JPS589938B2 - Photosensitive silver halide multilayer color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel light-sensitive silver halide multilayer color photographic material, and more particularly to a light-sensitive silver halide multilayer color photographic material capable of providing excellent color tone.

More particularly, the present invention relates to a photosensitive silver halide multilayer capable of providing a natural color image with improved tone upon color development, which contains a compound capable of forming a black dye image in response to exposed silver halide. Concerning color photographic materials.

Subtractive color photography
Silver halide color photography based on the principle of lorprocess is known.

In this method, the color of the object is separated into blue, green, and red components, and these color components are separated into a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler and a green-sensitive silver halide emulsion layer containing a magenta dye-forming coupler. Recording is performed on a silver halide photographic material having a combination of a silver halide emulsion layer and a red-sensitive silver halide emulsion layer containing a cyan dye image-forming coupler, and color development is performed to separate each color component from the other. A yellow dye image that is a complementary color,
By forming a magenta dye image and a cyan forming dye image, the color of the object can be reproduced.

Although color photographic images with excellent hue and saturation can be obtained by this method, there are still many points to be improved.

One of them is neutral gray.
There is a problem with reproducibility.

That is, in the subtractive color photography method, since a color image is created by superimposing dye images, a sufficient black tone image cannot be obtained, especially in high density areas, and the image tends to have a poor sense of depth.

This tendency becomes more pronounced as the colors become more mixed, and especially in neutral gray images, this tendency occurs from relatively low-density parts.

Furthermore, when photographing a subject with high contrast, high-density areas and low-density areas will exist close to each other on the screen, and in this case, the visual sharpness of the boundary area (Shar pn
ess).

Conventionally, in the field of color printing, for example, a black image, known as a black plate, was overlaid on magenta, cyan, and yellow dye images to improve the so-called "shading" of the image and improve the image quality. There is.

However, this technique has not been applied to light-sensitive silver halide photographic materials very often, and its effectiveness has also been questioned.

For example, a method is known in which a silver image using silver halide is used as a black image, but when a silver image is used as a black image component, the overall opacity is strong, and in addition, color development using paraphenylenediamine Because it is developed with a main chemical, it is difficult to obtain a black image.

) Also, there was a drawback that the graininess was inferior to that of dye images.

Furthermore, since the processing process of ordinary color photographic materials includes a step of removing image silver by bleaching, only the silver image as a black image component remains in the photographic material during the bleaching process. special measures were required.

Therefore, the first object of the present invention is to provide a light-sensitive silver halide multilayer color photographic material which does not have the above-mentioned drawbacks and has excellent gray-black reproducibility.

Another object of the present invention is to provide a novel light-sensitive silver halide multilayer color photographic material containing a compound (hereinafter referred to as black coupler) that forms a black dye in response to exposure through color development.

The object of the present invention is to form a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler on a support. A photosensitive silver halide multilayer color photographic material having a layer,
and (I) at least one photosensitive silver halide emulsion layer containing the coupler, and/or (n) at least one photosensitive silver halide emulsion layer provided separately from the photosensitive silver halide emulsion layer containing the coupler. A black dye is formed in the silver halide emulsion layer by color development, corresponding to the exposed silver halide in the layer.
2 [R1 and R2 are each a hydrogen atom, an alkyl group,
Alkenyl groups (e.g. methyl group, ethyl group, t-butyl group, octyl group, tesyl group, dotesyl group, octadecyl group, octadecenyl group, terpenyl group, norbornyl group, etc.), substituted alkyl groups, substituted alkenyl groups (e.g. the above alkyl groups) Or, one or more hydrogen atoms in the alkenyl group are substituted with a group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, or the skeleton carbon in the above alkyl group or alkenyl group is an ether bond, a 1,000-ether bond, or one N ＼ Including those substituted with a bond, etc., and those in which the hydrogen atom is substituted with a group such as a hydroxy group or a carboxyl group, or directly or by another alkyl group, alkenyl group, aryl group, peterocyclic group, etc. o
'-, lN/ -CONH-t-NHCO-, -8-,
Groups substituted via -So2NH-, -NHSO2, etc., such as 4-lauroylamidophenethyl group, m-
pentadecylphenoxyethyl group, α-dodecylphenoxyethyl group, etc.), substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups (e.g. 4-(
2,4-ditert-amylphenoxyacetamido)phenyl group, etc.);
2 may be different groups or may be the same group.

