JPS6340143A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a yellow dye layer having an excellent filter effect, halation preventive effect or the effect of adjusting the sensitivity of a photosensitive emulsion by providing a layer contg. a specific compd. CONSTITUTION:This photosensitive material is provided with the layer contg. at least one kind of the compd. expressed by formula I. In formula, X Y denote a cyano group, carboxyl group, alkyl carbonyl group, etc., which may be the same or different, R1, R2 denote a hydrogen atom, halogen atom, etc., which may be the same or different, R3, R4 denote a hydrogen atom, alkyl group, etc., which may be the same or different, L denotes a methine group (a methine group which may be substd. and the substituent is; for example, methyl, cyano group, etc.). At least one among X, Y, R1-R4 contains particularly preferably an org. residue of >=4C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver halide photographic material having a shoulder layer containing a yellow dye.

(Conventional technology) Generally, in silver halide photographic light-sensitive materials, for the purpose of light absorption filters, anti-halation, or sensitivity adjustment of light-sensitive emulsions, additives are added to the constituent layers of the light-sensitive material in order to absorb light of a specific wavelength. It is well known that dyes can be incorporated into the hydrophilic colloid layer, and therefore, it has been conventionally possible to color the hydrophilic colloid layer by incorporating the dye.

For example, a silver halide photographic light-sensitive material has a hydrophilic colloid layer such as a photosensitive silver halide emulsion layer on a support. When performing imagewise exposure, it is necessary to control the spectral composition of light incident on the silver halide emulsion layer in order to improve the overall photographic sensitivity. In such cases, a dye capable of absorbing light in a wavelength range that is not needed by the silver halide emulsion layer is usually added to the hydrophilic colloid layer, which is located on the side farther from the support than the photosensitive silver halide emulsion layer. A method is used in which a filter is made up of a single layer by containing a single layer of light, allowing only light in the target wavelength range to pass through.

Regarding the anti-halation layer, in order to improve the sharpness of the image, an anti-halation layer is provided between the light-sensitive emulsion layer and the support or on the back side of the support. This improves the sharpness of the image by absorbing harmful reflected light from the interface and the back surface of the support.

The dye used for this purpose must have a good absorption spectrum according to the purpose of use, and must be easily removed from the silver rodanide photographic light-sensitive material that is decolorized during the photographic development process. There is no substantial residual color staining caused by the dye after elution and development processing, there is no negative effect such as fog or desensitization on the photographic emulsion, and there is no color dispersion from the Lfc layer to other layers. Do not expose the product to liquids or
It must satisfy various requirements such as excellent stability over time in silver rodanide photographic materials and no deterioration.

Many efforts have been made to find dyes that meet these conditions. For example, the British patent jrO6.

31! Pyrazolone oxonol dyes, described in U.S. Pat. No. 3,2417. /, barbylic acid oxonol dye described in No. 27, US IN% Permit No. 2.370,
Azo dye described in No. 707, U.S. Pat. No. 2,2!1
No. 3,077, styryl dye described in British Patent No. s
r≠, hemioxonol dye described in No. 102, US Patent 2. ≠ 3.7 merocyanine dye described in No. 7, U.S. Patent 2. ♂≠3. ≠Cyanine dye described in r6, US patent 44.4tjθ, 1j! There are many benzylidene dyes with M and an an in the name.

When the layer containing the above-mentioned dye functions as a filter layer and an antihalation layer, it is necessary to selectively color that layer so that the coloring does not substantially spread to other layers. This is because, if the other layers are substantially colored, not only will it have a harmful spectral effect on the other layers, but also the effectiveness of the filter layer and antihalation layer will be diminished.

As a method for solving this problem, a method has been known in which a so-called acid dye having a sulfo group or a carboxyl group is localized in a specific layer using a mordant.

Such mordants include British patent TRJ.

Polymers of ethylenically unsaturated compounds carrying nfC dialkylaminoalkyl ester residues are known, as described in No. ≠7j, and reaction products of polyvinyl alkyl ketones and aminoguanidine as described in No. rso and No. 2ri.

(Problems to be Solved by the Invention) However, in the past, it has often been observed that such dyes diffuse into other layers. In addition, it is possible to use multiple mordants to eliminate diffusion, but not only is it impossible to completely eliminate diffusion, but the thickness of the layer that should be made to contain 7 becomes large, resulting in This has the disadvantage of causing a decrease in sharpness.

The first object of the present invention is to provide a silver halide photographic material in which a filter effect, an antihalation effect, or a sensitivity adjustment seedling of a light-sensitive emulsion supports a yellow dye layer.

The second object of the present invention is to create a yellow dye layer that selectively dyes a specific layer and does not spread to other layers. The object is to obtain a halogenated Sensha X light-sensitive material having I-.

A third object of the invention is to provide a silver halide photographic material having a yellow dye layer that is stable even during long-term storage and does not cause any deterioration in photographic performance.

