JPH0559420B2 - - Google Patents

Description

BACKGROUND TECHNICAL FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has improved decolorization properties during development processing, no recoloring during storage over time, and a reduction in sensitivity. This invention relates to a silver halide photographic material containing a novel diffusion-resistant dye that does not cause Prior art and its problems Generally, in silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), light absorption filters,
It is well known that for the purpose of preventing halation, preventing irradiation, or adjusting the sensitivity of a photosensitive emulsion, dyes are incorporated into the constituent layers of photosensitive materials in order to absorb light of a specific wavelength. Coloring of hydrophilic colloid layers has been conventionally practiced. Among the constituent layers of the above-mentioned light-sensitive material, a filter layer is usually located above a light-sensitive emulsion layer or between this emulsion layer and another emulsion layer, and changes incident light that reaches the emulsion layer into a preferable spectral composition. It plays a role. In addition, an antihalation layer is provided between the light-sensitive emulsion layer and the support, or on the back side of the support, for the purpose of improving the sharpness of the image. This improves image sharpness by absorbing reflected light. Furthermore, the sharpness of the image can be improved by coloring the photosensitive emulsion layer with a dye to absorb harmful reflected light and scattered light to the silver halide grains and prevent irradiation. It is being said. Dyes used for such purposes must, of course, have good absorption spectrum characteristics depending on the purpose of use; for example, they must be completely decolorized during development, easily eluted from the photosensitive material during development, and After processing, there is no residual color staining caused by the dye, there is no other negative effect on the photosensitive emulsion such as fogging or desensitization, and there is no diffusion from the colored layer to other layers. Furthermore, it must satisfy various conditions, such as excellent stability over time in photosensitive materials or aqueous solutions, and no discoloration or fading. To date, numerous studies have been conducted with the aim of developing dyes that satisfy the above conditions.
For example, US Pat. No. 3,540,887, US Pat. No. 3,544,325, US Pat.
Benzylidene dyes were proposed in British Patent No. 506355 and Japanese Patent Publication No. 39-22069, merocyanine dyes were proposed in U.S. Patent No. 2493747, and styryl dyes were proposed in U.S. Patent No. 1845404. Each is proposed. Some of these traditional dyes have a relatively small effect on emulsion performance and are bleached or bleached during processing.
Although it has properties such as being eluted and discolored, its performance was insufficient in terms of diffusion resistance. When selectively coloring a specific layer among multiple emulsion layers and using it as a filter layer or an antihalation layer, the diffusion to other layers is significant, which not only reduces the light absorption effect but also colors the other layers. On the other hand, there was a drawback that it gave an unfavorable spectral effect. For this reason, methods of fixing the dye using a mordant or methods of using a diffusion-resistant dye have been proposed as methods for selectively dyeing a specific hydrophilic colloid layer. Regarding the former method of fixing dyes using mordants, many studies have been conducted, for example, Japanese Patent Publications No. 57-46542, No. 57-46775, No. 43-13498,
No. 43-10254, No. 56-2942, No. 56-2941,
No. 49-15820, JP-A-52-128125, No. 57-
No. 51658, No. 57-46777, No. 57-46776, No. 52
−34716, No. 56-65132, British Patent No. 786592
No. 906083, No. 1162214, No. 850281
No. 1408410, U.S. Patent No. 3445231, U.S. Patent No.
No. 2882156, No. 3706563, West German Patent No. 1914361
No. 1914362, No. 2009498, etc. However, although this method has poor coating properties and suppresses interlayer diffusion, it has poor dissolution and decolorization properties during processing, requires a high pH processing bath, and is inferior in suitability for rapid processing. Furthermore, there was a drawback that desilvering properties were deteriorated. Many studies have also been conducted on the latter method using diffusion-resistant dyes. For example, West German Patent No. 1522427, West German Patent No. 2453217, West German Patent No. 2618057,
U.S. Patent No. 2709136, U.S. Patent No. 3615546, U.S. Patent No.
No. 4115126, JP-A-56-126397, JP-A No. 55-120660
