JPH01234844A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the good absorption spectrum characteristics of the title material, and to facilitate the decoloring of the sensitive material during photographic development processing, and to lessen the stain of the sensitive material due to a residual color after development processing by incorporating a specified merocyanine dyestuff in the sensitive material. CONSTITUTION:The merocyanine dyestuff shown by the formula is incorporated in the sensitive material. In the formula, (n) is an integer of 4 or 5, P is an integer of 1 or 2, Q1 is a heterocyclic ring group, Q2 is a carbon ring or a heterocyclic ring group, L1-L4 are each methine group, R is alkyl, alkenyl, alkynyl, aryl or a heterocyclic ring group. The merocyanine dyestuff shown by the formula has the characteristics of sufficiently absorbing a spectrum especially, in from a red color region to an infra-red region. Thus, the sensitive material is completely decolored during the photographic development processing, and the stain of the sensitive material due to the residual color of the dyestuff is reduced by easily eluting the dyestuff from the sensitive material after development processing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material containing a dye, and in particular a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. This invention relates to silver oxide photographic materials.

[Background of the invention]

In silver halide photographic materials (hereinafter referred to as photographic materials), dyes are added to the photographic material for the purpose of absorbing light of a specific wavelength for filters, anti-halation, anti-irradiation, or to adjust the sensitivity of photographic emulsions. It is well known that the hydrophilic colloid layer is colored with a dye.

The filter layer is usually an upper layer of the photosensitive emulsion layer or
It is located between the emulsion layers and plays the role of making the incident light that reaches the emulsion layer have a preferable spectral composition. In addition, in order to improve the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back of the support to prevent harmful effects at the interface between the emulsion layer and the support, or on the back of the support. It is a good practice to prevent irradiation by absorbing reflected light from silver halide grains, etc., to prevent halation, or by coloring the emulsion layer to absorb harmful reflected light and scattered light from silver halide grains, etc. It is being said.

Dyes used for such purposes must have good absorption spectral characteristics depending on the purpose of use, be completely decolorized during photographic processing, be easily eluted from the photographic material,
After development, there should be no residual color stains caused by dyes, and there should be no negative effects such as fogging or desensitization on photographic emulsions.
It must satisfy conditions such as not diffusing from the dyed layer to other layers, having excellent stability over time in solutions or photographic materials, and not changing color or fading.

To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. Few dyes were known that satisfied these conditions.

[Purpose of the invention]

The object of the present invention is to have good absorption spectral characteristics, be decolorized during photographic processing, and be eluted from photographic materials.
There is extremely little residual color staining after processing, and compared to photographic emulsions,
An object of the present invention is to provide a silver halide photographic material containing an inert dye.

[Structure of the invention]

This object of the present invention is achieved by a silver halide photosensitive material containing a novel merocyanine dye shown in Formation [I] below.

-Formation [I] n represents an integer of 4 or 5, p represents an integer of 1 or 2, Ql represents a heterocycle-forming group, Q2 represents a carbocycle or heterocycle-forming group, L r, L 2. t, s, L-represent a methine group, and R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

However, the compound represented by general formula [I] shall have at least one acid group in the molecule.

Next, the merocyanine dye represented by the formula -a [N will be described.

Q is a 5- or 6-membered heterocycle, such as thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, isoxazole, benzisoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, thiazoline, quinoline, Isoquinoline, 3,3-dialkylindolenine,
Represents the atomic group necessary to form a heterocycle such as pyridine and penzotelllazole.

Q2 is a carbocyclic ring such as 1,3-cyclobentanedione, , pyrazolopyridine, and quinolone.

L and -L4 represent a methine group, but also include an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, etc.), a phenyl group,
It may be substituted with a benzyl group, phenethyl group, hydroxy group, acyloxy group, halogen atom, etc. Also, L
, and the substituent of the methine group represented by L4 is a ring (for example, 5
,5-dimethyl-1-cyclohexen-1-yl-3-
ylidene, etc.).

