JPS6364044A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To produce enhanced filter and antihalation effects by incorporating specified dye compds. into a silver halide photographic sensitive material. CONSTITUTION:At least one kind of dye compd. represented by formula I and at least one kind of dye compd. represented by formula II or III are incorporated into a silver halide emulsion layer. In the formulae I-III, each of X, Y and Z is cyano, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfonyl or sulfamoyl, L is methine, each R1, R2, R5, R6, R9, and R10 is H, halogen, alkyl, alkoxy, hydroxy, carboxy, substd. amino, carbamoyl, sulfamoyl or alkoxycarbonyl, each of R3, R4, R7, R8, R11 and R12 is H, alkyl or aryl and R13 us aryl. Since the dye compds. having proper spectral absorption and causing no diffusion to other layer are incorporated, an enhanced filter effect can be produced.

Description

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

(Prior art) In general, in photosensitive materials, light absorption filters are used to absorb light at specific wavelengths for the purpose of preventing halation or adjusting the sensitivity of light-sensitive emulsions. It is a well-known technology to incorporate dyes into layers, and therefore, coloring of hydrophilic colloid layers with the dyes has been conventionally practiced.

For example, copper halide photographic light-sensitive materials are formed by forming a hydrophilic colloid layer such as a photosensitive silver halide shell emulsion layer on a support. When performing imagewise kojigen, it is necessary to control the spectral composition of light incident on the silver halide emulsion layer in order to improve photographic sensitivity. In such cases, the photosensitive silver halide emulsion layer usually absorbs light in a wavelength range that is not needed by the hydrophilic colloid layer located on the side far from the support. A method is used in which a single layer of filter is made by containing dyes that can be used to transmit light in a target wavelength range.

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

The dyes used for this purpose must have good absorption properties according to the purpose of use, have no adverse effects such as fogging or desensitization on the re-emulsion, and must not be colored. It must satisfy various conditions such as not diffusing from one layer to another, having excellent stability over time in a solution or in a silver halide photographic material, and not deteriorating in quality.

Numerous efforts have been made to find dyes that meet these conditions; for example, the birazolonol dye described in British Patent No.
g7. Barbylic acid oquinol dyes described in US Pat. No. 1, No. 320.707, azo dyes described in US Pat. ujj, styryl dyes described in No. 077, hemioquinol dyes described in British Patent No. j1≠, No. 602, US Pat. No. 2,4L3
．． Examples include merocyanine dyes described in US Pat. No. 7μ7, cyanine dyes described in US Pat.

When the layer containing the above-mentioned dye functions as a filter layer or an anti-ration layer, it is necessary to selectively color the layer so that the coloring does not substantially reach the other F@. It is. This is because, if the other layers are substantially colored, not only will it have a harmful spectral effect on the other layers (the effectiveness of the filter layer as an antihalation layer will also be diminished).

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

Such mordants include those described in British Patent No. tij.

Ethylenically unsaturated compound polymers having dialkylaminoalkyl ester residues described in No. 1776 and reaction products of polyvinyl alkyl ketones and aminoguanidine described in No. 110.21/ of the same are known.

However, in the past it has often been observed that such dyes diffuse into other layers. It is also possible to use a large amount of mordant to eliminate diffusion, but it is not only impossible to completely prevent diffusion, but also the thickness of the layer that should contain the mordant is too thick. The disadvantage is that the sharpness decreases!

(Problems to be solved by the invention) On the other hand, the dye compound represented by the general formula (I) is
It does not diffuse to other layers and has excellent stability over time. However, the dye compound represented by the general formula (I) has the disadvantage that it does not substantially decolor during the re-photodevelopment process and therefore has an unfavorable effect on color reproduction.

(Objective of the present invention) What is the object of the present invention? ! ll1IC, filter effect,...
An object of the present invention is to provide a silver halide photographic light-sensitive material having a dye layer having a poor effect of preventing ration or controlling the sensitivity of a light-sensitive emulsion.

The first object of the present invention is to obtain a silver halide photographic material having a dye M that selectively dyes a specific layer and does not diffuse into other layers.

An object of the present invention is to provide a silver halide photographic light-sensitive material having a third VC, a dye layer that is stable even during long-term storage, and does not deteriorate photographic performance.

A second object of the present invention is to provide a silver halogenide atmosphere photosensitive material having excellent color reproducibility.