There is a method described in the issue. However, although conventional diffusion-resistant dyes suppress interlayer diffusion, they tend to precipitate in the hydrophilic colloid layer, have poor decolorization and elution properties during processing, and even bleaching dyes recover their color over time. There was a drawback of doing so. Therefore, the reality is that a dye that satisfies the above conditions has not yet been developed, and the development of such a dye is desired. OBJECTS OF THE INVENTION Therefore, the first object of the present invention is to provide a dye containing a dye that has excellent dissolution properties and decolorization properties during the photographic processing process, does not restore color during subsequent storage over time, and is suitable for accelerated photographic processing. The object of the present invention is to provide a silver halide photographic light-sensitive material. A second object of the present invention is to provide a silver halide photographic material containing a diffusion-resistant dye in a light-sensitive silver halide emulsion layer or a light-insensitive colloid layer. A third object of the present invention is to provide a silver halide photographic material containing a dye that does not adversely affect photographic properties such as fog or desensitization of a light-sensitive silver halide emulsion. A fourth object of the present invention is to provide a silver halide photographic material containing a dye that can be added to an emulsion without using an organic solvent. A fifth object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye having good absorption spectrum characteristics in the light-sensitive material depending on the intended use thereof. Structure of the Invention The above object of the present invention is achieved by a silver halide photographic material having at least one photographic constituent layer containing a compound represented by the following general formula [] on a support. General formula [] [In the formula, A represents a hydrogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acyloxy group, an alkylsulfonyl group, or a halogen atom, and B represents an alkoxy group, an alkoxycarbonyl group, a sulfo group, carboxyl group, alkylsulfonyl group, sulfamoyl group, carbamoyl group, halogen atom, cyano group, acyloxy group, or acylamino group, a and b each represent an integer from 1 to 4, and R ₁ is a hydrogen atom ,
or represents an alkoxy group having 1 to 8 carbon atoms, R ₂ represents a hydrogen atom, an alkoxy group or a halogen atom, M represents a hydrogen atom or a cation, L represents a methine group, n and m are Each represents 1 or 2, and G represents a hydrogen atom, a halogen atom, a methyl group or an alkoxy group. ] The present invention will be explained in more detail below. The dye contained in the light-sensitive material in the present invention is represented by the above general formula [], and in the general formula [], A(-CH ₂ ) _a -- group, that is, a carbon having a substituent represented by A. Number of atoms: 1 to 4
Specific examples of lower alkyl groups include alkoxyalkyl groups (e.g., methoxyethyl group, propoxymethyl group, ethoxyethyl group, methoxypropyl group, etc.), alkoxycarbonylalkyl groups (e.g., methoxycarbonylmethyl group, ethoxycarbonylmethyl group, etc.). , methoxycarbonylethyl group, etc.), carboxyalkyl group (e.g., carboxymethyl group, carboxyethyl group, etc.), sulfoalkyl group (e.g., sulfomethyl group, sulfoethyl group, sulfopropyl group, etc.), sulfamoyl alkyl group (e.g., sulfa moylmethyl group, sulfamoylethyl group, etc.), carbamoylalkyl group (e.g. carbamoylmethyl group, carbamoylethyl group, etc.), acyloxyalkyl group (e.g. acetyloxymethyl group, acetyloxyethyl group, etc.), alkylsulfonylalkyl group (e.g. methylsulfonylethyl group, etc.), halogenoalkyl groups (chloromethyl group, chloroethyl group, bromoethyl group, chloropropyl group, fluoroethyl group, etc.), and the like. In the general formula [], B(-CH ₂ ) _b -- group, that is, the number of carbon atoms having a substituent represented by B is 1
Examples of the to 4 substituted lower alkyl groups include:
Alkoxyalkyl groups (e.g. methoxymethyl group, propoxymethyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, etc.), alkoxycarbonylalkyl groups (e.g. methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, etc.), Sulfoalkyl groups (e.g. sulfomethyl, sulfoethyl, sulfopropyl, etc.), carboxyalkyl groups (e.g. carboxymethyl, carboxyethyl, etc.), alkylsulfonylalkyl groups (e.g. methylsulfonylethyl, methylsulfonylpropyl, etc.), Sulfamoyl alkyl groups (e.g. sulfamoylmethyl group, sulfamoylethyl group, etc.), carbamoyl alkyl groups (e.g. carbamoylethyl group, carbamoylmethyl group, etc.), cyanoalkyl groups (e.g. cyanomethyl group,
cyanoethyl group, cyanopropyl group, etc.), acyloxyalkyl group (e.g. acetyloxyethyl group, acetyloxypropyl group, acetyloxymethyl group, etc.), acylaminoalkyl group (e.g. acetylaminoethyl group, diacetylaminoethyl group, etc.), halogeno Examples include alkyl groups (eg, chloromethyl group, chloroethyl group, promoethyl group, chloropropyl group, fluoroethyl group, etc.). In the general formula [], a and b are 1 to 4
are each an integer of 1 to 2, preferably 1 to 2. This a and b may be the same or different. In the general formula [], R ₁ represents a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a putoxy group. be able to. The alkyl portion of this alkoxy group may have a substituent. Examples of the substituent include an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.). In addition, in the general formula [], R ₂ is a hydrogen atom,
It represents an alkoxy group or a halogen atom. Among these, the alkoxy group can be the same as the alkoxy group mentioned in _R1 above, and the halogen atom can be a chlorine atom, a bromine atom, an iodine atom, or a halogen atom. Although elementary atoms can be mentioned, chlorine atoms are preferred. This R ₂ can be bonded to any position of the phenyl group,
Preferably it is attached to the 2nd position. It is preferable that the SO ₃ M group bonded to the phenyl group exist in a meta-position relationship. In the general formula [], the methine group represented by L can be further substituted with an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-
