JPS6334537A - Silver halide photogrpahic sensitive material containing merocyanine dyestuff - Google Patents

Abstract

PURPOSE:To obtain the titled material having decoloring property in a processing treatment, and capable of eluting satisfactorily from the titled material and reducing extremely residual color stain after processing, and of lessening exceedingly effect against the photogrpahic emulsion by incorporating the specific merocyanine dyestuff to at least any one layer of the titled material. CONSTITUTION:The titled material comprises at least one layer of the silver halide emulsion layer, and contains the merocyanine dyestuff shown by the formula I in at least any one of said layer. In the formula, X is a chalcogens atom, etc., L1-L6 are each methine group, R is alkyl or aryl group, R1 is a group which may be substd., R2 is aryl, heterocyclic ring, amino, acylamino, imido, ureido, carboxyl or alkoxycarbonyl group, etc., R3 is alkyl group, R4 is a group which may be substd., M is hydrogen atom or a cation ion, (l) is an integer of 0, 1 or 2, (m) is an integer of 1 or 2, (n1)-(n3) is an integer of 0 or 1, (p) is an integer of 0-5, (q) is an integer of 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a halogenated photographic material containing a merocyanine dye. In particular, the present invention relates to a silver halide photographic light-sensitive material which has good spectral characteristics by containing a certain merocyanine dye and is free from any disadvantages caused by the dye.

[Conventional technology]

In silver halide photographic light-sensitive materials (hereinafter sometimes abbreviated as light-sensitive materials, etc.), the purpose is to absorb light of a specific wavelength for the purpose of filtering, preventing halation, preventing irradiation, or adjusting the sensitivity of photographic emulsions. in,
It is well known that dyes are incorporated into photosensitive materials, and it is common practice to color, for example, hydrophilic colloid liquids with dyes.

The dye may be contained in, for example, a filter layer, an antihalation layer, an emulsion layer, etc. Among them, the filter layer is usually located above the photosensitive emulsion layer or between the emulsion layers, and serves to convert the incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, in order to improve the sharpness of photographic images, an antihalation layer is provided between the emulsion counterfeit support or on the back side of the support, so that harmful By absorbing reflected light and preventing halation, or by coloring the emulsion layer,
It is a common practice to prevent irradiation by absorbing harmful reflected light and scattered light by silver halide grains and the like.

Dyes used for such purposes are naturally required to have good absorption spectral characteristics depending on the purpose of use, and in addition, they are completely decolorized during photographic processing and are easily extracted from photographic materials. There is no residual color contamination caused by the dye after eluting and development processing, there is no adverse effect such as capri or desensitization on the photographic emulsion, there is no diffusion from the dyed layer to other layers, and there is no residual color contamination caused by the dye after the development process. Alternatively, it must satisfy various conditions such as excellent stability over time in photographic materials and no discoloration or fading.

To date, much effort has been made with the aim of finding dyes that satisfy the above conditions, and a large number of dyes have been discovered, including 12! It has been. For example, UK Patent No. 506,385, US Patent No. 3,247,127, US Patent No. 2.533,472, UK Patent No. 1.278.
, 621 specification, Japanese Patent Publication No. 39-22069, Japanese Patent Publication No. 43-13168, Japanese Patent Application Laid-open No. 52-34716
Oxonol dye described in US Patent No. 1, etc.
, 845°404, cyanine dyes as represented by U.S. Pat. No. 2,843,486,
U.S. Patent No. 2,493,747, U.S. Patent No. 3
, 148,187, U.S. Pat. No. 3,282,6
Specification No. 99, JP-A-50-145124, JP-A-52-134425, JP-A-52-29727
There are merocyanine dyes described in Japanese Patent Application Laid-open No. 52-65426 and the like. However, the reality is that there are very few good dyes that can be used in photographic materials that satisfy all of the above conditions.

[Purpose of the invention]

The object of the present invention is to provide a photosensitive material that satisfies the above conditions, that is, has good absorption spectrum characteristics, is decolorized during development processing, and is eluted from the photosensitive material to prevent residual color contamination after processing. An object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which is inert to a photographic emulsion and has a small amount of dye.

