JPH0693089B2 - Silver halide photographic light-sensitive material containing merocyanine dye - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material containing a merocyanine dye. In particular, the present invention relates to a silver halide photographic light-sensitive material which contains a specific merocyanine dye and has good spectral characteristics and does not cause any inconvenience due to the dye.

[Prior Art] In a silver halide photographic light-sensitive material (hereinafter, also abbreviated as a light-sensitive material, etc., as appropriate), a light of a specific wavelength is used for a filter, an antihalation, an anti-irradiation or a sensitivity adjustment of a photographic emulsion. For the purpose of absorbing
It is well known to incorporate a dye into a light-sensitive material, and for example, a hydrophilic colloid liquid is often colored with the dye.

The dye is contained in, for example, a filter layer, an antihalation layer, an emulsion layer or the like. Among them, the filter layer is usually located above the photosensitive emulsion layer or between the emulsion layers and plays a role of making 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. Absorbs various reflected light to prevent halation or color the emulsion layer,
Irradiation is often prevented by absorbing harmful reflected light and scattered light from silver halide grains and the like.

The dye used for such a purpose is, of course, required to have good absorption spectrum characteristics according to the purpose of use, and in addition, it is completely decolorized during the photographic development process and is easily removed from the photographic material. After elution, there is no residual color contamination due to the dye after development processing, it does not adversely affect the photographic emulsion such as fog and desensitization, it does not diffuse from the dyed layer to other layers, and in the solution Alternatively, it must satisfy various conditions such as excellent stability over time in a photographic material and no discoloration or fading.

To date, many efforts have been made and many dyes have been proposed in order to find dyes that satisfy the above conditions. For example, British Patent No. 506,385, U.S. Patent No. 3,247,127, U.S. Patent No. 2,533,472, British Patent No. 1,278,621, Japanese Patent Publication No. 39-22069, Japanese Patent Publication No. 43-13168, Oxonol dyes described in JP-A-52-34716, US Pat. No. 1,845,404
No. 2, styryl dyes, U.S. Pat.No. 2,843,486, cyanine dyes, U.S. Pat.No. 2,493,747, U.S. Pat.No. 3,148,187, U.S. Pat.
2,699, JP-A-50-145124, JP-A-52-134
There are merocyanine dyes described in JP-A No. 425, JP-A No. 52-29727, JP-A No. 52-65426 and the like. However, in reality, there are very few good dyes that can be used in photographic materials satisfying all the above-mentioned conditions.

[Object of the Invention] An object of the present invention is to provide a light-sensitive material satisfying the above-mentioned conditions, that is, having a good absorption spectrum characteristic, decolorized during development processing, and eluted from the light-sensitive material to leave a residue after processing. It is an object of the present invention to provide a silver halide photographic light-sensitive material containing a dye which has very little color contamination and is inactive to a photographic emulsion.

[Construction of the Invention] The object of the present invention is to provide a silver halide photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, and at least one of the photographic constituent layers described below is generally used. It is achieved by a silver halide photographic light-sensitive material containing a merocyanine dye represented by the formula [I].

General formula [I] In the formula, X is a chalcogen atom, Represents L ₁ , L ₂ , L ₃ , L ₄ , L ₅ and L ₆ each represent a methine group. R ₁ represents a group capable of substituting on the benzene ring.

R ₂ represents a heterocyclic group, an aryl group, or an alkyl group. R ₃ represents an alkyl group. R ₄ is an alkyl group, a halogen atom, an aryl group, a heterocyclic group, an amino group, an acylamino group, a ureido group, a nitro group, an alkoxy group, an alkoxycarbonyl group, a carboxy group, a hydroxy group, a carbamoyl group, a cyano group, an aralkyl group, It represents a sulfo group or a sulfamoyl group, and R _{4 s} may be condensed with each other to form a naphthalene ring.

R represents an aryl group or an alkyl group. M represents a hydrogen atom or a cation. m represents an integer of 0 to 2,
n ₁ , n ₂ , and n ₃ each represent 0 or 1, p represents an integer of 0 to 3, and q represents an integer of 0 to 4. However, m + q ≠
It is 0. When m = 2 and p and q are 2 or more, each SO ₃ M, R
₁ and R ₄ may be the same or different.

Further, constituent elements of the merocyanine dye will be specifically shown.