It has been found that this can be achieved by preparing a light-sensitive silver halide multilayer color photographic material containing a phenol having a substituent represented by the following.

In one embodiment of the present invention, the phenol according to the present invention is contained in at least one of the silver halide emulsion layers containing the cyan coupler, magenta coupler or yellow coupler.

In another embodiment of the present invention, the phenol is contained in at least one silver halide emulsion layer provided separately from the silver halide emulsion layer containing the cyan coupler, magenta coupler or yellow coupler. .

In another embodiment of the present invention, the phenol is contained in at least one of the layers containing the cyan coupler, magenta coupler, or yellow coupler and at least one layer provided separately from the layer containing each of the couplers. It is contained in two silver halide emulsion layers.

Based on its structure, the phenols provide a substantially pure black dye image through a coupling reaction with an oxidation product of a p-phenylenediamine color developing agent.

The phenols preferably used in the present invention contain compounds represented by the following general formula.

[In the formula, R1 and R2 each represent the above-mentioned group, and R3,
R4 each represents a hydrogen atom, a halogen atom, or a monovalent group selected from a monovalent organic group (for example, a hydroxy group, a substituted or unsubstituted alkyl group, an alkoxy group, an amine group, etc.), and X and Y each represent Hydrogen atoms, halogen atoms, sulfo groups, mercapto groups or monovalent organic groups (e.g. hydroxy groups, substituted and unsubstituted alkoxy groups, allyloxy groups, acyloxy groups, arylthio groups, arylseleno groups, amine groups, cyclic imides) represents a monovalent group selected from the group consisting of carbamoyloxy groups, allylsulfinyl, alkylthio, alkylseleno, alkyl- or allyl-substituted amines, alkylsulfoxy, alkyl- or allylsulfonamides, phenylsulfonyloxy groups, arylazo groups, etc. .

However, at least one of R1, R2, R3, R4, X and Y is a group containing an alkyl group having 8 or more carbon atoms or a group containing an aryl group having an alkyl group having 4 or more carbon atoms, and At least one of them is a group that can be separated during a coupling reaction with an aromatic primary amine color developing agent.

] In the compound represented by the above general formula, at least one of X and Y in the above general formula has a monovalent value other than a hydrogen atom that can be separated during a coupling reaction with an aromatic primary amine color developing agent. A compound having a group, preferably a halogen atom, a sulfo group, an alkoxy group, an allyloxy group, an acyloxy group, an allylsulfonyloxy group, an alkylsulfonamide group, or an allylsulfonamide group, has either X or Y, depending on its structure. The amount of silver is even lower than in compounds where both are hydrogen atoms or where either X or Y is a hydrogen atom and the other is a group that cannot be separated during the coupling reaction (e.g. amine group, alkyl group, etc.) With this method, excellent black dye images can be obtained.

Typical specific examples of the compounds represented by the above general formula are shown below, but the compounds used in the present invention are not limited to these.