(Means for Solving the Problems) The inventors of the present invention have requested that the above-mentioned objective is to form a layer containing at least/or at least a compound having the following characteristics (1). Silver halide photosensitive material

In the formula, X and YH may be the same or different, and a cyan group,
Carboxy group, alkylcarbonyl group (alkylcarbonyl group that may be substituted, 1), such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, /-oxo-7-chlorohebutyl group, etc.), arylcarbonyl group ( An arylcarbonyl group that may be substituted, such as benzoyl, l-ethoxycarbonylbenzoyl, 3-chlorobenzoyl group, an alkoxysulfonyl group (such as an optionally substituted alkoxysulfonyl group, such as methoxy sulfonyl, ethoxycarbonyl, butoxysulfonyl, t-amyloxysulfonyl, hexyloxycarbonyl, coethylhexyloxycarbonyl, octyloxycarbonyl, decyloxysulfonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, - monobutoxyethoxycarbonyl, cometersulfonylethoxysulfonyl, λ-cyanoethoxycarbonyl 1,2-(2-chloroethoxy)ethoxycarbonyl, u-(2-(+2-chloroethoxy)ethoxy)ethoxycarbonyl group, etc.), Aryloxycarbonyl group (replaced by gn) is a good aryloxycarbonyl group, for example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, ≠-ethylphenoxycarbonyl, ≠-fluorophenoxycarbonyl, ≠-nitrophenoxycarbonyl, ≠-methoxy phenoxycarbonyl, λ, II-C (t-amyl phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group that may be substituted with, for example, carbamoyl group, ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl,
≠-methoxyphenylcarbamoyl, s-i romophenylcarbamoyl, ≠-chlorophenylcarbamoyl, Hiro-ethoxycarbonylphenylcarbamoyl, u--j
Lopylsulfonylphenylrubamoyl, Hiro-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, ≠-hexyloxyphenylcarbamoyl, -, ≠-
Di(t-amyl)phenylcarbamoyl, -1chloro-3-(dodecyloxycarbonyl)phenylcarbamoyl, J-(hexyloxycarbonyl)phenylcarbamoyl group), sulfonyl group (e.g., methylsulfonyl, phenylsulfonyl group), It represents a sulfamoyl group (a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl group, etc.). Just in case, the combination of X and Y is [cyan group,
[substituted or unsubstituted arylcarbonyl group], [cyan group, substituted or unsubstituted alkyl carbonyl group], [cyan group, sulfonyl group] is excluded.

R1 and R2fl may be the same or different, and may be a hydrogen atom, a halogen atom (for example, F1a, Br11), an alkyl group (an alkyl group that may be substituted), such as methyl, ethyl, cochloroethyl, propyl, hexyl group, etc.), alkoxy group (an alkoxy group that may be substituted, such as methoxy, ethoxy, cochloroethoxy, butoxy, hexyloxy, octyloxy group, etc.), hydroxy group, carboxy group, substituted amino group [aliphatic Amine groups substituted with acyl groups derived from carboxylic acid #I or sulfonic acid (e.g. acetylamino, hexylcarbonylamino, methanesulfonylamino, ethanesulfonylamino, hexanesulfonylamino groups, etc.), alkylamino groups (e.g. methylamine) , etheramino, propylamine, hexylamino groups, etc.), dialkylamino groups (e.g., dimethylamino, dietheramino, dipropylamino groups, etc.)], carbamoyl groups (carbamoyl groups that may be substituted, such as carbamoyl, methylcarbamoyl, ethylcarbamoyl group, etc.), sulfamoyl group (sulfamoyl group that may be substituted, e.g. sulfamoyl, methylsulfamoyl, ethylsulfamoyl group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, pentyloxy Cartonyl, ocunalokine, rubonyl group, etc.) are applied.

R3 and R4 may be the same or different and are a hydrogen atom, an alkyl group (an alkyl group that may be substituted, for example,
Methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, ni-ethylhexyl, octyl, totinol, hexadecyl, nichloroethyl, 3-chloropropyl, λ-bromoethyl, 2-hydroxoethyl, cyanomethyl, λ-cyanoethyl, 3- cyanopropyl,
Comethoxoethyl, 3-methoxypropyl, λ-ethoxyethyl, 2-octylox7ethyl, 3-ethoxypentyl, 2-imbroboxy/ethyl, acetylmethyl, niacetylethyl, benzoylmethyl, acetyloxymethyl, 2-(ethyl carbonyloxy)ethyl,
di(heptanoyloxy)ethyl, λ-(impropylcarbonyloxy)ethyl, benzoyloxymethyl, tI-chlorobenzoyloxymethyl, ≠-nitropensoyloxyethyl, acetylaminoethyl, 2-(
Ethyl sulfonylamino)ethyl, methylcarbamoylmethyl, cometelaminoethyl, di(ethylamine)ethyl, di(dimethylamino)ethyl, 2-(diethylamino)ethyl, -monomethylureidoethyl, carboxymethenope-sulfoxoethyl, 3 -Karuhoki/
Propyl, 6-carboxyhexyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, λ-(futoquincarbonyl)ethyl, 3-(octyloxysulfonyl)propyl, '+'+'F')fluoroethoxycarbonylmethyl, isopropyloxy Carbonylmethyl, J-(t-amylox7carbonylJ-propyl, (nee ethylhexyl)oxycarbonylmethyl, λ-(ethoxycarbonyl)ethyl, etersulfonylmethyl, 2-fmethylsulfonyl)ethyl, s-(butylsulfonyl)ethyl, methylsulfonylaminomethyl, λ-(methylsulfonylamino)ethyl, There are good aryl groups, such as phenyl, l-chlorophenyl, ≠-cyanophenyl, ≠-hydroxyphenyl, ≠
-carboxyphenyl, -methoxyphenyl, ≠-methoxyphenyl, ≠-ethoxyphenyl, ≠-octyloxyphenyl, ≠-methylphenyl, ≠-nitrophenyl group fxt)? Alternatively, R3 and R4 may form a 3- to z-membered hetero@ (eg, piperidine ring, morpholine ring, etc.).