The methine group represented by L ₁ , L ₂ , L ₃ , L ₄ , L ₅ and L ₆ may have a substituent, and as the substituent, for example, a lower alkyl group having 1 to 6 carbon atoms (for example, , Methyl group, ethyl group, propyl group, isobutyl group, etc.), aryl group (eg, phenyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, Ethoxy group etc.), aryloxy group (eg phenoxy group etc.), aralkyl group (eg benzyl group,
Examples include phenethyl group, heterocyclic group (eg, thienyl group, furyl group, etc.), substituted amino group (eg, dimethylamino, tetramethyleneamino, anilino, etc.), alkylthio group (eg, methylthio group), etc. . Also L ₂
And L ₄ and L ₄ and L ₆ may be linked to each other to form a 5- or 6-membered carbocycle.

R ₁ represents a group capable of substituting on the benzene ring, and the substituent (in the present specification, the term “substituent” includes a substituent atom) is, for example, an alkyl group (eg, methyl group, ethyl group, butyl group, etc.). This alkyl group may be further substituted,
For example, it may be substituted with a halogen atom, a cyano group, a sulfo group, a hydroxy group or the like. ), An alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), a hydroxy group, a cyano group, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), a carbamoyl group, a sulfamoyl group, an acyloxy group (eg, acetyloxy). Group etc.) alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), carboxy group, sulfo group, aryl group (eg phenyl group etc.), aralkyl group (eg benzyl group), aryloxy group (eg phenoxy group etc.)
Etc.

The heterocyclic group represented by R ₂ is a furyl group, a pyridyl group, a thienyl group, an indolyl group or the like, which may be unsubstituted, but may be substituted, for example, an alkyl group (for example, a methyl group) as a substituent. , An ethyl group, a butyl group, etc. The alkyl group may be further substituted, for example, a halogen atom, a cyano group, a sulfo group, a hydroxy group, etc.) The alkyl group represented by R ₂ is substituted or unsubstituted. (For example, a methyl group, an ethyl group, a butyl group, a heptyl group, etc.), a cyclic (for example, a cyclopentyl group, a cyclohexyl group, etc.), and a substituent such as an alkoxy group (for example, a methoxy group, an ethoxy group, a butoxy group, etc.), Hydroxy group, cyano group, nitro group, halogen atom (eg chlorine atom, bromine atom, fluorine atom, etc.), carbamoyl group, sulfamoyl group An acyloxy group (e.g., such as an acetyl group), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), a carboxyl group, such as sulfo group. The aryl group represented by R ₂ is, for example, a phenyl group, a naphthyl group, an m-methanesulfonylphenyl group, a p-cyanophenyl group, a p-ethoxycarbonylphenyl group, a p-sulfamoylphenyl group, a carbamoylphenyl group or the like.

R ₃ represents an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms. The alkyl group represented by R ₃ may be an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, etc.) as well as a substituted alkyl group. Including, as a substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), cyano group, carboxy group, sulfo group, sulfoalkoxy group having 1 to 6 carbon atoms (eg, sulfopropoxy group, etc.),
It may have an alkoxycarbonyl group having 1 to 6 carbon atoms (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.) and the like.

R ₄ is an alkyl group, halogen atom, aryl group, heterocyclic group, amino group, acylamino group, ureido group, nitro group, alkoxy group, alkoxycarbonyl group, carboxy group, hydroxy group, carbamoyl group, cyano group, aralkyl group. , A sulfo group, or a sulfamoyl group.
A preferable R ₄ group is a sulfo group.

Examples of the chalcogen atom represented by X include an oxygen atom, a sulfur atom, a selenium atom and a tellurium atom.

Specific examples of the heterocycle formed by combining R and X will be given.