(Means for Solving the Problems) The present inventors have conducted various studies and found that the above-mentioned object contains at least /[a dye compound represented by the following general formula (I),
The general formula has been found to be achieved by an I-silver halide photographic light-sensitive material, which is characterized in that it contains at least one dye compound selected from the following general formulas (■) and (III): (I) General formula (II) General formula (III) General formula (In I1, X and YFi may be the same or different, a cyan group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, For example, acetyl, propionyl, heptanoyl, dodecanoyl, hemodecanoyl, 7-chloroheptyl group, etc.), arylcarbonyl group (arylcarbonyl group that may be substituted, such as benzoyl, diethoxyl group, etc.) benzoyl, 3-chlorobenzoyl group, etc.), alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as ethoxycarbonyl, ethoxycarbonyl, butomudicarbonyl, t-
Alkylcarbonyl group: dicarbonyl, octyloxycarbonyl, dicarbonyl in desilo, dodecyloxycarbonyl, hexadecyloxycarbonyl, ophtateryloxycarbonyl, λ-butoxyethoxycarbonyl, comethylsulfonylethoxycarbonyl, dicarbonyl in cone anoethoxycarbonyl 1.2 -(,2-chloroethoxy)ethoxycarbonyl, co(J-(2-chloroethoxy)ethoxy"ethoxycarbonyl group), aryloquincarzenyl group (optionally substituted aryloxycarbonyl group 't'a1JIFIJ For example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, ≠-ethylphenoxycarbonyl, l-fluorophenoxycarbonyl, Hiro-nitrophenoxycarbonyl, methoxyphenoxycarbonyl, 2,14-cy(t-
amyl) phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group that may be substituted, such as carbamoyl group, ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, μm methoxyphenylcarbamoyl, co-op mophenylcarbamoyl, e-chlorophenylcarbamoyl, Hiro-ethoxycarbonylphenylrubamoyl, daprovirsulfonylphenyllupamoyl, μm cyanophenylcarbamoyl, 3-
Methylphenylcarbamoyl, μm hexyloxyphenylcarbamoyl, λ, Hi-di(t-amyl)phenylcarbamoyl 1,2-chloro-5-(dodecyloxycarbonyl)phenylcarbamoyl, j-(hexyloxycarbonyl)phenylcarbamoyl group, etc. ), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl group, etc.), sulfamoyl group (sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl group, etc.). However, the combination of X and Y is [cyano group, arylcarbonyl group], [
Except when it is a cyano group, alkylcarbonyl group] or [cyano group, sulfonyl group].

R1 and R2 may be the same or different, and are hydrogen atoms,
・Rogen atoms (e.g., F%α, Br, I), alkyl groups (alkyl groups that may be substituted, such as methyl, ethyl, --chloroethyl, propyl, hexyl groups, etc.), alkoxy groups (substituted (e.g., methoxy, ethoxy, 2-chloroethoxy, butoxy, hexyloxy, octyloxy, etc.)
, hydroxy group, carboxy group, substituted amino group [amino group substituted with an acyl group derived from aliphatic carboxylic acid or nulphonic acid (e.g. acetylamino, hexylcarnylamino, methanesulfonylamino, ethanesulfonylamino, hexanesulfonylamino) , nomylmitoylai], co[29μm di(I-amyl)phenoxycobutyrylabano group, etc., alkylamino groups (
For example, methylamine, ethylamino, propylamine,
carbamoyl group (carbamoyl group that may be substituted, such as carbamoyl, methylcarbamoyl, ethylcarbamoyl, dodecyl) carbamoyl group, etc.), sulfamoyl group (sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl, ethylsulfamoyl group, etc.), alkoxycarbonyl group? E: <For example, methoxycarbonyl, ethoxycarbonyl, pentyloxycarbonyl, octyloxycarbonyl group, etc.).

R3 and R4 may be the same or different (, hydrogen atom, alkyl group (an alkyl group that may be substituted, for example,
Methyl, ethyl, propyl, butyl, inbutyl, pentyl, hexyl, -monoethylhexyl, octyl, dodecyl, hepodecyl, cone anoethyl, J-chloropropyl, cone anoethyl, cohydroxyethyl, cyanmethyl, cone anoethyl, 3-cyanopropyl,
Cone anoethyl, 3-methoxypropyl, -monoethoxyethyl, co-octyloxyethyl, 3-ethoxy is methyl, co-inproboxyethyl, acetylmethyl,
Coacetylethyl, benzoylmethyl, acetyloxymethyl, 2-(ethylcarbonyloxy)ethyl, co(heptanoyloxy)ethyl, 2-(impropylcarbonyloxinethyl, benzoyloxymethyl, ≠-chlorobenzoyloximethyl, μmNitrobenzoyloxyethyl, acetylaminoethyl, -1(ethylcarbonylamino)ethyl, methylcarbamoylmethyl, -1methylaminoethyl, λ-(ethylamine)
Ethyl 1.2-(dimethylamino)ethyl 5.2-(diethylamino)ethyl, co-methylureidoethyl, carboxymethyl, cocarpodiethyl, 3-carboxypropyl, 6-carboxyhexyl, dicarbonylmethyl, ethomo Cicalylmethyl, 2-(ptoxyylmethyl)ethyl, J-(octyloxycarbonyl)furovir, 2,2. coated trifluoroethoxycarbonylmethyl, inpropyloxycarbonylmethyl,
3-(t-amyloxymethyl)propyl, (-ethylhexyl)oxycarbonylmethyl, 2-(ethoxycarbonyl)ethyl, ethylsulfonylmethyl, 2
-(methylsulfonyl)ethyl, 2-(7”tylsulfonyl)ethyl, methylsulfonylaminomethyl, co(
Methylsulfonylamino)ethyl, 2-(ethylsulfonylamino)ethyl, J-(ethylsulfonylamino)
propyl, methylsulfamoylethyl, phenylmethyl group, etc.), aryl group (an aryl group that may be substituted, for example) engineering, <z-chlorophenyl, μm
cyanophenyl, μm hydroxyphenyl, ≠-hydroxyphenyl, -methoxyphenyl, methoxyphenyl, Hiro-ethoxyphenyl, ≠-octyl diphenyl, Hiro-methylphenyl, ψ-nitrophenyl, etc.) Express it with R3 and R4! ~6-membered heterocycles (eg, piperidine rings, morpholine rings, etc.) may be formed.