butyl groups) or aryl groups (eg phenyl groups). This alkyl group or aryl group may further have a substituent. In the general formula [], examples of the cation represented by M include alkali metal ions such as sodium ions and potassium ions. Further, when M is a hydrogen atom, it may form a salt with an organic base (eg, pyridine, triethylamine, etc.). Preferably, M is an alkali metal ion such as a sodium ion or a potassium ion. In the general formula [], G represents a hydrogen atom, a halogen atom, a methyl group or an alkoxy group,
Among these, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, with a chlorine atom being preferred. Further, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and examples of such alkoxy groups include methoxy group, ethoxy group, butoxy group, etc., and preferably methoxy group. be. This alkoxy group may have a substituent. -SO ₃ M represented by the above general formula []
The group may be bonded at any of the ortho, meta, and para positions relative to the phenyl group bonded to the pyrozolone ring, and when there are two -SO ₃ M groups, the group may be bonded at the ortho and meta positions or the meta and meta positions. can be combined in position. The dye according to the present invention represented by the above general formula [] can be synthesized by combining an aldehyde compound represented by the following general formula [] and a pyrazolone compound represented by the following general formula []. General formula [] General formula [] In the formula, R ₁ , R ₂ , G, A, B, M, a, b, m
and L represents a group having the same meaning as the group in the general formula []. Moreover, p and q represent 1 or 2. However, since there is a relationship n=p+q-1 with n in the general formula [], p and q cannot be 2 at the same time. The above reaction is performed using a basic condensing agent, such as pyridine,
This is carried out by heating a mixture of the above general formulas [] and [] in the presence of piperidine, triethylamine, etc. The above reaction can be carried out using methanol, ethanol, ethylene glycol, methylcellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane, etc. in the presence or absence of the above basic binder.
It can also be carried out in an inert solvent such as acetic acid or water. The aldehyde compound represented by the above general formula [] can be produced by a known method. For example, an aldehyde compound with p=1 in the general formula [] can be prepared by using dimethylformamide as a formylating agent and by the reaction of Vilsmeyer and Hatsuta (Berichte, Vol. 60, p. 119, 1927) to produce the corresponding substituted aniline. It can be made from. on the other hand,
The aldehyde with p=2 is prepared using N-methylanilinopropane(1)-al(3) and the appropriate aniline,
It can be produced in the same manner as the Vilsmeier reaction, as described in Berichte, Vol. 91, p. 850 (1958). Also Berichte, vol. 61, p. 2074 (1928)
It can also be obtained from the reaction of the corresponding substituted aminobenzaldehyde with paraldehyde as described in . Pyrazolone compounds of the general formula [] where q=1 can be prepared by condensing various sulfoarylhydrazines with appropriate substituted esters by known methods practiced in dye chemistry. The intermediate represented by q=2 in the general formula [] can be obtained by condensation of the product represented by the general formula [] with q=1 and a dialkyl ketone, alkylaryl ketone or aliphatic aldehyde. The pyrazolone compound represented by the general formula [] can be prepared, for example, by the method described in Organic Syntheses, Vol.
Volume 66, page 1849 (1944) Method described, J.Am.
Chem.Soc., Vol. 65, p. 52 (1943), J.Am.Chem.Soc., Vol. 64, p. 2136 (1942)
It can be obtained by using the method described in 2010). Typical specific examples of the dyes according to the present invention are described below. Next, the method for synthesizing the dye according to the present invention will be specifically explained by showing synthesis examples. Synthesis Example (Synthesis of Exemplary Dye (1)) 1.7g of 3-phenyl-1 in 50ml of methanol
-(4-sulfophenyl)-2-pyrazoline-5-
and 0.8 g of 4-(N-methyl-N-chloroethylamino)benzaldehyde were added, and further 1.5 g of pyridine was added, followed by reaction under heating under reflux for 2.5 hours. After the reaction, 3 g of anhydrous potassium acetate was added, and reflux was continued for an additional 30 minutes. After washing with methanol and drying, 2 g of the above exemplary dye was obtained. This dye was analyzed using a spectrophotometer, elemental analysis, IR, NMR, and FD-Mass.
Confirmed with etc. The aqueous solution λmax. of this dye is 480nm
It was hot. The results of elemental analysis are C: 55.8%, H:
3.4%, N: 11.9%. The dye according to the present invention produced by the above method is
As shown in the general formula [], the pyrazolone ring has a phenyl group substituted with a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms as R ₁ at the 3-position, and further at the 1-position, As R ₂ ,
A dialkylamino group substituted at the para position of the phenyl group which has a phenyl group substituted with a hydrogen atom, an alkoxy group, a halogen atom, and a sulfone group and is bonded to the 4-position of the pyrazolone ring via a methine group (