Examples of the nucleus forming such a heterocycle include thiazole-based (eg, benzothiazole; 5-sulfobenzothiazole; 5-chlorobezothiazole; 6-chlorobenzothiazole; 5-methylbenzothiazole; 6-methylbenzothiazole 5-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole: 6-phenylbenzothiazole; 5-methoxybenzothiazole; 6-methoxybenzothiazole; Five
-Sulfobenzothiazole; 6-ethoxybenzothiazole; tetrahydrobenzothiazole; 5,6-dimethylbenzothiazole; 5,6-dimethoxybenzothiazole; 5,6-
Dioxymethylenebenzothiazole; 6-ethoxy-5-
Methylbenzothiazole; 5-phenethylbenzothiazole; naphtho [1,2-d] thiazole; naphtho [2,1-d]
Thiazole; naphtho [2,3-d] thiazole; 5-methoxynaphtho [1,2-d] thiazole; 8-methoxynaphtho [2,1-d] thiazole; 7-methoxynaphtho [2,1-d]
Thiazole; 8,9-dihydronaphtho [1,2-d] thiazole; 4,5-dihydronaphtho [2,1-d] thiazole etc.),
Oxazoles (e.g. benzoxazole; 5-phenoxybenzoxazole; 6-chlorobenzoxazole; 5-methylbenzoxazole; 5-sulfobenzoxazole; 6-methylbenzoxazole; 5,6-dimethylbenzoxazole; 5-methoxybenzoxazole ;Five
-Ethoxybenzoxazole; 5-phenethylbenzoxazole; 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-bromobenzoxazole; 5-methyl-6-chlorobenzoxazole; naphtho [1,2-d] oxazole; Naft [1,2-
d] oxazole; naphtho [2,1-d] oxazole;
Naphtho [2,3-d] oxazole and the like), selenazoles (eg benzoselenazole; 5-chlorobenzoselenazole; 5-methoxybenzoselenazole; 5-methylbenzoselenazole; tetrahydrobenzoselenazole; naphtho [1, 2-d] selenazole; naphtho [2,1-d] selenazole and the like), tellurazole series (for example, benzoterrazole; 5-methylbenzoterrazole; 5-methoxybenzoterrazole; 5,6-dimethylbenzoterrazole; naphtho) [2,1-d] tetrazole; naphtho [1,2-d] telrazole, etc.), 3,3-dimethylindolenine system (eg, 3,3-
Dimethyl indolenine, 3,3-dimethyl-5-sulfo-
Indolenine; 1,1-dimethyl-7-sulfonaphtho [2,1
-D] indolenine; 3,3-dimethyl-5- (dimethylamino) indolenine, etc., imidazole series (eg, imidazole; 1-alkylimidazole, 1-alkyl 4-
Phenylimidazole; 1-alkyl-4,5-dimethylimidazole: 1-alkylbenzimidazole: 1-phenyl-5,6-dichlorobenzimidazole; 1-alkyl-
5-Cyanobenzimidazole; 1-alkyl-5-chlorobenzimidazole; 1-alkyl-5,6-dichlorobenzimidazole; 1-alkyl-5-chloro-6-cyanobenzimidazole; 1-alkyl-5-trifluoro Methylbenzimidazole; 1-alkyl-5-methylsulfonylbenzimidazole; 1-alkyl-5-methoxycarbonylbenzimidazole; 1-alkyl-5-acetylbenzimidazole; 1-alkyl-5- (N, N-
Dimethylamino) sulfonylbenzimidazole; 1-alkylnaphtho [1,2-d] imidazole; 1-alkylnaphtho [2,1-d] imidazole; 1-alkylnaphtho [2,3
-D] imidazole and the like).

The 1-alkyl group is an alkyl group having 1 to 10 carbon atoms represented by R (when it has a substituent, the number of carbon atoms of the substituent is not included), and an alkoxy group having 1 to 6 carbon atoms,
Those substituted with an alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a carbamoyl group, a cyano group, a halogen atom, a sulfo group, a phenyl group, a substituted phenyl group, a vinyl group and the like are also included. Specific examples of the substituent include a methyl group, an ethyl group, a cyclohexyl group, a butyl group, a decyl group, a 2-methoxyethyl group, and a 3-group.
Butoxypropyl group, 2-hydroxy-ethoxyethyl group, ethoxycarbonylmethyl group, carboxymethyl group, 2-carboxyethyl group, 2-cyanoethyl group, 2
-Carbamoylethyl group, 2-hydroxyethyl group, 2
-Fluoroethyl group, 2,2,2-trifluoroethyl group,
2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, phenethyl group, benzyl group, sulfophenethyl group, carboxybenzyl group, allyl group and the like can be mentioned.

M is a hydrogen atom or an alkali metal (for example, sodium,
Potassium, etc.), alkaline earth metals (eg magnesium, calcium, barium etc.), ammonium, organic bases (eg triethylamine, pyridine, piperidine,
Morpholine, etc.) and the like.

The merocyanine dye represented by the general formula [I] is a compound having an acyl group at the 3-position of 5-pyrazolone.

Typical specific examples of the merocyanine dye represented by the general formula [I] (hereinafter, appropriately referred to as "dye according to the present invention") are shown, but the dye according to the present invention is not limited thereto.