(1) N-tesyl-m-aminophenol (2) N
-Dodecyl-m-aminephenol (3) N-octatecenyl-m-aminephenol (4) N-octadecyl-m-aminophenol (5) 3-(p-dodecylbenzylamino)phenol (6) 3-( 4-( 2, 4-G tert
-amylphenoxyacetamido)anilino]phenol (7) 3-{(α-(hexadecyloxycarbonyl)ethyl]amine}phenol (8) N-(α-(dodecylcarbamoyl)ethynolyl m-aminophenol (9) N-(β-(dodecylrubamoyl)ethyl)1m-aminophenol(10)N-{β-[2-chloro-5-(2,4-di-
tert-amylphenoxybutyramide) phenylcarbamoyl]ethyl} 1m-aminophenol (11) N - (4-lauroylamidophenethyl) 1m-aminophenol (12) N - { 4 - (α- (2,4-Gt
ert-amylphenoxy)propionamide]phenethyl}-m-aminephenol (13) 4-chloro-N-octadecyl-m-aminophenol (14) 4-sulfo-N-octadecyl-m-aminophenol (15) N,N-didotesyl-m- Aminephenol (16) N-methyl-N-octadecyl-m-aminophenol (17) N-{α-carboxytridecyl}-m-aminophenol (18) N-{β-[2-sulfo-5-(N-methyl −
N-octatecylamino)phenylcarbamoyl]ethyl}1m-aminephenol (19) 2-penzoylamide-5-[β-(m-pentatecylphenoxy)ethylamino]-phenol (2D) 6-chloro N-octadecyl-m-aminophenol ■l) 5-ethoxy-3-hexadecyl-m-aminophenol (22) 5-dodecyloxy-m-N-ethylaminophenol (23) 5-hydroxy-3 - { N - (α
-(hexatecyloxycarbonylethyl)]amino}
Phenol (24) 5-penzoylamide-3 - { N -
(α-(dodecylcarbamoyl)ethylamino]}phenol ■5) 2-acetamido-3 − { N − [α-
(hexadecyloxycarbonyl)ethyl]amino}phenol (2G 2-benzenesulfonamide-3-N-dodecylaminophenol ■7) 2-palmitamide-3-N-ethylaminophenol ■8) 2. 5-dimethyl-3-N-octatecylaminophenol (29) 2-hydroxy-4-chloro-5-N-octatecylaminophenol (30) 2,4,6-trichloro-3-N-octatecylaminophenol ( 3υ2,4-disulfo-5-N-hexadecylaminophenol (32) 4-phenylthio-3-N-octadecylaminophenol (33) 6-phenylthio-3-N-octadecylaminophenol (34) 2. 4-diphenylthio -5-(4-(
2,4-di-t-amylphenoxyacetamido)anilino)}phenol (35) 2-chloro-4-phenylthio-5-(N-
{β-(dotecylcarbamoyl)ethyl}amine]phenol (36) 4-(1-phenyltetrazolium-
5-thio)-3-{N-Cβ-(m-pentadecylphenoxy)ethyl]amino}phenol (37) 2-mercapto-5-N-octatecylaminophenol (38) 4-phenylseleno-3- N-Octadecylaminophenol (39) 4-Ethoxy 3-N-Octadecylaminophenol (40) 2-Chloroethoxy-5-N-Octadecylaminophenol (41) 2-Chloro-4-(iso-propylene rubbermoylmethoxy -5-N-Octadecylaminophenol (42) 4-(isopropylcarbamoylmethoxy)-3-N-Octadecylaminophenol (43) 2,4-dichloro-3-methoxy-5-
N-hexadecylaminophenol (44) 4-phthoxycarbonylmethoxy-3-{N-
[α-(hexadecyloxycarbonyl)ethyl]amine}phenol (4Φ4-(p-carboxyphenoxy)3-{N-[
α-(p-dodecylphenylcarbamoyl)ethyl]amine}phenol (46) 4-penzoyloxy-3-N-dodecylaminophenol (47) 4-acetoxy3[N-(o-hexatecyloxyphenylcarbamoyl) Methyl]aminophenol (48) 4-berfluoropropylcarbonyloxy-3-(N-(o-hexadecyloxyphenylcarbamoyl)methyl)aminophenol (49) 2-Phenoxy-5-N-octadecylaminophenol (50 ) 4-Benzenesulfonyloxy-3-N-octadecylaminophenol (51) 2-k4-4-benzenesulfonyloxy-
5-N-octadecylaminophenol (52) 2-
Succinimide-5-N-hexadecylaminophenol (53) 4-phthalimido-5-N-hexadecylaminophenol (54) 4-(1)-benzenesulfonylphenoxy)
-3-N-octatecylaminophenol (55) 4
-Phenylsulfonamide 3-N-octadecylaminophenol (56) 4-Methanesulfonamide-3-N-octadecylaminophenol (57) 2-Phenylsulfonamide 4-chloro-N-octadecylaminophenol ( 58) 4-Trifluoroacetamide-3-N-dodecylaminophenol (59) 2-amino-5-N-hexattecylaminophenol (60) 2-anilino 5-N-octatecylaminophenol (61) 2-ethylaminophenol 5 -N-hexadecylaminephenol (62) 4-phenylsulfonyl-3-N-1rtadecylaminophenol (63) 2-(octatecylsuccinimide)-5-N
Mono(ω-sulfobropylamino)phenol sodium salt (64) 4-dotesylcarbamoylmethoxy 5-N
-ethylaminophenol (6) 4-dotecylrubamoylmethoxy-3-N-(
ω-Sulfopropylamino)phenol sodium salt (66) 4-(1)-dodecylbenzenesulfonyloxy')-3-N-(ω-sulfopropylamino)phenol sodium salt (67) 2-chloro-4-( o-dodecyl phenyl)
Carbamoylmethoxy5-N-carboxymethylaminephenol (68) 2-(m-balmitamidophenylsulfonamide)-5-(N-methoxylponylmethyl)
Aminephenol (69) 4-C 2-chloro{5-[α-dodecyloxycarbonyl)ethoxy]carbonyl}phenylazo]-3-(N-(γ-sulfofurovir)amine)
Phenol (70) 4-dodecylrubamoylmethoxy-5-aminophenol (71) 4-(p-dodecylbenzenesulfonyloxy)-3-N-ethylaminophenol (72) 4-(p-methoxyphenylrubamoyloxy )-3-N-octadecylaminophenol (73) N-Cβ-(dodecylrubamoyl)ethynolym-aminophenol (74) N-(4-lauroylamidophenethyl)-m-aminophenol (75) 4- 4-4-(N,N'-di-n-octatecyl)aminephenol (76) 4-{(3-lauroylamidophenyl)carbamoyloxy}-3-(N-γ
-sulfopyl)aminephenol (77) 4 - {(3-lauroylamidophenyl)carbamoylmethoxy}-m-aminophenol (78) 4-(p-dodecylbenzenesulfonyloxy)-m-aminophenol (79) 4-(p-totecylbenzenesulfonylamino)-m-aminophenol (80) 4-(dodecylcarbamoylmethoxy)-m-
Aminephenol (81) 4-(dodecylrubamoylmethoxy)-3-
(N-carboxymethyl)aminophenol (8[F]4-(dodecylcarbamoylmethoxy)-3
-(N-ethyloxycarponylmethyl)aminophenol These black couplers preferably used in the present invention can be synthesized by the method described in Japanese Patent Application No. 121004/1982.