Also, R1 and R3%R2 and R4 are respectively connected and j
~6-membered heterocycle may be formed. L is a methine group (a methine group that may be substituted; examples of the substituent include,
methyl, cyan group, etc.).

X%Ys At least one of R1, R2, R3, and R4 has an organic residue with carbon number μ or more! It's good to have it.

In general formula (II), Z has the same meaning as X and Y in general formula (I). Rs, Ra Ir1 general formula (I
) is synonymous with R1%R2 in K. R7 and R8 have the same meanings as R3 and R4 in general formula (I)K.

It is preferable that at least one of 2% R5, R6, R7, and R8 has an organic residue having a carbon number of μ or more.

In the general formula (III), R9, RIG is the general formula (I
) has the same meaning as R 1 s R2. R11, R
12 has the same meaning as R3 and R4 in general formula (I).

R13 is an aryl group (an aryl group which may be substituted; for example, a phenyl group, etc.).As examples of the substituent, those having a substituent constant (σ) of +0°7λ or less are preferable.

Substituent constant (σ) can be selected based on the table described in "Structure-activity relationship of drugs" (Nankodo), pages 26-/Q3 (/7 years). , methylsulfonyl group, i-halogen (F.

α, Br), sulfamoyl group, etc. ).

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

Exemplary compounds of the compound represented by general formula (I) are shown below.

Y-/ -j Y-HiroY-4 Y-ta-ii Y-/ko'l'-/J Y-/ HiroY-/! Y-/A Y-/7 y-/r Y-10Y-col Y-co--g NH802CH3 Y-coj +1 y-, tr Y-co? -J Q -J1 Y-jλ '1'-34! -3j H3 H3 Y-j りY-弘O Exemplary compounds represented by general formulas (U) and (III) are shown below.

YM-/ YM-2 YM-J Y M-μ YM-j YM-6 M-7 YM-1 YM-ta YM-10 Y to i-/ / YM-/ Ko YM-/J YM-/ Hiroshi YM-/ YoYM-/A YM-/7 YM-/I YM-/RiYM-20 YM-1/ YM-CocoYM-,23 YM-2μ YM-2j YM-ColoYM-27 C2) 15 YM -2t CR3 YM-Kota YM-3゜CR3 YM-J/ YM-32 YM-33 YM-Jj YM-jA Y Ni -3zaYM-Jriα YM-μ O YM-4ci YM-Hiroko α O )I YM-μ3 The dye compound used in the present invention can be easily synthesized by the following method. Typical synthesis examples are listed below, but other compounds can also be synthesized in a similar manner.

(Synthesis example) 30.1g of cyanacetic acid dodecyl ester (0゜lcomo
b), ref.-formyl-heethyl-N-(2-methylsulfonylaminoethyl)-J-methylaniline λr, 1
I9 (0,/mol) was stirred in acetonitrile iaom, diluted with ammonium acetate, and heated under reflux for about 2 hours. After filtering to remove dust, it was allowed to cool, and crystals precipitated were collected by filtration. It was washed with a small amount of acetonitrile and dried. Yield: jO,r9 (7.1%) This was recrystallized from acetonitrile to obtain the exemplified compound Y-butsu. Yield: 6.μg<r; ) 2MeOHII j 2 nm Melting point! , 2-
t J 'CaX Cyanacetic acid butyl ester 7, Iji (0,05jmo
l,μm formyl-N,N-dihexylaniline 7μ
, zji (o, OjmoJ) acetonitrile rO
The mixture was stirred in a boiling room temperature, 3 g of ammonium acetate was added, and the mixture was heated under reflux for about 3 hours. After filtering to remove dust, the filtrate was concentrated, and the exemplified compound y was extracted by column chromatography.
- got r.

Yield /7. jp (I! 俤) Cyanacetic acid dodecyl ester 7.6g, acetic acid formula J4
A! ml and ethyl alcohol/7λI+! 7w/l
Pour 3 liters of carbonated soda into a Mitsuro flask.

