JPS63184749A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having the excellent stability, even in case of preservating it for long period, and having the excellent processing stability, without reducing the photographic performance by providing a dye layer contg. at least one kind of a specific compd. on the titled material. CONSTITUTION:The layer contg. at least one kind of the dye compd. shown by formula I is provided on the titled material. In formula I, R1 is an electron donative group, R2 is hydroxy, RSO2-NH-, RCONH- or RNHCONH- group wherein R is 1-6 C a hydrocarbon group, R3 is hydrogen or halogen atom, hydroxy, 1-3 C alkyl, 1-3 C alkoxy, 1-3 C alkylsulfone amido or 1-3 C alkylcarbon amido group. The dye shown by formula I is used in an amount of 1-800mg per 1m<2> of the area of the titled material. Thus, the titled material which has the excellent secular stability and does not change in quality, is obtd.

Description

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

(Prior Art) Generally, in silver halide photographic materials, for the purpose of light absorption filters, antihalation, or sensitivity adjustment of light-sensitive emulsions, the constituent layers of the light-sensitive material are designed to absorb light of a specific wavelength. The inclusion of dyes is well known, and therefore, it has been conventionally practiced to color hydrophilic colloid layers with the above-mentioned dyes.

For example, silver halide photographic light-sensitive materials are formed by forming 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 photographic sensitivity. In such cases, the hydrophilic colloid layer that is present on the side farther from the support than the photosensitive silver halide emulsion layer usually absorbs light in a wavelength range that is unnecessary for the silver halide emulsion layer. A method is used in which a dye is contained in the filter to form a single layer, and only light in the target wavelength range is transmitted.

Regarding the antihalation layer, in order to improve the sharpness of images, an antihalation 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.

Dyes used for such purposes must have good absorption characteristics depending on the purpose of use, and must be decolorized during photographic processing and easily eluted from the silver halide photographic light-sensitive material. It should prevent inherent residual color staining caused by dyes after development processing, it should not have any negative effects on photographic emulsions such as fogging or desensitization, and it should not diffuse from colored layers to other layers. Furthermore, it must satisfy various conditions such as excellent stability over time in a solution or a silver halide photographic light-sensitive material and no deterioration.

Many efforts have been made to find dyes that meet these requirements. For example, British Patent No. rot.

3/! pyrazolone oxonol dyes described in U.S. Pat.
0.707, U.S. Patent No. 2,2
! ! r, styryl dyes described in U.K. Pat. 2. ♂'73,4t
Examples include the cyanine dye described in No. 6.

When the layer containing the above-mentioned dye functions as a filter layer, . be. This is because, if the other layers are also substantially colored, not only will it have a harmful spectral effect on the other layers, but 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 in a specific layer using a mordant.

As such a mordant, British Patent No. 6♂! .

4t2! Ethylenically unsaturated compound polymers having dialkylaminoalkyl ester residues described in the same No. ♂jO, No. 21/, reaction products of polyvinylnalkyl ketones and aminoguanidi/ are known.

(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 a large amount of mordant to eliminate diffusion, but not only is it not possible to completely eliminate diffusion, but the thickness of the layer that should contain it increases, resulting in a decrease in sharpness. The drawback is that it is complicated.

Also, U.S. Patent No. 9. The pendziligen dyes described in GUCO 0 and JJJF have the tendency to diffuse into other layers and desensitize the blue-sensitive emulsion layer. Furthermore, since the storage stability is rather poor, there is a problem that the concentration decreases over time and spectral sensitivity adjustment becomes insufficient.

(Objectives of the Present Invention) The first object of the present invention is to provide a photographic material that is stable even during long-term storage, does not reduce photographic performance, and has excellent processing stability.

A second object of the present invention is to provide a silver halogenide photographic light-sensitive material having a yellow dye layer which is excellent in filter effect, anti-ration effect, or sensitivity adjustment effect of a light-sensitive emulsion.

A third object of the present invention is to obtain a silver halide photographic material having a yellow dye layer that selectively dyes a specific layer and does not diffuse to other layers.

A ninth object of the present invention is to provide a silver halide photographic light-sensitive material having a yellow dye layer that does not adversely affect photographic performance due to decolorization or dissolution during photographic processing.

(Means for Solving the Problems) The present inventors have conducted various studies, and have found that the above object is to have a dye layer containing at least one compound represented by the following general formula ([3]...Silver halide photographic photosensitive We have discovered what can be achieved with different materials.

General formula [! ] In the above formula, R1 represents an electron-donating group, preferably having a Hammett's σρ value of 10, θ! Represents a smaller electron-donating group, such as an alkyl group (e.g. methyl, ethyl, propyl, butyl, 1-butyl, carboxymethyl,
cycloalkyl groups (e.g., cyclohexyl group), hydroxy groups, alkoxy groups (e.g., methoxy, ethoxy, butoxy, carboxymethoxy, comethoxyethoxy, cohydroxyethoxy groups, etc.), amino groups ( For example, amino, methylamino, dimethylamino, dimethylamino group, etc.)
Examples include ureido groups (eg, ureido, methylureido, ethylureido groups, etc.). The Hammett's σρ value is described in "Drug Structure-Activity Relationship" (Nankodo) No. 26-
You can choose based on the table on page 10J (17 years).

