JP2676212B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a dye, and more particularly to a halogen containing a hydrophilic colloid layer colored with a dye useful as a light absorbing dye. The present invention relates to a silver halide photographic light-sensitive material.

[Background of the Invention]

Silver halide photographic material (hereinafter referred to as photosensitive material)
It is well known that a photographic material contains a dye for the purpose of absorbing light of a specific wavelength for the purpose of absorbing light of a specific wavelength in order to prevent a filter, antihalation, prevention of irradiation, or sensitivity adjustment of a photographic emulsion. It is common practice to color sexual colloid layers.

The filter layer is usually located above the photosensitive emulsion layer or between the emulsion layer and the emulsion layer, and serves to convert incident light reaching the emulsion layer into light having a preferable spectral composition. For the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back surface of the support to prevent harmful effects on the interface between the emulsion layer and the support or on the back surface of the support. It is often performed to prevent halation by absorbing such reflected light or to color the emulsion layer to absorb harmful reflected light or scattered light due to silver halide grains, etc. to prevent irradiation. ing.

The dye used for such a purpose has good absorption spectrum characteristics according to the purpose of use, is completely decolorized during the photographic development process, and is easily eluted from the photographic material. No residual color contamination, no adverse effects such as fog or desensitization on the photographic emulsion, no diffusion from the dyed layer to other layers, and aging in solution or photographic material It must satisfy various conditions such as excellent stability and no discoloration.

To date, many efforts have been made and a number of dyes have been proposed for the purpose of finding dyes satisfying the above-mentioned conditions, but in particular dyes that absorb from the red region to the infrared region, and as described above. Few dyes satisfying various conditions have been known.

(Object of the present invention)

The object of the present invention is to have good absorption spectral properties,
Provided is a silver halide photographic light-sensitive material containing a dye that is decolorized during photographic development and eluted from the photographic material, has very little residual color stain after processing, and is inactive to a photographic emulsion. Especially.

[Configuration of the invention]

The object of the present invention is achieved by a silver halide light-sensitive material containing a novel oxonol dye represented by the following general formula [I].

General formula [I] [In the formula, n represents an integer of 3 or 4, Q ₁ and Q ₂ represent a carbocyclic or heterocyclic group, and L represents a methine group. The oxonol dye represented by the general formula [I] used in the present invention will be described.

Q ₁ and Q ₂ are carbocycles such as 1,3-cyclopentanedione, 1,3-indandione and pyrazolone, isoxazolone, barbituric acid, thiobarbituric acid, 3-
Oxythionaphthene, rhodanine, 2-thiohydantoin, 2-thioxazolidinedione, pyrazolopyridine,
Represents the group of atoms necessary to form a heterocycle such as quinolone.

L represents a methine group, but may be substituted with an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.), phenyl group, benzyl group, phenethyl group, hydroxy group, acyloxy group, halogen atom, etc. good. Further, the substituent of the methine group may form a ring (for example, 5,5-dimethyl-1-cyclohexen-1-yl-3-ylidene).

The oxonol dye represented by the general formula [I] preferably has an acid group (sulfo group, carboxy group, phosphoric acid group, etc.) in the molecule, and more preferably has at least two sulfo groups or carboxy groups. . Examples of the oxonol dye represented by the general formula [I] include pyrazolone oxonol dyes represented by the following general formula [I] -1 and barbituric acid and thiobarbituric acid dye compounds represented by [I] -2. Can be mentioned.

The methine group preferably forms a ring such as 5,5-dimethyl-1-cyclohexen-1-yl-3-ylidene in terms of ease of synthesis.

In the formula, n represents an integer of 3 or 4. R ₁₁ and R ₁₂ represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group.

Examples of the alkyl group represented by R ₁₁ and R ₁₂ include linear, branched, and cyclic groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and cyclohexyl, and examples of the aralkyl group include benzyl and phenethyl. Examples of the aryl group include phenyl, naphthyl, and the like, and examples of the heterocyclic group include benzothiazolyl, pyridyl, pyrimidyl, sulforanyl, and the like, among which an alkyl group, an aralkyl group, and an aryl group are preferable.