As described above, these black couplers according to the present invention include a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. A photosensitive halogen contained in an emulsion layer and/or a photosensitive silver halide emulsion layer provided separately from these layers, preferably a photosensitive silver halide emulsion layer provided separately from the photosensitive silver halide emulsion layer containing the above-mentioned coupler. It is contained in the silver oxide emulsion layer.

In a particularly preferred embodiment of the invention, the black coupler of the invention is provided adjacent to the support or in a light-sensitive silver halide emulsion layer provided closer to the support than any light-sensitive silver halide emulsion layer containing said coupler. It is contained in the photosensitive silver halide emulsion layer.

When the black coupler according to the present invention is incorporated into a light-sensitive silver halide emulsion layer containing each of the above-mentioned couplers, particularly when it is incorporated into a light-sensitive silver halide emulsion layer containing a yellow coupler, the black coupler is It is desirable to add the additive in a small amount so as not to excessively increase the maximum density obtained by color development.

This is because when a high-density black image is overlaid on a yellow image, "cloudiness" becomes noticeable in the color image, which may deteriorate the image quality.

Therefore, when the black coupler according to the present invention is contained in a light-sensitive silver halide emulsion layer containing the coupler, it is preferably a green-sensitive silver halide emulsion layer containing a magenta coupler or a red-sensitive silver halide emulsion layer containing a cyan coupler. It is desirable to add it to the emulsion layer.

Furthermore, in the present invention, when a black coupler is contained in a light-sensitive silver halide emulsion layer containing the coupler, the light-sensitive silver halide emulsion layer containing the coupler is further divided into a plurality of layers, and one of them or The black coupler of the present invention may be used in further layers.

For example, dividing a red-sensitive silver halide emulsion layer containing a cyan coupler into a relatively high-sensitivity layer and a relatively low-sensitivity layer,
The black coupler according to the present invention can also be contained in a relatively low-sensitivity layer.