R2 is a hydroxy group, R802NH- group, RCONH-
group, or RNHCONH- group (where R is the number of carbon atoms)
~6 hydrocarbon groups, such as methyl, ethyl,
Propyl, butyl, i-butyl represent methyl, trifluoromethyl, trichloromethyl, chloromethyl, phenyl, dihydroxyphenyl, etc.). However, R
1 and R2 are never hydroxy groups at the same time.

R3 is a hydrogen atom, a rogen atom (for example, F, (?J
, Br%I, etc.), hydroxyl group, alkyl group having ~3 carbon atoms (e.g., methyl, ethyl, propyl group, etc.),
Alkoxy groups having ~3 carbon atoms (e.g., methoxy, ethoxy, propyloxy groups, etc.), alkylsulfonamide groups having ~3 carbon atoms (e.g., methane, sulfonylamino, ethanosulfonylamino groups, etc.); Alkylcarbonamide groups (e.g. acetylamino, α-
(chloroacetylamino, trifluoroacetylamino group, etc.).

R4 and R5 may be the same or different, and each represents an alkyl group (optionally substituted) having 2 to 2 carbon atoms or a phenyl group (optionally substituted). Also R4
, with R5! ~6-membered ring may be formed.

Specific examples of substituents for the alkyl groups of R4 and R5 include halogen atoms (F, C7?, Br, I, etc.), hydroxy groups, alkylsulfonyl, acyloxy, alkylsulfonamide, alkylcarbonamide, ureido, alkylcarbonyl, arylcarbonyl, Alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylamino, aryloki7carponylamino, amine, alkylamino, dialkylamino, phenyl, substituents for the phenyl groups of R4 and R5 include alkyl groups,
Examples include alkoxy groups and hydroxy groups. Sara K
Examples include groups that can form a ring with R4 and R5 (eg, piperidine ring, morpholine ring, etc.).

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

(Exemplary compound) The dye compounds used in this invention are described in US Patent No. y.

4 can be easily synthesized according to the method described in No. 10, jjj. Typical synthesis examples are listed below, but other compounds can also be synthesized according to the above method.
6.2 g of bis(fropoxycarbonylmethyl)-3-methylaniline was stirred in 70 ml of acetonitrile, and piperidine was added as a catalyst. Add dropwise and heat to reflux. After about 2 hours, the reaction solution was concentrated and diluted with isopropyl alcohol/! θ
ml was added to crystallize. Coarse crystals? Fi was collected and recrystallized from inopropyl alcohol and a small amount of acetonitrile to obtain the exemplified compound/. Yield ♂, jg (7!%)
λMeOH412jnm Melting point 103~1or0ca
X Dermethoxy 3-(meth/sulfonamido)benzoylacetonitrile y,og,y-formyl-N,N-bis(ethoxycarbonylmethyl)-3-methylaniline u,tg was stirred in 10 ml of acetonitrile, and P was used as a catalyst. lysine! Add dropwise and heat to reflux. After about 2 hours, the reaction solution was concentrated and inpropyl alcohol/! θme
was added and crystallized. The crude crystals were collected and recrystallized from isopropyl alcohol to obtain exemplified compound J/.

Yield t, og (to%) 2”eOHIIujnm, melting point /o, ~/07”
Cax Generally, the dye of general formula [1] is 7 to 7.0% per m2 of area on the light-sensitive material. Roomg is used.

When using the dye represented by general formula [1] as a filter dye or antihalation dye, any effective amount can be used, but the optical density is 0.0! No,
It is preferable to use a 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 various known ways.

(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 such as methyl alcohol, ethyl alcohol, flobyl alcohol, methyl alcohol, JP-A-1-27/J, US patent! ,
It can also be added to the emulsion in the form of a solution dissolved in Rogge alcohol, acetate, water, pyridine, etc., or a mixed solvent thereof, as described in LT 4.230.

(2) A method in which a solution in which the 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 tto'c or more, is added to a hydrophilic colloid solution and dispersed.

This high boiling point solvent includes U.S. Patent No. λ, 322°02
No. 7, for example, phthalic acid alkyl esters (dibutyl phosphate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.) ), 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 tributyl trimesate) and the like can be used. In addition, organic solvents having a boiling point of about 3θ0C to about /jo0C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and water. It is also possible to use easily soluble solvents, for example alcohols such as methanol and ethanol.

Here, the usage ratio of dye and high boiling point solvent is 70~/
/10 (weight ratio) is preferable.

