JPH0572574B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to a silver halide photographic material containing a novel diffusion-resistant dye, and more specifically, to a silver halide photographic material containing a novel diffusion-resistant dye.
The present invention relates to a silver halide photographic material containing a novel diffusion-resistant dye that has improved decolorization properties during development processing, does not restore color during storage over time, and does not cause a decrease in sensitivity. 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 is improved by coloring the photosensitive emulsion layer using a dye to absorb harmful reflected light and scattered light to the silver halide grains and prevent irradiation. It is. 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 are used in British Patent No. 506385 and Japanese Patent Publication No. 39-22069, merocyanine dyes are used in U.S. Patent No. 2493747, and styryl dyes are used in U.S. Patent No. 1845404. Each is proposed. Some of these conventional dyes have a relatively small effect on emulsion performance and have the ability to be bleached, eluted, and decolorized during the processing process, but they are insufficient in terms of diffusion resistance. It was warm with excellent performance. That is, when a specific layer among multiple emulsion layers is selectively colored and used as a filter layer or an antihalation layer, diffusion to other layers is significant, not only reducing the light absorption effect but also coloring other layers. The disadvantage was that it imparted unfavorable spectral effects to the layer. Therefore, as a method for selectively dyeing a specific hydrophilic colloid layer, a method of fixing the dye using a mordant or a method of using a diffusion-resistant dye has been proposed. Many studies have been conducted on the former method of fixing dyes using mordants, such as Japanese Patent Publication 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 not suitable 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
It is stated in the number etc. 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. 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 that has excellent dissolution and decolorization properties during the photographic processing process, does not recolor after storage over time, and is suitable for accelerated photographic processing. An object of the present invention is to provide a silver halide photographic 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 light-sensitive material having at least one photographic constituent layer containing a compound represented by the following general formula []. General formula []