In the present invention, it is desirable that the silver halide emulsion layer containing the black coupler has relatively low sensitivity;
Preferably, the sensitivity is lower than that of any light-sensitive silver halide emulsion layer containing the coupler, more preferably l/1.
It is desirable that the sensitivity be as low as 0 or less.

When the black coupler according to the present invention is contained in a light-sensitive silver halide emulsion layer provided separately from the light-sensitive silver halide emulsion layer containing the various couplers described above, the layer in which the black coupler is to be contained must be photosensitive. Anywhere in the component of the material, e.g. the layer closest to the support,
It can be provided as a protective layer or a layer adjacent to the photosensitive silver halide emulsion layer containing each of the above couplers, but if the support is an opaque support for photographic paper, it can be provided as a layer adjacent to the support. It is desirable to have one.

As mentioned above, the black coupler used in the present invention is contained in various light-sensitive silver halide emulsion layers constituting the light-sensitive silver halide multilayer color photographic material according to the present invention. The concentration of
Although it varies depending on various factors such as the type of layer to be added, the position of the layer, the sensitivity and gamma of the layer, other couplers coexisting in the layer, and the type of support, in general, the total amount of O. The amount necessary to give a maximum concentration of 1 to 1.5 is added.

In general, the black coupler is added in an amount that does not make the maximum concentration too high (for example, 0 .7 or less) is desirable.

Furthermore, when the black coupler of the present invention is added to a relatively sensitive layer, it is desirable to prevent the gamma of the layer from becoming too high.

On the other hand, when the black coupler of the present invention is added to a relatively low-sensitivity light-sensitive silver halide emulsion layer in which no other couplers coexist, a high gamma silver halide emulsion is used.
It can be added in any amount necessary to give a high maximum concentration.

The black coupler used in the present invention is oil protected or Fischer dispersed in a hydrophilic colloid solution such as gelatin by a known method.

In oil protect dispersion, well-known high-boiling point solvents such as diethyl phthalate, tricresyl phosphate, and triphenyl phosphate, and low-boiling point solvents such as ethyl acetate, butyl acetate, and chloroform are used in the coexistence of surfactants. This can be carried out in a conventional manner using a colloid mill, an ultrasonic dispersion machine, etc.

In addition, in Fischer dispersion, it is common to dissolve the solution using caustic potash, caustic soda, ammonia, etc., add it to the hydrophilic colloid liquid, disperse it, and then neutralize it with an inorganic or organic acid.

According to the present invention, in order to use a coupler which reacts with a p-phenylenediamine color developing agent which is commonly used in the development of color photographic materials to form a pure black or substantially black dye, the black color as described above is used. An improvement in image quality that could not be expected from a technique that uses a silver image as an image component was observed.

Theoretically, if you mix magenta, cyan, and yellow couplers appropriately, you should be able to obtain a black image, but generally speaking, due to differences in the coupling speed and extinction coefficient of the couplers used, it is difficult to obtain a black image in low-density areas. It is impossible to uniformly maintain the reproducibility of medium gray from the to the high density area.

However, according to the present invention, the reproducibility of medium gray, especially the reproducibility of medium gray for medium to high concentration is improved.

Although the effects achieved by the present invention can be seen in negative images, positive images, and stamped images, they were particularly significant in stamped images.

Silver halides used in the photosensitive silver halide multilayer color photographic material of the present invention include, for example, silver chloride, silver bromide, silver iodide,
Mixed silver halides (for example, silver chlorobromide, silver iodochlorobromide, silver iodochlorobromide) or the like can be arbitrarily selected depending on the purpose of use.

Further, these silver halide emulsions are prepared by any known method.

For example, the silver halide emulsion according to the present invention may be a so-called conversion emulsion, a Lippmann emulsion, a covered grain emulsion, or one that has been optically or chemically fogged in advance, depending on the type of photographic material, It is selected appropriately depending on the purpose.

Furthermore, the type of silver halide, halogen content and mixing ratio, average grain size, size distribution, etc. are similarly selected appropriately depending on the type and use of the photographic light-sensitive material.

For example, in photographic materials that require relatively low sensitivity and high image quality, emulsions mainly consisting of silver chloride emulsions with fine grains and narrow size distribution are used; , an emulsion with relatively large grain size and low silver chloride content is used.

In direct reversal type photographic materials, emulsions that have been previously fogged are used.