(2) A method of incorporating the dye of the present invention and other additives together with a polymer latex composition filling 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,
dobuflu 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 ester (vinyl acetate, vinyl butyrate, etc.), vinyl halides , (vinyl chloride, etc.),
...Logenated vinylizo/(vinyrizo chloride 7, etc.), vinyl ether (vinyl methyl ether, vinyl octyl ether, etc.), styrene, X-substituted styrene (α-methylstyrene, etc.), nuclear substituted ethyl/(hydroxystyrene, lyrostyrene , methylstyrene, etc.), ethylene, propylene, butylene, butadiene, acrylonitrile, etc. 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, acrylic acid, methacrylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate,
Examples include sulfoalkyl acrylate, sulfoalkyl methacrylate, styrene sulfo/acid, and the like. ] etc. can be used.

These filled polymer latexes are special! /-39/
! No. 3, Tokukai Akira! /-jri94t3, same5s-iJy
Isi issue, same! Lee 32j octopus, j4 -107 4t/, jj-/339t & j, j6-/ri Q
ri No. 3, J6-/90417, J6-/Colo/3
It can be produced according to the method described in No. 0 and J1-/4T9031.

Here, the usage ratio of dye and polymer latex is 1
0 to //10 (weight ratio) is preferable.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may be oligomers or polymers.

For details of this polymer, see JP-A-40-/J/DA3.
It is described on page 19 of the specification tube of No. 7 to the core page.

(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 (1) above. This method is described in US Pat. No. 3, for example. t/9,195, West German patent/6
It is described in J7,4T Go No. 2.

■ Tokukai Akira! ? -//3da A microcapsule method using a polymer having a carboxyl group, sulfo/acid group, etc. in the side chain as described in No. 3da.

Further, in the hydrophilic colloid dispersion obtained above, for example, a lipophilic polymer hydromisol described in Japanese Patent Publication No. Sho Tough-39/31 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.

The silver halide grains in the photographic emulsion layer may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape.
It may have a crystalline form (egular) or a composite form of these crystalline forms.

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

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

The silver halide emulsion used in the present invention has a thickness of 0.5 microns or less, preferably 0.3 microns or less, a diameter of preferably 0.6 microns or more, and all grains have an average aspect ratio of 1 or more. It may be a tabular grain that occupies jO% or more of the projected area. Death to death! It is preferable to use the tabular emulsion grains described above in combination with the filter dye of the present invention in order to provide a silver halide color photographic light-sensitive material having extremely excellent sharpness and color reproducibility. For more information on tabular emulsions and how to use them, see RESEARCH DISCLO8 (JRE Item
22!3t, t, p, 20-%-p, jr
(Jan,, /q, r3), same I tem 22 evening 3
0, p, 237-p, 2410 (May.

/9rj) etc.

Furthermore, in the silver halide emulsion used in the present invention, grains with a grain size within ±4 tO% of the average grain size account for 2j% of the number of grains.
It may be a monodisperse emulsion that occupies the above amount.

The photographic emulsion used in the present invention is P.
, Glafkides), Shimmy Eng.
Photographic (Chimie erPhysi
que Photogroheque) (Bo/L
/Moatil Publishing, 7947), Photographic Emulsion Chemistry, by G. F. Duffin.
picEmulsion Chemistry (7 Ocalp L/S, 1996), Bouy El Zelikman (v.

Making and Coating Photographic Emulsions (M.L., Zelikman) et al.
King and Coating Photogra
phicEmulsion) (Published by Focal Press, /
It can be prepared using the method described in, for example, 1994@year).

In addition, during the formation of silver halide grains, in order to control the growth of the grains, active silver halide solvents such as ammonia, rhodium halide/ammony, thioether compounds (for example, US Pat. No. 3.27/, 117, US Pat. Takuda, No. 62/No. 3,704t, No. 730,
Same No. 2? the law of nature.

No. 39, Daukoku No. 4. No. J74, etc.), thione compounds (e.g., JP-A-Sho! 3-HA (gj/? No., jJ
-r2'lOr No. Jj-77737, etc.), amine compounds (e.g. JP-A-Sho!Chu No. 1007/7, etc.)
etc. can be used.

...In the process of forming Rogge/silveride grains or physically ripening, cadmium salt, zinc salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or iron complex salt, etc. may be present.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel (H.

Fr1eser), Die Grundlage der Fotografisien Prozesse Mituto Zilbe A//”ICI Geniden (Die Grundlage
Under Photography Pro
zessemit Silberhalogenide
n) (7.
ri4/), <7! The method described on page 234 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); reducing substances (e.g., stannous salts, Reduction sensitization using 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 Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as pe/dithiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or...rogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles; , mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), mercaptopyrimidines: the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo Antifoggants or stabilizers such as compounds such as oxazolinthione: azaindenes such as tetraazaindenes (particularly dihydroxy-substituted (/, 3.3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; Many compounds known as agents can be added.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD)&/7+4t3. (2) It is described in the patents listed in C to G. As dye-forming couplers, the three subtractive primary colors (i.e. yellow, agenta and cyan)
It is important to have a coupler that gives a color development property of
+ Da 3. In addition to the couplers described in the patents described in Sections 1-C and D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is a hydrophobic one having a pallast group. - Pyrazolone and pyrazoloazole couplers may be mentioned.