R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and the alkenyl group includes an allyl group, the alkynyl group includes a propargyl group, and the alkyl group has 1 to 1 carbon atoms. Linear, branched, or cyclic alkyl groups of 6 are preferred, such as methyl, ethyl, isopropyl, n-butyl, cyclohexyl, etc., and these alkyl groups, alkenyl groups, and alkynyl groups may be further substituted, For example, halogenated alkyl groups (e.g., β-chloroethyl, etc.), hydroxyalkyl groups (e.g., β-hydroxyethyl, etc.)
, an alkoxyalkyl group (e.g., β-methoxyethyl, etc.), a carboxyalkyl group, a luponylalkyl group (e.g., β-ethoxycarbonylethyl, etc.), an aryloxyalkyl group (e.g., phenoxymethyl, etc.),
Examples include sulfoalkyl groups (e.g., eva, β-sulfoethyl, 7-sulfopropyl, δ-sulfobutyl, etc.), carbamoylalkyl groups (e.g., carbamoylmethyl, etc.), aralkyl groups (e.g., benzyl, phenethyl, etc.), and R represents The aryl group is preferably a phenyl group, and the heterocyclic group includes, for example, pyridyl, sulfolanyl, and tetrahydrofuryl.

The nucleus of the aralkyl group, aryl group, and heterocyclic group represented by R may be substituted, and the substituents to be introduced include methyl,
Examples include alkyl groups such as ethyl, alkoxy groups such as methoxy and ethoxy, hydroxy groups, carboxy groups, and sulfo groups.

-Formation [Il compounds have at least one acid group (
sulfo group, carboxy group, phosphoric acid group, etc.), and it is preferable that at least one group among R, Q 2 , and Q z groups has an acid group.

Further, the methine group represented by R3 and R4 is preferably a ring-forming one such as 5,5-dimethyl-1-cyclohexerin-1-yl.3-ylidene from the viewpoint of ease of synthesis.

Examples of the merocyanine dye represented by the general formula [1] include compounds represented by the following general formulas [Il-1 and [1]-2.

[11-1 to 2 In the formula, Y is an oxygen atom, a sulfur atom, a selenium atom, R3 is an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group.

The methine group represented by L , , L 4 has the general formula (as described above for Il, and each group represented by R 1 is -
Formation [As described above in the explanation of R in 11.

R2 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group.

Examples of the alkyl group represented by R3 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 7-enethyl. ,
Examples of the aryl group include phenyl, naphthyl, etc., and examples of the heterocyclic group include benzothiazolyl, pyridyl, pyrimidyl, sulfolanyl, etc., with preference given to alkyl groups, aralkyl groups, and aryl groups.

The alkyl group, aralkyl group, aryl group, and heterocyclic group represented by R7 can have various substituents, such as sulfo, carboxy, hydroxy, cyano, halogen (
(e.g. fluorine, chlorine, etc.), alkyl (e.g. methyl,
isopropyl, trifluoromethyl, t-butyl, ethoxycarbonylmethyl, sulfomethyl, etc.), amino (
For example, amino, dimethylamino, sulfoethylamino,
piperidino, morpholino, etc.), alkoxy (e.g., methoxy, ethoxy, sulfopropoxy, etc.), sulfonyl (e.g., methanesulfonyl, ethanesulfonyl, etc.), sulfamoyl (e.g., sulfamoyl, dimethylsulfamoyl, etc.), acylamino (e.g., acetamide, benzamide, sulfamoyl, etc.), benzamide, etc.), carbamoyl (e.g., carbamoyl, phenylcarbamoyl, sulfophenylcarbamoyl, etc.), sulfonamide (e.g., methanesulfonamide, benzenesulfonamide, etc.), alkoxycarbonyl (e.g., ethoxycarbonylndyloxycarbonylcarbonyl (e.g., phenoxycarbonyl, nitro), phenoxycarbonyl, etc.), and the like.

The aralkyl group and aryl group represented by R2 desirably have at least one group selected from a sulfo group, a carboxy group, and a phosphate group on their aromatic nucleus, and more preferably have at least one sulfo group. This is desirable.

In the formula, R3 is an alkyl group, an aryl group, an aralkyl group, a heterocyclic group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a ureido group, a thioureido group, an acylamino group, an acyl group, an imido group, a cyano group, Represents a hydroxy group, an alkoxy group, or an amine group.

an alkyl group, an alkoxycarbonyl group represented by R3,
Specific examples of the aryloxycarbonyl group, carbamoyl group, acylamino group, alkoxy group, and amino group are the same as the specific examples of the substituents introduced into the alkyl group, aralkyl group, aryl group, and heterocyclic group represented by R2 described above. I can list things.