These silver halides can be used with commonly used sensitizers such as activated gelatin, sulfur sensitizers, selenium sensitizers, reduction sensitizers, noble metal sensitizers, or water-soluble salts such as ruthenium, rhodium, and iridium. Sensitizers can be used alone or in combination as appropriate (for example, a combination of gold sensitizers and sulfur sensitizers,
Chemically sensitized using a combination of gold sensitizers and selenium sensitizers, etc.

Furthermore, this silver halide can be used alone or in combination (for example, supersensitization) with an optical sensitizer such as cyanine dyes such as Shichikoma methine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes (for example, supersensitization). It can be optically sensitized in the spectral range.

The silver halide used in the present invention constitutes various photosensitive silver halide emulsion layers according to the present invention by dispersing it in a suitable hydrophilic colloid and coating it on a suitable support. In addition to the light-sensitive silver halide emulsion layer, the light-sensitive silver halide multilayer color photographic material according to the invention may have other constituent layers such as an intermediate layer, a protective layer, a filter layer, and other hydrophilic colloid layers.

The hydrophilic colloid commonly used in the hydrophilic colloid layer and the silver halide emulsion layer is generally gelatin, and other hydrophilic colloids such as derivative gelatin, colloidal albumin,
Synthetic resins such as cellulose derivatives or polyvinyl compounds (e.g. polyvinyl alcohol), which can be used alone or in combination, include acetyl cellulose with an acetyl content of about 19 to 26%, water-soluble ethanolamine cellulose, etc. Acetate and the like can also be used in combination.

The silver halide color photographic light-sensitive material of the present invention contains a coupler for forming a color image, and examples of useful couplers include open-chain methylene yellow couplers, 5-pyrazolone magenta couplers, phenolic couplers, Naphthol-based cyancap. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and in combination with these couplers, azo-type colored couplers, osazone-type compounds, It is also possible to use a developmentally diffusible dye-releasing coupler.

Furthermore, in order to improve the photographic properties, the photoreceptor may contain so-called competing couplers, DIR couplers, BAR couplers, etc., which are used in combination with various couplers.

Open-chain ketomethylene compounds have conventionally been used as yellow couplers; for example, pivalylacetanilide-type yellow couplers or penzoylacetanilide-type yellow couplers are effective, and furthermore, so-called 2-equivalent type couplers, which have an active point of 10 Monoallyl substitution, active point 10-acyl substitution, active point hydantoin compound substitution, active point urazole compound substitution, active point substitution with succinimide compound, active point substitution with monooxoimide compound, active point substitution with pyritazone compound, active point fluorine substitution , active point chlorine or bromine substitution, or active point substitution 10-sulfonyl yellow couplers can also be used.

Among these yellow couplers, those disclosed in U.S. Patent No. 3,408,194 and Japanese Patent Application Laid-open No. 48
Couplers described in Japanese Patent Application No. 48-79309, and Japanese Patent Application Laid-open No. 48-66834 can be mentioned.

Examples of magenta couplers used in the present invention include known pyrazolone, virazolotriazole, virazolinobenzimidazole, and indazolone compounds.

Particularly preferred magenta couplers used in the present invention include those described in Japanese Patent Application No. 44-8433 and the 3-anilinopyrazolone magenta coupler described in U.S. Pat. No. 3,127,269. I can do it.

Further, useful cyan couplers used in the present invention include known phenol and naphthol compounds.

Further, the photosensitive silver halide emulsion layer and/or other constituent layers according to the present invention can contain various photographic additives depending on the purpose.