Add 300g of an aqueous solution containing Jg, and then add Hiro-Amino-
7 g of 3-methyl-h-ethyl-N-(2-methylsulfonylaminoethyl)aniline/j was added, and a water bath solution rOxly containing ammonium persulfate/l, j9f was added.
l added. After stirring for 3Q minutes at room temperature, column chromatography (
Bath medium: Purified with n-beef starch/ethyl acetate = co//),
Exemplary compound '$3Y M-7 was obtained. Collection@i, 7. ! i
2, m, p, Pj ~ A °C Exemplary Compound YM In the same manner as /, 10-1 g of cyanoacetic acid octadecyl ester and 7 g of Exemplary Compound YM-J were obtained.

cOEt m, p 944~j 'C, cmax 1QjX/
(I) 'Synthesis of exemplified compound YM-u/) Synthesis of J-balmitoylamino-N,N-dimethylaniline 3-Amino-N,N-dimethylaniline≠9, balmitoyl in 20ml of acetonitrile Chloride r, j9
After stirring at room temperature for 1 hour, the mixture was poured into an aqueous solution and the precipitated crystals were filtered. Recrystallized from acetonitrile. Yield /2fimp/21-/3/'C 2) Synthesis of Exemplary Compound YM-Hiroshi/Hiroshi-dichloroaniline 3. -2μ9% salt fg
An aqueous solution containing nitrites unda i and zg was dropped into ice water Jjyl at 30C or less. After dropping, at a temperature of 500 ml or less, J (stirred for 7 minutes,
N-dimethylaniline 7,! A methyl alcohol solution containing 2 gf (added at 71 dVC/0'C or less) was stirred at room temperature for 1 hour, filtered, and recrystallized from a mixed solution of acetone and methyl alcohol to obtain exemplified compound YM-Hiroshi/.

Revenue 7. IIIm, p, 107-I'C Generally, the dyes of the general formulas (Iin) and (ill) are used in an amount of about 100 .mu.m per area/m on the light-sensitive material.

When the dyes of general formula (I) (If) and (I[I) are used as filter dyes, anti-ration dyes or color correction dyes, any effective amount may be used, but the optical density is 0.0! It is preferable to use it in a range of 3.0 to 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, anti-lane 3 layers, filter layers, etc.) in various known ways.

When used as a color correction dye, the ratio of dyes of general formulas (II) and (III) to 1 mole of dye of general formula (I) is preferably 1 mole or less.

(2) A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye of the present invention is dissolved or dispersed in an aqueous solution or solvent and then used in an emulsion layer or a hydrophilic colloid layer. Suitable solvents, e.g., methyl alcohol, ethyl alcohol, propyl alcohol, methyl alcohol, JP-A-127/J, U.S. Pat. No. 3.7J
It can also be added to the emulsion in the form of an IC solution in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in No. 6,130.

(2) A method in which a compound is added to an aqueous colloid solution of vR dissolved in an oil, that is, a high-boiling solvent that is substantially water-insoluble and has a boiling point of about 14,060 or higher, and then dispersed therein. As this high boiling point solvent, US Pat. No. 1, No. 32 is used.

For example, phthalic acid alkyl esters (diphenyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.) as described in No. 0.27. ), citric acid esters (e.g. acetyl tributyl citrate)
, benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauryl abad), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. Can be used. Also, organic solvents with a boiling point of JO0C to about ljo'C, such as lower alkyl acelates such as ethyl acetate and butyl acetate,
It is also possible to use ethyl propionate, 2R sulfur alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, methyl seron rub acetate, and solvents that are not easily soluble in water, such as alcohols such as methanol and ethanol.

Here, the usage ratio of dye and high boiling point solvent is 70~/
// 0 (TL weight ratio is preferred.

(2) A method of incorporating the dye of the present invention and other 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 polymerized from 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, glycidyl methacrylate, etc.), acrylamide (butylacrylamide, hexyl acrylamide, etc.), α-substituted acrylamide (butyl methacrylamide, dibutyl methacrylamide, etc.), vinyl esters (vinyl acetate, vinyl butyrate, 1. vinyl halides, (Vinyl chloride 1. Vinylidene halides (vinylidene chloride, etc.), vinyl ethers (vinyl methyl ether, vinyl octyl ether, etc.), styrene sXa substituted styrene (α-methylstyrene, etc.), nuclear substituted styrene (hydroquinestyrene, chlorostyrene, methyl styrene, etc.), ethylene, propylene,
Examples include styrene, phtadiene, acrylonitrile, and the like. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomers as a minor component. Other vinyl monomers include itaconic acid,
Examples include acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydrodialkyl methacrylate, sulfoalkyl acrylate, nulphoalkyl methacrylate, and styrene sulfone. j etc. can be used.

These filled polymer latexes are special! l-321
JJ No., JP Sho J/-J Tata 4cJ No., J3-/37
/J/ issue, jJ-321! 2, jμ-7079 Hiro 7, 5s-i33IAts, j6-/riO Hiro 3
No. 14-/riQμ7, 56-i, zbr3o, same! I-/Hiroshi 203 can be produced according to the method described in No.

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

■Method of dissolving compounds using surfactants.

Useful surfactants may be oligomers or polymers.

For details of this one combination, please refer to JP-A-60-/sr.
7, pages 1 to 27 of the specification.

(2) A method in which a hydrophilic polymer is used in place of the high-boiling point solvent or in combination with the high-boiling point solvent in (2) above. This method is described, for example, in US Pat. It is described in Hiroshi 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. 2003-110001/3≠3≠.

Further, in the residual aqueous colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 133 of Sho J/-J, 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 emulsion that can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodobromide or silver iodochlorobromide.

Silver halide grains in photographic milk may be regular crystals such as cubes and octahedrons (or irregular crystals such as spheres and plates).
It may have a regular crystal form or a composite form of these crystal forms. It may also consist of a mixture of various crystalline forms.