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and containing a melon aniline dye represented by the following general formula [I] in at least one of the layers. achieved.

General formula (1) % formula % represents a group, L+, Lm, L, 3. L4+ Ls+
Lm represents a methine group, R represents an alkyl group or an aryl group, R1 represents a substitutable group, R8 represents an aryl group, a heterocyclic group, an amino group, an acylamino group,
Represents an imido group, ureido group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, hydroxy group, substituted alkyl group, cyano group, R1 represents an alkyl group, R4 represents a substitutable group 0M represents a hydrogen atom or a cation, 1 represents an integer of 0.1°2, m represents an integer of 1 or 2, n l + R2+ R3 represents O or an integer of 1, p represents O~ represents an integer of 5, and q represents an integer of 0 to 3.

Each of the above groups will be explained in detail below.

R1 represents a group that can be substituted for a phenyl group (in this specification, the word substituent includes a substituent atom), and this R2
As the group represented by, for example, an alkyl group (eg, methyl group, ethyl group, butyl group, etc.).

In addition, this alkyl group may be further substituted (e.g., substituted with a halogen atom, a cyano group, a sulfo group, a hydroxy group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a butoxy group, etc.), a hydroxy group, a cyano group, etc. groups, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom, etc.), carbamoyl group, sulfamoyl group, acyloxy group (e.g. acetyloxy group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), carboxy group, Examples include a sulfo group, an aryl group (eg, phenyl group, etc.), an aralkyl group (eg, benzyl group-containing aryloxy group (eg, phenoxy group, etc.)), and the like.

Examples of the aryl group represented by Rz include phenyl group,
Examples include tolyl group, p-methoxyphenyl group, p-pentadecyloxyphenyl group, p-sulfophenyl group, p-carbamoylphenyl group, p-cyanophenyl group, p-butylsulfonylphenyl group, etc., and Rz The heterocyclic group represented by R2 includes, for example, thienyl group, furyl group, benzofuranyl, etc., and the amine group represented by R2 includes substituted amino groups, such as n-butylamino group, phenylamino group, etc. Examples of the acylamino group represented by R8 include a benzoylamino group, an acetylamino group, and a 2-(2,4-di-t-pentylphenoxy)butyrylamino group.

Examples of the imide group represented by R1 include a phthalic acid imide group and a succinimide group, and examples of the ureido group include N'-methylureido group, N'-(2-
Examples of the alkoxycarbonyl group include ethoxycarbonyl groups and hydroxyethoxyethoxycarbonyl groups, and carbamoyl groups include substituted carbamoyl groups, such as N-phenyl. Carbamoyl group, N-
p-methylsulfonylphenylcarbamoyl a, N-p
-carboxyphenylcarbamoyl group, etc., and examples of the aryloxy group include phenoxy group, p
Examples of the alkoxy group include methoxy and ethoxy groups.

Substituents for the substituted alkyl group represented by R2 include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.),
Cyano group, sulfo group, hydroxy group, carboxy group, alkoxycarbonyl group (e.g. methoxycarbonyl group,
ethoxycarbonyl group, etc.).

R1 represents an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms. The alkyl group represented by R1 includes unsubstituted alkyl groups (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, etc.) as well as substituted alkyl groups. , halogen atom (e.g. chlorine atom, bromine atom, etc.) as a substituent
, cyano group, carboxy group, sulfo group, sulfoalkoxy group having 1 to 6 carbon atoms (e.g. sulfopropoxy group), alkoxycarbonyl group having 1 to 6 m carbon atoms (e.g. ethoxycarbonyl group, butoxycarbonyl group, etc.)
etc.