Such photographic additives include, for example, stabilizers (mercury compounds, triazoles, azaintenes, quaternary benzothiazolium, zinc or cadmium salts, etc.); sensitizers such as quaternary ammonium salts, polyethylene glycols, etc. ;
Film property improvers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, amides of acrylic acids, emulsified dispersions of polymers, etc.: hardening film agents such as formaldehyde, halogen-substituted fatty acids such as mucochloric acid, mucopromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, disulfonic acid chlorides, biesters of methanesulfonic acid,
Sodium bisulfite derivatives of dialdehydes, bisaziridines, ethyleneimines, etc. in which the aldehyde groups are separated by 2 to 3 carbon atoms; spreading agents such as saponins, lauryl or oleyl monoethers of polyethylene glycol, sulfated and Alkylated polyethylene glycol salts etc.; Coating aids such as sulfosuccinates; organic solvents such as coupler solvents (high boiling point organic solvents and/or low boiling point organic solvents, specifically dibutyl phthalate, tricresyl phosphate, acetone, methanol); , ethanol, ethylene cellsolve, etc.): So-called DIR compounds that release color development inhibitors and produce substantially colorless compounds during color development, as well as other antistatic agents, antifoaming agents, ultraviolet absorbers, and fluorescence enhancers. Various agents such as whitening agents, anti-slip agents, matting agents, anti-halation or irradiation agents can be used alone or in combination.

By providing these photosensitive silver halide emulsion layers according to the present invention on a support together with a subbing layer, an intermediate layer, a single filter layer, an anti-curling layer, a protective layer, etc. as necessary, the present invention can be applied. A light-sensitive silver halide multilayer color photographic material is prepared, and supports that can be used include paper, laminate paper (for example, a laminate of polyethylene and paper), glass, cellulose acetate, cellulose nitrate, Examples include film or sheet substrates made of polyester, polycarbonate, polyamide, polystyrene, polyolefin, and the like.

These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion to each constituent layer, such as saponification treatment, corona discharge treatment, subbing treatment, etc.
Processing such as setting processing is performed.

After exposure, the silver halide photographic material according to the present invention is color-developed with a developer containing a color developing agent as a main component.
Representative examples of phenylenediamines include diethyl p-phenylene diamine hydrochloride, monomethyl p-phenylene diamine hydrochloride, and monomethyl p-phenylene diamine hydrochloride.
Phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminetoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β- Methanesulfonamidoethyl-5-methyl-4-aminoaniline sulfate, N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline, 4-N-ethyl-N-
β-hydroxyethylaminoaniline, 4-amino-3
-Methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3
-β-(methanesulfonamido)ethyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-m-1 luidine, etc. are used.

These color developing agents can be used alone or in combination of two or more, and if desired, can be used in combination with a black and white developing agent such as hydroquinone.Furthermore, the color developing solution is generally an alkaline agent such as sodium hydroxide, water, etc. It contains ammonium oxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and may further contain various additives such as alkali metal halides such as potassium bromide, or development regulators such as citradinic acid.

This color developer is pre-contained in the image-receiving material in some types of diffusion transfer methods, for example, but in such techniques, only an alkaline agent is used separately from the color developer. Alternatively, it is also possible to use a method of containing a color developing agent and to process with the other solution at the time of development.

The light-sensitive silver halide multilayer color photographic material of the present invention can also be subjected to a known dye image reinforcement treatment.

When silver halide or developed silver is removed from the system, a fixing solution, a combination of a bleaching solution and a bleaching solution, a bleach-fixing solution, etc. are generally used. It is used in combination with liquid processing, etc.
As the fixing component, a silver halide solvent such as sodium thiosulfate or ammonium thiosulfate is used, and as the bleaching component, red blood salt, ferric ammonium or sodium salt of ethylenediaminetetraacetate, etc. are used.

EXAMPLES The present invention will be illustrated in more detail with reference to Examples below, but the present invention is not limited in its aspects by the Examples below, and various applications are possible.

Example-1 Samples A and B were prepared as follows.

(Sample A) 2-(1-benzyl-2,4-dioxoimidazolidin-3-yl)-2-pivalyl-/-kuro 5'-(
4-2.4-di-tert-pentylphenoxy)butanamide]acetanilide was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and then mixed with a silver bromide emulsion and coated.

The coating amounts of the coupler and silver used at this time were 8.23 to 11 for the coupler and 4.0 for silver.

A gelatin intermediate layer was provided on top of this. Then, 3-{2-chloro-5-(1-octatecenylsuccinimide]anilino}-1-( 2
, 4, 6-Trichlorophenyl)-5-pyrazolone was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a green-sensitive silver chlorobromide emulsion, and then coated and dried.

The amount of coupler used in this ortho layer was 4.3 cm/100 cm2, and the amount of silver was 4.5~.