1 star R1 and R3, R2 and R4 are respectively connected and 5~
A 6-membered heterocyclic tube may be formed.

L is a methine group (which may be substituted), and the substituent (7) represents a methyl, cyano, etc. group.

XS Y% It is particularly preferred that at least one of R1, R2, R3, and R4 contains an organic residue having V or more carbon atoms.

Next, all specific examples of compounds used in the present invention will be listed, but the present invention is not limited thereto.

In the above-mentioned -characteristic ((), the combination of X and Y is [
Preferred are dye compounds having a cyano group, alkoxycarbonyl group], [cyan group, aryloxycarbonyl group], [cyano group, carbamoyl group], [cyan group, carboxy group], and [cyan group, cyano group].

Y-/ -x Y-j -g -r -b I ”l'-IO Y-/ / Y-/3 Y-/ gu Y-/ z Y-/j Y-/7 y-/ ♂ Y- KO If C) (a Y-2≠ Y-λyoQ (X”Ha (] Y-270 Y-, 2F Y-λri'1'-J10 Y-J ≠ -34r CE (3 0(tears) 3 I Y-J11' Y-JriY-≠O The compound used in the present invention can be easily synthesized by the method described in JP-A-76-3 and the like.

Although it is advantageous to carry out the condensation reaction using a solvent that has the property of dissolving the starting material, there are many reactions that proceed even if the starting material is not dissolved. Suitable solvents include alcohols (e.g., methanol, ethanol, isopropanol, etc.), acetonitrile, ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether, etc.), amides (e.g., acetamide, dimethylformamide, etc.). ), ethers (e.g.
(dioxane, etc.), dimethylsulfoquinide, and chloroform. These may be used alone or in combination. The reaction is preferably carried out at a temperature range from room temperature to the boiling point of the solvent used, preferably at 5o-r.
o It is better to do it at 0c. To accelerate the reaction, use pyridine, piperidine, diethylamine, triethylamine, ammonia gas, potassium acetate, ammonium acetate,
It is advantageous to add acids, bases, such as acetic acid. The reaction time is usually about IO minutes to j hours.

Typical synthesis examples thereof are listed below, but other compounds can also be easily synthesized by similar methods.

(Synthesis example) Cyanoacetic acid dode/lester 3θ,≠? (0°/λmo
l ), ≠-formyl-N-ethyl-N-(2-methylsulfonylaminoethyl) -3-mer-j-lua :=
Rin, 2r, ti? The mixture was stirred in (0,/mol)k acetonitrile/20R1, and ammonium acetate was added, followed by heating under reflux for about 2 hours. After removing dust and filtering,
When allowed to cool, crystals precipitated.

Filter the crystals, wash with a small amount of acetonitrile, and dry L7.
'n. Collection @to, r? (97.1%) This 1 was recrystallized from acetonitrile to obtain exemplified compound Y-≠. Collection flt
lt, II? II9.2%) Exemplary compound Y-4 @ cyanogen acetic acid butyl ester 7, I? (0,Ojr mo
l), ≠-formyl-N, N-dihexylanily: y/
lA,! ? (0, Ojmall) k acetonitrile ro
ml, add 3° of ammonium acetate,
The mixture was heated under reflux for about 3 hours. After filtering to remove dust, the filtrate was concentrated and subjected to column chromatography to obtain exemplified compound Yr.

Collection t/7. jt? (11%) Generally, the general formula (area of H on the dye layer photosensitive material/rrL2
Approximately V/~♂00m9 is used.

- When using the dye shown in property (1) as a filter dye or antihalation dye, any effective t can be used, but the optical density is 0. There is no Oj,
It is preferable to use it so that it is in the range of 3.0. The addition time may be any step before coating.

The dyes according to the invention can be dispersed in emulsion layers and other hydrophilic colloid layers (interlayers, protective layers, antihalation layers, filter layers, etc.) in a convenient manner.

■ A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid N, or a method in which it is dissolved or dispersed in an aqueous solution or a solvent, and then used in an emulsion layer or a hydrophilic colloid layer, as appropriate. What solvent? lJ, t, methyl alcohol, ethyl alcohol, propyl alcohol,
Methyl cellulph, l! P! f Kaisho ttr-2711, US Patent J, 7! In the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, etc., as described in No. t, No. 130,
It can also be added to emulsions.

(2) A method in which a compound is dissolved in an oil, that is, a high-boiling solvent that is substantially insoluble in water and has a boiling point of about 71,006 or higher, and then dispersed in a colloidal solution. As this high boiling point solvent, Ting, US Pat. No. 1, 3λλ.