R4 represents a substitutable group, and examples of the group represented by R4 include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a carbamoyl group, and a sulfamoyl group. The halogen atom represented by R4 includes, for example, a fluorine atom, a chlorine atom, and a bromine atom, and the alkyl group includes, for example, a methyl group, an ethyl group, a t-butyl group, a methoxymethyl group, a carboxymethyl group, etc. Examples of alkoxy groups include methoxy groups, ethoxy groups, etc.
Examples of aryloxy groups include phenoxy groups, examples of alkoxycarbonyl groups include ethoxycarbonyl groups and butoxycarbonyl groups, and examples of carbamoyl groups include N,N-dimethylcarbamoyl groups, N,N-tetra There are various groups such as methylenecarbamoyl group and morpholinocarbonyl group, and examples of sulfamoyl group include various groups such as N,N-dimethylsulfamoyl group and piperazinosulfonyl group.

The chalcogen atom represented by X includes, for example, an oxygen atom,
Examples of the alkyl group represented by R in which a sulfur atom, a selenium atom, or a tellurium atom are the same as those exemplified as those represented by R3. R represents -
Examples of the group include phenyl group, tolyl group, p-sulfophenyl group, p-carboxyphenyl group, and p-sulfamoylphenyl group.

The methyl groups represented by L+, L heavy, R3, L4+ Ls and
For example, methyl group, ethyl group, propyl group, isobutyl group, etc.), aryl group (e.g., phenyl group, p-1lyl group, p-chlorophenyl group, etc.), alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), aralkyl group (e.g., benzyl group, phenethyl group, etc.), heterocyclic group (e.g., thienyl group, furyl group, etc.), substituted amino group (e.g., dimethylamino, Examples include various substituents such as tetramethyleneamino, anilino, etc.), alkylthio groups (for example, methylthio group), etc. Also, a 5- or 6-membered carbocyclic ring is formed by connecting Lm, La, and the like. can also be formed.

The cations represented by M include ions of alkali metals (for example, lithium, sodium, potassium, etc.), alkaline earth metals (for example, magnesium, calcium, barium, etc.), ammonium or organic base cations (for example, triethylammonium, pyridinium, piperidinium, etc.).
ions such as morpholinium), etc.

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

Exemplary compound [11 to SO3 SO3)+ C113C113 5υ, Na tos 0 Ja (B) Kiri3Na X Near : : : , , , 7 Ctls　C11s C! II% Naps) U3NaCI! )U3Na aOsS So, Na Ct If 5 (CHHz) *5OsNa OJa Margin below C, l+.

The merocyanine dye according to the present invention is disclosed in U.S. Pat.
No. 3,747 and U.S. Patent No. 3.148.187
It can be easily synthesized according to the synthesis method described in the specification.

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 photographic material.

Usually, photographic processing is carried out under alkaline conditions for a short period of time, and dyes are extracted from the photographic material during the photographic processing, especially in large quantities. In order to be completely eluted from the coated photosensitive material, a water-soluble group is required in the molecular structure of the dye, and the merocyanine dye according to the present invention satisfies this condition.

Further, in order to incorporate this dye into a light-sensitive material, it can be easily carried out simply by adding an aqueous solution of the dye to the coating liquid. In the case of water-insoluble dyes, the residual dye once decolorized during the development process leaves a slight residual color during the next processing step or during storage over time, resulting in staining. Also.

In order to incorporate such a dye into a light-sensitive material, it must be dissolved in an organic solvent such as methanol or dimethylformamide and emulsified and dispersed, which is undesirable from the viewpoint of workability and toxicity. As shown, the merocyanine dye according to the present invention has the characteristics of being decolorizable and water-soluble, and staining from the fatigue treatment solution in recent waterless washing treatments can be avoided.

The merocyanine dye according to the present invention can be contained in any layer of a light-sensitive material to exhibit its effects. 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 formula [1] above can be incorporated into a halogenated photographic emulsion and used as an ylaninisilane-preventing dye, or can be used as a non-photosensitive dye. It can also be incorporated into a hydrophilic colloid layer and used as a filter dye or an 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. The dye according to the present invention can be easily incorporated into a silver halide photographic emulsion layer or other hydrophilic colloid layer by a conventional method. In general, a dye or an organic or inorganic alkali salt of a dye is dissolved in water to form an aqueous dye solution with an appropriate concentration, and the solution is added to a coating solution and coated using various methods, such as known methods, to coat the photosensitive material. It can contain dyes. The content of these dyes varies depending on the purpose of use, but in general, it is preferably applied in an amount of 1 to 800 cm per area on the photosensitive material.