Further, the aryl group represented by R1 includes, for example, phenyl, sulfopropoxyphenyl, cyanophenyl, carboxyphenyl, nitrophenyl, sulfophenyl, etc., and the aralkyl group includes, for example, benzyl, phenethyl, sulfobenzyl, etc. Examples of the heterocyclic group include furyl, thienyl, etc., examples of the ureido group include methylureido, phenylureido, etc., examples of the thioureido group include methylthioureido, phenylthioureido, etc., and examples of the imide group include Examples include succinimide, 7-talimide, etc., and examples of the acyl group include acetyl, pivalyl, etc.

Examples of the group represented by R3 include an alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a ureido group, an acylamino group, an acyl group, an imido group, a cyano group,
Hydroxy groups, alkoxy groups, and amine groups are preferred, but
More preferably, an alkyl group, a carboxy group, an alphkidicarbonyl group, a carbamoyl group, an acyl group, a cyano group,
Alcoquine group, amino group.

R1 and R5 are hydrogen atoms, alkyl groups, alkokyne groups,
It represents an alkoxycarbonyl group, an aryl group, or a carboxy group, and R4 and R6 may form a benzene ring or a naphthalene ring.

The alkyl group, alkoxy group, and alkoxycarbonyl group represented by R1 and R6 include the same substituents as those exemplified as the substituent introduced into the group of R7 in the general formula [N-1].

As the aryl group of R4 and R6, a )-nyl group is preferable, and the substituent introduced into the phenyl group is represented by the general formula [1
All of the substituents exemplified as substituents to be introduced into the group R7 of F-1 can be mentioned.

When a benzene ring is formed by R6 and R6, various substituents can be introduced onto the benzene ring, and the substituents are similarly exemplified as the substituents introduced into the R2 group of general formula [I]-1. I can list all the things I did.

[I]-2 In the formula, n, , L 3. L 4. R1, Y l, R4,
RS has the same meaning as described above in general formula [I]-1, and represents Wti oxygen atom and sulfur atom, and R2 and R7 are hydrogen atom, alkyl group, aryl group, aralkyl group, and heterocycle. represents a group.

The groups represented by R2 and R7 include the above-mentioned general formula [I
]-1 The same groups as explained for R2 can be mentioned.

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

specific compound ≧υ3K ≧3h ShiH3 (I8) 0IK SO, Na O3X Next, a method for synthesizing the compound of the present invention will be described.

Examples of the methine chain donor for the compound of the present invention include, for example, The Cyanine Soy and Related Compounds by F.M.
ine dies and relatedcompo
undsJ (1964) Interscience
R, R2H-CH=CH-CH=CH-CH=CH-C as described on pages 249 to 251 of Publishers)
H-NR,R,X or R,R2H-CH=C)l-
CH=CH-CH=C)I-Cll-CI(-CH=N
R, R2X (RIR2N is methylaniline, 1.2.3
．． It is an amine such as 4-tetrahydroquinoline, and
is halogen etc. ), RIR2N CI'1=CHCH-CCH-CHCH-
NR+RJ- or OR' R,R,N-CH=CH-CI-C-CI(=C)I-
Using a compound such as CH-CH-CH=NR,R,X (RIR2N is an amine as above, R' is a hydrogen atom or an acyl group, and X- is a halogen, etc.) Can be done.

1 mole of methine chain donor and 1 mole of e.g. 2-methyl-
It can be synthesized by reacting a 3-alkyl oxacillium compound to obtain an aminopolymethine-substituted oxacillium compound, which is then reacted with 1 mole of an acidic core compound such as pyrazolone.

Alternatively, after reacting 1 mol of a methine chain donor with 1 mol of an acidic core compound such as pyrazolone to synthesize an aminopolymethine-substituted core compound, further 1 mol of, for example, 2-methyl-
It can also be synthesized by reacting with a 3-alkyloxacillium compound.

The merocyanine dye of the present invention containing a cyclic group such as a cyclohexene ring in the methyl chain can be synthesized by, for example, synthesizing a chemical/chlorhexenylidene substituted mother nucleus.

On the other hand, compound (4) can be obtained by reacting with the intermediate shown below according to a conventional method.

Synthesis of compound (4) The synthesis of compound (10) is base It can be synthesized by the following method.