The alkyl group, aralkyl group, aryl group, and heterocyclic group represented by R ₁₁ and R ₁₂ may have various substituents, for example, sulfo, carboxy, hydroxy, cyano,
Halogen (eg fluorine, chlorine etc.), alkyl (eg methyl, isopropyl, trifluoromethyl, t-butyl, ethoxycarbonylmethyl, sulfomethyl etc.), amino (eg amino, dimethylamino, sulfoethylamino, piperidino, morpholino etc.), Alkoxy (eg methoxy, ethoxy, sulfopropoxy etc.), sulfonyl (eg methanesulfonyl, ethanesulfonyl etc.), sulfamoyl (eg sulfamoyl, dimethylsulfamoyl etc.), acylamino (eg acetamide, benzamide, sulfobenzamide etc.), carbamoyl (eg For example, carbamoyl, phenylcarbamoyl, sulfophenylcarbamoyl, etc.), sulfonamide (eg, methanesulfonamide, benzenesulfonamide, etc.) ), Alkoxycarbonyl (e.g. ethoxycarbonyl, hydroxy ethoxycarbonyl, benzyloxycarbonyl), aryloxycarbonyl (e.g. phenoxyethanol carbonyl, nitro phenoxyethanol carbonyl), there can be mentioned groups such as.

The aralkyl group and aryl group represented by R ₁₁ and R ₁₂ desirably have at least one group selected from the group consisting of a sulfo group, a carboxy group and a phosphoric acid group on the aromatic nucleus, and more preferably at least one sulfo group. It is desirable for the group to have.

In the formula, R ₁₃ and R ₁₄ are alkyl groups, aryl groups, aralkyl groups, heterocyclic groups, carboxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, ureido groups, thioureido groups, acylamino groups, acyl groups, imide groups. Represents a cyano group, a hydroxy group, an alkoxy group, and an amino group.

Specific examples of the alkyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylamino group, alkoxy group and amino group represented by R ₁₃ and R ₁₄ are the alkyl group and aralkyl represented by R ₁₁ and R ₁₂ described above. Specific examples of the substituent introduced into the group, the aryl group and the heterocyclic group can be mentioned. Furthermore, examples of the aryl group represented by R ₁₃ and R ₁₄ include phenyl, sulfopropoxyphenyl, cyanophenyl, carboxyphenyl, nitrophenyl, sulfophenyl, etc., and examples of the aralkyl group include benzyl, phenethyl, sulfobenzyl, etc., and heterocyclic groups. Is, for example, furyl, thienyl, etc.
Examples of the ureido group include methylureido, phenylureido and the like, examples of the thioureido group include methylthioureido, phenylthioureido and the like, examples of the imide group include succinimide and phthalimide, and examples of the acyl group include acetyl and pivalyl. To be

The groups represented by R ₁₃ and R ₁₄ include an alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group,
A ureido group, an acylamino group, an acyl group, an imide group, a cyano group, a hydroxy group, an alkoxy group and an amino group are preferable, and an alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group and an alkoxy group are more preferable. And amino groups.

n represents an integer of 3 or 4, W represents an oxygen atom and a sulfur atom, L represents a methine group, and R _{21 to} R ₂₄ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. .

Examples of the methine group represented by L include those mentioned above in the section of the general formula [I].

Examples of the alkyl group represented by R _{21 to} R ₂₄ include the same as the alkyl groups of R ₁₁ and R ₁₂ mentioned in the item of the general formula [I] -1, and the alkyl group may have a substituent. ,
As the substituent, for example, various ones mentioned as the substituent introduced into the groups of R ₁₁ and R _{12 in} the section of the general formula [I] -1 can be mentioned.

The aryl group represented by R _{21 to} R ₂₄ is preferably a phenyl group, and the substituent introduced into this phenyl group is the group introduced into R ₁₁ and R _{12 in} the formula [I] -1. Although various substituents can be mentioned, it is desirable to have at least one of a sulfo group and a carboxy group on the aromatic nucleus.

The aralkyl group represented by R _{21 to} R ₂₄ is preferably a benzyl group or a phenethyl group, and examples of the substituent introduced on the aromatic nucleus include the same substituents as the aryl group of R _{21 to} R ₂₄ described above. You can

Examples of the heterocyclic group represented by R _{21 to} R ₂₄ include, for example, pyridyl, pyrimidyl, etc., and the substituent introduced on this heterocyclic ring is a substituent of the aryl group of R _{21 to} R ₂₄ described above. The same as the group can be mentioned.

The groups represented by R _{21 to} R ₂₄ are preferably an alkyl group and an aryl group, and further include barbituric acid and thiobarbituric acid represented by the general formula [I] -2, a carboxy group and a sulfo group in the molecule of the oxonol dye. It is desirable to have at least two of the groups.

