, sulfites, lead salts,
A thallium salt, a ruthenium salt, an osmium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

The emulsion after the physical ripening is desirably subjected to desalting and washing to remove excess halide and the like and to further concentrate the silver halide emulsion. Although there are various methods for the desalting / washing step in the present invention, it is preferable to use a flocculation method. As the flocculation method, there are a sulfate method, an organic solvent method, an organic gelatin flocculant method, and a gelatin derivative method, and any of these methods can be used, or a combination thereof can be used.

The emulsion after physical ripening may be subjected to desalting and washing treatments, and then may be coated with necessary additives.

The silver halide emulsion used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention can be subjected to chemical sensitization. The chemical sensitization can be performed by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allyl isothiocyanate, cystine,
Rhodanin and U.S. Pat. Nos. 1,574,944;
278,947, 2,410,689, 2,4
Nos. 40,206, 3,187,458, 3,41
Sulfur-containing compounds as described in 5,649, 3,501,313 and the like can be used. Along with sulfur sensitization, U.S. Pat.
540,086, 2,556,245, 2,5
No. 66,263 can be used in combination with a sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium or ruthenium. Also,
A sensitization method using various gold compounds such as potassium chloroaurate and auric trichloride and a palladium compound such as palladium chloride can be used in combination.

Gelatin is advantageously used as a protective colloid that can be used in the photographic constituent layers such as the emulsion layer and the intermediate layer of the silver halide photographic light-sensitive material of the present invention, but other hydrophilic colloids may also be used. Can be used.
For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic water-soluble polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bul
Enzyme-treated gelatin as described in l. Soc. Sci. Phot. Japan, No. 16, P30 (1996), or a hydrolyzate or enzymatic degradation product of gelatin can also be used.

The silver halide emulsion used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention includes, for example, known stabilizers such as mercaptotetrazole, mercaptotriazole, benzotriazole, benzimidazole and azaindenes, and antifoggants. And various development accelerators such as polyalkylene oxides, thioether compounds and quaternary ammonium salt compounds.

The silver halide emulsion used in the photosensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention may be spectrally sensitized with a methine dye or the like. As the dye used, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxonol dye, and the like can be used. These dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. A specific example is U.S. Patent No. 2,688,54
No. 5, No. 2,977,229, No. 3,397,060, No. 3,522,0
No. 52, No. 3,527,641, No. 3,617,293, No. 3,628,
No. 964, No. 3,666,480, No. 3,672,898, No. 3,67
9,428, 3,703,377, 3,769,301, 3,8
No. 14,609, No. 4,026,707, British Patent 1,344,
No. 271, No. 1,507,803, JP-B-43-4936, No. 53-1237
No. 5, JP-A-52-110618 and JP-A-52-109925. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the light-sensitive silver halide emulsion layer and other photographic constituent layers. For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4
-Dichloro-6-hydroxy-S-triazine) or the like can be used alone or in combination.

The light-sensitive silver halide emulsion layer and other photographic constituent layers of the photographic light-sensitive material of the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic characteristics (eg, development acceleration, A surfactant may be contained for various purposes such as high contrast and sensitization. For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl) Nonionic surfactants, such as amines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agent, alkyl carboxylate, alkyl sulfate, alkyl benzene sulfone Carboxy group, sulfo group, phospho group, sulfate group, phosphoric acid such as salts, alkyl phosphates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants containing an acidic group such as an ester group, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, and aliphatic or aromatic quaternary ammonium salts. Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium and imidazolium can be used.

The light-sensitive silver halide emulsion layer and other photographic constituent layers of the photographic light-sensitive material of the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product for the purpose of improving dimensional stability and the like. . For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, α , Β-unsaturated dicarboxylic acids,
A polymer having a combination of hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Any support known to those skilled in the art can be used in the photographic light-sensitive material of the present invention. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (for example, polyethylene and polypropylene), laminated paper, polystyrene film, polycarbonate film, and metal plates such as aluminum.
These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating by a known method as necessary.

The photosensitive silver halide emulsion layer and other photographic constituent layers of the photographic light-sensitive material of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. These dyes are
Depending on the purpose, it may be added to the emulsion layer or added together with the mordant to the upper part of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the support than the silver halide emulsion layer, and fixed. It is preferably used. The dye can be dissolved in a suitable solvent (for example, water, alcohols such as methanol and ethanol, acetone, methyl cellosolve and the like, or a mixed solvent thereof) and added to the coating solution. These dyes can be used in combination of two or more. Specific examples of these dyes are disclosed in
-64039. In addition, U.S. Pat.
No. 794, No. 3,352,681, No. 3,499,762, No. 3,53
No. 3,764, No. 3,700,455, No. 3,705,805, No. 3,7
Ultraviolet absorbing dyes described in JP-A Nos. 07,375 and 4,045,229, JP-A-46-2784, West German Patent Application Advertising 1,547,863, JP-A-2-93839 and the like can also be used. Others, U.S. Pat.No. 2,274,782, JP-A-62-185755, Pyrazolone oxonol dyes described in JP-A 63-2045, U.S. Pat.
No. 6,879, diarylazo dyes described in U.S. Pat.
No. 3,207, styryl dyes and butadienyl dyes described in 3,384,487, merocyanine dyes described in U.S. Pat.No. 2,527,583, U.S. Pat.No. 3,486,897, 3,652,284
No. 3,718,472, merocyanine dyes and oxonol dyes, U.S. Pat. Kaisho 49-99620
No., JP-A-49-11420, U.S. Pat.No. 2,533,472,
No. 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3,575,704, No. 3,653,905,
Dyes described in JP-A-62-133453 can also be used.