For example, phthalic acid alkyl esters (dibutyl phthalate, diethyl azelate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), as described in No. 027. , citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters. (eg, triphthyl trimesate), etc. can be used. Further, organic solvents having a boiling point of about 3°C to about /J00C, such as lower alkyl acelates such as ethyl acetate and butyl acetate, ethyl propionate, -butyl alcohol, methyl isobutyl ketone, β-ethoxyether acetate, methyl cellosolve acetate, etc. It can also be dissolved in water or a diluted solvent, such as an alcohol such as methanol or ethanol.

Here, the usage ratio of dye and high boiling point solvent is 10-/
/10 (!amount ratio) is preferable.

(2) A method of incorporating the dye of the present invention and other foil additives into a polymer latex composition filled with a photographic emulsion layer or other hydrophilic colloid layer.

Examples of the polymer latex include polyurethane polymers, polymers made of vinyl monomers (suitable vinyl monomers include acrylic esters (methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate,
dodecyl acrylate, glycidyl acrylate, etc.),
α-substituted acrylic ester (methyl methacrylate,
butyl methacrylate, octyl methacrylate, chrycidyl notacrylate, etc.), acrylamide (butylacrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl ester (vinyl hexate, vinyl butyrate, etc.), Vinyl halide, (vinyl chloride, etc.),
Vinylidene halide (vinyritine chloride, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether f5), styrene, etc.), ethylene, phlopylene, styrene, Tsutajie/, acrylonitrile, etc. These may be used alone or in combination of λ or more types, or may be mixed with other vinyl monomers as a minor component (2 may be used.As other vinyl monomers,
Examples include itaconic acid, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, and the like. ]
etc. can be used.

To these filled polymer latex, Tokko Shoj/-3rit
r3@, JP-A-5i-ryri≠3, same jJ-/37/
J/ issue, same! ≠-32, 5λ, same! ≠-107ri 4L
No. 1, same! j-/33≠A, same as A-/90≠3
No., same j&-/10 hiro 7, same! t-/26130,
let s r -i g ta.

It can be produced according to the method described in No. 3g'.

Here, the usage ratio of dye and polymer latex is 1
0 to ///0 (weight ratio) is preferable.

(2) A method of dissolving the entire compound using a surfactant; useful surfactants may be oligomers or polymers.

For details of this polymer, please refer to JP-A-1.0-/! r≠
It is described on pages 1 to 27 of the specification of No. 37.

(2) A method in which a hydrophilic polymer is used in place of the high-point solvent or in combination with a high-boiling point solvent in (2) above. Regarding this method, there are US Patent Nos. 3 and 6, No. 5, and West German Patent No. 5. 7. ≠Described in No. 67.

■A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group, etc. in the side chain as described in Japanese Patent Application Laid-open No. ShojP-//3173≠.

'1st Step: In the above-obtained hydrophilic colloid dispersion, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. Shoj/-3213j, may be added.

Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be used for photography can be used.

The silver halide photographic emulsion used in the silver halide photographic light-sensitive material of the present invention may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. . Preferred silver halides are silver bromide, silver chlorobromide, silver halide or silver iodochlorobromide.

The silver halide grains in the photographic emulsion layer may be regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
egular) crystal form, or
It may also have a composite form of these crystal forms.

It may also consist of a mixture of particles of different crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

The latent image may be formed mainly on the surface of the grain (for example, a negative emulsion), or it may be formed mainly inside the grain.
It is also possible to process grains that are similar to those of other types (e.g., internal latent image emulsions, prefogged direct inversion emulsions).

The silver halide emulsion used in the present invention has a thickness of 01j microns or less, preferably nO,,3 microns or less, a diameter of preferably o,t microns or more, and grains with an average aspect ratio of 5 or more account for the total projected area. They may be tabular grains that account for jO% or more. 'Also, the average particle size
It may be a monodisperse emulsion in which grains with a grain size of ot4 or less account for 51 or more grains.

The photographic emulsion used in the invention is B. Gerafkides (P.
, Glafkides), Shimmy Eng.
Photography (Chimie er Physi)
quePhotogrohequej (Ballmontel Publishing, /!P67), G, F, Tuffin CG,
Photographic Emulsion Chemistry (Photographic Emulsion Chemistry) by F.
ulsion Chemistry) (Focal Press, 1966), Bui, El, Zelikma 7 (
Making and Coating Photographic Emulsion by V. L. Zelikman et al.: /
(Making and Coating Photo
It can be prepared using the method described in I. Focal Press, 6≠2000).

In order to control grain growth during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, aryne ammonium, and thioether compounds (for example, U.S. Pat. No. 3.27/167, U.S. Pat. No. 3, 7744, Aur No. J, 7011
．． No. 130, Ko No. 1.2 7゜≠32, No. ≠, 2
7J, J74 (etc.), thione compounds (e.g., JP-A No. 53-1≠≠31, JP-A-53-♂covOr, JP-A-11-77737, etc.), amine compounds (e.g., JP-A-1983-1987) ≠−/θθ7/7 etc.).

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts, iron complex salts, etc. may be co-existed.

Silver halide emulsions are commonly chemically sensitized.

