JPS59211041A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve residual color stain after processing by forming a hydrophilic colloidal layer colored with a novel light absorbing dye. CONSTITUTION:A compound represented by general formula I is incorporated into a photosensitive silver halide material. In the formula, G is methyl, methoxy or hydroxy; R1 is a univalent group having <=-0.05 Hammett's sigmap value such as alkyl, cycloalkyl, hydroxy or alkoxy; R2 is phenyl having at least one sulfo group; R3 is a univalent group such as alkyl, halogen or hydroxy; each of X and Y is H, alkyl or substituted alkyl (the total SIGMApi of the hydrophobic substituent constants pi of the substituents is >=-4.70, and the substituents include cyano, hydroxy and haloalkyl); X and Y may bond to each other to form a 5- or 6- membered ring; L is methine; m is 1, 2, 3 or 4; and n is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention can be utilized in photographic technology, particularly in manufacturing technology for photographic light-sensitive materials.

The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having a hydrophilic colloid layer colored with a novel light-absorbing dye and having improved residual color staining after processing. .

Prior Art Generally, in silver halide photographic materials (hereinafter referred to as "photosensitive materials"), light of a specific wavelength is used for the purpose of light absorption filters, antihalation, antiirradiation, or sensitivity adjustment of photosensitive emulsions. It is well known that dyes are included in constituent layers of photosensitive materials for absorption, and therefore, it has been conventionally practiced to color hydrophilic colloid layers with the dyes.

Among the constituent layers of the above-mentioned light-sensitive material, one filter layer is usually located above a light-sensitive emulsion layer or between this emulsion layer and another emulsion layer, and converts incident light reaching the emulsion layer into light having a preferable spectral composition. It plays the role of changing the Regarding the antihalation layer, in order to improve the sharpness of images, an antihalation layer is provided between the light-sensitive emulsion layer and the support, or on the back side of the support. This improves the clarity of images by absorbing harmful reflected light from the interface and the back surface of the support.

Furthermore, the photosensitive emulsion layer is colored using a dye,
It is also often done to improve the sharpness of images by absorbing harmful reflected light, scattered light, etc. on silver halide grains and preventing irradiation.

Dyes used for such various purposes need to have good absorption spectrum characteristics depending on the purpose of use, but also dyes that are completely decolorized during the development process and easily eluted from the photosensitive material during the development process. After processing, it does not cause residual color staining due to dyes, does not have any other negative effects on photosensitive emulsions such as fogging or desensitization, and does not diffuse from colored layers to other layers. Furthermore, it must satisfy various conditions, such as not causing color change or fading, and having excellent stability over time in photosensitive materials or aqueous solutions.

To date, numerous studies have been carried out with the aim of developing dyes that satisfy the above conditions, such as U.S. Pat. No. 3.540.887, U.S. Pat. .214, Special Publication No. 31-10578
Benzylidene dyes were proposed in British Patent No. 506.385 and Japanese Patent Publication No. 39-22069, and meshilidene dyes were proposed in U.S. Patent No. 2,493.747. Cyanine dyes and styryl dyes have been proposed in US Pat. No. 1,845.404.

However, at present, no dye has been found that satisfies the above conditions.

OBJECTS OF THE INVENTION Therefore, the objects of the present invention are to have optimal absorption spectrum characteristics, to be completely decolored during development processing, to have extremely little residual color contamination after processing, and to have little diffusion to other layers.
Another object of the present invention is to provide a dye having excellent stability over time in a light-sensitive emulsion or an aqueous solution, and a silver halide photographic light-sensitive material containing such a dye.

Structure of the Invention As a result of various studies, the present inventors have achieved the above object in a silver halide photographic material containing a compound represented by the following general formula [■]. 5-2 In formula 1, G represents a methyl group, methoxy group or hydroxy group, R1 represents a monovalent group with a Hammett's p value of less than -0.05, R2 represents a phenyl group having at least one sulfo group, R3 represents a monovalent group; may be combined with each other to form a 5-membered ring or a 6-membered ring. L represents a methine group, m represents an integer of 1.2.3 or 4, and n represents an integer of 1 or 2.゛I The present invention will be explained in more detail below.