[Formula] [In the formula, X and Y each have 1 carbon atom
~5 alkyl groups, at least one of the above X and Y represents an alkyl group having a substituent for which the sum of the values of hydrophobic substituent constant π (Σπ value) is larger than -4.7, and G is hydrogen represents an atom or a halogen atom, R ₁ represents an alkyl group having 5 to 10 carbon atoms, R ₂ represents a hydrogen atom, an alkyl group,
Represents an alkoxy group or a halogen atom, M
represents a hydrogen atom or a cation, L represents a methine group, and m and n each represent 1 or 2.
represents an integer. ] The present invention will be explained in more detail below. In the present invention, the dye contained in the light-sensitive material can be represented by the general formula [], and in the general formula [], a straight chain or Examples of branched alkyl groups include methyl group, ethyl group,
There are propyl groups, butyl groups, t-butyl groups, etc.
The above alkyl group may have a substituent. At least one of the above X and Y is an alkyl group having a substituent whose total hydrophobic substituent constant π (Σπ value) is larger than −4.7. Examples of alkyl groups having such substituents include cyanoalkyl (e.g. cyanomethyl,
cyanoethyl, cyanopropyl), hydroxyalkyl (e.g. hydroxymethyl, hydroxyethyl, hydroxypropyl), alkoxyalkyl (e.g. methoxymethyl, propoxymethyl,
methoxyethyl, ethoxyethyl, methoxypropyl), halogenoalkyl (e.g. chloromethyl,
Chloroethyl, bromoethyl, chloropropyl,
fluoroethyl), alkylthioalkyl (e.g. methylthiomethyl, methylthioethyl, ethylthioethyl), alkylsulfonylalkyl (e.g. methylsulfonylethyl, ethylsulfonylethyl), acylaminoalkyl (e.g. acetylaminoethyl, propionylaminomethyl),
Alkylsulfonamidoalkyl (e.g. methylsulfonamidoethyl, ethylsulfonamidoethyl, methylsulfonamidopropyl), acylalkyl (e.g. acetylmethyl, acetylethyl, propionylethyl), acyloxyalkyl (e.g. acetyloxyethyl, propionyloxyethyl), amino Alkyl (e.g. aminomethyl, aminoethyl, dimethylaminoethyl,
(aminopropyl) and the like. The value of the hydrophobic substituent constant π can be found in, for example, "Drug Structure-Activity Relationship" (Nankodo)
96 (1979), and the value of π can be calculated from this document. The methine group represented by L in the general formula [] can have a substituent, and examples of the substituent include a straight chain or branched alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n -butyl group, t-butyl group, etc.) or an aryl group (for example, phenyl group, etc.). Next, the alkyl group having 5 to 10 carbon atoms represented by R ₁ is a linear or branched alkyl group, and may further have a substituent.
For example, halogen atoms, hydroxy groups, cyano groups,
Examples include an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylsulfonyl group, a carbamoyl group, an acylamino group, a sulfamoyl group, and a sulfonamide group. Specific examples of these alkyl groups include n-pentyl, 2-
Methylbutyl, 2,3-dimethylbutyl, n-hexyl, 1-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 4-methylhexyl,
2,4-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, 2-methylheptyl, 4,5-dimethylhexyl, 5-ethylhexyl, 1,3,5-trimethylpentyl, n-nonyl, 4-methyloctyl, 3-ethylnonyl, 3,5,5-trimethylhexyl, n-decyl, 1-methylnonyl, 4,
6,6-trimethylheptyl, 5,5,5-trifluoropentyl, 2,3,5-trichloropentyl, 5-hydroxypentyl, 3-hydroxyhexyl, 5-hydroxyheptyl, 5-methoxypentyl, 5-ethoxypentyl , 5-carboxypentyl, 4-ethoxycarbonylheptyl, 5-cyanopentyl, 6-cyanohexyl,
Examples include 6-cyanoheptyl, 5-methylsulfonylpentyl, 3-methylsulfonylhexyl, 6-methylcarbamoylhexyl, 5-acetylaminopentyl, 5-sulfamoylpentyl, 4-methylsulfonamidohexyl, and the like. can. The group represented by R ₂ in the general formula [] is a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. be able to. In addition, the alkyl group includes a straight chain or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
Examples include t-butyl group. As an alkoxy group, the number of carbon atoms in the alkyl part is 1 to 3
Preferred are alkoxy groups, such as methoxy and ethoxy groups. Further, in the general formula [], G represents a hydrogen atom or a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and the like. Furthermore, examples of the cation represented by M in the general formula [] include alkali metal ions such as sodium ion and potassium ion, and when M represents a hydrogen atom, this cation may be an organic base ( For example, salts may be formed with pyridine, triethylamine, etc.). The dye according to the present invention represented by the above general formula [] can be synthesized by condensing an aldehyde compound represented by the following general formula [] and a pyrazolone compound represented by the following general formula []. General formula []

【formula】 General formula []

[Formula] In the formula, R ₁ , R ₂ , G, X, Y, M, 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, between n in the general formula []
Since there is a relationship of =p+q-1, 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 in the presence or absence of the above basic condensing agent using methanol, ethanol, ethylene glycol, methylcellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane,
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 [ It can be made from aniline. On the other hand, for the aldehyde with p=2, using N-methylanilinopropane(1)-al(3) and a suitable 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 [] with q=1 can be prepared by condensing various sulfoarylhydrazines with suitable 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 q=1 in the general formula [] and a dialkyl ketone, an alkylaryl ketone or an aliphatic aldehyde. The pyrazolone compound represented by the general formula [ ] can be prepared, for example, by the method described in Organic Syntheses, Vol. 28, p. 87 (1948), J. Am. Chem Soc. No. 66.
Volume, p. 1849 (1944), J.Am.Chem
Soc., vol. 65, p. 52 (1943), J.
It can be obtained by using the method described in Am. Chem Soc., Vol. 64, p. 2136 (1942). Typical specific examples of the dyes according to the present invention are described below.