For chemical 'RI' feeling, for example H, 717-zel (H
, Fr 1eser), Tee Ning Grundlagen
Die Grundlag
ender Photography Pr
ozesse mitSilberhalogenid
The method described in (Akademitsche Verlags Geserschacht/9!, r) pages 67j to 73 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g., total complex salts,
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as pt, Ir, and Pdl can be used alone or in combination.

The photographic emulsion used in the present invention includes ! of a light-sensitive material. ! For the purpose of preventing fog during the manufacturing process, storage, or photographic processing, or for stabilizing photographic performance, a chemical compound may be contained. Namely, azoles such as benzothiandylium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (with nitro or halogen replaced); heterocyclic mercapto compounds fI, such as mercaptothiazoles, mercapto; Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), mercaptopyrimidines; Terocyclic mercapto compounds; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene, especially ≠-hydroxy substituted (/, 3.3a, 7
); benzenethiosulfonic acids; bayinsulfinic acid; and many other compounds known as antifoggants or stabilizers can be added.

The light-sensitive material of the present invention may be used in combination with an ultraviolet absorber such as benzo)IJ azoles, and a typical example is as described in Research Disclosure, 24L Co. There is.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

In other words, it may contain an adduct that can develop a color by oxidative coupling with an aromatic primary amine developer (such as a phenylene diamine derivative or an amine phenol visiting compound, if activated) during color development. For example, as a magenta coupler, a j-pyrazolone coupler, a pyrazolobenzimidazole coupler, a 7-anoacetylcoumarone coupler, an open-chain acylacetonitrile coupler, and a U.S. patent ratio of 3.72! , No. 067, pyrazolo [s, i
-c][i +21≠]triazoles or pyrazolo[t,/-b] described in European Patent No. 11, rto
[/, Ko, Hiro] There are triazoles, etc., yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include naphthol couplers and phenol couplers, etc. , can be preferably used for couplers that are robust against humidity and temperature, and a representative example thereof is U.S. Patent No. 3,772.
, 00λ, etc.; JP-A-75'-J/RI-53, JP-A-Sho! ? -≠247/issue and JP-A-6R-/332! Co,j-diacyl aminophenol couplers described in Publication i'3, etc.;
Okobi Yoneko Patent No. ≠, 333. A phenylureido group is placed at the J-position as described in the Tata issue, etc.! A phenolic coupler having an acylamino group at the − position, furthermore,
Tokukai Sho tO-, 2J7 ≠ Hiro r1 Tokukai Shoj ter 2A44u
77, same! Tar 26r/3j/C listed nth! Typical examples include position-substituted naphthol couplers and polymer couplers thereof. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler is ≠ equal or λ for the silver ion.
Hit tt! ! Either E is fine. Also, colored couplers that have a positive effect, or couplers that release a development inhibitor during development (so-called DIR couplers).
It may be.

In addition to the DIR coupler, the coupling reaction product may contain an iu-colored DIR coupling compound which is colorless and releases a development inhibitor.

For the purpose of increasing the ag degree, increasing contrast, or accelerating development, the photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane. It may also include derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

In the silver halide photographic emulsion of the present invention, known water-soluble dyes other than the dye of general formula (1) used in the present invention (for example, oxonol dyes; hemioxonol dyes, It may be used in combination with (kol dye and merocyanine dye). ″
Further, as a spectral sensitizer, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

Uninvented photographic emulsions contain divine surfactants for a variety of purposes such as coating aids, antistatic properties, improvement of slippage, emulsification dispersion, prevention of adhesion, and improvement of photographic properties (e.g., promotion of current processing, high contrast, and sensitization). It may also contain an agent.

ifc, photosensitive material Kfl of the present invention anti-fading agent, hardening agent,
We specifically research and conduct research on color antifoggants, ultraviolet absorbers, protective colloids such as gelatin, and individual additives.
Tisfroger vol.1. /7A (/971,
X[1)RD-/7A! J'z and VC are written n.

The finished emulsion is coated on a suitable support, such as baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates. .

The silver halide photographic light-sensitive material of the present invention includes a photographic light-sensitive material for color negative film plate making (for example, lith film,
Lis du dupe film! ), photosensitive materials for cathode ray tube displays (e.g. photosensitive materials for emulsion X-ray recording, materials for direct and indirect photography using screen capture), silver salt diffusion transfer process (Silver 5alt diffusio
n transfer process) photosensitive materials,
Photosensitive material for color diffusion transfer process, die transfer process fimbibitiontransfe
Photosensitive materials for process J, emulsions used in silver photosensitive materials, photosensitive materials for recording printout images, photosensitive materials for photodevelopment type printing (Direct Pr1nt image), photosensitive materials for heat development, photosensitive materials for physical development, etc. Can be done.

Exposure to obtain a photographic image may be carried out using a conventional method. That is, various known light sources such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flat lamps, and cathode ray tube flying spots can be used in the chair. Exposure times range from the 171,000 seconds normally used in cameras to the 1 second exposure time (of course, exposures shorter than 171,000 seconds, such as those using xenon flash lamps or cathode ray tubes)
Exposures of 4 to 0' seconds can also be used;
Exposures longer than 7 seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

For photographic processing of light-sensitive materials made using the present invention, for example, research
Disclosure)/No. 76, No. +2r~30
As described on page (R1) -/7A≠3),
Any known method and known treatment liquid can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between /I and jo 0c, but it may also be lower than /r 0c or higher than so 0c.