! The -pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and coloring density of the coloring dye. Furthermore, the general formula (I!/) on page 199 of the specification of Japanese Patent Application No. 4/1983-324t12 (as amended on December 7, 1986),
Page 13, line 9 - page 376! It is preferred to use pyrazolotriazole couplers, which are described in more detail in line 1.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. Couplers that can also form cyan dyes that are stable against humidity and temperature are
Preferably used, and a typical example thereof is a phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus, described in US Pat. No. 3.27.2.002. - diacylamino-substituted phenolic couplers, phenolic couplers having a phenylureido group at the co-position and an acylamino group at the j-position, and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 41. Specific examples of magenta couplers are described in JET, No. 237, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 94,77θ.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. 'IJ-/,
It is described in No. ♂-O, etc.

Specific examples of polymerized magenta couplers are described in U.S. Pat.
, No. 347, 212, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor has the above-mentioned RDi2t<t3,
The patent couplers described in Sections 4-2 are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. 2. θ97゜790, same No. 2. /3/
, No. 117.

For the purpose of increasing sensitivity, 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 derivatives. , urea derivatives, imiguzole derivatives, 3-virazolidones, 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, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. It may be used in combination with (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.

The photographic emulsion of the present invention may contain 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.

Further, regarding the photosensitive material of the present invention, anti-fading agents, hardening agents, anti-color capri agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, specifically, Research Disclosure Vol. /74 (/?7J',)l
) RD-/74g.

The finished emulsion is prepared on a suitable support such as baryta paper, resist/coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
Applied on other plastic pastes or glass plates.

Examples of the silver halide photographic material of the present invention include color positive film, color beno e, color negative film, color reversal film (which may or may not contain a coupler), and photographic material for plate making (e.g. , lithium dupe film, etc.), photosensitive materials for cathode ray tube displays (e.g. photosensitive materials for emulsion X-ray recording, materials for direct and indirect photography using screens), silver salt diffusion transfer process (Silver 5alt diffusion transfer process)
transfer process), photosensitive materials for color diffusion transfer process, gui transfer process, photosensitive material for color diffusion transfer process,
process (imbibition transfer)
photosensitive materials for heat development, etc.

Exposure for obtaining a photographic image may be carried out using a conventional method. That is, any of the various known light sources can be used, such as natural light (sunlight), a tungsten electric lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube flying spot. Exposure times range from 777,000 seconds to 7 seconds, which is normally used in cameras, as well as exposure times shorter than //1,000 seconds.
For example, using a xenon flashlight or cathode ray tube //104
An exposure of ~//'/06 seconds can be used, or an exposure longer than 7 seconds can 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.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) / No. 76, No. 2r ~ JO
Any of the known methods and known treatment liquids as described on page (RD-/7.<4tj)K can be applied. The processing temperature is usually chosen between // and rooc, but it may also be lower than /♂0C or above jo0C.

In particular, favorable effects can be achieved when applied to color photographic processing consisting of development processing to form a dye image.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., daramino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, guamino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-9-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-quaamino-N-ethyl-N
-β-methanesulfamide ethylaniline, guamino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, "Photographic Processing Chemistry" by F. A. Menon, published by Focal Press (/
2.26~. 2.22 pages, US Patent λ, /
3. θ/! No., same number, j9J, J6da, Tokukai Shogu♂-44t? You may use the one described in No.jj.

The developer may also contain pH buffering agents such as alkali metal sulfites, bisulfites, carbonates, borates, and phosphates;
Development inhibitors or antifoggants such as bromides, iodides, and organic anti-capri agents can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers,
Competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifiers, US patents! , 0jrJ , 7J
The polycarboxylic acid chelating agent described in No. J, West German Publication (
OLS) λ, ≦22゜wa! It may contain the antioxidant described in No. O.

The pH of the developer is preferably 2 or more, and more preferably 9 or more. The concentration of sulfite or bisulfite in the developer is preferably at least lo-3 mol/liter, more preferably at least 10-2 mol/liter.

Preferably, the fixer or bleach-fixer contains sulfite or bisulfite.