Specific examples of the dye compound represented by the general formula [I] used in the present invention are shown below, but the scope of the present invention is not limited thereto.

Specific compounds Next, a method for synthesizing the compound of the present invention will be described. Examples of the methine chain supplier of the compound of the present invention include, for example, Harmer's "The cyanine soybean and relayed compounds" (FM Hamer "The cyanine dyes and rel
ated compounds "1964, Interscience Publishers) P2
49-P251 (Wherein R ₁ R ₂ N is an amine such as methylaniline or 1,2,3,4-tetrahydroquinoline, and X ⁻ is a halogen, etc.), or (Wherein R ₁ R ₂ N is an amine, R ′ is a hydrogen atom or an acyl group, X ⁻ is a halogen, etc.) as in the above compounds, and the like. .

The symmetrical compound of the present invention can be obtained by reacting 1 mol of the methine chain donor with 2 mol of an acidic mother nucleus compound such as pyrazolone. Regarding the asymmetric type compound, first, 1 mol of the methine chain supplier and 1 mol of the mother nucleus compound are reacted to synthesize an aminopolymethine-substituted mother nucleus compound, and then 1 mol of an appropriate mother nucleus compound is further reacted. Can be synthesized.

Regarding these condensation reactions, for example, Japanese Patent Publication No.
Japanese Patent Publication No. 52-38056, Japanese Patent Publication No. 49-99620, Japanese Patent Publication No. 50
It is described in detail in -91627 etc. and can be referred to.

The synthesis of the oxonol dye of the present invention containing a cyclic group such as a cyclohexene ring in the methine chain can be performed by, for example, compound (16).
about As described above, first, an acid mother nucleus is reacted with isophorone to synthesize a cyclohexenylidene-substituted mother nucleus.

On the other hand, the compound (16) can be obtained by reacting with the intermediate shown below according to a conventional method.

Synthesis of compound (74) As shown in the above-mentioned synthetic scheme, first, the compound (II) as a methine chain donor was synthesized according to the above-mentioned literature.

Next, 150 mg of compound (I), 100 mg of compound (II) and 70 mg of triethylamine were dissolved in 5 ml of dimethylformamide, and the mixture was heated and stirred at a bath temperature of 50 to 60 ° C. for 1 hour and a half.

After cooling, isopropyl ether was added, and the product was purified by decantation to obtain compound (74).

Synthesis of compound (75) In the synthesis of compound (74), 1- (4-sulfophenyl) -3-carboxy-5 was used instead of compound (I).
-Compound (75) was obtained by a similar synthesis except that pyrazolone was used.

Synthesis of compound (76) In the synthesis of compound (74), 1- (2,5-disulfophenyl) -3-methyl-5 was used instead of compound (I).
-Compound (76) was obtained according to this method except that pyrazolone was used.

Synthesis of compound (77) Synthesis of compound (74) was conducted according to this method except that 1- (4-sulfophenyl) -3-ethoxycarbonyl-5-pyrazolone was used instead of compound (I) in the synthesis of compound (74). The compound (77) was obtained.

Synthesis of compound (78) In the synthesis of compound (74), 1- (2,5-disulfophenyl) -3-acetyl- was used instead of compound (I).
Compound (78) was obtained according to this method except that 5-pyrazolone was used.

If the mother nucleus is selected, an asymmetric type oxonol dye of the mother nucleus can be obtained, and a nonamethine dye can be synthesized by synthesizing the above intermediate by using pentadiene dianil instead of propene dianil.

For the synthesis of heptamethine and nonamethine oxonol dyes containing these cyclic groups, see, for example, US Pat.
No. 404 describes the method for synthesizing a merocyanine dye in detail and can be referred to.

In the light-sensitive material of the present invention, the oxonol dye represented by the general formula (I) can be contained in a silver halide emulsion to be used as an anti-irradiation dye, or a non-photosensitive hydrophilic dye. It may be contained in the colloid layer and used as a filter dye or an antihalation dye. Further, two or more dyes may be used in combination depending on the purpose of use, or may be used in combination with another dye. The dye according to the present invention can be easily incorporated into a silver halide emulsion layer or other hydrophilic colloid layer by a conventional method. Generally, a dye or an organic / inorganic alkali salt of a dye is dissolved in water to prepare a dye aqueous solution having an appropriate concentration,
It is possible to add the dye to the coating solution and to apply the dye by a known method to make the dye contained in the light-sensitive material. The content of these dyes varies depending on the purpose of use, but is generally used by coating so as to be 1 to 800 mg per 1 m ² area on the photographic material.