In carrying out the present invention, other dyes may be used in addition to the merocyanine dye of general formula (1) according to the present invention. As the dye used in combination, for example, U.S. Patent No. 2,27
pyrazolone oxonol dyes described in U.S. Pat. No. 4,782, diarylazo dyes described in U.S. Pat. No. 2,956.879, U.S. Pat.
4.487, merocyanine dyes described in U.S. Pat. No. 2,527.583, U.S. Pat. No. 3,486.897, U.S. Pat. No. 3.6
52.284, the merocyanine dyes and oxonol dyes described in U.S. Pat. No. 3.718,472, and U.S. Pat.
76.661 and British Patent No. 584,609, British Patent No. 1.177.4
No. 29, JP-A-48-85130, JP-A No. 49-9962
No. 0, No. 49-114420, U.S. Patent No. 2,533
．． No. 472, No. 3.148.187, No. 3.17
7.078, 3.247.127, 3.5
No. 40.887, No. 3,575,704, No. 3.
653,905 may 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. Various sensitizing dyes can be used, such as cyanine dyes, merocyanine dyes, complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, and streptocyanine dyes. One type or a combination of two or more types can be used.

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 silver halide emulsion can be used. It is usually prepared by mixing a water-soluble root salt (for example, silver nitrate) i8 solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer Re such as gelatin. As the silver halide, any silver halide used in ordinary light-sensitive materials such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. Can be done.

These silver halide emulsions can be prepared by any method, such as known methods,
conventional methods (e.g. single or double jet method,
It is made according to the control tuple jet method. Furthermore, two or more types of silver halide emulsions formed separately may be mixed. Furthermore, even if the crystal structure of the silver halide grains is uniform to the inside, or the crystal structure of the silver halide grains may be a layered structure in which the inside and outside are different. It may be a so-called conversion emulsion, a Lippmann emulsion, a covered grain emulsion, or one that has been optically or chemically fogged in advance, or it may be a type that mainly forms a latent image on the surface.
These silver halide emulsions, which may be of the internal layer image type formed inside the grains, can be prepared by various methods such as the ammonia method, neutral method, acid method, etc.
I can do it. The distribution of the 710 particles may be either monodisperse or polydisperse, but monodisperse is preferable for uniform particle sensitivity. Further, the grain crystal habit may be of any shape such as cubic, octahedral, dodecahedral, dodecahedral, spherical, or tabular.

These methods are described in the book by P. Glafkides, Chimie et Physique Photography, Inc.
tPhysique Photographique)
(Paul Monte1, 1967), G.
Photographic Emulsion Chemistry by F. Duffin
lsion Chemistry) (The Fo
Cal Press, 1966), V.
Making and Coating Photographic Ink Emulsion by L. Zeliklian et al.
Photographic Emulsion) (Th
e Focal Press, 1964), JP-A No. 54-48, No. 521, No. 58-113, No. 928, No. 58-37゜634, No. 58-95, No. 337, etc.

In order to create the photosensitive 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, such as an intermediate layer,
As protective colloids used in the layer structure of protective layers, filter layers, etc., alkali-treated gelatin is generally used, as well as acid-treated gelatin, derivative gelatin, colloidal albumin, cellulose derivatives, or synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. These can be used alone or in combination.

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers include noble metal sensitizers (calcium aurithiocyanate, ammonium chloroprotate, potassium chloroplatinate, etc.), sulfur sensitizers (allylthiocarbamide, 1,000 urea, cystine, etc.), and selenium sensitizers. They are roughly divided into four types: (active and inactive selenium compounds, etc.) and reduction sensitizers (stannic salts, polyamines, etc.). Silver halide emulsions can be chemically sensitized using these sensitizers alone or in combination as appropriate.