In the present invention, the dye contained in the photosensitive material can be represented by the general formula (1), and the dye can be represented by the general formula I
In J), the monovalent group represented by R3 and having a Hammett's 6-value p value of less than -0.05 is preferably an optionally substituted linear or branched alkyl group having 1 to 4 carbon atoms. groups (e.g. methyl group, ethyl group,
n-propyl group, n-butyl group, tert-butyl group,
carboxymethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, benzyl group, phenethyl group, etc.),
Cycloalkyl group (e.g. cyclohexyl group), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group, n-butoxy group, 2-methoxyethoxy group, ethoxymethoxy group, 2-hydroxyethoxy group), amino group (
For example, amino group, methylamino group, dimethylamino group,
(ethylamino group, diethylamino group, anilino group), ureido group (for example, ureido group, methylureido group, ethylureido group), and the like. The Hammett's ~p value is described in "Structure-Activity Relationship of Drugs" (Nankodo), page % (1979), and substituents can be selected based on this table. Furthermore, in the general formula (T), the phenyl group having a sulfo group represented by R2 may have other substituents in addition to the sulfo group, such as a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.).
, hydroxy group, alkoxy group (methoxy group, ethoxy group, n-propoxy group, etc.), aryloxy group (phenoxy group, etc.), alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group) , n-butyl group, etc.), carboxyl group, alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), nitro group, ami7 group (e.g. amino group, methylami7 group, diethylamino group, anilino group), cyano group, Alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, etc.), arylsulfonyl groups (phenylsulfonyl, etc.), carbamoyl groups (carbamoyl, methylcarbamoyl, ethylcarbamoyl, etc.), sulfamoyl groups (sulfamoyl, methylsulfamoyl group, ethylsulfamoyl group, etc.), sulfonamide group (
methylsulfonamide group, ethylsulfonamide group, etc.)
, 7 acylamino groups (acetylamino group, benzoylamino group, etc.). Specific examples of these include 3-sulfophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-chloro-4
-sulfophenyl group, 4-chloro-3-sulfophenyl group, 2-chloro-5-sulfophenyl group, 2-methoxy-4-sulfophenyl group, 2-hydroxy-4-sulfophenyl group, 2,5-dichloro -4-sulfophenyl group, 2.6-cymethyl-4-sulfophenyl group, 4-7 enoxy-3-sulfophenyl group, 2-chloro-6-methyl-4-sulfophenyl group, 3-carboxy-2-hytronoxy5 -sulfophenyl group, 2.5-disulfophenyl group, 3.5-disulfophenyl group, etc.

Next, the monovalent group represented by R8 has 1 to 4 carbon atoms.
alkyl groups (e.g. methyl group, ethyl group, n-butyl group), halogen atoms (e.g. fluorine atom, chlorine atom,
bromine atom), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group), nitro group, amino group (e.g. amino group, ethylamino group, dimethylamino group, anilino group), acylamino group (acetylamino group, benzoyl group) (amino group), sulfonamide group (e.g. methylsulfonamide), carboxyl group, cyan group, sulfo group, alkyl dicarbonyl group (methoxycarbonyl group, propoxycarbonyl group, etc.), alkylsulfonyl group (methylsulfonyl group, ethylsulfonyl group, etc.) ), carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group), sulfamoyl group (e.g. sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group), mercapto group, alkylthio group (methylthio group, ethylthio group, etc.) ) etc.

Furthermore, the alkyl groups represented by X and Y are as follows:
There are alkyl groups having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group), and the above-mentioned substituents with Σπ larger than -4,70 Examples of the alkyl group include a cyanoalkyl group, a hydroxy-10-alkyl group, a halogenated alkyl group, a carboxyalkyl group, an alkoxycarbonylalkyl group, an acylalkyl group, an acyloxyalkyl group, an alkoxyalkyl group, a phenoxyalkyl group, and a dialkyl group. Preferred examples include an aminoalkyl group, a phenylaminoalkyl group, an acetylaminoalkyl group, an alkylsulfonylaminoalkyl group, an alkylsulfonylalkyl group, an alkylthioalkyl group, an aminoalkyl group, and an aralkyl group. Further, X and Y may be the same or different from each other, and examples of the 5- or 6-membered ring formed by combining X and Y with each other include a pyrrolidino ring, a piperidino ring, and a morpholino ring.