Bleach solutions, bleach-fix solutions and their prebaths contain compounds already known as bleach accelerators, such as U.S. Pat.
♂! ♂ Specification, German Patent No. 1 Kota 07/Co Specification, German Patent No. 20j9ri No. 22, JP-A-63-32734
No. Publication, same! 3-j7r37, 374t/♂, j3-637j2, j3-72623
Publication No. j3-916JO, Publication No. j3-9!637, Publication jj-10 Dako No. 32, Publication No. ! 3-7 Orlλda publication, same j3-/da/623 publication, same! 3-2♂4
tJj Publication, Research Disclosure No. 12/λ
Compounds having a mercapto group or a disulfide group as described in No. 3, thiazo derivative visiting conductors as described in Japanese Patent Publication No. 4TJ-/4tO/;
Publication No. 306, Japanese Unexamined Patent Publication No. 2-20!32, same! 3
-327Jj publication, thiourea derivatives described in US Patent No. 370 & 14/, German Patent No. 1/J771
Specification No. 5, JP-A rr-/lλ3! Iodide described in German Patent No. 96t'110, German Patent No. 27G♂
Polyethylene/Oporium oxides described in specification No. 4130,
Special public Akiragu! -♂♂3 is the polyamine compound described in the publication, JP-A No. 4t9-Dakoda 34 is published in the publication, Geta-j96
Publication of 4t4, same! 3-Tada Publication No. 922, same j4t
-3j722 publication, same 1! -26106/Publication, same type ♂-763? It is also possible to use the ``Gr. θ Publication'' in combination.

The processing method of the present invention includes processing steps such as color development, bleaching, and fixing as described above. After the fixing step or bleach-fixing step, processing steps such as washing with water and stabilization are generally performed; A simple treatment method such as performing only a stabilization treatment step can also be used.

As the stabilizing liquid used in the stabilization process button, a processing liquid capable of stabilizing a dye image is used. For example, a solution having a buffering capacity of pHj to B, a solution containing an aldehyde such as formalin, etc. can be used. The stabilizer may contain fluorescent brighteners, chelating agents, fungicides, fungicides, etc. as necessary.
A hardening agent, a surfactant, etc. can be used.

In addition, the stabilization step may be carried out using more than one tank if necessary, and multi-stage countercurrent stabilization (for example, 2 to 9 stages)
As a result, the amount of stabilizing liquid can be reduced, and the water washing step can also be omitted.

The washing water used in the washing step may contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
A bactericidal agent or antifungal agent to prevent the growth of various bacteria and algae, a hardening agent such as a magnesium salt or an aluminum salt, a surfactant to prevent drying load and unevenness, etc. can be used. Or L, E, West, “Wa
terQuality Cr1teria 'Ph
ot, Sci, and Eng,, vol, RiA 6
Compounds described in page j 41 u to 3 j wa (/wa≦yo) and the like can also be used.

Further, the water washing step may be carried out using a tank of λ type or more if necessary, and the washing water may be saved by carrying out multi-stage countercurrent washing (for example, 2 to 9 stages).

(Effects of the Invention) The Rogge/Silver Cide photographic light-sensitive material of the present invention has excellent filter effects of the yellow dye layer, anti-ration effects, or sensitivity adjustment effects of the light-sensitive emulsion.

In the silver halide photographic material of the present invention, the dye in the dye layer has appropriate spectral absorption and has an excellent effect of selectively dyeing the dye layer and not diffusing to other layers.

In the silver halide photographic light-sensitive material of the present invention, the dye layer containing the dye compound is easily decolorized or eluted by photographic processing, so there is no risk of adversely affecting photographic performance.

Furthermore, the silver halide photographic material of the present invention provides images with improved sharpness. Further, photographs obtained from the silver halogenide photographic light-sensitive material of the present invention do not cause staining, are stable even during long-term storage, and do not deteriorate in photographic performance.

(Example) Next, the present invention will be explained in more detail based on examples.

Example-/ On a subbed cellulose triacetate film support,
Sample 10/, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) Coating amounts are expressed in g/m2 of silver for silver halides and colloidal silver, and g/m2 for couplers, additives and gelatin. For sensitizing dyes, silver halide 1 in the same layer
Expressed in moles per mole.