Exemplified compound The synthesis examples of the merocyanine dye of the present invention are shown below.

Synthesis of Compound Example (21) 2- (4-acetanilide-1,3-butenyl) -3-ethyl-5-sulfonate benzoxazolium inner salt
Suspend 4.1 g in 20 ml of dimethylformamide. Next, 2- (3-acetyl-5-oxo-2-pyrazoline-1
-Yl) Benzene-1,4-disulfonic acid potassium salt 4 g dimethylformamide solution 10 ml and morpholine 3 g are added, and the mixture is heated with stirring for 30 minutes on a water bath.

After cooling, it is precipitated in isopropyl ether and the supernatant is decanted and separated. The precipitate is washed with acetone, then dissolved in methanol and potassium acetate is added, and salting out purification is repeated. The maximum absorption in a 1.6 g aqueous solution was 552 nm.

Other dyes can also be synthesized according to the synthetic method described in U.S. Pat. Nos. 2,493,747 and 3,148,187 and the above synthetic method.

The merocyanine dye according to the present invention has good absorption spectrum characteristics, is decolorized in a photographic processing bath, and is completely eluted from a light-sensitive material.

Usually, the photographic development process is carried out in a short time under alkaline conditions, and in order for the dye to be completely eluted from the photographic material during the photographic development process, particularly from the light-sensitive material coated in multiple layers, the dye molecule is Although a water-soluble group is required in the structural formula, the merocyanine dye according to the present invention satisfies this condition. Further, the incorporation of this dye in the light-sensitive material can be easily performed by adding an aqueous solution of the dye to the coating liquid. In the case of the water-insoluble dye, the residual dye once decolorized during the development process is slightly recolored at the time of the next processing step or during the time-lapse storage, resulting in contamination. Further, in order to contain such a dye in a light-sensitive material, it must be dissolved in an organic solvent such as methanol or dimethylformamide and emulsified and dispersed, which is not desirable in terms of workability and harmfulness. In this respect,
As described above, the merocyanine dye according to the present invention is characterized in that it is decolorizable and water-soluble, and dyeing contamination from the fatigue treatment liquid in the recent anhydrous washing treatment can be avoided.

The merocyanine dye according to the present invention is contained in any layer of a light-sensitive material to exert its effect. It may be contained in the silver halide emulsion layer or in another layer, and in the case of a multilayer structure, it may be contained in a plurality of layers.

For example, in the light-sensitive material of the present invention, the merocyanine dye represented by the general formula [I] can be used as an anti-irradiation dye by incorporating it in a silver halide photographic emulsion. It may be contained in the hydrophilic colloid layer and used as a filter dye or an antihalation dye. Further, two or more kinds of dyes may be used in combination depending on the purpose of use, or may be used in combination with other dyes. The dye according to the present invention can be easily incorporated into a silver halide photographic light-sensitive 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, and the dye is added to a coating solution, and various methods, for example, coating by a known method, Dyes can be included. The content of these dyes varies depending on the purpose of use, but in general, they are preferably applied by coating so that the amount per 1 m ² of area on the light-sensitive material is 1 to 800 mg.

In carrying out the present invention, other dyes may be used in addition to the merocyanine dye of the general formula [I] according to the present invention. Examples of dyes used in combination include, for example, U.S. Pat.
Pyrazolone oxonol dyes described in 782, cyarylazo dyes described in U.S. Pat.No. 2,956,879, U.S. Pat. U.S. Pat.Nos. 3,486,897, 3,65
2,284, 3,718,472 merocyanine dyes and oxonol dyes, U.S. Pat.No. 3,976,661 enaminohemioxonol dyes and British Patent 584,609
No. 1,177,429, JP-A-48-85130, and JP-A-49-99620.
No. 49-114420, U.S. Patent Nos. 2,533,472, and 3,14.
No. 8,187, No. 3,177,078, No. 3,247,127, No. 3,5
The dyes described in 40,887, 3,575,704 and 3,653,905 can be used.

The photographic emulsion used in the photographic light-sensitive material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. 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.