In the present invention, as described above, the substituent of the alkyl group having the substituents represented by X and Y is a substituent whose total value Σπ of the hydrophobic substituent constant π is larger than −4.70. It is characterized by That is, when X and/or Y are represented as -R-X and/or -R-Y' (where R represents an alkylene group and Y' and Y' each represent a substituent), Y The substituents X' and Y' are selected such that the sum of the hydrophobic substituent constants π of each of ' and Y', Σπ, is greater than -4.70. The value of this hydrophobic substituent constant π is described on the same page of the above-mentioned publication, and the substituent can be selected based on the description in this table.

Furthermore, the methine group represented by L in the general formula [I] is substituted with an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-butyl group, etc.) or an aryl group (e.g., phenyl group). may have been done.

The dye according to the present invention represented by the above general formula [I] is synthesized by condensing an aldehyde compound represented by the following general formula CI'I)-= with a pyrazolone compound represented by the following general formula] be able to.

General formula l] 2 [wherein R+, R2, Rs, X, Y, G, L and m
represent the same groups and numbers as in the general formula [■], respectively. p and q represent an integer of 1 or 2. However, between n in the above general formula [■], n =
Since there is a relationship p + q -1, p and q cannot be 2 at the same time.

The above reaction is carried out by heating a mixture of the above general formulas [■] and [■] in the presence of a basic condensing agent such as sodium acetate, pyridine, piperidine, triethylamine, etc. The above reaction may be carried out in an inert solvent such as methanol, ethanol, ethylene glycol, methylcellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane, acetic acid, or water in the presence or absence of the above basic condensing agent. Among them, 13- can also be done.

The aldehyde compound represented by the above general formula [■] can be produced by a known method. For example, general formula (II
:), the aldehyde compound with p=1 is prepared using dimethylformamide as a formylating agent and the Vilsmeyer-Hack reaction (Berichte, Vol. ω, Vol. 11).
9, 1927) from the corresponding substituted anilines. On the other hand, p-2 aldehyde is N-
Using methylanilinopropane(1)-al(3) and the appropriate aniline, Berichte % Vol. 91 8
It can be made in the same manner as the Vilsmeier reaction, as described on page 50 (1958).

Berichte, Vol. 61, p. 2074 (1)
It can also be obtained from the reaction of the corresponding substituted aminobenzaldehyde with valaldehyde as described in J.D. 928).

The pyrazolone compound represented by q=1 in the general formula
Various sulfoarylhydrazines can be made by condensation with appropriate substituted esters by methods known in dye chemistry. The intermediate represented by q=2 in the general formula 1] can be obtained by condensation of the product represented by q-1 in the 14-general formula 1] with a dialkyl ketone, alkylaryl ketone or lli group aldehyde.

The birazoline compound represented by the general formula [m] can be prepared, for example, by the method described in Qrganic 5yntheses, Vol. 87, p. 87 (1948), J. Am, Chem.
Soc, Vol. 66, p. 1849 (1944), J. Am. Chem, 3oc, Vol. 5
2 (1943), J, Am, Che
m.

Soc, Vol. 2, p. 2136 (194, 2). Typical specific examples of the dyes according to the present invention are described below.

(Exemplary compounds) 15- 03K So, K 03Na 17- 16- ・-18- 5O3Na SO, Na 5O3H ・(CtHa)aN 0sNa 翰21- 0sNa 0sNa 22- 5OsNa Next, regarding the method for synthesizing the dye according to the present invention A synthesis example will be shown and concretely explained.