Decametine melonanine dye can be synthesized in the same manner by selecting an appropriate methine chain donor and using the synthesis method described above.

A method for synthesizing octamethine and decamethine merocyanine dyes containing these cyclic groups is described, for example, in U.S. Pat.
No. 6404 describes a method for synthesizing merocyanine dyes in detail and can be referred to.

In the light-sensitive material of the present invention, the oxonol dye represented by the above formula can be incorporated into a silver halide emulsion and used as an anti-irradiation dye.
It can also be incorporated into a non-photosensitive hydrophilic colloid layer and used as a filter dye or antihalation dye.

Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. Incorporation of the dye according to the present invention into a silver halide emulsion layer or other hydrophilic colloid layer can be easily carried out by a conventional method. Generally, dyes or organic or inorganic alkali salts of dyes are dissolved in water to form an aqueous dye solution with an appropriate concentration, and the solution is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. be able to. The content of these dyes varies depending on the purpose of use, but is generally 1 to 1 per square meter of area on the photographic material.
It is applied and used in an amount of 800 mg.

Examples of the support in the light-sensitive material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin-coated paper, and polypropylene. synthetic paper,
There are glass plates, metals, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

Examples of hydrophilic colloids in the photosensitive material of the present invention include gelatin, derivative gelatin such as heptalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid, and synthesized materials such as polyvinyl alcohol and polyvinylpyrrolidone. Examples include resins and cellulose derivatives such as carboxymethylcellulose, and these can be used alone or in combination.

The silver halide emulsion in the light-sensitive material of the present invention includes:
Any of those commonly used in silver halide emulsions, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

The silver halide emulsion used in the light-sensitive material of the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, for example,
6-7772, or as described in U.S. Pat. No. 2,592,250,
That is, forming an emulsion of silver salt grains consisting of at least some silver salts having higher solubility than silver bromide, and then converting at least a part of these grains to silver bromide salt or silver iodobromide salt, etc. The manufacturing method of so-called conversion emulsion or 0.
It can be produced by any production method such as the production method of a Puman emulsion made of fine grain silver halide having an average grain size of 1 μm or less. This silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, active or inactive selenium sensitizers, potassium chloride sensitizers, etc. Gold compounds such as aurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride etc., palladium compounds such as ammonium chlorovaladate, sodium chlorovaladite etc., potassium chloroaurate etc. Sensitization can be performed using noble metal sensitizers such as platinum compounds, ruthenium compounds, etc. or combinations of such sensitizers. In addition to chemical sensitization, this emulsion can be reduced-sensitized with a reducing agent, such as triazoles, imidazole necks, azaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. In addition, a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound can be contained.

The silver halide emulsion used in the light-sensitive material of the 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.

In the light-sensitive material of the present invention, in the emulsion layer and other hydrophilic colloid layers, glycerin, dihydroxyalkane such as 1,5-bentanediol, ester of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, etc. obtained by emulsion polymerization are contained. It can contain a wetting agent such as a water-dispersible particulate polymer compound, a plasticizer, a film property improver, etc., and an aldehyde compound, N,
N-methylol compounds such as N'-dimethylol urea,
Active halogen compounds such as mucohalogen acids, divinyl sulfones, 2.4-'; chloro-6-hydroxy-5-) riazine, hardening agents such as dioxane derivatives, divinyl ketones, isocyanates, carbodiimides, saponins, and polyalkylenes. Surfactants such as glycol, polyalkylene glycol ether, alkyl sulfonate, alkylbenzene sulfonate, and alkylnaphthalene sulfonate, as well as optical brighteners, antistatic agents, antistain agents, ultraviolet absorbers, stabilizers, etc. Photographic additives may be included.

In the light-sensitive material of the present invention, the emulsion layer may contain a color coupler, and the coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for masking or a coupler that releases a development inhibitor. You can.

As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamide-based couplers, as magenta-forming couplers, pyrazolone-based compounds, and as cyan-forming couplers, phenol-based or sulfur-based compounds are usually advantageously used. .

Furthermore, the photosensitive material of the present invention can have any layer structure that can be used in conventional photosensitive materials.