As the support in the light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, a polyester film such as polyethylene terephthalate, a polyolefin film such as polyethylene, a polystyrene film,
There are polyamide film, polycarbonate film, baryta paper, polyolefin coated paper, polypropylene synthetic paper, glass plate, metal, etc., and these supports are appropriately selected according to the intended use of the photosensitive material.

As the hydrophilic colloid in the light-sensitive material of the present invention,
Gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymer such as agar and casein or alginic acid, synthetic resin such as polyvinyl alcohol and polyvinylpyrrolidone, and cellulose derivative such as carboxymethyl cellulose. 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 those usually 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,
Various production methods including the usual production method, for example,
No. 46-7772, or U.S. Pat.
No. 2,592,250, i.e., forming an emulsion of silver salt grains consisting of at least a portion of the silver salt, the solubility of which is greater than that of silver bromide, and then at least a portion of the grains is silver bromide salt. Alternatively, it can be prepared by any method such as a method for producing a so-called conversion emulsion such as conversion to a silver iodobromide salt or a method for producing a Lippmann emulsion comprising fine grain silver halide having an average grain size of 0.1 μm or less. This silver halide emulsion comprises a chemical sensitizer, for example, a sulfur sensitizer such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate and cystine, an active or inactive selenium sensitizer, potassium chlorosensitizer. Gold compounds such as aurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride, etc., palladium compounds such as ammonium chlorovaradate, sodium chlorovaladite, etc., platinum such as potassium chloroplatinate. Compounds, noble metal sensitizers such as ruthenium compounds, or combinations of such sensitizers can be used for sensitization. Further, this emulsion can be reduction-sensitized with a reducing agent in addition to chemical sensitization, and triazoles, imidazoles, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans or mixtures thereof. Can be stabilized with a thioether-type, quaternary ammonium salt-type, or polyalkylene oxide-type sensitizing compound.

The silver halide emulsion used in the light-sensitive material of the present invention,
If necessary, it may be spectrally sensitized with a sensitizing dye. As the sensitizing dyes, various dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, streptocyanin dyes can be used. Can be used alone or in combination of two or more.

In the light-sensitive material of the present invention, glycerin, dihydroxyalkanes such as 1,5-pentanediol, esters of ethylenebisglycolic acid, bisethoxydiethyleneglycol succinate, etc. are obtained by emulsion polymerization in the emulsion layer and other hydrophilic colloid layers. A wetting agent such as a water-dispersible fine particle polymer compound, a plasticizer, a film physical property-improving agent, etc. can be contained, and an aldehyde compound, N,
N-methylol compounds such as N'-dimethylol urea, mucohalogen acid, divinyl sulfones, 2,4-dichloro-
Hardeners such as active halogen compounds such as 6-hydroxy-S-triazine, dioxane derivatives, divinyl ketones, isocyanates, carbodiimides, saponins, polyalkylene glycols, polyalkylene glycol ethers, alkyl sulfonates, alkylbenzene sulfonic acids. Surfactants such as salts and alkylnaphthalene sulfonates, and photographic additives such as optical brighteners, antistatic agents, antistain agents, ultraviolet absorbers and stabilizers may be contained.

In the light-sensitive material of the present invention, the emulsion layer may contain a color coupler, and the coupler may be either a 4-equivalent or a 2-equivalent, and is a coupler for releasing a colored coupler for masking or a development inhibitor. May be. As the yellow-forming coupler, open-chain ketomethylene compounds such as acylacetamide-based compounds, pyrazolone-based compounds as magenta-forming couplers, and phenol- or naphthol-based compounds as cyan-forming couplers are usually advantageously used.

Further, the light-sensitive material of the present invention can have any layer structure that a normal light-sensitive material can have.

〔Example〕

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

Example 1 3.5 g of gelatin was added to and dissolved in 35 ml of distilled water.
5 ml of an aqueous solution containing 2.0 × 10 ^-4 mol of each of the exemplary dyes (9), (21) and (22) of the present invention was added, and further 1.25 ml of 10% saponin aqueous solution and 0.75 ml of 1% formalin solution were added, Water was added to bring the total volume to 50 ml. The dye solution was applied on an acetylcellulose film support and dried to obtain Samples 1, 2 and 3. Comparative Samples 4 and 5 were prepared in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention.