These chemical sensitization methods are described, for example, in US Pat. No. 1,574.
No. 944, No. 1,623,499, No. 2,410,6
No. 89, No. 2.448,060, No. 2.399.08
No. 3, No. 2,642.361, No. 2,487,850
No. 2,518,698, No. 1,623,499, No. 1,602,592, etc. Further, polyalkylene oxide compounds and the like can also be used as other sensitizers.

Furthermore, various other additives can be added to the above silver halide emulsion. For example, aldehydes such as formaldehyde, halogen-substituted fatty acids such as mucobromic acid, epoxy compounds, active halogen compounds, active vinyl compounds, active Hardening agents such as ester compounds and ethyleneimine compounds, saponins, surfactants such as nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, azoles, l-F5 Heterocyclic mercapto compounds such as 5-mercaptotetrazole, 4-hydroxy-6-methyl-1,3,3a.

7 - Azaindenes such as tetrazaindene, anti-capri agents or stabilizers such as henzenethiosulfonic acid and henzenesulfinic acid, physical property improvers such as aqueous dispersion (latex) of glycerol, 5-pyraduron magenta couplers, dye image-forming couplers and colored couplers such as acylacetanilide yellow couplers or phenol and naphthol cyan couplers, conting couplers for improving image sharpness and graininess or adjusting gradation, and development inhibition. Agent-releasing coupler (D
LR couplers), ultraviolet absorbers such as hensitriazoles, triazines, benzophenone compounds, W-converted hydroquinone, p-alcoquinephenols, 6-chromanol M, 6,6'-dihydroxy -2゜2゛- Various photographic additives are added, such as anti-stain and anti-fading agents such as spirochromans and their alkoxy derivatives, and brightening agents such as sunarhenes, triazines, oxazoles or coumarins. It's okay.

The light-sensitive material of the present invention can be constructed by coating a silver halide emulsion layer and, if necessary, other layers on a support. The support used is arbitrary, but it is preferably a support that has good flatness, good dimensional stability and little dimensional change during the manufacturing process or treatment. In this case, examples of the support include cellulose nitrate film,
Cellulose ester film, polyvinyl acetate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass,
Paper, metal, polyolefin, such as polyethylene, polypropylene, etc. coated paper, etc. can be used.

These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion with the silver halide emulsion layer, such as saponification treatment, corona 7F discharge treatment, subbing treatment, Processing such as setting processing is performed.

The light-sensitive material of the present invention has a silver halide emulsion layer, but depending on the light-sensitive material, a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a back layer, a protective layer, etc. auxiliary layers may be suitably combined.

The present invention can also be applied to multilayer color light-sensitive materials 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 usually has a structure having at least one layer each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer in order from the support side on a support, but the order of these layers is necessary. It can be arbitrarily selected depending on the situation. The red-sensitive emulsion layer contains a cyan coupler, the green-sensitive emulsion layer 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 included. It's okay.

The silver halide emulsion used in the present invention can be used as a filter dye, to prevent irradiation, and for other purposes. In addition to the merocyanine dye according to the present invention, a water-soluble dye may be contained separately.Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes other than the present invention, anine dyes, and ab dyes. be done.

Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

Exposure to obtain a photographic image can be carried out using conventional methods. That is, various known light sources such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon night lamps, xenon flash lamps, cathode ray tube flying spots, laser beams, and light emitting diodes can be used. It can also be used. Exposure times include not only exposure times of 1/1000 seconds to 1 second, which are normally used with cameras, but also exposure times shorter than 1/1000 seconds, such as 1/I
Exposures of seconds can be used, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light may be used for exposure, or exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, r-rays, α-rays, or the like.

The photosensitive material of the present invention can be used, for example, in Research Disclosure, No. 176, pages 20 to 30 (RD-17643).
) The treatment can be carried out using known treatment methods and treatment solutions such as those described in . This photographic processing method may be a black and white photographic processing to obtain a silver image or a color photographic processing to obtain a dye image, and the processing temperature applied in the photographic processing is usually 18°C to 50°C. But 18
Treatment is possible at temperatures lower than 50°C or higher than 50°C.