Synthesis Example l (Synthesis a of Exemplary Dye (2) > Methanol 40
2.549 of 3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one and 2.1 g of 4
-Diethylamino-2-methylbenzaldehyde was added, and 1.69 g of pyridine was further added, and the mixture was reacted under heating under reflux for 2 hours. Thereafter, 2.0 g of anhydrous potassium acetate dissolved in 101 grams of distilled water was added, and reflux was continued for 5 minutes. The reaction solution was cooled, and the precipitated crystals were collected in a furnace and recrystallized from 250 methanol to obtain 2.4 g of the above exemplary dye. The λmax of the aqueous solution of this dye was 513 nm.

Synthesis Example 2 (Synthesis of Exemplary Dye (4)) In 20 ml of methanol, 1.2711 3-methyl÷1-(4-sulfophenyl)-2-pyrazoline-5-
1.09 of 4-dimethylamino-2-methoxybenzaldehyde was added thereto, and 0.8 I of pyridine was further added, followed by reaction under heating under reflux for 2 hours. After that, 51Lt of distilled water
Add 0.82.9% of anhydrous sodium acetate dissolved in
Reflux was continued for a minute. Cool the reaction solution, separate the precipitated crystals, and add acetic acid to the mixed solvent of water and methanol)
It was purified by salting out with Jum. 1.1. The above-mentioned exemplary dye of jil is obtained, and the λmax of this dye in an aqueous solution is 4.
It was 98 nm.

Synthesis Example 3 (Synthesis of Exemplary Dye α■) In methanol 4ON, 3.069 3-ethoxy-5
- -1-(4-sulfophenyl) -2-Hilazoline-5
-one sodium salt and 1.71 g of 4-dimethylamino-2-methylbenzaldehyde were added, followed by pyridine 1.
．． 6 g was added and reacted under heating under reflux for 3 hours. after that,
Anhydrous sodium acetate 0.8 dissolved in 51 rL of distilled water
2. Jil was added and reflux was continued for 5 minutes.

The reaction solution was cooled, and the precipitated crystals were collected, thoroughly washed with methanol, and then dried to obtain the exemplified dye 4.329.

The λmBx of the aqueous solution of this dye was 482 nm.

The dye according to the present invention produced in the above manner has a methyl group, methoxy group, or hydroxy group as the substituent G at the ortho position of the benzylidene group, and has a pyrazotetraline ring. Its structural feature is that it has a monovalent group as R+ at the 3rd position, which has a Hammett value smaller than -0.05. In addition to significantly improving the stability in (acidic aqueous solution), by introducing an alkyl group having a substituent having a specific value of the hydrophobic substituent constant π into the X and Y It prevents the diffusion of dyes, and also has excellent leakage and decolorization properties during the processing process, so there is no residual color staining, and the spectral absorption properties are good, so there is no adverse effect on photographic properties, and photographic performance is improved. It is an excellent dye.

The dye according to the present invention is used by being contained in the emulsion layer and/or the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention.

In the light-sensitive material of the present invention, the oxonol dye represented by the general formula [■] can be incorporated into a silver halide emulsion and used as an irradiation-preventing dye, or can be used as a non-photosensitive hydrophilic colloid. It can also be incorporated into a layer and used as a filter dye or antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes as long as the effects of the present invention are not impaired. Incorporation of the dye according to the present invention into a silver halide emulsion layer or other non-photosensitive hydrophilic colloid layer can be easily carried out by a conventional method. Generally, dyes or organic/inorganic alkali salts of dyes are dissolved in water,
The dye can be incorporated into the light-sensitive material by preparing an aqueous solution of the dye at an appropriate concentration, adding it to a coating solution, and coating by a known method. The content of these dyes varies depending on the purpose of use, but in general, they are applied in an amount of 1 to 800 cm per 1 ba 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, polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin-coated paper, polypropylene synthetics, etc. paper,
There are glass plates, metals, etc., and these supports are appropriately selected depending on the intended use of the photographic material.

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, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. , cellulose derivatives such as carboxymethyl cellulose, etc., and these can be used alone or in combination.