Each of these samples was immersed in a developer having the following composition at 25 ° C. for 1 minute, washed with water for 20 seconds, and then dried.

(Composition of developer) Methol 3.0 g Sodium sulfite (anhydrous) 45.0 g Hydroquinone 12.0 g Sodium carbonate (monohydrate) 80.0 g Potassium bromide 2.0 g Add water to make 1

The visible spectrum of each sample before and after immersion in the developer was measured, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below.

(E ₁ is the absorbance before the developer immersion, E ₂ is the absorbance after the developer immersion.) As is clear from Table 1, the dye of the present invention was found to exhibit excellent decolorization properties as compared with the comparative dye.

Example 2 80 mol% of silver chloride, 19.5 mol% of silver bromide and 0.5 of silver iodide
A silver chloroiodobromide gelatin emulsion having an average grain size of 0.32 μm was prepared. 1 kg of this gelatin emulsion (4 silver
Contains 8g, 75g gelatin. ) Per 2,4-dichloro-6
After adding 35 ml of hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) and 50 ml of saponin (10% aqueous solution), 50 mg of silver was contained per 100 cm ² on a polyethylene terephthalate film support which had been subjected to subbing treatment. And dried.

Further, a protective layer having the following composition containing the exemplified dye (16) of the present invention was coated on the emulsion layer so that the dry film thickness was 2 μm. (Sample 6) (Protective layer composition) Gelatin 40 g Water 850 ml Exemplified dye (16) of the present invention (2% aqueous solution) 100 ml 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (1 % Aqueous solution) 20 ml Saponin (10% aqueous solution) 30 ml Similarly, instead of the exemplary dye (16) of the present invention, exemplary dyes (20) and (24) and the comparative dyes (A) and (B) used in Example 1 were used. ), Make a sample containing
The samples were 7, 8, 9 and 10, respectively.

Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using a developing solution and a fixing solution having the following compositions. Development was performed at 20 ° C. for 1.5 minutes, fixing was performed at 20 ° C. for 2 minutes, water washing was performed at 20 ° C. for 5 minutes, and then dried.

(Developer composition) Hydroquinone 15g Formaldehyde sodium bisulfite adduct 55g Anhydrous sodium sulfite 3g Sodium carbonate (monohydrate) 80g Boric acid 5g Potassium bromide 2.5g Ethylenediaminetetraacetic acid disodium 2g Water is added 1,000ml (fixer composition ) Sodium thiosulfate 160 g Anhydrous sodium sulfite 14 g Glacial acetic acid 12 ml Borax 12 g Potassium alum 5 g 1,000 ml of water-added developed samples were piled up 10 times each, and the presence or absence of color contamination on the sample was examined. The results obtained are shown in Table 2 below.

In the sample using the comparative dye, coloring stain was observed in the sample. However, the dye of the present invention was excellent in outflow and decolorization properties, and did not have any coloring stain.

Example 3 A silver chlorobromide emulsion comprising 70 mol% of silver chloride and 30 mol% of silver bromide and having an average grain size of 0.3 μm was prepared. For each 1 kg of this gelatin emulsion (including 48 g of silver and 75 g of gelatin), 20 ml of formalin (1% aqueous solution) and 50 saponins (10% aqueous solution)
After adding ml, it was coated on a polyethylene terephthalate film support which had been subjected to a subbing treatment, and a protective layer having the following composition was further coated on this emulsion layer.

(Protective layer composition) Gelatin 40 g Water 960 ml Formalin (1% aqueous solution) 12 ml Saponin (10% aqueous solution) 30 ml Next, a gelatin layer containing a dye having the following composition is formed on the back surface of the support coated with the emulsion layer and the protective layer. Dry film thickness is 3
It was applied to a thickness of μm. (Sample 11) (Gelatin layer composition) Gelatin 50g Water 835ml Exemplified dye according to the present invention (37) (2% aqueous solution) 100ml Formalin (1% aqueous solution) 15ml Saponin (10% aqueous solution) 50ml Similarly, the present invention In place of the exemplified dye (37) of (1) and the comparative dye (B) of the present invention
Samples were prepared by using and were designated as Samples 12 and 13.

Developing treatment was performed in the same manner as in Example 2, and each sample 10
The sheets were superimposed one by one to evaluate coloring contamination. The results obtained are shown in Table 3 below.