1st layer (antihalation layer) Black colloidal silver...0.2 Gelatin...7.3 Colored coupler C-i...-0,0≦UV absorber UV-/
... θ, / same as above UV-2 ...0.
2 Dispersion oil 0il-/...0.0/Same as above 0i1-2...θ, 0/0th/(intermediate layer) Fine grain silver bromide (average particle size 0.07 μ) ・ ・ ・・ ・ 06 / ! Gelatin...7.0 Colored Cower C-Co...0.0.2 Dispersion Oil 04
l-/・・・・・・ 0. /Third layer (7th red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide λ morch, average grain size θ, 3μ) ... 0.4t silver Gelatin ... 0.1 increase Sensitive dye I
.../, Ox10-4 sensitizing dye■ ...
・3.0×10-4 sensitizing dye■ ・・・・ /
×10-4 coupler C-s...0.
06 coupler C-a...θ, θ6 coupler C-tr...θ, O4t coupler C-J...θ, OJ dispersion oil 0il-/...0.03 Same as above 0i1-J
...0.0/2nd gray layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! Morch, average grain size 0.jμ) ...0.7 Sensitizing dye !
.../x10-4 sensitizing dye■
...3x10-4 sensitizing dye m...
.../X10-4 Coupler C-3...0.241 Coupler C-G...0.24t Coupler C-/...0.0G Coupler C-
2...θ, Og dispersion oil 0il-/...0. /j Same as above 0
i1-j...0.02nd! Layer (Third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 molti, average grain size 0.7μ)...Silver/, 0 gelatin
... /, 0 sensitizing dye 1
・・・・・・／×70 4 sensitizing dye■ ・・
・・・j×10-4 sensitizing dye■ ・・・・・・／
X10-4 coupler C-t...θ,
OS coupler C-7... θ, / Dispersion oil 0il-/ ...0.0/Same as above 0
il-2...o, o! 6th layer (middle layer) Gelatin 7.0 Compound C
p d −A ...0.03 Dispersed oil 0il-/ ...0.0! 2nd layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide emulsion, average grain size θ, 3μ) ...0.3v sensitizing dye■
...J-x10-4 sensitizing dye■
...0.3x10-4 sensitizing dye V...
...AXlo-4 gelatin ...
・ /, 0 coupler C-9...Qo, 2 coupler C-t...0.03 coupler C-/...θ, OJ dispersion oil 0
il-/...0.6 2nd female layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide j morch, average grain size θ, jμ)...0.4 Sensitizing dye■...J-x10-4 sensitizing dye V
...2X10-4 sensitizing dye ■...
・・0.3×10-4 coupler C-ta・・
...0. ．． 2j coupler C-/・・・・
・0.03 Coupler C-10...θ, 0/j Coupler C-z...0.0/minute oil 0il-/...O, Co 9th layer (3rd
Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 molt, average grain size 0.7μ) ・・・・Silver 0. rj gelatin
..., ... 7.0 Sensitizing dye■
...1. ! X10-4 sensitizing dye■...
・/, 4t×10-4 coupler C-// ・・
...0.0/Cazolar C-/Co...0.
03 coupler C-/3...0.20 coupler C-i...0.02 coupler C
-/! ...0.02 dispersion oil 0il-
/ ...0.20 Same as above Oi 1-2 ...
...0.0! 1st O layer (yellow filter single layer) Gelatin...7.2 Yellow colloidal silver...0.0♂ compound Cpd-B
...0.7 dispersion oil 0il-/
...0.3 11th layer (7th sensitized emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide damolti, average grain size 0.3
μ) ...Silver 0.4t gelatin
... /, 0 sensitizing dye ■ ...
・λ×10-4 Kazolar C-74t ・・・・
・0.9 coupler C-z ・・・・・・0.
07 Dispersion oil 0il-/...0.2 1st λ layer (2'# emulsion layer) Silver iodobromide (silver iodide/θ morch, average grain size/, !μ)...・Silver o, r gelatin
... O0 sensitizing dye■
.../X10-4 coupler C-/l, t
...0. ．． 26 Dispersion oil 0il-/
...0.07 73rd layer (first protective layer) Gelatin ... O0! Ultraviolet absorber UV-/・・・・・・ 0.7 Same as above UV-z
...0.2 Dispersion oil 0il-/ ...0. O/dispersed oil 0il-1...0.0/14th layer (protective layer No. 1) Fine grain silver bromide (average particle size 0.07μ)/0.3 gelatin...o, ar polymethyl methacrylate particles (diameter/, jμ)...0.2 Hardener H
-/ ...... O, 4t Formaldehyde Skahe/Shear S-/... ・ ・ ・ ・ Q
, taformaldehyde scavenger S-λ...O
oj In addition to the above components, a surfactant was added to each layer as a coating aid. Sample 10 was prepared as above.
/.

The chemical structural formula of the compound used in the preparation is shown below.

UV-/x/y=7/j (weight ratio) UV-2 Oil-/tricresyl phosphate 0il-27 dibutyl talate 0i1-j Bis(-monoethylhexyl) phthalate C
-/ α -a C-gu -r -t CH2 C(CH313 -r C-? C-/t C-/J -t4t C-/! H3 CpdA Cpcta sensitizing color 1 Sensitizing dye ■ Sensitizing Dye■ Sensitizing dye■ C2H.

Sensitizing dye■ Sensitizing dye■ C2H5 Sensitizing dye■ -t CH2=CH-3O2-CH2-CONH-CH2CH
2=CH-8O2-CH2-CONH-CH2S-/5
-2 (Preparation of sample 102) Sample 10 except that yellow colloidal silver in the first θ layer of sample 10/ was removed and comparative dye R-/ was used instead at o, jg/m2.
/ was produced in the same manner.

(Preparation of sample 103) The yellow colloidal silver of the 70th layer of sample /θ/ was removed, and instead, 0.23 g 7 m2 of comparative dye R-2 and 0il-/ of θ,
It was prepared in the same manner as sample /θ/ except that Jjg/m2 was used.

(Preparation of Samples 104t to /θ6) The yellow colloidal silver in the first O layer of Sample 10/ was removed, and exemplified compounds -/, 7, . 0゜2gg/each of 2♂
It was produced in the same manner as Sample 10/, except that m2 and Oil-/ were used at 0.24♂g/m2.