The light-sensitive material of the present invention has at least one silver halide emulsion layer. The silver halide emulsion used in the present invention is not limited and any one can be used. It is usually prepared by mixing a water-soluble silver salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. As this silver halide, use is made of any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. which are commonly used in light-sensitive materials. You can

These silver halide emulsions can be prepared by any method such as known methods,
Conventional methods (eg single or double jet method,
Control double jet method, etc.). Further, two or more kinds of silver halide emulsions formed separately may be mixed. Further, even if the crystal structure of the silver halide grains is uniform even in the inside, it has a layered structure in which the inside and the outside are different, a so-called conversion emulsion, Lippmann emulsion, covered grain emulsion or previously chemically or It may be chemically fogged. The latent image may be mainly formed on the surface or the internal latent image type may be formed inside the particles. These silver halide emulsions can be prepared by various methods such as the commonly used ammonia method, neutral method and acidic method. The distribution of silver halide grains may be either monodisperse or polydisperse, but monodispersion is preferred for uniform grain sensitivity. The grain crystal habit may be any of cubic, octahedron, dodecahedron, tetradecahedron, spherical, tabular and the like.

These methods are described by P. Glafkides, Chimie et Physique Photogr
aphique) (Paul Montel, 1967), GF Duffin, Photographic Emulsion Chemistry (Ph
otographic Emulsion Chemistry) (The Focal Press
Publishing, 1966), Making and Coating Photographic Emulsion by The VL Zelikman et al (The
Published by Focal Press, 1664), JP-A-54-48521, 58-11
3928, 58-37634 and 58-95337.

To prepare the light-sensitive material of the present invention, silver halide is
For example, it is dispersed in a suitable protective colloid and coated on a suitable support to form a silver halide emulsion layer. The photosensitive layer and other auxiliary layers formed as necessary, for example, an intermediate layer,
Alkali-treated gelatin is generally used as the protective colloid used in the layer structure of the protective layer, filter layer, etc., and other acid-treated gelatin, derivative gelatin, colloidal albumin, cellulose derivatives or synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. And these are used alone or in combination.

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers are precious metal sensitizers (calcium aurithiocyanate, ammonium chloroparadate,
Potassium chloroplatinate etc.), sulfur sensitizers (allylthiocarbamide, thiourea, cystine etc.), selenium sensitizers (active and inactive selenium compounds etc.) and reduction sensitizers (stannous salts, polyamines etc.) It is roughly divided into four types. The silver halide emulsion can be chemically sensitized with these sensitizers alone or in combination.

These chemical sensitization methods are described, for example, in US Pat.
Issue, 1,623,499, 2,410,689, 2,448,060,
2,399,083, 2,642,361, 2,487,850, 2,5
18,698, 1,623,499, 1,602,592, etc. Further, a polyalkylene oxide compound or the like can be used as the other sensitizer.

Further, various other additives can be added to the silver halide emulsion. Aldehydes such as formaldehyde, halogen-substituted fatty acids such as mucobromic acid, epoxy compounds, active halogen compounds, active vinyl compounds, active ester compounds, hardeners such as ethyleneimine compounds, saponins, nonionic surface active agents. Agents, cationic surfactants, anionic surfactants, surfactants such as amphoteric surfactants, azoles, heterocyclic mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 4-
Azaindenes such as hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, antifoggants or stabilizers such as benzenethiosulfonic acid and benzenesulfinic acid,
Physical property improvers such as aqueous dispersions of glycerin polymers (terax), dye image-forming couplers and colored couplers such as 5-pyrazolone type magenta couplers, acylacetanilide type yellow couplers or phenols, naphthol type cyan couplers, image sharpness, granularity , A computing coupler to adjust the gradation with improved
Development inhibitors releasing couplers (DIR couplers) and other couplers, benzotriazoles, triazines, UV absorbers such as benzophenone compounds, the substituted hydroquinones, p-alkoxyphenols, 6-chromanols, 6, 6'-dihydroxy-2,2'-spirochroman and anti-staining agents such as alkoxy derivatives thereof, anti-fading agents, stilbene type, triazine type,
Various photographic additives such as oxazole-based or coumarin-based whitening agents may be added.

The light-sensitive material of the present invention can be constituted by coating a silver halide emulsion with a layer and, if necessary, other layers on a support. The support used is optional, and preferably has good flatness and has good dimensional stability and little dimensional change during the manufacturing process or treatment. As the support in this case, for example, a cellulose nitrate film,
Cellulose ester film, polyvinyl acetate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass,
Paper, metal, paper coated with polyolefin such as polyethylene, polypropylene or the like can be used.

These supports can be subjected to surface treatments such as various hydrophilic treatments for the purpose of improving the adhesion with the silver halide emulsion layer. For example, saponification treatment, corona discharge treatment, undercoating treatment and setting treatment. Processing such as processing is performed.