As shown in the above table, the samples using the comparative dyes showed color stains, but the dyes according to the present invention did not show any color stains. It was also found that the dye according to the present invention can provide a light-sensitive material having an excellent antihalation effect without adversely affecting the photographic emulsion such as fog and desensitization.

Example 4 On a support made of polyethylene-coated paper, the following layers were sequentially provided from the support side to prepare a color photographic material (Sample 14).

First layer: yellow coupler; α-pivalyl-α- (1-benzyl-2-phenyl-3,5-dioxotriazolidine-
4-yl) -2'-chloro-5 '-[γ- (2,4-di-
(t-amylphenoxy) butyramide] acetanilide, a hardener (dichlorotriazine) and a surfactant (saponin) containing a blue-sensitive silver halide emulsion layer (90
A silver chlorobromide emulsion containing mol% of silver bromide and sensitized with a sensitizing dye was provided so that the coated silver amount was 3.5 mg / 100 cm ² .

Second layer: a gelatin layer (intermediate layer) was provided.

Third layer ... Magenta coupler; 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacedamide) benzamide] -5-pyrazolone, hardener Green-sensitive silver halide emulsion layer containing (dichlorotriazine) and a surfactant (saponin) (a silver chlorobromide emulsion containing 80 mol% of silver bromide and sensitized with a sensitizing dye). Was set so that the coated silver amount was 4.5 mg / 100 cm ² .

Fourth layer: a gelatin layer (intermediate layer) was provided.

Fifth layer: cyan coupler; 2,4-dichloro-3-methyl-
6- (2,4-di-t-amylphenoxyacetamide)
Red-sensitive silver halide emulsion layer containing phenol, hardener (dichlorotriazine) and surfactant (saponin) (a silver chlorobromide emulsion containing 75 mol% of silver bromide, sensitized with a sensitizing dye). The coated silver amount was set to 2.0 mg / 100 cm ² .

Sixth layer: A gelatin layer (protective layer) was provided.

Furthermore, a red-sensitive emulsion (fifth layer coating solution) was prepared by adding 200 ml of a 2% aqueous solution of the known dye C or the known dye C according to the present invention to 1 kg of the emulsion.
Sample [15] and sample [16] were prepared in the same manner as in.

Known dye (C) These samples 14, 15 and 16 were exposed and then processed according to the following processing steps.

[Processing step (31 ° C)] Processing time 1. Color development 3 minutes 2. Bleach-fixing 1 minute 3. Washing with water 2 minutes 4. Stabilization 1 minute 5. Washing with water 2 minutes Composition of processing solution used in each processing step Is as follows.

(Color developer composition)

 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.8g anhydrous sodium sulfite 4.0g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 28.0g potassium bromide 1.5g Potassium hydroxide 1.0g Add water to make 1.

(Bleach-fix solution composition)

 Ethylenediaminetetraacetic acid ferric salt 65.0 g Ethylenediaminetetraacetic acid disodium salt 3.0 g Anhydrous sodium sulfite 9.5 g Ammonium thiosulfate 77.5 g Anhydrous sodium carbonate 4.0 g Add water to make 1.

(Fixer composition)

 Glacial acetic acid 9 ml Sodium acetate 3 g Add water to make 1.

 Table 4 shows the density of the unexposed portion of each sample after the treatment.

As is clear from Table 4, in the sample containing the dye of the present invention, no coloring stain due to the residual color of the dye as shown in the sample containing the known dye was observed. When the sensitivities of the respective samples were compared, it was found that the dye of the present invention had very little adverse effect on the emulsion.

〔The invention's effect〕

According to the present invention, it has good absorption spectrum characteristics, is decolorized during the photographic development process, and is eluted from the photographic material,
Very little residual color contamination after processing, and for photographic emulsions,
It was possible to provide a silver halide photographic light-sensitive material containing an inactive dye.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-316853 (JP, A) JP-A-63-231445 (JP, A) JP-A 64-44441 (JP, A) JP-A 48- 85130 (JP, A) JP 63-55544 (JP, A) JP 55-155350 (JP, A) JP 62-123454 (JP, A) JP-B 7-74889 (JP, B2) Japanese Patent Publication 7-31384 (JP, B2) Japanese Patent Publication 6-87131 (JP, B2) Japanese Publication 6-81756 (JP, B2)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material containing an oxonol dye represented by the following general formula [I]. General formula [I] [In the formula, n represents an integer of 3 or 4, Q ₁ and Q ₂ represent a carbocycle or a heterocycle-forming group, and L represents a methine group. ]