【table】

【table】

【table】

【table】

[Table] Next, the method for synthesizing the dye according to the present invention will be specifically explained by showing synthesis examples. Synthesis Example 1 (Synthesis of Exemplary Dye (5)) 7.2g of 3-heptyl-1 in 100ml of methanol
-(4-sulfophenyl)2-pyrazoline-5-
4.14 g of 4-(N-methyl-N-cyanoethylamino)benzaldehyde were added, and 2.5 g of pyridine was added thereto, followed by reaction under heating under reflux for 2.5 hours. After the reaction, 5 g of anhydrous potassium acetate was added, and reflux was continued for an additional 30 minutes. After cooling the reaction solution, the precipitated crystals were collected by filtration, washed with methanol, and dried to obtain 4 g of the above exemplary dye. This dye can be analyzed using a spectrophotometer, elemental analysis, IR,
Confirmed by NMR, FD-Mass, etc. The aqueous solution λmax of this dye was 477 nm. Further, the results of elemental analysis were: C: 57.4%, H: 5.5%, and N: 9.7%. Synthesis Example 2 (Synthesis of Exemplary Dye (6)) 6.3g of 3-heptyl-1 in 100ml of methanol
-(4-sulfophenyl)2-pyrazoline-5-
4-(N-methyl-N-chloroethylamino)benzaldehyde and 3.1 g of 4-(N-methyl-N-chloroethylamino)benzaldehyde were added thereto, followed by addition of 1.5 g of pyridine, and the mixture was reacted under heating under reflux for 2.5 hours. After the reaction, 5 g of anhydrous potassium acetate was added, and reflux was continued for an additional 30 minutes. After cooling the reaction solution, the precipitated crystals were collected by filtration, washed with methanol, and dried to obtain 3.5 g of the above exemplary dye. This dye can be analyzed using a spectrophotometer, elemental analysis, IR,
Confirmed by NMR, FD-Mass, etc. The aqueous solution λmax of this dye was 486 nm. In addition, the results of elemental analysis were C; 55.1%, H;
5.3%, N: 7.2%. The dye according to the present invention produced by the above method has an alkyl group having 5 to 10 carbon atoms as R ₁ at the 3-position of the pyrazolone ring, and further has an alkyl group having 5 to 10 carbon atoms at the 1-position as shown in the general formula []. has a phenyl group substituted with an alkyl group, an alkoxy group, a halogen atom, and a sulfonic acid group as _R2 , and the N at the 4-position of the phenyl group is substituted at the 4-position of the pyrazolone ring via a methine group. X and Y shown as substituents of
The structural feature is that at least one of them is an alkyl group having a substituent with a total hydrophobic substituent constant π value (Σπ value) of -4.7 or more, and this makes it unique compared to conventionally known dyes. The outflow decolorization property during the development process is significantly improved, and not only is there no recoloring during storage over time, but also the diffusion of the dye in the contained silver halide emulsion layer or other hydrophilic colloid layer is prevented. Therefore, it is a dye that has excellent photographic performance with no decrease in sensitivity. 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 being contained in a silver halide emulsion layer, or can be used as a filter dye or an anti-halation dye by being contained in a non-photosensitive hydrophilic colloid layer. It can also be used. Further, depending on the purpose of use, two or more of the dyes of the present invention may be used in combination, and as long as the effects of the present invention are not impaired, they may be used in combination with other dyes. 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 added to a coating solution and coated by a known method to coat the photosensitive material of the present invention. It can contain dyes. 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 carboxymethyl cellulose, 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. are included. 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. Contains surfactants such as acid salts, alkylbenzenesulfonates, and alkylnaphthalenesulfonates, as well as photographic additives such as fluorescent brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers. be able to. 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 4-equivalent or 2-equivalent, and may release a colored coupler for masking or a development inhibitor. It may also be a coupler. As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based compounds are used, as magenta-forming couplers, pyrazolone-based compounds, and as cyan-forming couplers, phenolic or naphthol-based compounds are usually advantageously used. Furthermore, the photosensitive material of the present invention can have any layer structure 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 3.5 g of gelatin was added and dissolved in 35 ml of distilled water, and to this was added 5 ml of an aqueous solution containing 2.0 x 10 ^-4 mol each of exemplary dyes (1), (5) and (9) according to the present invention. ,
Add 1.25 ml of 10% saponin 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 acetylcellulose film support, dried, and sample [1]
[2] and [3]. Comparative samples [4] and [5] were also created in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention. Comparative dye (A)