The developer used in black-and-white photographic processing can contain conventionally known developing agents. As a developing agent,
Dihydroxybenzenes (e.g. hydroquinone), 3
-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-
(aminophenol), 1-phenyl-3-pyrazolines, ascobic acid, and a complex compound such as a fused 1,2,3,4-tetrahydroquinoline ring and an intrene ring described in U.S. Pat. No. 4,067.872. Ring compounds and the like can be used alone or in combination. The developer contains this known preservative, alkaline agent, pH buffer agent, antifogging agent, etc., and further contains a solubilizing agent, a color toning agent, a color swelling agent, a development accelerator, a surfactant, and an antifoaming agent as necessary. agent, water softener,
It may also contain a hardening agent, a viscosity-imparting agent, and the like.

The photosensitive material of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a development process in which dihydroxynzenes are usually used as a developing agent and a low sulfite ion concentration is used for photographic reproduction of line images or halftone images. It refers to a developing process that is carried out contagiously (details are described in Mason, Photographic Processing, J (1966), pp. 163-165).

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

As the fixing agent, in addition to periosulfate and thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used.

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

When forming a dye image, conventional methods can be applied.

Negative-positive method (for example, Journal of the Society of Motion Picture and Television Engineers (Journal of the 5
Ociety of Motion Picture
and Television Engineers)
61 'J (1953), pp. 667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other A color reversal method in which a dye-positive image is obtained by performing appropriate fogging treatment and subsequent color development; a photographic emulsion layer containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye. A silver dye bleaching method is used.

The color developer may generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (eg 4-amino-N.

N-diethylaniline, 3-methyl-4-amino-N,
N-diethylaniline, 4-amino-N-ethyl-N-
β- and dolokidiethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methquinethylaniline, etc.)
can be used.

In addition, F, ^, Photographic Processing Chemistry (Photograph) by Mason.
hicProcessing Ches+1sLry
) (Focal Press, 1966), pages 226-229, U.S. Patent No. 2°193.015
No. 2,592.364, JP-A-48-64, 9
The color developer described in No. 33 may be used. In addition, the color developer may include alkali metal sulfites, carbonates, borates,
and pH 11 buffering agents such as phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants.

In addition, if necessary, water softeners, preservatives such as hydroquinoamine, organic solvents such as hensyl alcohol and dielene gellicol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, and pigments may be added. Forming couplers, competitive couplers, fogging agents such as sodium polyhydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, U.S. Pat. No. 4,083,72
The polycarboxylic acid chelating agent described in No. 3, West German Publication (
OLS) 2°622, 950, etc. may also be included.

The emulsion layer after color development is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, compounds of polyvalent metals such as iron (I[I), cobalt (■), chromium (Vl), uA(n), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide compounds, dichromates, iron(II[) or cobalt(IV) complex salts,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
1. Aminopolycarboxylic acids such as 3-diamino-2-propatoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. .

Of these, ferricyanide compounds, sodium iron(1) ethylenediaminetetraacetate and ammonium iron(If) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (m) iff salts are useful in both stand-alone bleach solutions and hot source white liquors.

U.S. Patent No. 3.042.52 for bleaching or bleach-fixing solutions
No. 0, No. 3,241.966, Special Publication No. 45-8506
In addition to the bleaching accelerator described in JP-A No. 45-8836 and the thiol compound described in JP-A-53-65732, various additives can also be added.

The silver halide emulsion used in the present invention includes, for example, polyalkylene quinide or its derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomorpholines, and May contain quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc. For example, US Patent No. 2,400,532
No. 2,423°549, No. 2,716.062, No. 3,617,280, No. 3772.021,
No. 3,808,003, British Patent No. 1,488,991
You can use those listed in the No.