〔Example〕

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

Example 1 Add and dissolve 3.5 g of gelatin in 35 ml of distilled water,
In addition, exemplary dyes (5), (6) and (
lO) respectively 2. 5 mff containing 10-' moles of OX
Add an aqueous solution of 1.2% saponin aqueous solution
Add 511Q and 1% formalin solution 0.75+Q,
Water was added to bring the total volume to 50+*ff h. This dye solution was coated onto an acetylcellulose film support and dried to provide samples 112 and 3. Comparative samples 4 and 5 were also created in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention.

Comparative dye (A) Comparative dye (B) in SO3 Each sample 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) Meter
3.0g
Sodium sulfite (anhydrous) 45.0g Hydroquinone 12.0g Sodium carbonate (l hydrate) 80.0g Potassium bromide
Add 2.0g water to make 1Q.

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

(E l is the absorbance before immersion in the developer solution, and E2 is the absorbance after immersion in the developer solution.) As is clear from Table 1, the dyes according to the present invention are more effective than the comparative dyes. It was found that it exhibits excellent decolorizing properties.

Example 2 Consists of 80 mol% of silver chloride, 19.5 mol% of silver bromide and 0.5 mol% of silver iodide, with an average grain size of 0.32 μm
A silver chloroiodobromide gelatin emulsion was prepared. 2,4-dichloro-6-hydroxy-1,3,5-1 per gelatin emulsion 1 & 9 (containing 48 g of silver and 75 g of gelatin)
- After adding 35mQ of riazine sodium salt (1% aqueous solution) and 50+l112 of saponin (10% aqueous solution), coat it on a subbed-treated polyethylene terephthalate film support so that 50rrr9 of silver is contained per 100C+1" and dry. Shitko.

Further, one of the emulsion layers contains an exemplary dye (1) according to the present invention.
A protective layer having the following composition containing 1) was applied to a dry film thickness of 2 μm. Sample 6 (protective layer composition) Gelatin 409 water

850m12 Exemplary dye (11) according to the present invention (2% aqueous solution) 100mQ2
．． 4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) 20raQ saponin (10% aqueous solution) 30mQ Similarly, in place of the exemplary dye (11) according to the present invention, Samples containing exemplified dyes (19) and (33) and comparative dyes (A) and (B) used in Example 1, respectively, were prepared and designated Samples 7.8°9 and 10, respectively.

Each of these samples was cut into small pieces, exposed through a photographic flashlight, and processed using a developer and fixer having the following composition.

Development was carried out at 20°C for 1.5 minutes, fixing was carried out at 20°C for 2 minutes, water washing was carried out at 20'C for 5 minutes, and then dried.

(Composition of developer) Hydroquinone 159 formaldehyde sodium bisulfite adduct 55g anhydrous sodium sulfite 3g sodium carbonate (-
water salt) 80g boric acid
59 Potassium bromide
2.5゜Disodium ethylenediaminetetraacetate 29 Add water
l, 000mρ (composition of fixer) Sodium thiosulfate 160g Anhydrous sodium sulfite 14g Glacial acetic acid
12+IIQrIM sand
12g potash alum
5゜ Add water
Ten sheets of each sample subjected to the 1,000mQ development process were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 2 below.

In the samples using the comparative dyes in Table 2, colored stains were observed in the samples, but with the dyes according to the present invention, there was no colored staining at all due to excellent run-off and decoloring properties.

Example 3 A silver chlorobromide gelatin emulsion containing 70 mol % of silver chloride and 30 mol % of silver bromide and having an average grain size of 0.3 μm was prepared. This gelatin emulsion lkt (48g silver, 7g gelatin)
Formalin (1% aqueous solution) 2Qm (including 5g)
After adding 50 mQ of saponin and saponin (10% aqueous solution), the mixture was coated on a subbed-treated polyethylene terephthalate film support, and a protective layer having the composition shown below was further coated on this emulsion layer.

(Protective layer composition) Gelatin 40y water

960m12 Formalin (1% aqueous solution>
12m (2 saponins (10% aqueous solution)
30 m (First, on the back side of the support coated with the emulsion layer and the protective layer, a gelatin layer containing a dye having the following composition was coated so that the dry film thickness was 3 pm. (Sample 11)) (Gelatin Layer composition) Gelatin 50g water

835TRQ Exemplary dye according to the present invention (9) (2% aqueous solution) 100mQ
Formalin (1% aqueous solution) 15IIIQ saponin (10
% aqueous solution) 50m12 Similarly,
Samples were prepared using the exemplary dye (18) according to the present invention and the comparative dye CB) in place of the exemplary dye (9) according to the present invention, and were designated as samples (12) and (13).