[ka] Comparative dye (B)

[C] (Example 1 of Japanese Patent Publication No. 45-20635) Each of these samples was added to a developer having the following composition at 25°C.
After soaking for 20 seconds, washing with water for 20 seconds, and drying. (Composition of developer) Metol 3.0g Sodium nitrite (anhydrous) 3.8g 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 dyes according to the present invention were found to exhibit superior decolorizing properties compared to the comparative dyes. 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, and A ₂ is the absorbance after the decolorization test each week.)

[Table] As is clear from Table 2, it was found that the samples according to the present invention showed no color restoration compared to the comparative samples. Example 3 The elution rate in water and alkaline solution (PH10.0) from the coating films of Samples 1 to 5 used in Example 1 was
The absorbance of the eluting dye was examined over time. The results are shown in Table 3 below. Conditions for absorbance measurement (time = 2 hours, temperature = 20°C)

[Table] As is clear from Table 3, the dyes according to the present invention were found to have a lower elution rate in water and faster elution in alkaline solutions than the comparative dyes. Example 4 On a polyethylene terephthalate support, the first
A gelatin solution 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 Exemplary 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 Saponin (10% aqueous solution) 30ml Next, iodine containing 96 mol% silver bromide and 4 mol% silver iodide, with an average particle size of 0.8 μm. 2,4-dichloro- per 1 kg of gelatin emulsion in silver gelatin emulsion
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 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)
% aqueous solution) 50ml water 940ml Similarly, samples were prepared using the following comparative dyes (C), (D) and (E) in place of the exemplary dye (6) according to the present invention in the first layer. In addition, a sample containing no eyelid dye was prepared in the same manner. These samples were divided into samples (6), (7), (8), and (9), respectively.
and (10). Comparative dye (C)

【formula】 Comparative dye (D)

[ka] Comparative dye (E)

[C] (Example 1 of Japanese Patent Publication No. 46-42667) Each of these samples was cut into small pieces and heated at 50℃±2℃ and relative humidity 80± to test the stability under high temperature and high humidity conditions.
Aging treatment was performed at 5% for 72 hours. 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. Develop and fix at 25℃ for 2 minutes, then wash with water.
After heating 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 make 1000ml. After development, a photographic characteristic curve was determined, and the relative sensitivity was determined, setting the unaged sensitivity of sample (10) containing no dye as 100.

[Table] Sample (6) containing the dye according to the present invention, both aged and untreated, shows no decrease in sensitivity beyond that due to the light absorption effect, and furthermore, no color staining is observed after development. That is, the dye according to the present invention hardly diffuses from the dyed layer to other layers, does not adversely affect photographic properties, and is completely decolorized after development. On the other hand, it can be seen that comparative sample (8) has insufficient diffusion resistance, and the sensitivity decreases significantly after aging, which has an adverse effect on photographic properties. Comparative samples (7) and (9) have a diffusion-resistant effect, but stains remain after treatment. Effects of the Invention The dye according to the present invention has excellent flowability in the development processing bath, does not restore color after processing, and is prevented from diffusing in the layer in which it is contained, so that sensitivity does not decrease. It is stable in photosensitive materials and has good spectral absorption characteristics.

[Brief explanation of the drawing]

The drawing shows an absorption spectrum curve of Exemplary Compound (5) 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, X and Y each have 1 carbon atom]
~5 alkyl groups, at least one of the above X and Y represents an alkyl group having a substituent for which the sum of the values of hydrophobic substituent constant π (Σπ value) is larger than -4.7, and G is hydrogen represents an atom or a halogen atom, R ₁ represents an alkyl group having 5 to 10 carbon atoms, R ₂ represents a hydrogen atom, an alkyl group,
Represents an alkoxy group or a halogen atom, M
represents a hydrogen atom or a cation, L represents a methine group, and m and n each represent 1 or 2.
represents an integer. ]