The melonanine dye according to the present invention has the above-mentioned excellent properties and can provide a photosensitive material with high sensitivity and good storage stability, so it is particularly useful as an excellent antihalation or irradiation agent for color photosensitive materials. tion-preventing dye,
It is not only useful as a filter dye, but also useful in various photosensitive materials, such as white field photosensitive materials, various photosensitive materials for plate making,
Furthermore, it can also be applied to color photosensitive materials containing colored dyes produced by a silver dye bleaching method.

〔Example〕

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

Example 1 3.5 g of gelatin was added and dissolved in 1 distilled water 35-1, and the dye according to the present invention or comparative dye was added to it at 2.0×1 O-
Add 5 ml of water containing 4 mol, and then add 11.25 mf of 10% saponin water and 1% formalin (MO075).
...2 was added, and water was added to bring the total volume to 50 ml. This dye solution was coated on an acetyl cellulose support and dried to prepare samples Nos. 1 to 32, which were treated with model fatigue fluids loaded with the following dyes.

Each sample was added to an aqueous sodium hydroxide solution (PH=10.4) containing twice the same dye compound as the sample (10.1 mole of extinction coefficient) for 30 seconds at 30°C with stirring. i
? The sample was washed with water for 15 seconds in a water tank containing no dye (11 molar extinction coefficient), and dried. '(3:,
? Measure the visible spectrum of each sample before n and after infiltration/Il, and calculate the elution rate from the absorbance at the pilot flame absorption wavelength.
Shown in 1.

E, -El Elution rate-X100 (%) E.

E, represents the absorbance before immersion in sodium hydroxide aqueous solution I, and E8 represents the absorbance after immersion.

Further, the sample was immersed in a developer having the following composition at 30° C. for 30 seconds, washed with water for 15 seconds in a water tank containing a dye having a molar concentration of 17 molar absorption coefficient, and then dried.

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

E3-E.

Decolorization rate - xlOO (%) E.

E represents the absorbance before immersion in the developer, and E represents the absorbance after immersion in the developer.

Composition of developer ■ Thor 3.0g
Add water to make up to 1 liter.

The following margin comparison dye 011 SO3Na NaOmS OHONHCH25OJa As is clear from Table 1, the sample of the present invention showed extremely high values for both the elution rate and the decolorization rate, and the exemplary dye according to the present invention was easily eluted from the gelatin layer. It was also found that the dye exhibited superior decolorizing properties compared to comparative dyes.

Example 2 Color photosensitive materials for printing were prepared as described in (1) below, and after these samples were imagewise exposed, they were processed using the following color developer and bleach-fix solution to form each dye image. We measured the performance related to

(1) Preparation of sample A paper support whose surface was coated with polyethylene containing anatase-type titanium oxide as a white pigment was pretreated with 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 containing 5 mol % of silver chloride, as well as the following yellow coupler (Y-1) and 2°5-diter
Coating was performed using an emulsified dispersion prepared by dissolving t-octylhydroquinone in dioctyl phthalate.

Layer 2: First intermediate layer was coated using an emulsified dispersion prepared by dissolving 2.5-di-tert-octylhydroquinone in dioctyl phthalate.

Layer 3: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 1115 mol % of chloride, and the following magenta coupler (M-1) and 2°5-jet
An emulsified dispersion prepared by dissolving er t-octylhydroquinone in dioctyl phthalate and an aqueous dye solution shown in Table 3 below were added for coating.

Layer 4: Second intermediate layer Ultraviolet absorber (UV-1) and 2,5-te
An emulsified dispersion prepared by dissolving rt-octylhydroquinone in dioctyl phthalate and 78 liquids of dye water shown in Table 3 were added for coating.

Layer 5: Red-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 25 mol% of silver chloride, and the following Noan coupler (C-1) and 2°5-No Ler.
Coating was performed using an emulsified dispersion prepared by dissolving t-octylhydroquinone in dioctyl phthalate.

Layer 6: Protective layer Coating was done mainly by adding gelatin and a hardening agent.

(Y-1) (M-1) C1 The amounts of components in each layer (amounts per 100) are shown in Table-2.