(Preparation of sample 107) The amount of yellow colloidal silver used in the 70th layer of sample 10/ is θ,
The weight was reduced to Ot1g/m2, and the exemplified compound -/ was reduced to 0. /2g
/m2 and 0il-/0. It was produced in the same manner as Sample 10/, except that lxg/m2 was used.

[Comparative dye]

The coated sample prepared in this way was kept at room temperature for 7 days, and then wedge-exposed using a tungsten light source through a filter that only transmits 17 color lights.Then, the sensitivity of the sample was developed at 3♂0C according to the processing steps below. Sensitivity was measured immediately after.

On the other hand, after being left at room temperature for two days after application, it got even worse! ♂O at 0C
The sensitivity obtained by performing the same exposure and development processing at VC7 Hioki under high temperature and high humidity of %RH was defined as the sensitivity after aging.

Table 1 shows the blue sensitivity of the above sample when exposed to the blue filter, as well as the green sensitivity, which is an index representing the absorbance of the yellow filter, immediately after exposure and after the passage of time. Sensitivity was expressed as a relative value when the sensitivity of sample 10/ was set to 10θ. In color-existing exposure, higher sensitivity is preferable, and lower green sensitivity is preferable.

From the results in Table -/, the dye of the present invention has excellent efficiency as a yellow filter that cuts 1♂ color light, and also does not lose its ability due to decomposition or diffusion when stored under high temperature and high humidity. It can be seen that the performance is maintained stably. In addition, the dye of the present invention has excellent decolorizing properties,
It can be seen that the residual color density is very small.

This photographic element was given a wedge exposure of 2ICMS using a tungsten light source with a color temperature adjusted to 4t, roooK with a filter, and then 3r0c according to the processing steps below.
Development processing was performed.

Color development 3 minutes/! seconds Bleached White 6 minutes 30 seconds Water washing 2 minutes 70 seconds Fixed arrival time: λo seconds Water Washing 3 minutes/j seconds Stability/min Oj seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, θg/-hydroxyethylidene/, /-diphospho/acid 2.0g Sodium sulfite 9.0g Potassium carbonate
3theta,og potassium bromide
/, 4♂g potassium iodide
/ , j mg hydroxylamine sulfate
λ, 9gg-(N-ethyl-N-β-hydroxyethylamino) 111 methylaniline sulfate g, jg Add water /, 01 pH 10,
0 bleaching solution ethylenediaminetetraacetic acid ferric ammonium salt 100, Og ethylenediaminetetraacetic acid disodium salt 10, Og ammonium bromide /! 0,0g ammonium nitrate Add 70.0g water
/,01pHt,.

Fixer ethylenediamine/tetraacetic acid disodium salt /, 0g sodium sulfite, 01g ammonium thiosulfate/monium aqueous solution (70%) /7j, 0ml sodium bisulfite, add 6g water
/, 0lpHt, stabilized liquid formalin (g0'4) 2. Add θml polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3g water /, θg Actual implementation Here, each layer with the composition shown below was coated on a transparent support to form a multilayer Color photosensitive material 20/ was produced. The results are shown in Table 2.

(Photosensitive layer composition) Numbers corresponding to each component are shown using the same notation method as shown in Examples.

(Sample 2θ/) 1st layer: antihalation layer black colloidal silver ... silver 0. /jUV-/
・・・・・・ 0. jUV-2...
... 0.2 0i1-j ...... 0.4t gelatin / ... /, j-th λ layer: intermediate layer C-/6 ...... 0. l0C-1
...O8//ko, j-ji-t-
Octylhydroquinone...0.0jOil-
／ ・・・・・・υ、10 gelati／
・・・・・・／、! θth NFt: First red-sensitive emulsion layer silver iodobromide emulsion (silver iodide j morch, monodisperse average grain size o with a coefficient of variation regarding grain size of 77 inches, 4tμ emulsion)...0.9C -3・
...o, 3I C-da ...o, 32C-1
...θ, /2C-/2
...0, Oj, 20i1-j
...---0,30 sensitizing dye X ...
・Da, j×10-4 same X ・ ・ ・
・ ／、￥×／θ−5 Same cut ・ ・ ・
・2.3X/θ-4 same XI [I ・・
・・３． oxlo-5 gelati/...
・・・／、! 0th layer: λth red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mole, monodisperse average grain size /, θμ emulsion with a coefficient of variation regarding grain size of 76%) Sensitizing dye ... da, j x 10-4 sensitizing dye
・ ・ ・ λ, 3X10-4 same X[I
I-...2.0X10-5C-/r
・ −・ ・ o, o2rC
-2・ ・ ・ ・ 0.0'1j Oil −/ ・ ・ ・
・0.0/θ gelatin...
0. ♂ Oth! Layer: Intermediate layer λ, j-t-octylhydroquinone...0. /-0il-/
・-・・-0,20 gelatin
... 1.0 6th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide! Morch, monodisperse average grain size θ, 4tμ emulsion with a coefficient of variation regarding grain size of 72%) )...0.6 sensitizing dye XIV...9.0x10-5 same ■
・ ・ ・ ・ 3, θX10-4 same
XV ・ ・ ・ ・r, 0X70-40
-79 ...0.27C-/
・ ・ ・ ・ 0.0?
Ko C-/6 ・ ・ ・ ・
・0, /2C-Evening
・ ・ ・ ・ 0.0100il-/
・ ・ ・ ・ θ , /! Gelatin...0.70 7th layer: Green-sensitive emulsion layer Silver iodobromide emulsion (silver iodobromide 2 molt, coefficient of variation regarding grain size/male, average grain size 0.9μ emulsion) ...0. ! O sensitizing dye
■...Da, 0x70-5 same ■
・ ・ ・ ・ ／、! r×10-4 same
XV ・ ・ ・ ・ 3. O×IQ-4
C-/wa...0.07/C-/
°...θ, θ2/C-/6
...o, oitOil-2 ...0
．． 70 Gelatin...0.9/1st layer:
Middle layer, j-t-octylhydroquinone...θ, θ! 0i1-2
・ ・ ・ ・ ・ θ ,
10 Gelatin...0.70 No. 9
Layer: Emulsion layer Silver iodobromide (silver iodide q morch, emulsion with an average grain size of 0.4 tμ at a coefficient of variation regarding grain size/J-'4)...o, 4t.