[Formula] group) is a structural feature, and as a result, compared to conventionally known dyes, it has excellent storage stability in photosensitive materials and solutions, and has significantly improved decolorization properties during development processing. It is a dye that not only does not recover its color even after storage over time, but also has excellent photographic performance as it prevents the dye from diffusing in the emulsion layer or other hydrophilic colloid layer in which it is contained, so there is no decrease in sensitivity. be. In addition to the above, the dye according to the present invention has optimal spectral absorption characteristics, and is also capable of forming clear images. In the photosensitive material of the present invention, the general formula []
The dye represented by can be used as an anti-irradiation dye by containing it in a silver halide emulsion, or can be used as a filter dye or a dye by containing it in a non-photosensitive hydrophilic colloid layer.
It can also be used as an antihalation dye. Furthermore, two or more types of dyes may be used in combination depending on the purpose of use, and may be used in combination with other dyes as long as the effects of the present invention are not impaired. The dye according to the present invention is contained in a silver halide emulsion layer or
Incorporation into other hydrophilic colloid layers can be easily carried out by conventional methods. Generally, a dye or an organic or inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, and this is applied to a coating solution by a known method to incorporate the dye into the photosensitive material. can be done. The content of these dyes varies depending on the purpose of use, but is generally applied in an amount of 1 to 800 mg per ^square meter of area on the photosensitive material. Supports in the photosensitive material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate,
For example, there are polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin coated papers, polypropylene synthetic papers, glass plates, metals, etc. These supports are used depending on the intended use of the photosensitive material. , is selected as appropriate. Hydrophilic colloids in the photosensitive material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid;
Examples include synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone, and cellulose derivatives such as carboxymethylcellulose, and these can be used alone or in combination. The silver halide emulsion in the light-sensitive material of the present invention may be any of the silver halide emulsions normally used for silver halide emulsions, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Includes: The silver halide emulsion used in the light-sensitive material of the present invention can be produced by various manufacturing methods including the usual manufacturing method.
For example, the method described in Japanese Patent Publication No. 46-7772 or the method described in U.S. Pat. It can be produced by any method such as a so-called conversion emulsion method in which an emulsion of silver salt grains is formed and then at least a portion of the grains is converted into silver bromide salt or silver iodobromide salt. This silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloride sensitizers, etc. Aurate,
Gold compounds such as orithic trichloride, potassium orithic thiocyanate, 2-orothiabenzthiazole methyl chloride, etc., palladium compounds such as ammonium chloroparadate, sodium chloropalladite, etc., platinum compounds such as potassium chloroplatinate, etc. , ruthenium compounds, etc., or a combination of such sensitizers. In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. In addition, a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound can be contained. The silver halide emulsion used in the light-sensitive material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. Sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes,
Various dyes such as oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, and streptocyanin dyes can be used, and one type of sensitizing dye or a combination of two or more types of each can be used. In the light-sensitive material of the present invention, glycerin, 1,5
- dihydroxyalkanes such as pentanediol,
It can contain wetting agents such as esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, water-dispersible fine particulate polymer compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc. , aldehyde compounds,
N-methylol compounds such as N,N'-dimethylol urea, mucohalogenic acid, divinylsulfonic acid,
Active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine, hardening agents such as dioxane derivatives, divinyl ketones, isocyanates, and carbodiimides, saponins, polyalkylene glycols, polyalkylene glycol ethers, and alkyl sulfones. Contain surfactants such as acid salts, alkylbenzene sulfonates, and alkylnaphthalene sulfonates, as well as photographic additives such as optical brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers. I can do it. In the light-sensitive material of the present invention, a color coupler may be contained in the silver halide emulsion layer, and the coupler may be either a 4-equivalent type or a 2-equivalent type, and a colored coupler for masking or a development inhibitor may be released. It may also be a DIR coupler.
As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, pifsolone-based compounds, and as cyan-forming couplers, phenolic or naphthol-based compounds are usually advantageously used. Further, the photosensitive material of the present invention can have any layer formation that can be used in conventional photosensitive materials. Specific Examples of the Invention Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
To this, 5 ml of an aqueous solution containing 2.0 x 10 ^-4 mol each of exemplary dyes (1), (7) and (R) according to the present invention was added,
Add 1.25 ml of 10% sabonin solution and 0.75 ml of 1% formalin solution, and add water to bring the total volume to 50 ml.
And so. This dye solution was applied onto an acetyl cellulose film support, dried, and
[2] and [3]. Comparative samples [4] and [5] were also prepared in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention. Comparative dye (A) Comparative dye (B) Each of these samples was added to a developer with the following composition at 25°C.
After soaking for 20 minutes, washing with water for 20 seconds, and drying. (Composition of developer) Meter 3.0g Sodium sulfite (anhydrous) 45.0g Hydroquinone 12.0g Sodium carbonate (monohydrate) 80.0g Potassium bromide 2.0g Add water to make 1. The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below. Decolorization rate=E ₁ −E ₂ /E ₁ ×100 (%) (E ₁ is the absorbance before immersion in the developer, and E ₂ is the absorbance after immersion in the developer.