- Silver rhodanide grains may have different phases inside and on the surface, or may consist of a uniform phase.

It may also be a grain in which the latent image is mainly formed on the surface (for example, a negative emulsion), or a grain in which the latent image is mainly formed inside the grain (for example, an internal latent image emulsion, a pre-fogged direct reversal emulsion). ).

The silver rhodanide emulsion used in the present invention has a thickness of o, z.
Even if it is a tabular grain in which grains having a diameter of 6 microns or less, preferably 0.3 microns or less, a diameter of preferably B'-A microns or more, and an average aspect ratio of 5 or more occupy jO% or more of the total projected area. good. Also, the average particle size ≠ Q%
The number of particles is within the particle size! More than a chi! It may also be a monodisperse emulsion, such as a monodisperse emulsion.

The photographic emulsion used in the present invention is B-Graphic (P
, Glafkides), Chimie erPhy Photographic (Chimie erPhy Photography)
sique PhotogrohequeJ (Published by Paul Montell, / 1967), written by G. F. Duffin, Photographic
Emulsion Chemistry (PhotographicE)
Mulsion Chemistry (Focal Press, 1966), Bouy El Zelikman (V,
Making and Coating Photographic Emulsion: / (Making and Coating Ph.
PAa-r can be carried out using the method described in otographic emulsion (published by Focal Press, 1993).

In addition, during the formation of silver rhodanide grains, silver rhodanide solvents such as ammonia, rhodanpotash, ammonium chloride, and thioether compounds (e.g., U.S. Pat. No. 3.27/117,
No. 3,57 Hiro, No. 62, No. 3,70 Hiro, No. 730, Same? 5hiro, 27゜hiro3P issue, same i<c, core/;,
J74A), thione compounds (e.g. JP-A-Sho J3-
/≠1. A3/ri issue, same issue! 3-j-Hiroor No. 3
6-77737, etc.), amine compounds (for example, JP-A No. 6-77737, etc.), etc. can be used.

...In the process of silver rhodanide grain formation or physical ripening, a cadmium salt, zinc salt, thallium salt, iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel()i, F
rieser) MA, Die Grundlagen der Fotografisien Brozeese Mituto Zilbe Al Halogenide y (Die Grundlagend
er Photography Proz
essemit Silberhalogenide
n) (Academic Mitsushini Fälllagskaserschacht 126g) 675-73≠pages r The method described here can be used.

Namely, the sulfur sensitization method uses sulfur-containing compounds that can react with active gelatin and silver (e.g., thioFA salts, thioureas, mercapto compounds, rhodanines); Reduction sensitization method using noble metal compounds (e.g., total complex salts, as well as compounds of group Ⅰ of the periodic table such as Pt, Ir, and Pd); metal complex salts)
Precious metal sensitization method using etc.! They can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or 4-photo processing of the light-sensitive material, or for stabilizing the photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles; mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-722!-mercaptotetrazole), mercaptopyrimidines; the above-mentioned betero rings containing a water-soluble group such as a carboxyl group or a sulfone group Mercapto compounds; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (first μm hydroxy-substituted (/, J, Ja, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as antifoggants or stabilizers can be added.

The photosensitive material of the present invention can also be used in combination with ultraviolet absorbers such as zotriazoles.
etc. are listed.

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 a compound that can develop a color by oxidative coupling with an aromatic 7th class amine developer (for example, a phenylene diamine derivative, an amine phenol derivative, etc.) in a color development process. flJt, as a magenta coupler! -Hyrazolone coupler, pyrazolobenzimidazole coupler, cyanoacetylcoumarone coupler, EH afluacetonitrile coupler, and also pyrazolo(j, /-cl(/, co, Triazoles, or pyrazolo (j, /
-b) [/, 2. [Hiroshi] There are triazoles, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, piparoylacetanilides @), etc., and cyan couplers include naphthol couplers and phenol couplers, but they are particularly sensitive to humidity and temperature. In contrast, couplers that are robust can be preferably used;
, 77-2.00-, etc.; JP-A Shojter 3/ri No. 53, JP-A Shojtar/4
6-ri No. 56 and JP-A-Sho SR-/JJ Kota No. 3, and the like; and the 2-position vc described in U.S. Pat. No. 333, Tatata, etc. It has a phenylureido group! −
Phenolic couplers having an acylamino group at the
1, u277, same s? Typical examples include the 5-position substituted naphthol coupler described in -26r/3s and its polymer coupler. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either equivalent or bi-equivalent to the silver ion. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

In the photographic emulsion number of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxides or derivatives thereof such as ethers, esters, and amines,
It may also contain thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The silver halide photographic emulsion of the present invention may contain known water-soluble dyes other than the dyes disclosed in the present invention (for example, oquinol dyes, hemioquinol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. It may be used in combination with (dye). It may also be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes as spectral sensitizers.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

In addition, the photosensitive material of the present invention contains anti-fading agents, hardening agents, anti-color fogging agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as described in Research Disclosure vO1, /76. (/7F, Kari) RD-
/7A4! It is described in J.