The silver halide emulsion in the light-sensitive material of the present invention includes:
Any of those commonly used in 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 manufactured by various manufacturing methods including the usual manufacturing method, for example,
6-7772, or as described in U.S. Pat. No. 2,592,250, i.e. from at least some silver salts whose solubility is greater than silver bromide A so-called convergence emulsion manufacturing method in which an emulsion of silver salt grains is formed and then at least a part of the grains is converted into silver bromide salt or silver iodobromide salt, or an average grain size of 0.1 μ or less It can be produced by any production method such as the production method of Lippmann emulsion consisting of Q silver-genide-41 into fine grains having the following properties. This silver halide emulsion contains chemical sensitizers such as thiosulfates, thiolyl chlorides,
Sulfur sensitizers such as thiourea, allyl isothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride, etc. noble metal sensitizers such as gold compounds, ammonium chlorovaladate, sodium chlorotetravaladite, etc., palladium compounds such as platinum compounds such as potassium chloroaurate, ruthenium compounds, etc. Combinations can be used for sensitization. In addition to chemical sensitization, this emulsion can also be reduced sensitized using a reducing agent, such as triazoles, imidazoles, azaindenes,
It can be stabilized with benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof, and sensitizing compounds of the thioether-added type, quaternary ammonium salt type, or polyalkylene oxide type. can be contained.

The photographic 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, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes,
Various dyes such as streptocyanin dyes can be used, and one type or a combination of two or more types of sensitizing dyes can be used.

In the light-sensitive material of the present invention, glycerin, dihydroxyalkanes such as 5-bentanediol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol, etc. Wetting agents such as succinate, water-dispersible particulate polymer compounds obtained by emulsion polymerization,
Plasticizers, film property improvers, etc. can be contained, and aldehyde compounds, N-methylol compounds such as N,N'-dimethylol urea, mucohalogen acids, divinyl sulfones, 2,4-dichloro-6- Active halogen compounds such as hydroxy-8-triazine, dioxane derivatives, divinyl ketones, isocyanates, hardening agents such as carbodiimides, saponins, polyalkylene glycols, polyalkylene glycol ethers, alkyl sulfonates, alkylbenzene sulfonates, Surfactants such as alkylnaphthalene sulfonates, optical brighteners,
Photographic additives such as antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers can be included.

In the light-sensitive material of the present invention, in the silver halide emulsion layer,
It may contain a color coupler, and the coupler is 4.
It may be either equivalent or biequivalent, and may be a colored coupler for masking or a coupler that releases a development inhibitor. As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, virazoquaternic compounds, and as cyan-forming couplers, phenol-based 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.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 2. Exemplary dye (2) according to the present invention. OXIO-!
Add 0.5 ml of glacial acetic acid to too mJ of aqueous Ml solution and stir to obtain a decomposition rate measurement solution (pH 2.8 to 2.9).
adjusted. A spectrophotometer measures the decrease in absorbance at the maximum absorption wavelength of this solution over time (every 10 minutes for 1 hour).
The initial decomposition rate was determined. In the same manner, measurements were also carried out for the exemplary dyes (7), (16), α9 and C■, as well as the following comparative dyes, ■, 0.0 and (g). Dye 0 Comparative Dye ■ From the results in Table 1 above, it can be seen that the dye according to the present invention has improved decomposition in an aqueous solution (acidic aqueous solution) and has significantly excellent stability. On the other hand, it was also shown that comparative dyes other than the present invention, which do not satisfy the structure of the general formula (0), are significantly decomposed in an aqueous solution. It was also revealed that, like Comparative Dye (■), which has a methyl group at the ortho-position of the benzylidene group but in which the 1-position of the pyrazolone ring is substituted with an alkyl group, similarly has poor storage stability. Ta.

Example 2 3.5 g of gelatin was added and dissolved in 351 g of distilled water, and illustrative dyes (1), (4) and α1 according to the present invention were added thereto.
2 each. A 5N aqueous solution containing 10-' moles of OX was added, and an additional 1.25 mJ of a 10% saponin aqueous solution was added!
and 0.751 nl of 1% formalin solution were added thereto, and water was added to make the total volume 50-. This dye solution was applied onto an acetylcellulose film support, dried, and sample [1]
] [2] and [3]. Also, instead of the dye according to the present invention, using the following comparative dyes [F] and 0,
Comparative samples [4] and [5] were prepared in the same manner.