Based on the above layer structure, the dyes in the green-sensitive silver chlorobromide emulsion layer and layer 4 (intermediate layer 1) were changed to prepare the samples shown in Table 3, and the evaluations shown below were performed.

(2) An unexposed sample of Capri was processed according to Example 2 of JP-A-58-134636, and the degree of magentan was measured using a Greetak D-122 densitometer.

■Residual color contamination In order to investigate the degree of color contamination due to residual color of the dye after the development process, N-ethyl-N-β in the color developing solution in
-Methanesulfonamidoethyl-3-methyl-4-aminoaniline A solution without using sulfate was prepared, and the same experiment as in (2) was conducted. The results are shown in Table-3.

In the table above, each number for dye is 100-per application! (
■).

As for the whiteness desired as a color photosensitive material for printing, Capri needs to have a whiteness of o, oos or less.
It is clear from Table 3 that the samples of the present invention satisfy this requirement. In addition, color contamination due to residual color of the dye, which is observed in samples containing comparative dyes, is hardly observed in the samples of the present invention. That is, it was found that the dye according to the present invention has extremely 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 decolorization properties during development processing, and has good elution from the light-sensitive material. There is very little residual color staining after processing, and the effect on the photographic emulsion is extremely small.

Patent applicant: Roku Konishi Photo Industry Co., Ltd. Patent attorney agent
Toru Takatsuki Procedural Amendment (Jio 1, Indication of the case 1986 Patent side No. 179583 2, Name of invention Silver halide photographic light-sensitive material containing merocyanine dye 3, Person making the amendment! Relationship with 11 cases Patent Applicant Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photograph - [Dia Palace Co., Ltd. No. 506 Nibancho FAX 03 (221) 1! 1245 Date of amendment order Voluntary 6 Subject of amendment "Detailed description of the invention" in the specification column.

(1) In the specification, 8tt, lines 19 to 20, 1
Henidifuranyl, etc.] is changed to "Henidfuranyl)S, etc."
And corrected it.

(2) [Sulfopropoxy group] in the 1st O row, 16th line is corrected to "sulfopropoxy group".

(3) ``Methyl group'' in line 9 of the 12th Tei of the same text is changed to ``methine group'' (IW correct.

(4) On page 12, line 17 of the same page, replace [phea-thyl group, etc.] with "
phenethyl group, etc.),” is corrected.

(5) Correct “pyridinium” in line 13 @ line 9 to “1 pyridinium”.

(6) The structural formula on page 19 (17) of the same is amended as follows.

(7) In the 11th line of page 27, 1, ``The dye is contained in the light-sensitive material'' is corrected to ``The dye is contained in the light-sensitive material.''

(8) Amend ``1 just by adding'' to ``just by adding'' on page 27, line 12.

(9) "Epoxy compound" on page 34, line 9 is corrected to "epoxy compound."

Ol) Amend "The support is optional" in lines 19 and 20 of the same No. 35 Tei to "The support is optional."

OB In the same page 39, lines 14 to 15, [ascobic acid] is corrected to "ascorbic acid."

(2) Correct "antioxidant, etc." in line 8 of No. 43 of the same law to "antioxidant, etc."

C1■ Delete "In the above table..." from the 1st to 2nd lines of page 58.

that's all

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer, containing a merocyanine dye represented by the following general formula [I] in at least one layer. Characteristic silver halide photographic materials. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, X represents a chalcogen atom, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a group, L_1, L_2, L_3, L_4, L_5, L
_6 represents a methine group, R represents an alkyl group or an aryl group. R_1 represents a substitutable group. R_2 is an aryl group, a heterocyclic group, an amino group, an acylamino group,
It represents an imide group, a ureido group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, a hydroxy group, a substituted alkyl group, and a cyano group. R_3 represents an alkyl group. R_4 represents a substitutable group, and M represents a hydrogen atom or a cation. l represents an integer of 0, 1, or 2, m represents an integer of 1 or 2, n_1, n_2, n_3 represents an integer of 0 or 1, p represents an integer of 0 to 5, and q represents an integer of 0 to 5. Represents an integer of 3.