Sensitizing dye X■...j, O×1O-4
C-t...0, Oj/C-
2o...0.09!0il-
/ ...O3/! l −λ
・ ・ ・ ・ ・ 0 , /
Tagelatin...0.60 No. 7
0 layer: yellow filter, yellow colloidal silver layer...0. /2λ,! −
G-t-octylnohydroquinone ・・・・θ, /jOil-/
...O, ko O gelatin
...o, t.

1st/Layer: First blue-sensitive emulsion layer Silver iodobromide (silver iodide g morch, average grain thickness 0.7 jμ, average grain diameter /, 0 μ tabular grain emulsion)...0. <1 Sensitizing dye
...0. θ! 00il-/
...o, os.

Gelatin, ... /, 1 12th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 1 mole, coefficient of variation regarding grain size 79 inches, average grain size 0.7μ emulsion) Sensitizing dye χm.../! ×1O-4C-
/da...θ, 310il-/
...0. /2 gelatin
...0. l/13th layer: Intermediate layer UV-/...0. /2UV-
2...0. /go0i1-3...θ,/2 gelatin...0.7! 141st layer: Protective layer Silver iodobromide emulsion (silver iodide emulsion, coefficient of variation regarding grain size 10 cm = f' average grain size o, oz μ) ...0. /j polymethyl methacrylate particles (diameter/, jμ) S-/...0.02S-2
...0. /j- Gelatin...0. In addition to the above composition, a surfactant and a gelatin hardening agent H-/ were added to each IO layer.

The chemical structural formulas of the compounds used in Example-λ other than those shown in Example-/ are shown below.

α C-/7 (U.S. Patent No. DA & 7,143, JP-A-Sho!
Coupler included in 9-/λ91 da No. 9 and 4/-14t63j) C-// C-/? Mu.

Average molecular weight 30.000 C-λθ (JP-A-67-/j'123'1, same!9-
/, 2wa/No. 19, same t/-/4tt3j) Sensitizing dye Remove colloidal silver and replace comparative dye R
-1 is 0.3rg/m2 and 0il-/ is 0, J♂g/m
Sample 10/ was prepared in the same manner as Sample 10/, except that Sample 2 was used.

[Sample 203. Preparation of O4T] Yellow colloidal silver in the first O layer was removed, and exemplified compounds - and 2r were added at 0.3 rg/m2 and Oil-/, respectively.
It was prepared in the same manner as sample 10/, except that o, 3rg/m2 was used.

The exposure of each sample, development processing method, and data display method were performed in exactly the same manner as in Examples.

Table 1 shows the results. The present invention efficiently cuts blue light without reducing sensitivity, and furthermore, the yellow filter layer does not deteriorate its performance during storage.
A color photographic material with stable and excellent color reproduction performance could be obtained.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by having a layer containing at least one dye compound represented by the following general formula [I]. [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 is an electron-donating group, R_2 is a hydroxy group,
RSO_2NH- group, RCONH- group, or RNHC
Represents an ONH- group (R represents a hydrocarbon group having 1 to 6 carbon atoms). However, R_1 and R_2 are never hydroxy groups at the same time. R_3 is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkylsulfonamide group having 1 to 3 carbon atoms, or a hydroxy group having 1 to 3 carbon atoms.
R_4 and R_5 may be the same or different and represent an alkyl group or phenyl group having 1 to 7 carbon atoms, and R_4 and R_5 represent 5
~6-membered ring may be formed.