The finished (finshed) emulsion is coated onto 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 material of the present invention includes a color negative film, a photographic material for plate making (e.g., lith film, lith dupe film, etc.), a light-sensitive material for cathode ray tube reproduction (e.g., a light-sensitive material for emulsion X-ray recording, a nuclean materials for direct and indirect photography), silver salt diffusion transfer process (Silver 5alt diffusi
on transfer process), color diffusion transfer process, thai transfer process (imbibition tran)
sfer process), emulsions used in the trowel dye bleaching method, photosensitive materials for recording printout images,
Photo-developing type printing Direct Pr1nt im
(age) photosensitive materials, photosensitive materials for heat development, photosensitive materials for physical block method, etc.

Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of a variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, etc. The exposure time is not only an exposure time of 1 second from 171,000 seconds that is normally used in a camera, but also an exposure time shorter than 171,000 seconds,
For example, 17io' using a xenon flashlight or cathode ray tube.
Exposures of ~//106 seconds can be used, or exposures as long as //second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. A laser source can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X@, r-rays, α-rays, or the like.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure)/No. 76, pp. 21-30 (
RD-/744! J) Any of the known methods and known treatment liquids described in ttc can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between /l and jo'c, but it may also be lower than /r0c or above jooC.

(Effects of the Invention) The silver rhodanide photographic light-sensitive material of the present invention has improved filtering effect, antihalation effect of the dye layer, or sensitivity adjustment effect of the light-sensitive emulsion. In the silver halide photographic light-sensitive material of the present invention, the dye layer contains a dye that has appropriate spectral absorption, selectively dyes a specific layer, and does not diffuse to other cores.

Furthermore, the silver fluoride photographic material of the present invention has excellent stability over time and excellent brown color reproducibility.

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

Example 1 A multilayer color photographic material, sample 015f, was prepared on a cellulose triacetate film support coated with an undercoat *'v, each layer having the composition shown below.

7th layer;--Ration prevention layer black colloidal silver...0.1197m2 Ultraviolet absorber C-/...0. /29/Wind 2 UV absorber C
-2--Second gelatin layer containing 0,1797 m2; intermediate layer j, j-jet- is ntantadecylhydroquinone...0.1197 m2 coupler C-3-...0.039/m2 silver iodobromide Emulsion (silver iodide 7 molt, average grain size 0.07μ) - Silver coating amount (same below) Gelatin layer 3rd layer containing o, irg, ha 2; 1st red-sensitive emulsion layer Silver iodobromide emulsion - ...0.72F/m2 (6 molti silver iodide, average grain size o, thμ) Sensitizing dye I
... 7.0xlO-5 mol sensitizing dye for 7 mol of silver... 2.0x10- for 1 mol of silver
5 mol sensitizing dye ■... per 1 mol of silver, rX10-
4 mol sensitizing dye ■... per 1 mol of silver, oxio
Molar coupler C-u --0,3209/rn2 coupler C-j...0.0109/m2 coupler C
4th L layer of gelatin layer containing -3...0.0!097 m2; 2nd red-sensitive emulsion layer silver iodobromide emulsion... /, 69/1n2 (silver iodide/Q morch, average grain size 1.jμ) Sensitizing dye I
... for 1 mole of silver! +2 × 10 mol sensitizing dye ■ ... per 1 mol of silver /, jXlo
Molar sensitizing dye■...+2Y/×/Q per 1 mole of silver
Molar sensitizing dye ■ ... per mole of silver /,! ×10
Molar coupler C-u...0.0!09/J coupler C-6...0.21017/m2 coupler C-J-
3rd layer of gelatin layer containing 097 m2 of -o and o; 3rd red-sensitive emulsion layer silver iodobromide emulsion ... /, 6 g/m2 (silver iodide molten, average grain size 2.0 μ) Sensitizing dye I ・
...for 1 mole of silver! ×10""5 mol sensitizing dye ■.../, 4X/Q for 1 mol of silver
-cru sensitizing dye ■ ... λ, coxio' for 1 mole of silver
-5 mol sensitizing dye■...for 7 mol silver/, jXlo
Molar coupler C-g...0. 6th gelatin layer containing /109/J coupler C-j...0, 0069/m''; Intermediate gelatin layer 7@; 1st green-sensitive emulsion, silver iodobromide emulsion...0. J6i/rn2 (silver iodide j morti, average grain size 0.jμ) sensitizing dye■ ・
... 3, txio mole sensitizing dye for 7 moles of silver... J, O x 10 for 1 mole of silver
Molar sensitizing dye ■... 1, coxlO- per mole of silver
e Nyl coupler C-7--o, +2ri077/m2 coupler C-1...0.0110g/m2 turnip, y-C-P
Gelatin layer rth layer containing @10.060f//m2; λth green-sensitive emulsion j silver iodobromide emulsion ...... /, 69/m2 (silver iodide 6 grains, average grain size 1 ．jμ) Sensitizing dye■ ・・
・2.7×10 moles of sensitizing dye for 1 mole of silver ■ λ, /×10 for 1 mole of silver
'Molar sensitizing dye■... r, 5xio for 1 mole of silver
-5 mole coupler C-7@-o, co109/m2 coupler C
-r...0.0/29/m2 coupler C-ta
・・0.00pH/m2 coupler C-10--0,
Gelatin layer containing 0//fl/m2 Second layer; Intermediate gelatin layer No. 1 O; Third green-sensitive emulsion layer Silver iodobromide emulsion...
L2 (silver iodide 10 mol, average grain Piusco, Qμn sensitized color Thv... @ 3.0 x 10 per 1 mol)
Molar sensitizing dye ＼1... per mole of silver, axio
Molar sensitizing dye■...J x 10 per 7 moles of silver
Gelatin layer 1/layer containing molar coupler C-//-・0.0/Jfj/rn2 coupler C-10--0,07097m"; yellow filter layer yellow colloidal silver...0.0μ9/m"- 9! −
G is tadecyl halodroquinone --・-0,03//
l/rys2! Gelatin layer containing No. 72; Blue-sensitive emulsion layer Silver iodobromide emulsion 0.32 fl/rn2 (6 moles of silver iodide, average grain size Q, μμ) coupler C
-t2...0.739/semi-2 coupler C-/
3 - Gelatin layer 13th layer included in exposure 0, 032g/yt2: Second blue-sensitive emulsion layer Silver iodobromide emulsion...O0ψ09/lyg2 (silver iodide/Q momolar coefficient average grain size i, oμ) Sensitizing dye■
... u for 1 mole of silver, JX/Q molar coupler C-/2--- 0.3! Gelatin layer 7th layer containing jl/m2; Fine grain emulsion layer Silver iodobromide emulsion...O, Ko! 11/m2 (2 molar silver iodide, average grain size 0.l!μ) gelatin layer 1st layer; 3rd blue-sensitive emulsion layer silver iodobromide emulsion /, 00j9/m2 ( Silver iodide 10 momole coefficient average grain size/, Aμ) Sensitizing dye 1
... Ko for 1 mole of water! ×10 Gelatin layer containing Molkabuku C-/2...0.1197m2*/A layer; first protective layer ultraviolet absorber C-/...0. /μi/m2 Ultraviolet absorber C-λ...06.22!9/1yL2? Gelatin layer No. 1779 containing: Protective layer polymethyl methacrylate particles (rl diameter 1.jμ) --
---0,0!97m2 Silver iodobromide emulsion...0. JO9/ys2 (silver iodide λ molar coefficient, average grain size 0.07μ)! Each gelatin layer contains, in addition to the above composition, μ-hydroxy-6-methyl (/, J, ja, 7) tetrazaindene as a stabilizer, a gelatin hardening agent H-t, and a surfactant! Coated.