The light-sensitive material of the present invention comprises a silver halide emulsion layer. Depending on the type of light-sensitive material, an undercoat layer, if necessary,
Auxiliary layers such as an intermediate layer, a filter layer, an antihalation layer, a back layer and a protective layer may be appropriately combined.

The present invention can also be applied to a multilayer color light-sensitive material in which at least two light-sensitive emulsion layers having different spectral sensitivities are coated on a support. The above-mentioned multilayer color light-sensitive material is usually composed of at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on the support side from the support side. It can be arbitrarily selected depending on the situation. The red-sensitive emulsion layer usually contains a cyan coupler, the green-sensitive emulsion contains a magenta coupler, and the blue-sensitive emulsion contains a yellow coupler, but in some cases, a combination different from the above may be contained. Good.

The silver halide emulsion used in the present invention may further contain a water-soluble dye in addition to the merocyanine dye according to the present invention as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes other than the present invention, cyani dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

The exposure for obtaining a photographic image can be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, laser light and light emitting diode can be used. it can. The exposure time is not limited to 1/1000 second to 1 second which is usually used in cameras, but it is shorter than 1/1000 second, for example, 1/1 × 10 ⁴ to 10 ⁶ second exposure using a xenon flash lamp or cathode ray tube. It can be used or an exposure longer than 1 second can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light may be used for the exposure, or exposure may be performed by light emitted from the phosphor excited by electron beam, X-ray, γ-ray, α-ray or the like.

The light-sensitive material of the present invention can be processed using a known processing method and processing solution as described in Research Disclosure, No. 176, pp. 20-30 (RD-17463). This photographic processing method may be either black photographic processing for obtaining a silver image or color photographic processing for obtaining a dye image. The processing temperature applied to photographic processing is usually 18 ℃ to 50 ℃, but even if the temperature is lower than 18 ℃, it is 50 ℃.
Treatment is possible even at temperatures above.

The developing solution used for black photographic processing may contain a conventionally known developing agent. As a developing agent,
Dihydroxybenzenes (eg hydroquinone), 3
-Pyrazolidones (for example hydroquinone), 3-pyrazolidones (for example 1-phenyl-3-pyrazolidone), aminophenols (for example N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines,
Ascobic acid, and 1, described in U.S. Patent No. 4,067,872
A heterocyclic compound in which a 2,3,4-tetrahydroquinoline ring and an indole ring are condensed can be used alone or in combination. The developer contains these known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, dissolution aids, toning agents, color swelling agents, development accelerators, surfactants, defoamers. Agents, water softeners, hardening agents, viscosity imparting agents and the like may be included.

A so-called "lith type" development process can be applied to the light-sensitive material of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or the reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent, and the development process is performed under low sulfite ion concentration. It means a contagious development process (for details, see Mason's "Photographic Process Chemistry" (1966), pages 163-165).

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Conventional methods can be applied to form a dye image. Negative-Positive Method (eg, Journal of the Society of Motion Pictu
re and Television Engineers) 61 (1953), pp. 667-701), to develop a negative silver image by developing with a developer containing a black developing agent, and then at least once. A color reversal method in which a positive dye image is obtained by exposure or other suitable fog treatment followed by color development, and a photographic emulsion tank containing the dye is exposed and developed to form a silver image, which is used as a bleaching catalyst. A silver dye bleaching method for bleaching a dye is used.

The color developer can generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino). -N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfoamidoethylaniline, 4
-Amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

In addition, Photographic Processing Chemistr by LFA Mason
y) (Focal Press, 1966), pages 226 to 229, U.S. Pat. Nos. 2,193,015 and 2,592,364, and JP-A-48-64933 may be used. The color developer must also contain a pH buffer such as alkali metal sulfite, carbonate, borate, and phosphate, a development inhibitor or antifoggant such as bromide, iodide, and organic antifoggant. You can

If necessary, a water softener, a preservative such as hydroxyamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler. , Fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid type chelating agents described in U.S. Pat. No. 4,083,723, West German publication (OLS) 2,6
It may include the antioxidant described in No. 22,950.

The emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III) cobalt (IV), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used. For example, ferricyanide compounds, dichromic chloride, organic complex salts of iron (III) or cobalt (IV), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or quinic acid. Complex salts of organic acids such as acids, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used.

Of these, potassium ferricyanide, sodium iron (III) diamine tetradiamine tetraacetate and ammonium iron (III) triamine diamine tetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleaching solution.