Comparative Dye [F] First Edition - Comparative Dye 0 Each of these samples was immersed in a developer having the following composition at 5° C. for 1 minute, washed with water for a second, and then dried.

(Developer group S, > 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 absorption maximum wavelength. The results are shown in Table 2 below.

E.

- Haichi (El is the absorbance before immersion in the developer, and E is the absorbance after immersion in the developer.) As is clear from Table 2, the dyes according to the present invention are more effective than the comparative dyes. It was found that it exhibits excellent decolorizing properties. Comparative dye 0 of sample 4 outside the present invention is a dye having a pentyloxy group at the ortho position of the benzylidene group in the general formula [■], and is a dye according to the present invention having a methoxy group at the ortho position of the benzylidene group. It can be seen that they are inferior in decolorizing properties.

Example 3 A silver chloroiodobromide gelatin emulsion containing 80 mol % of silver chloride, 19.5 mol % of silver bromide and 0.5 mol % of silver iodide and having an average grain size of 0.32 μm was prepared. Per 1 kg of this gelatin emulsion (containing 48 g of silver and 75 fl of gelatin), 35 ml of 2,4-dichloro-6-hydroxy-1,3°5-triazine sodium salt (1% aqueous solution) and 50 ml of saponin (10% aqueous solution) were added. - on the undercoated polyethylene terephthalate film support,
It was coated to contain 50 μg of silver per 100 crI and dried.

Further, on this emulsion layer, an exemplary dye (21
A protective layer containing the following composition was coated to have a dry film thickness of 2 μm. (referred to as Sample 6) (Protective layer composition) Similarly, in place of the exemplified dye (2) of the present invention, exemplified dyes (5) and a according to the present invention and the comparative dye (T) used in Example 2 were used. ) and 0 were prepared, and designated as samples 7, 8, 9 and 10, respectively.

Each of these samples was cut into small pieces, exposed to light through a photographic lens, and processed using a developer and a fixer having the following compositions. Development was carried out at 20"C for 1.5 minutes, fixing was carried out at 20"C for 2 minutes, washing was carried out at 20"C for 5 minutes, and then dried.

(Composition of developer) 41- (Composition of fixer) Stack 10 sheets of each developed sample,
The presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 3 below.

In the sample using the comparative dye, color staining was observed in the sample, but with the dye according to the present invention, there was no color stain at all due to excellent run-off and decolorization properties.

Example 4 A silver chlorobromide gelatin emulsion containing 70 mol % of silver chloride and I mol % of silver bromide and having an average grain size of 0.3 μm was prepared. This gelatin emulsion tkg (silver 48g, gelatin 759g)
After adding 20 ml of formalin (1% aqueous solution) and 501 Lt of saponin (10% aqueous solution) per emulsion layer (including A protective layer was applied.

(Protective layer composition) Next, on the back side of the support coated with the emulsion layer and the protective layer, a gelatin layer containing a dye having the following composition was applied to a dry film thickness of 3 μm.
It was applied so that the thickness was m. (Sample 11) (Gelatin layer composition) Similarly, instead of the exemplary dye (3) according to the present invention,
Exemplary dye (a) according to the present invention and the following comparative dye 0
Using this method, samples were prepared and designated as samples a2 and Q3).

Comparative dye 0 Developed in the same manner as in Example 3, and each sample 10
The sheets were stacked one on top of the other and colored contamination was evaluated. The results obtained are shown in Table 4 below.

Table 4 As shown in the above table, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes according to the present invention. Furthermore, it has been found that the dye according to the present invention can provide a photographic material having an excellent antihalation effect without causing any adverse effects such as fog or desensitization on the photographic emulsion.

Example 5 On a polyethylene terephthalate film support, the first
A gelatin solution containing the following dye and having the following composition was applied as a layer to a dry film thickness of 2 μm.