Compound V used to prepare the sample is shown below.

Sensitizing dye 1 S(J3~a Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ h Sensitizing dye■ Sensitizing dye... Sensitizing dye■ C-/ C-co -J C-Hiroshi -s α Molecular weight approx. o, oo.

C-♂ C-ta α α c-70cl! α C-/2 Next, samples 70 to 70 were prepared using the following materials in place of the yellow colloidal silver in the first layer of sample 10.

Sample 102 The following water-soluble dye S-/ is λ, oxio-'mol/rn2
Added sample 103 The following water-soluble dye 3-2 was added at 2.0 x 10'mol/rn
2 Added sample 1oIA The following dye S-J was used at 0x10 mol/7m Added S-J was dissolved in a mixed solvent of ethyl acetate and tricresyl phosphate and dispersed in an aqueous gelatin solution using a colloidal bar. there was.

Sample 10, dye Y-≠ 2. O x 10-' mol/rIL2 addition Y-
The addition of Hiro was carried out in the same manner as for sample 1O Hiro.

Sample iot Dye Y-/It (2,0x10-'mol/m2 Addition y
-/r was added in the same manner as sample IO Hiro.

Sample 107 Dye YM-3 was applied to the seventh layer of sample lOj, and O×l0-5
Mol/m addition. YM-J was dissolved in a mixed solvent of ethyl acetate and tricresyl phosphate and dispersed in an aqueous gelatin solution using a colloid mill.

Sample ior Apply dye YM-3j to 5JJ1 layer of sample 106, O×I
Addition of Q-5 mol/rn2. YM-Js was added to sample 10.
This was done in the same manner as in step 7.

For sample 10, 7 m of dye yr was added to 2.0 x 10 mos instead of the yellow colloidal silver of sample ioi. Furthermore, dye YM-2 was added to the first layer, and 0x10-5 mol/ns2
Addition. Addition of Y-r and YM-λ was performed in the same manner as Sample 107.