[Table] As is clear from Table 1, the dye according to the present invention was found to exhibit decolorizing properties equivalent to or better than the bleach-type diffusion-resistant comparative dyes (A) and (B). Example 2 Samples 1 to 5 after the decolorization test were stored at room temperature for 2 weeks and 4 weeks, and the visible spectrum of each sample was measured to determine the color recovery rate. The results are shown in Table 2 below. Color recovery rate = A ₂ / A ₁ × 100 (%) (A ₁ is the absorbance before immersion in the developer, A ₂ is
It represents the absorbance after the decolorization test in each week. )

[Table] As is clear from Table 2, compared to the comparative dyes, the dyes according to the present invention show no color recovery even when stored at room temperature for 2 and 4 weeks. Example 3 The rate of elution of the dye from the coated films of Samples 1 to 5 used in Example 1 into water and an alkaline solution was investigated over time based on the absorbance of the eluted dye. The results are shown in Table 3 below. Note that the absorbance measurement was carried out after a period of 2 hours. Temperature: 20℃

[Table] As is clear from Table 3, the dye according to the present invention has a lower dissolution rate in water and is better in alkali dissolution than comparative dyes (A) and (B). I found out. Example 4 For the exemplary dyes (1), (3), (6), and (10) according to the present invention and the comparative dye (B), aqueous solutions of a constant molar concentration were prepared, and measurements were carried out under acidic and alkaline conditions. The relative hydrolysis rate of each dye was determined by setting the hydrolysis rate of the comparative dye (B) as 100. The rate of hydrolysis is determined by adding a solution under each condition to a constant molar concentration, stirring, and then setting a portion of the solution in a spectrophotometer to measure the change in absorbance over time. The results are shown in Table 4 below.