(Effects of the Invention) The silver halide photographic light-sensitive material of the present invention has a yellow dye layer's filter effect, no-ration prevention effect, or a light-sensitive emulsion's sensitivity adjustment effect.

In particular, when the yellow dye of the present invention was used as a yellow filter, a significant increase in sensitivity was achieved in the green-sensitive emulsion layer compared to when conventionally known colloidal silver was used.

In the silver halide photographic material of the present invention, does the dye layer have appropriate spectral absorption? ! -1 and selectively dyes a specific lvi and carries a yellow dye that does not diffuse to other layers.

Further, the halogenated button photographic material of the present invention provides images with improved sharpness. Furthermore, photographs obtained from the silver halide photographic light-sensitive material of the present invention are stable even when stored for a long period of time, and their photographic performance does not deteriorate.

(Examples) The present invention will be described in more detail below with reference to Examples, but the invention is not limited thereto.

A multilayer color photographic material, Sample 10, was prepared on a cellulose triacetate film support provided with an undercoat layer and each layer having the composition shown below.

1st layer: Harenyon prevention layer Black colloidal silver・・・・・・・・・・・・・・・・・・
0. /♂9/m2 Ultraviolet absorber C-1・・・・・・・・・
...o, i? /m2 UV absorber C-λ...
....o, / 79/m2 gelatin layer 2nd layer: intermediate layer λ,! -G-t-bentatecylhydroquinone・・・・・・・・・・・・0.119
7m2 Kazoler C-J・・・・・・・・・・・・・・・
・0, OJ r/@2 Silver iodobromide emulsion (silver iodide per mole, average grain size 0.07μ)...
...Amount of silver applied (same below) 0. 3rd gelatin layer containing /3f/m2; 1st red-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
...0.72 f//m2 (6 moles of silver iodide, average grain size 0.1 μ) Sensitizing dye I...7.0 x 10 per mole of silver Molar sensitizing dye■・・・・・・・・・・・・Co, oxio per 1 mole of silver Molar sensitizing dye■・・・・・・・・・・・・For 1 mole of silver Lever, lrX/θ molar Sensitizing dye・・0.320
f/m2 coupler C-r・・・・・・・・・・・・o
, oio? 7m2 coupler C-3・・・・・・・・・
...o, oro? /, gelatin layer containing 7r2 ≠ layer; ! Red-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
.../, A 97m2 (silver iodide 10 moles, average grain size 1.!μ) Sensitizing dye I......
For 1 mole of silver! , 2×10 moles of sensitizing dye■・・・・・・・・・・per mole of silver/,! ×10 mole sensitizing dye■・・・・・・・・・2+/X10 mole sensitizing dye for 1 mole of silver■・・・・・・・・・・・・For 1 mole of silver te/, j×10 molar coupler C-≠・・・・・・・・・0.060
9/m2 coupler C-Otsu・・・・・・・・・0
．． 2109/m2 coupler C-j・・・・・・・・・
...0. Gelatin layer J layer containing 2 layers; 3rd red-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・／
,t? /m2 (10 moles of silver iodide, average grain size 2.0μ) Sensitizing dye I......For 1 mole of silver! , ! ×/ 0 moles of sensitizing dye ■・・・・・・・・・ i, tXio per mole of silver Sensitizing dye ■・・・・・・・・・・・・ per mole of silver 2.2 x 10 moles of sensitizing dye ■・・・・・・・・・・・・ per mole of silver /,! X10 Molar coupler C-A・・・・・・・・・0 ,/
109/m2 coupler C-3・・・・・・・・・・・・
・0.001? 6th gelatin layer containing /m2; Intermediate gelatin layer 717; 1st green-sensitive emulsion layer Silver iodobromide emulsion
・・0.1617m2 (Silver iodide! Morti, average grain size o, rμ) Sensitizing dye■・・・・・・・・・・・・Silver 1
3, tXio moles per mole sensitizing dye ■・・・・・・・・・・・・ J, O×10 moles per mole of silver ■・・・・・・・・・・・・・ ・ For silver, for 1 mol, 2 × 10 mola conplar C -7 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ OL -Ta O
v/rrL2 coupler C-r・・・・・・・・・・・・
・O6O≠09/7FL 2 coupler C-ta...
...... Gelatin layer r-th layer containing 0.0609/m2; Second green-sensitive emulsion layer Silver iodobromide emulsion ...... ...
.../, 397 m2 (6 moles of silver iodide, average grain size/, 1μ) Sensitizing dye ■......Co, 7X/l for 1 mole of silver:) Mole increase Sensitizing dye ■・・・・・・・・・λ for 1 mole of silver, /×10 mol Sensitizing dye ■・・・・・・・・・・・・r for 1 mole of silver , zXio Molar Coupler C-7・・・・・・・・・・・・0.210
? /m2 coupler C-t・・・・・・・・・0
．． O/λ7/TL2 coupler C-7...
...0.00ri? / m2 coupler C-/
0=-------0, o//? Gelatin layer containing /rrL2; Intermediate layer Seratin layer 1st layer; 3rd green-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・・・・
.../, s Y/m2 (silver iodide 10 moles, average grain size λ, θμ) Sensitizing dye V...
3, oXio moles per mole of silver sensitizing dye■・・・・・・・・・2, Hiroshi x lO moles sensitizing dye per mole of silver■・・・・・・・・・...for 1 mole of silver? ,! ×10 molar coupler C-/ / ----------o, o
i J y7rrL2 coupler C-7o...
Ceratin layer 1/re: yellow filter containing 0.07097 m2 yellow colloidal silver 0.0≠ f
/m2r, r-di-pentadecylhydroquinone...
・・・・・・・・・1st and 2nd gelatin layers containing 0.03/fl/m2; 1st γr-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・...0
．． 32? /712 (silver iodide 6 molt, average grain size O
6ψμ) Coupler c-/ko・・・・・・o, 7
3? /m2 coupler C-/3・・・・・・・・・
0.0! Gelatin layer containing core/m2 13th layer: λ-th emulsion layer Silver iodobromide emulsion 0
．． 11O? /rn2 (silver iodide 70 mole, average grain size /, 0μ) Sensitizing dye■・・・・・・・・・・・・Silver 1
2.2X10 mole coupler C-/2----0.3 for moles! 9
Gelatin layer containing 7 m2 1st ≠ layer; @grain emulsion layer Silver iodobromide emulsion 0
．． Gelatin layer 1 containing λj y/m2 (silver iodide λ morch, average grain size 0.7jμ)! Layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion 1
．． oo 97m2 (silver iodide 10 moles, average grain size/, zμ) sensitizing dye■・・・・・・・・・・・・Silver 1
2.3×io per mole Molar coupler C-7x・・・・・・0. /! 9
Gelatin layer 1st layer containing 7m2; 1st protective layer ultraviolet absorber C-ha...o, i≠y 7
77L2 Ultraviolet absorber C-λ・・・・・・0.2
2 17th layer of gelatin layer with an area of 97 m2; λth protective layer polymethyl methacrylate particles (diameter i, sμ)...
...0.0! 97m2 silver iodobromide emulsion...
In addition to the above composition, each gelatin layer containing 0.3O97m2 (2 molt silver iodide, average grain size 0.07μ) contains ≠ as a stabilizer. -Hydroxy-6-methyl (/, !, Ja, 7) tetrazaintene, gelatin hardening agent H-/, and surfactant were all applied.