(Gelatin liquid composition) 45- Next, per 1 kg of gelatin emulsion was added to a silver iodobromide gelatin emulsion consisting of silver bromide % mol % and silver iodide 4 mol % and having an average grain size of 0.8 μm. 2,4-dichloro-6-
Hydroxy-1,3,5-)riazine sodium salt (1
% aqueous solution) and 20 rLe of sodium dodecylbenzenesulfonate (1% aqueous solution) were added, and a second layer was applied so that the dry film thickness was 5 μm.

Furthermore, a gelatin solution having the following composition was applied as a protective layer on top of this emulsion layer so that the dry film thickness was 2 μm, and the sample (
14 was prepared.

(Gelatin liquid composition) Gelatin 20.946 In the same manner, instead of the above-mentioned exemplary dye (3) in the first layer, exemplary dyes a [and αe and the following comparative dyes (I) and (J) according to the present invention were used. Samples were prepared using the following methods. At the same time, samples containing no dye were also prepared, and these samples were sequentially divided into sample a5), chain, αη, αL.
Q'l and ■ were closed.

Comparative Dye (J) Each of the above samples was cut into small pieces, exposed through a photographic lens, and processed using a developer having the composition shown below and the fixing solution used in Example 3 to prepare a comparative dye. Development was carried out at 5°C for 2 minutes, and fixation was carried out at 5°C.
The sample was washed at 5°C for 2 minutes, washed with water at 5°C for 5 minutes, and then dried.

(Development tfIffII formation) After the development process, sensitometry was performed to obtain a characteristic curve, and the relative sensitivity was determined by setting the sensitivity of sample (2) containing no dye as 100. The results obtained are shown in Table 5 below.

Table 5 As is clear from the above table, the sample containing the dye according to the present invention shows less decrease in sensitivity than the sample containing the comparative dye. This means that the dye according to the invention has less diffusion of the dye from the mordanted layer to other adjacent layers. On the other hand, the value of the hydrophobic substituent constant π of the substituent of the substituted alkyl group in the substituted alkylaminobenzylidene group substituted at the 4-position of the pyrazolone ring as in the comparative dyes σ), () and wholesale is −4,70. The smaller one (SO, the π value of -4,76
), the sensitivity of samples containing these dyes is greatly reduced.

Effects of the Invention The dye according to the present invention has improved decomposition in an acidic aqueous solution, has significantly excellent stability, has good flow out in a processing solution, does not cause residual color contamination, and Diffusion in the layer is small and sensitivity does not decrease.

Agent Kuwahara Anmi 50- Procedural amendment 1984 1611711 Name of the invention Silver halide photographic light-sensitive material 3 Relationship to the Nagisa case involving supplementary marketing Patent 1''1 Applicant's address 1-26 Nishi-Shinjuku, Shinjuku-ku, Tokyo Number 2η Name (+27) Konishiroku Photo Industry Co., Ltd. 1 Director Nobuhiko Kawamoto 4 Agent 191 K. Tokyo Exit u! ) rli Sakuramachi 11 Reiji Konishi Rokushasei ``Business stock owner i, day 5, date of amendment order'' Self-issued 6, "Detailed description of the invention" column 7 of the specification subject to the amendment, Contents of the amendment (1) Amend the detailed description of the invention as follows O 2-

Claims (2)

[Claims] (1) A silver halide photographic material containing a compound represented by the following general formula [I]. 1 [In the formula, G represents a methyl group, methoxy group or hydroxy group, R represents a monovalent group with a Hammett's 17'' p value of less than -0.05, and R2 represents at least one sulfo group. X represents a monovalent group, and X and Y each represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent whose sum of hydrophobic substituent constant π values Σπ is larger than -4.70 represents a group, and X and Y may combine with each other to form a 5-membered ring or a 6-membered ring.L
represents a methine group, m represents an integer of 1, 2.3 or 4, and n represents an integer of 1 or 2. ] (2) Claims characterized in that the monovalent group having a Hammett Owp value of less than -0.05 is an alkyl group, a cycloalkyl group, a hydroxy group, an alkoxy group, a ureido group, or an amine 7 group. The silver halide photographic material according to item (1).