[Table] As is clear from Table 4, compared to the comparative dyes, the exemplary dyes according to the present invention were found to be weakly acidic and less susceptible to hydrolysis. That is, it is suggested that the dye according to the present invention has excellent storage stability in solutions and in photosensitive materials. Example 5 On a polyethylene terephthalate support, the first
Gelatin containing a dye and having the composition shown below was applied as a layer to a dry film thickness of 2 μm. (Gelatin liquid composition) Gelatin 40g Water 900ml Poly-[2-diethylaminoethyl acrylate] (5% aqueous solution) 120ml Dye (2) according to the present invention (2% aqueous solution) 80ml 2,4-dichloro-6-hydroxy-1,3 ，
5-triazine sodium salt (1% aqueous solution)
20ml saponic acid (10% aqueous solution) 30ml Next, add 2,000 g of saponic acid per 1 kg of gelatin emulsion to a silver iodobromide gelatin emulsion consisting of 96 mol% silver bromide and 4 mol% silver iodide with an average grain size of 0.8 μm. 4-dichloro-
Add 20 ml of 6-hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) and 20 ml of sodium dodecylbenzenesulfonate (1% aqueous solution) and apply the second layer so that the dry film thickness is 5 μm. did. Furthermore, a gelatin solution having the composition shown below was coated as a protective layer on top of this emulsion layer to a dry film thickness of 2 μm to prepare sample (6). (Gelatin liquid composition) Gelatin 20g 2,4-dichloro-6-hydroxy-1,3,5
-Triazine sodium salt (1% aqueous solution) 10ml Sodium dodecylbenzenesulfonate (1% aqueous solution) 50ml water 940ml Similarly, in place of the exemplary dye (2) according to the present invention in the first layer, the exemplary dye according to the present invention ( Each sample was prepared using 6) and (9) and the following comparative dyes (C), (D), and (E). In addition, a sample containing no eyelid dye was also prepared in the same manner. Samples (7), (8), (9), (10), (11) and
(12). Comparative dye (C) Comparative dye (D) Comparative dye (E) 50±2 to test stability under high temperature and high humidity.
Aging treatment was carried out for 72 hours at a temperature of 80±5% relative humidity. The aged sample and the untreated sample were each exposed to light through an optical wedge and processed using the developer having the composition shown below and the fixer used in Example 2. Development was carried out at 25℃ for 2 minutes, and fixing was carried out at 25℃ for 2 minutes.
After washing at 25°C for 2 minutes and washing with water at 25°C for 5 minutes, it was dried. (Composition of developer) Phenidone 0.5g Anhydrous sodium sulfite 50g Hydroquinone 12g Anhydrous sodium carbonate 60g Potassium bromide 2g Benzotriazole 0.2g Add water to 1000ml After processing, determine the photographic characteristic curve, and sample without dye (12) Assuming that the unaged sensitivity of is 100,
The relative sensitivity was determined and the results are shown in Table 5 below.

[Table] In the sample containing the dye according to the present invention, both aged and untreated, there was less decrease in sensitivity than Sample 11 containing the comparative dye (E), and there was no deterioration in photographic properties. No color staining was observed. That is, it can be seen that the dye according to the present invention hardly diffuses from the dyed layer to other layers and is completely decolored after treatment. On the other hand, in comparison dyes (9) and (10), the dyes faded after aging treatment and the light absorption effect disappeared. Comparative sample (11) also exhibits a desensitizing effect that is greater than the light absorption effect, indicating that its diffusion resistance is insufficient, adversely affecting photographic properties, and furthermore leaving stains after development. Specific Effects of the Invention The dye according to the present invention has excellent flowability in the developing processing solution, does not restore color after processing, and is prevented from diffusing in the layer in which it is contained, thereby reducing sensitivity. Moreover, the spectral absorption characteristics are also good.

[Brief explanation of the drawing]

FIG. 1 shows an absorption spectrum curve of Exemplified Compound (1) according to Example 1 before being immersed in a developer.

Claims (1)

[Scope of Claims] 1 At least one photographic constituent layer containing a compound represented by the following general formula [] is provided on a support.
A silver halide photographic material characterized by having a layer. General formula [] [In the formula, A represents a hydrogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acyloxy group, an alkylsulfonyl group, or a halogen atom, and B represents an alkoxy group, an alkoxycarbonyl group, Sulfo group, carboxyl group, alkylsulfonyl group, sulfamoyl group, carbamoyl group,
represents a halogen atom, a cyano group, an acyloxy group, or an acylamino group, a and b each represent an integer of 1 to 4, R ₁ is a hydrogen atom,
or represents an alkoxy group having 1 to 8 carbon atoms, R ₂ represents a hydrogen atom, an alkoxy group, or a halogen atom, M represents a hydrogen atom or a cation, L represents a methine group, n and m represent ,
Each represents 1 or 2, and G represents a hydrogen atom, a halogen atom, a methyl group or an alkoxy group. ]