For bleaching or bleach-fixing solutions, U.S. Pat.
Various additives may be added in addition to the bleaching accelerators described in 3,241,966, JP-B-45-8506 and JP-B-45-8836, and the thiol compound described in JP-A-53-65732.

The silver halide emulsion used in the present invention is, for example, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester or amine, thioether compound, thiomorpholine, quaternary ammonium. It may contain a salt compound, a urethane derivative, a urea derivative, an imidazole derivative, 3-pyrazolidones and the like. For example, U.S. Patent Nos. 2,400,532 and 2,4
23,549, 2,716,062, 3,617,280, 3,772,02
Those described in No. 1, No. 3,808,003, US Pat. No. 1,488,991 and the like can be used.

The merocyanine dye according to the present invention has excellent properties as described above, and it is possible to obtain a light-sensitive material having high sensitivity and good raw storability, and therefore, an excellent antihalation or irradiation particularly for color light-sensitive materials can be obtained. Anti-dye,
Not only useful as a filter dye, but also various photosensitive materials, such as black and white photosensitive materials, various photosensitive materials for plate making,
Further, it can be applied to a color dye-containing color light-sensitive material prepared by a silver dye bleaching method.

[Examples] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Example 1 To 35 ml of distilled water, 3.5 g of gelatin was added and dissolved, and 5 ml of water containing 2.0 × 10 ⁻⁴ mol of the dye according to the present invention or the comparative dye was added thereto, and further 1.25 ml of 10% saponin aqueous solution and 1%. 0.75 ml of formalin solution was added, and water was added to bring the total volume to 50 ml. This dye solution was applied onto an acetyl cellulose support and dried to prepare samples 1 to 23, which were then treated with a model fatigue solution in which the following dyes were accumulated.

Each sample contained the same dye compound as the sample (10 / mol extinction coefficient) in a molar concentration of sodium hydroxide aqueous solution (pH =
It was immersed in 10.4) for 30 seconds with stirring at 30 ° C., washed with water for 15 seconds in a water tank containing a dye having a (1 / molar extinction coefficient) concentration, and dried. The visible spectrum of each sample before and after immersion was measured, and the elution rate was determined from the absorbance at the maximum absorption wavelength and is shown in Table 1.

E ₁ is the absorbance before immersion in the aqueous sodium hydroxide solution,
E ₂ represents the absorbance after immersion.

The sample was dipped in a developer having the following composition for 30 seconds at 30 ° C. (1 / molar extinction coefficient), washed with water for 15 seconds in a water tank containing a dye having a molar concentration, and then dried.

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

E ₃ represents the absorbance before immersion in the developing solution, and E ₄ represents the absorbance after immersion in the developing solution.

Composition of developer Metol 3.0g Sodium sulfite (anhydrous) 45.0g Hydroquinone 12.0g Sodium carbonate (monohydrate) 80.0g Potassium bromide 2.0g Dye [Molecular weight] x [10 / Mole extinction coefficient] g Add water to 1 To do.

Comparative dye As is clear from Table 1, the sample of the present invention shows extremely high values in both the elution rate and the decolorization rate, and the exemplary dyes according to the present invention are easily eluted from the gelatin layer and exhibit excellent decolorization properties. I understood.

Example 2 A color light-sensitive material for printing was prepared in the same manner as in the following (I), these samples were imagewise exposed, and then processed with the following luminescent developing solution and bleach-fixing solution to form each dye image. Performance was measured.

(1) Preparation of sample A paper support, the surface of which was coated with polyethylene containing anatase-type titanium oxide as a white pigment, was subjected to pretreatment by gelatin subbing, and then the following layers were sequentially coated to prepare a sample. .

Layer 1: Blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion consisting of cubic crystals containing 0.7 mol% of silver bromide and having an average side length of 0.7 μm, and a yellow coupler (Y- The emulsion dispersion prepared by dissolving 1) and 2,5-di-tert-octylhydroquinone in dioctylphthalate was used for coating.

Layer 2: First intermediate layer Coating was performed using an emulsion dispersion prepared by dissolving 2,5-di-tert-octylhydroquine in dioctylphthalate.

Layer 3: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion consisting of cubic crystals containing 0.4 mol% of silver bromide and having an average side length of 0.4 μ, and the following magenta coupler (M-1) And an emulsion dispersion prepared by dissolving 2,5-di-tert-octylhydroquinone in dioctylphthalate, and an aqueous dye solution shown in Table 4 below was added and applied.