[0032]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is of course not limited by these descriptions.

Example 1 Preparation of Emulsion Using a lime-processed gelatin as a protective colloid, a halogen solution containing 5 × 10 ⁻⁷ mol of a water-soluble rhodium salt per mol of silver and an aqueous silver nitrate solution were mixed by a pAg control double jet method and averaged. A silver iodobromide emulsion composed of cubic monodispersed grains having a grain size of 0.2 μm was prepared. The emulsion was washed and re-dissolved in the precipitate by flocculation. The content of silver iodide was set to 1 mol%, and the silver iodide was distributed throughout the grains.
This emulsion was divided, and sodium thiosulfate, chloroauric acid and ammonium thiocyanate were added.
After a chemical sensitization treatment by heating for 6 minutes, 6-methyl-4-hydroxy-1,3,3a,
Emulsion A was obtained by adding 7-tetraazaindene.

Emulsion A obtained above was divided, and the compounds of the present invention and comparative compounds were added to each of them as shown in Table 1. Further, as a sensitizing dye, anhydrous-5,
5'-Dichloro-ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium hydroxide was added, and sodium dodecylbenzenesulfonate was further added to obtain a finished emulsion. Immediately after these finished emulsion finish, and at 36 ° C. in After 40 hours aging, 5 g / m ² with silver nitrate in a polyethylene terephthalate film, gelatin was coated so as to 3 g / m ^2. 1.0 g / m ² of gelatin, a surfactant, a matting agent, and a hardening agent were added and coated as a protective layer to prepare Samples A-1 to A-9 shown in Table 1. Separately, the finished emulsion was aged at 36 ° C. for 40 hours and 80 hours, and the viscosity was measured.

The sample thus obtained was exposed and developed, and the sensitivity value was measured. A tungsten lamp was used for the exposure, and the sensitivity value was determined as the reciprocal of the exposure amount necessary to obtain a transmission density of 3.0. The relative value is shown when the sensitivity value of 1 is set to 100. In order to measure the state of fogging, the unexposed portion of the sample was measured with a densitometer, and the minimum density is shown in Table 1. Further, the condition was evaluated as follows in order to evaluate the shortage of the characteristic curve. Insufficient = ｛log (minimum density + exposure to give 0.03)-log
(Exposure to give a density of 1.0)｝ Development was carried out using a CD-231 developer manufactured by Mitsubishi Paper Mills and a CF-6001 fixing solution manufactured by Mitsubishi Paper Mills at 38 ° C. for 20 seconds. N from Nippon Screen
D221QT).

[0036]

[Table 1]

From the results in Table 1, it can be seen that the dehydroacetic acid of the present invention,
It can be seen that the use of a photosensitive silver halide emulsion containing salicylic acid and sorbic acid enables storage in a solution state without affecting photographic characteristics at all. Further, it can be seen that the solution can be stored without any change in physical properties. It can also be seen that the effect is apparent even when the amount is small.

Example 2 Emulsion A obtained in Example 1 was divided, and the compounds of the present invention and comparative compounds were added at the same ratio as in Example 1 as shown in Table 2. Put them in a refrigerator below 5 ° C,
Stored in gel form. After 12 weeks, these were taken out, dissolved at 36 ° C. to form a solution, and a sensitizing dye and an activator were added in the same manner as in Example 1 to obtain a finished emulsion (B-1 to B-1).
B-9) to produce a polyethylene terephthalate film with silver nitrate onto 5 g / m ² Immediately after finishing, gelatin 3
g / m ² . A sample was prepared by adding 1.0 g / m ² of gelatin, a surfactant, a matting agent, and a hardening agent as a protective layer thereon. Photographic characteristic values were measured in the same manner as in Example 1 at the same time as the samples coated with the emulsion which had not been stored in the refrigerator, and the emulsion aged for 12 weeks was checked for the presence or absence of perishable odor. Table 2 shows the results.

[0039]

[Table 2]

From the results in Table 2, it can be seen that the dehydroacetic acid of the present invention,
It can be seen that the use of a photosensitive silver halide emulsion containing salicylic acid and sorbic acid enables long-term storage in a gel state without affecting photographic characteristics at all. It can also be seen that the effect is apparent even when the amount is small.

[0041]

According to the present invention, during the production and storage of a light-sensitive silver halide emulsion, it can be stored for a long period without adversely affecting the photographic characteristics (sensitivity, fog, tone, etc.) of the light-sensitive silver halide emulsion. A method could be provided.

Claims (1)

[Claims] 1. A silver halide photographic material comprising at least one compound selected from the following group. A: Dehydroacetic acid or its salt B: Salicylic acid or its salt C: Sorbic acid or its salt