The compounds used to prepare the samples are shown below.

C-/ C-r (n) C-r -A CH3 C-♂ α C-/ / Ω Sensitizing dye ■ 03Na Sensitizing dye ■ ■ 03Na Sensitizing dye ■ YO O3Na C2H5 Sensitizing dye ■ Sensitizing dye ■ H-/ Next, samples 102 to 70 g each were prepared using the following materials in place of the yellow colloidal silver in the first layer of sample 10/.

"Sample 70" The following water-soluble dye S-/'i, Ox/0 mol/rrL2 addition S-/ Sample io3 The following water-soluble dye 3-2 was added to 2. O×10 mol/m2
Added sample I O A dispersed version was used.

*f2jyor Addition of the following dyes 5-afa, oxlo' mol/m2 The test was carried out in the same manner as S-Hiro's addition strip sample 10≠.

S-≠ Sample IOA Dye Y-ta, z, oxlo 'mol/, 2 addition Y
-≠ was added in the same manner as Sample 10 Hiro.

Sample/θ7 Dye Y-r 2.0×10'mol/rrL2 addition Y
-J' was added in the same manner as sample 10≠.

Sample 101 Dye Y-/l'f2.0 x 10' mol/rrL2-added Y-/I was added in the same manner as Sample 70 Hiro.

Samples 10/-10r obtained as described above were wet-exposed with white light, and then subjected to the treatment shown in F at 3♂ 0C, and the photographic performance was evaluated.

Processing/, color development...3 minutes/! sec λ, bleached
Wash with water for 30 minutes and 30 seconds.
...3 minutes/! Second cap fixed allowance...30 seconds! ,Washing・・・・・・・・・3 minutes lj seconds t
, stable...3 minutes/second The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate・・・・・・・・・・・・・・・
.../, θ? Sodium sulfite・・・・・・・・・・・・
・・・・・・・・・・・・・・・≠、0? sodium carbonate·······················
・・・・・・30.0? Potassium bromide・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
.../, lIf hydroxylamine sulfate...
・・・・・・・・・・・・λ,≠1≠−(N-ethyl−
N-β Hydroxyethyl a1))-λ- Methyl-aniline sulfate・・・・・・・・・・・・・・・・
・≠, j′? Add all the water...
・・・・・・・・・・・・・・・・・・・・・・・・／、θ
! Bleach liquid ammonium bromide・・・・・・・・・・・・・・・・・・
.../lzO,0? Ammonia water (21r%)...
・・・・・・・・・・・・2 j, OCX:.