Layer 4: Second intermediate layer Emulsion dispersion prepared by dissolving 2,5-di-tert-octylhydroquinone in dioctylphthalate and Table 4
The dye aqueous solution shown in 1 was added and applied.

Layer 5: Red-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion consisting of cubic crystals containing 0.4 mol% of silver bromide and having an average side length of 0.4 μm, and the following cyan coupler (C-1) And 2,5-di-tert-octylhydroquinone were dissolved in dioctyl phthalate to prepare an emulsified dispersion, and an aqueous solution of Dye D-1 was added thereto for coating.

Layer 6: Protective layer Coating was carried out using an emulsion dispersion prepared by dissolving the following ultraviolet absorber (UV-1) and 2,5-di-tert-octylhydroquinone in dioctylphthalate.

Layer 7: Protective Layer 2,5-di-tert-octylhydroquinone was dissolved in dioctyl phthalate to prepare an emulsion dispersion, and a hardener (H
-1) was added and applied.

The amounts of the components of each layer (mg amount per 100 cm ² ) are shown in Table-2.

Further, each photosensitive silver halide emulsion was subjected to gold-sulfur sensitization by adding optimum amounts of sodium thiosulfate and chloroauric acid and ripening at 50 ° C. for 100 minutes, and spectral sensitizing dyes ( The kind and the addition amount are shown in Table-3), and a methanol solution of the compound (E) having the following structure is further added.
Add 1.0 × 10 ⁻³ mol / mol silver.

Based on the above layer structure, the dyes in the green-sensitive silver chlorobromide emulsion layer and layer 4 (intermediate layer) were changed to prepare the samples shown in Table 4, and the following evaluations were performed.

The fog unexposed sample was subjected to the treatment described below, and Gretak D-
A 122 type densitometer was used to measure the magenta density.

<Processing step> Color development 35 ° C 45 seconds White fixing 35 ° C 45 seconds Water washing 30-35 ° C 90 seconds Dry 60-68 ° C 60 seconds The composition of the color developing solution and bleach-fixing solution used is as follows. . (Per 1) (color developer) (Bleaching fixer) Residual Color Contamination In order to examine the degree of colored contamination in the residual color of the dye after development processing, N-ethyl-N-β of the color developing solution in
-Methanesulfonamidoethyl-3-methyl-4-aminoaniline Sulfate-free solution was prepared and the same experiment was performed. The results are shown in Table-4.

In the above table, each number of the dye shows the coating amount (mg) per 100 cm ² .

Fog is required to be 0.005 or less as the whiteness desired as a color light-sensitive material for printing, and it is clear from Table 4 that the sample of the present invention satisfies this. In addition, the coloring stain due to the residual color of the dye, which is observed in the sample containing the comparative dye, is hardly observed in the sample of the present invention. That is, it was found that the dye according to the present invention had very little adverse effect on the emulsion.

[Effects of the Invention] As described above, the silver halide photographic light-sensitive material of the present invention is useful as a photographic dye, has good decolorizing property during development, and has good elution from the light-sensitive material. The residual color stain after processing is extremely small, and the influence on the photographic emulsion is extremely small.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, and at least one of the photographic constituent layers is represented by the following general formula [I]. A silver halide photographic light-sensitive material containing a merocyanine dye. General formula [I] [Wherein X is a chalcogen atom, And L ₁ , L ₂ , L ₃ , L ₄ , L ₅ and L ₆ each represent a methine group. R ₁ represents a group capable of substituting on the benzene ring.
R ₂ represents a heterocyclic group, an aryl group, or an alkyl group. R ₃ represents an alkyl group. R ₄ is an alkyl group, a halogen atom, an aryl group, a heterocycle, an amino group, an acylamino group, a ureido group, a nitro group, an alkoxy group, an alkoxycarbonyl group, a carboxy group, a hydroxy group, a carbamoyl group, a cyano group, an aralkyl group, a sulfo group. Represents a group or a sulfamoyl group, and R _{4 s} may be condensed with each other to form a naphthalene ring. R represents an aryl group or an alkyl group. M represents a hydrogen atom or a cation. m represents an integer of 0 to 2, n ₁ , n ₂ , and n ₃ each represent 0 or 1, and p represents 0.
Represents an integer of 3 and q represents an integer of 0-4. However, m + q ≠ 0. When m = 2 and p and q are 2 or more, each SO ₃ M, R ₁ and R ₄ may be the same or different. ]