The development process was carried out in the same manner as in Example 2, and 10 samples were prepared for each sample.
The sheets were stacked one on top of the other and colored contamination was evaluated. The results obtained are shown in Table 3 below.

Table 3 As shown in the above table, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes according to the present invention. Furthermore, it has been found that the dye according to the present invention can provide a photographic material having an excellent antihalation effect without causing any adverse effects such as fog or desensitization on the photographic emulsion.

Example 4 A color photographic material was prepared by sequentially depositing the following layers on a support made of polyethylene-coated paper from the support side (
Sample (14)).

1st layer...yellow coupler; α-pivalyl α-(l-
benzyl-2-phenyl-3,5-dioxotriasilidin-4-yl)-2'-chloro-5'-[γ-(2,
A blue-sensitive silver halide emulsion layer containing 4-di-t-amylphenoxy)butyl, amido]acetanilide, a hardener (dichlorotriazine) and a surfactant (saponin) (salt containing 90 mol% silver bromide) A silver bromide emulsion sensitized using a sensitizing dye) was applied in an amount of 3.5 ml? /
100c+x''.

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

Third layer...magenta coupler; i(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-
amylphenoxyacetamide)benzamide]-5-
A green-sensitive silver halide emulsion layer containing pyrazolone, a hardener (dichlorotriazine) and a surfactant (saponin) (silver chlorobromide emulsion containing 80 mol% silver bromide, sensitized using a sensitizing dye) The amount of silver applied was 4.5 + i9.
/100c+++'.

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

5th layer... cyan coupler; 2,4-dichloro-3-
A red-sensitive silver halide emulsion layer containing a methyl-6-(2,4-di-t-amylphenoxyacetamide) phenolic hardener (dichlorotriazine) and a surfactant (saponin) (75 mol% silver bromide) A silver chlorobromide emulsion containing silver chloride (silver chloride bromide emulsion) sensitized using a sensitizing dye) with a coated silver amount of 2.
0119/100CII+'.

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

Furthermore, a red-sensitive emulsion (fifth layer coating solution) was prepared by adding 20 On+72 of a 2% aqueous solution of the exemplary dye (8) according to the present invention or the known dye C per 1 kg of the emulsion, and the emulsion was prepared in the same manner as in the above sample [14]. Sample [15] and sample [16] were prepared.

Known Dye (C) After exposing these samples (14), (15) and [16], they were processed according to the following processing steps.

[Processing process (310C)] Processing time 1, color development 3 minutes 2, bleaching and fixing 1 minute 3, water washing 2 minutes 4, stabilization 1 minute 5, water washing 2 minutes The composition of the processing solution used in each geographical step was , as follows.

[Composition of color developer]

4-Amino-3-methyl-N=ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8g anhydrous sodium sulfite
4.0g Hydroxylamine 1/2 sulfate 2.09 Anhydrous potassium carbonate
28.0g potassium bromide
1.5g potassium hydroxide 1.0
g Add water to make IQ.

[Composition of bleach-fix solution]

Ethylenediaminetetraacetic acid iron salt 65. (h Ethylenediaminetetraacetic acid disodium salt 3.09 Anhydrous sodium sulfite 9.5 g Ammonium thiosulfate 77.5 g Anhydrous sodium carbonate 4. Add o9 water to make If.

[Fixer composition]

Glacial acetic acid 9 + mff Sodium acetate 3g Add water °l
Let's say Q.

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

Table 4 As is clear from Table 4, in the samples containing the dye of the present invention, color staining due to residual color of the dye was not observed, as was the case with the samples containing the known dye. Furthermore, when the sensitivity of each sample was compared, it was found that the dye according to the present invention had extremely little adverse effect on the emulsion.

〔Effect of the invention〕

According to the present invention, it has good absorption spectrum characteristics, is decolored during photographic processing, is eluted from photographic materials, has extremely little residual color staining after processing, and is inert to photographic emulsions. It is possible to provide a silver halide photographic material containing a dye.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by containing a merocyanine dye represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It represents a ring-forming group, L_1, L_2, L_3, and L_4 represent a methine group, and R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. However, the compound represented by the general formula [I] shall have at least one acid group in the molecule.