Ethylenediamine-sodium iron salt of tetraacetate・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・/30.0? Glacial acetic acid・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・／≠、Add OCc water・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／, θj Fixer Sodium Tetrapolyphosphate・・・・・・・・・・・・
2.01 Sodium sulfite・・・・・・・・・・・・
・・・・・・・・・・・・・・・・02Ammonium thiosulfate (70%)・・・・・・・・・／7! ,OCC Sodium bisulfite・・・・・・・・・・・・・・・・
...Hiroshi, 6? Add water...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／、Ol stabilizer formalin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・♂、Add OCC water・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・／、01 I# degree measurement was carried out on the treated sample obtained as above. The results are shown in Table 1.

*1: Relative sensitivity when the blue sensitivity of sample 10/ is set to 100.2: Relative sensitivity table when the green sensitivity of sample 10/ is set to 100. From dye S-/~S-co? Samples used 10-1
In 03, a markedly low sensitivity of the blue-sensitive layer was observed, and the dyeing hs-
In sample ior using Hiroshi, the sensitivity of the green sensitive layer decreased significantly.

On the other hand, in samples iot to 10♂ of the present invention, no decrease in the sensitivity of the blue-sensitive layer was observed, and furthermore, a significant increase in sensitivity of the green-sensitive layer was observed.

Example Sample 101-101 obtained in Example 1 was stored under high temperature and high humidity conditions in an atmosphere of 0% relative humidity for 3 days, and then similarly wet exposed to white light. The same treatment as in Example 1 was carried out, and the decrease in blue-sensitive layer sensitivity and ΔSR were measured for those subjected to the same exposure treatment without being stored under high temperature and high humidity conditions.

The results are shown in Table 7-2.

7,,-2 Samples IO2-1 using dyes S-/-S-J from Table-Co
When 0≠, the sensitivity decrease of the blue-sensitive layer was large, but this decrease in sensitivity was not observed in samples 106 to ior of the present invention.

Example 3 Sample 10/~IO? obtained in Example 1 After wet exposure with white light, the following treatment was carried out at 3.1-'C, and the photographic performance was evaluated in the same package as Example.

Processing Color development・・・・・・・・・・・・・・・・・・
...3 minutes/j seconds 2 bleaching period...
・・・・・・・・・・・・! Minute 00 seconds 3 Wash with water...
・・・・・・・・・・・・・・・・・・3 minutes/j seconds 4 Stable・・・・・・・・・・・・・・・・・・3
minutes! The composition of the treatment liquid used in each step is as follows.

Bleach-fix solution Ferric ammonium ethylenediaminetetraacetate ioo, oy Ethylenediaminetetraacetic acid secondary sodium salt tt, oy Ammonium thiosulfate aqueous solution (70%) 173.0ml Sodium sulfite ≠, j? ammonia water
/j rnl Add all the water
/.Ol [pH=t, r] The color developer and stabilizer used had the same composition as in the treatment of Example 1.

Table 3 P-3 shows that samples 104 to 70♂ of the present invention showed no decrease in sensitivity in the blue-sensitive layer, and a remarkable increase in sensitivity in the green-sensitive layer.

From the above findings, it is clear that the sample based on the present invention is superior in the sensitivity adjustment effect of the yellow dye layer and has excellent stability over time.

! +! f Patent Applicant Applicant Photographic Film Co., Ltd. Procedural Amendment Document
5,71, - = Indication of above note Showa 6/rl-Long-awaited application No. 113 ≠ Yoshi) 2. Name of the invention Silver halide photographic light-sensitive material 3. Relationship with the person making the amendment Patent application Person 4, Subject of amendment Amend the statement in the "Scope J of the description" and the "Detailed description of the invention" column 5, and the "Claims" section of the description of the contents of the amendment, as shown in the attached sheet. do.

The description in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) Page 2, line 20 "with or without substitution" Delete.

2) Page 10, line 1 "with or without substitution" Delete all.

Attached Claims: A silver halide photographic material characterized by containing at least a compound represented by property (1) below.

General formula (1) In the formula, X and Y may be the same or different from each other, and include a cyan group, a carboxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfonyl group. , represents a sulfamoyl group. However, the combination of X and Y is [cyano group, arylcarbonyl group], [cyan group,
Alkyl carbonyl group], [cyan group, sulfonyl group]
except when R1 and R2 may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amine group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group. . R3 and R4 may be the same or different and represent a hydrogen atom, an alkyl group, an aryl group,
At R3 and R4! ~6-membered ring may be formed.

Also, R1 and R3, and R2 and R4 are each connected!
~ may form a member ring. L represents a methine group.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a layer containing at least one compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X and Y may be the same or different from each other, and include a cyano group, a carboxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, Represents an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group. However, this excludes cases where the combination of X and Y is [cyano group, substituted or unsubstituted arylcarbonyl group], [cyano group, substituted or unsubstituted alkylcarbonyl group], [cyano group, sulfonyl group]. R_1 and R_2 may be the same or different,
Hydrogen atom, halogen atom, alkyl group, alkoxy group,
Represents a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group. R_3 and R_4 may be the same or different,
Represents a hydrogen atom, an alkyl group, an aryl group, R_3,
R_4 may form a 5- to 6-membered ring. Furthermore, R_1 and R_3, and R_2 and R_4 may be connected to each other to form a 5- to 6-membered ring. L represents a methine group.