Samples 10/-/Q obtained as described above were wedge-exposed with white light and then subjected to the following treatment using a Jr'C, and their photographic performance was evaluated.

process 1. Color development...3 minutes! seconds λ Bleaching...4 minutes 30 seconds 3゜Washing・・・・・・3 minutes lj seconds 4. Fixation...6 minutes 30 seconds &　Washing・・・・・・3 minutes/j seconds 6. Stability...3 minutes is seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate...i, og Sodium sulfite...4.0g Sodium carbonate...
・・・・・・・・・30.09 Potassium bromide・・・・・・・
.../, 4cg hydrodylamine sulfate...
...-0 hirogμm (N-dityl-β-hydroxyethylamino)-2-methyl-aniline sulfate...U, sg Add water... /, Q! Bleach solution ammonium bromide...iAo, og aqueous ammonia (2r%)...az, occ ethylenediamine-tetraacetic acid sodium iron salt...fist, Φ...i3o, og glacial acetic acid・・・
...Enjoy.../lL, add Occ water...
・・・・・・・・・・・・／、O1 Fixer Sodium Tetrapolyphosphate・・・・Co、Q9 Sodium Sulfite・・・・・・μ、Og Ammonium Thiosulfate (70%)・・173 .000 Sodium bisulfite・・・・・・μ、Add 6g water・・・・・・・・・
......i, ol stabilized formalin...r, add occ water....../, 011 Obtained as above. Concentration measurements were performed on the treated samples.

The results are shown in Table 1.

Table-7 *1: Relative sensitivity when blue sensitivity of sample 10/ is ioo *2: Relative sensitivity when green sensitivity of sample 10/ is ioo From Table-7, dye S-/-8-co 10 samples using
10J, a significant decrease in sensitivity of the blue-sensitive layer was observed, and dye S
In the 10μ sample using -j, the sensitivity of the green sensitive layer was greatly reduced. On the other hand, the dye according to the present invention! Sample used IOj~
In /Q, no decrease in sensitivity Vi was observed in the blue-sensitive layer, and a significant increase in sensitivity was observed in green and black.

Example 2 Samples 10/-109 obtained in Example 1 were subjected to high-temperature, high-humidity conditions, and an atmosphere of relative humidity V of ROQB in zooc.
C After storing for 3 days, illuminate with white light in the same way,
The reduction in blue sensitivity j-sensitivity, ΔSB, was measured for those subjected to the same treatment as in Example 1 and subjected to the same exposure treatment without being stored under high temperature and high humidity conditions.

The results are shown in Table 2I/C.

Table 2 From Table 1, 10 samples using dye S-/-3-2
103 has a large decrease in sensitivity in the blue-sensitive layer, whereas the original F
! This decrease in sensitivity was not observed in samples 10j to 10 using dyes related to AK.

Example 3 Sample 10/~10? obtained in Example 1 After wet exposure with white light, the following treatment was performed at ¥3t0C, and the photographic performance was evaluated.

Processing 1 Color development... River... 3 minutes/j seconds 2
R white fixing ・・・・・・・・・・・・ 5 minutes 00 seconds 3
Washing with water ・mm・・・3 minutes/J seconds 4mm
Fixed ・For m1... 3 minutes/! The composition of the treatment liquid used in each step is as follows.

Bleach-fix solution Ethylenediaminetetraacetic acid diferric ammonium salt ioo, og Ethylenecyan ξanetetra6choic acid dibasic sodium salt Hiroshi, og ThioMe
Ammonium water mG (70%) /7! , 0tnl Sodium sulfite ≠, sg Ammonia water /j Go water! In addition
/, Ol (ph=g, r) The composition Vi of the color developer and stabilizer was the same as that used in the treatment performed in Example 1.

Concentration measurements were performed on the obtained treated samples.

The results are shown in Table-3.

Table J Samples IO- to 103 using dye S-/-8-2 had a significant decrease in sensitivity in the blue-sensitive layer, and samples using dye S-3/θ4
t has a large decrease in sensitivity for greenness.

In contrast, samples IO3-1 using the dye according to the present invention
In No. 09, no decrease in sensitivity was observed in the blue-sensitive layer, and a significant increase in sensitivity was observed in the green-sensitive layer.

Example 4 Macbeth charts were photographed using samples ioi and ioz~10, and after being subjected to the same processing as in VC Example 1, they were printed on color paper using an auto printer. 3 from the high concentration of the gray part of the Macbase chart
Table 4 shows the degree of printing at each stage! Shown below.

Sample 106.10/> used for dye ye, y-try no. No such color shift was observed, and good color reproduction was obtained.

From the above results, it was revealed that the sample based on the present invention was excellent in the sensitivity adjustment effect and stability over time of the yellow dye layer, and had excellent brown color reproducibility.

Claims (1)

[Claims] Contains at least one dye compound represented by the following general formula (I) and at least one selected from dye compounds represented by the following general formulas (II) and (III). A silver halide photographic material characterized by: General formula (I) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (General formula (I) ), X and Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group,
Represents a sulfonyl group or a sulfamoyl group. However, X
, Y is excluded when the combination is [cyano group, arylcarbonyl group], [cyano group, alkylcarbonyl group], or [cyano group, sulfonyl group]. R_1, R_2
may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a substituted amino group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group. R_3, R_4
may be the same or different; a hydrogen atom, an alkyl group,
It represents an aryl group, and R_3 and 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. In general formula (II), Z has the same meaning as X and Y in general formula (I). R_5 and R_6 are general formulas (I)
It has the same meaning as R_1 and R_2 in . R_7, R_8
are synonymous with R_3 and R_4 in general formula (I). In general formula (III), R_9 and R_1_0 have the same meanings as R_1 and R_2 in general formula (I). R_1
_1, R_1_2 are R_3, R in general formula (I)
It is synonymous with _4. R_1_3 represents an aryl group. )