A gelatin solution is applied on top of this layer, and 2-(2-(2,4-tert-
Pentylphenoxy)butanamide)-4,6-dichloro-5-methylphenol was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a red-sensitive silver chlorobromide emulsion, and then coated and dried.

Furthermore, a gelatin protective layer and an ultraviolet blocking layer containing an ultraviolet inhibitor were coated on this layer to obtain a color paper sensitive material.

The amount of coupler used for the puncture layer was 100CI11.
The amount of silver was 29 cm per hit, and the amount of silver was 3.0 cm.

(Sample B) On the same support as Sample A, a color-sensitized fine-grain silver chlorobromide emulsion in the ortho layer and the puncture hole and exemplified compound (4) as a black coupler were dissolved in dibutyl phthalate, and protected and dispersed in an aqueous gelatin solution. Mix the above and use loOcI
i! The coating amount per L is 1.3 Tn9, silver 1
．． Sample B was obtained by sequentially coating to obtain the same layer structure as Sample A, except that a gelatin layer was further coated on top of the gelatin layer.

After photographing gray charts on these samples A and H, enlarged printing exposure was carried out using a negative color film which had been subjected to a normal negative development process.

Samples A and B were then processed according to the following processing steps.

Development (3.5 minutes) → bleach-fixing (1.5 minutes) → washing with water (2 minutes) → stabilization (1 minute) → drying (processing temperature 30° C.) The composition of the processing solution using the above processing is shown below.

Color developer Dilute to 1 liter with water and adjust pH to 1 liter. Adjust to 3 Ru.

bleach-fix solution Iron ethylenediaminetetraacetate After adding 800ml of water Adjust pH to 3.5-4.0 with sodium acetate Adjust and finish to ll.

Comparing the screens of samples A and B, A appeared to have good image quality when viewed alone, but compared to sample B, the dark areas were not as sharp and the three-dimensional view seemed to be lacking. Ta.

On the other hand, Sample B according to the present invention exhibited particularly excellent reproducibility of medium gray color of medium density or higher.

In addition, as the black coupler of sample B, the exemplified compound (41
) similarly good results were obtained.

Example-2 Sample C was prepared as described below.

2-(2,4-dioxo-3,3-di-n-propyl-acetidin-l-yl)-2-pivalyl-2-klow 5'- as a coupler on a resin-coated paper support. C4-2.4-di-tert-pentylphenoxy)butanamide]acetanilide was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and then mixed with a silver chlorobromide emulsion and coated.

The coating amount of the coupler and silver used at this time per 100i was 8.00 m9 for the coupler and 0.40 m9 for the silver.

On top of this was a gelatin intermediate layer containing dioctylhydroquinone.

Then, as a coupler, 3-[2-chloro-5-[l-octadecenylsuccinimide]anilino}-1-(2,4.6-trichlorophenyl)-5-pyrazolone was added to dibutyl phthalate. Dissolve in
After protection was dispersed in an aqueous gelatin solution, it was mixed with a green-sensitive silver chlorobromide emulsion, and then coated and dried.

The amount of coupler used in this ortho layer was l 0 0ci
The silver amount was 4.3 ■ and the silver amount was 0.40 ■.

A gelatin solution of dioctylhydroquinone is coated on this layer as a color stain prevention layer, and 2-(2-(2.4-diter t-pentylphenoxy)butanamide]-4 as a coupler is applied on top of this layer. .6-dichloro-5-methyl-phenol was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a red-sensitive silver chlorobromide emulsion, and then coated and dried.

Furthermore, a gelatin protective layer and an ultraviolet ray prevention layer containing an ultraviolet ray inhibitor were coated on this layer to obtain a color paper sensitive material.

The amount of coupler used for the puncture layer was 2 per 100.
．． 9 7Q, the amount of silver was 0.3■.

After print exposure of this photosensitive material through a gray scale, Sample C was then processed according to the processing steps described below.

Development (1 minute) → Reinforcement (2 minutes) → Bleach-fixing (1 minute) → Washing with water (1 minute) → Drying (processing temperature: 30°C) Developer solution This process makes it no different from that created by normal color development. A good image was obtained.

On the other hand, the exemplified compound -
A dispersion of the black coupler (47) oil-protected using dibutyl phthalate was mixed with a puncture-sensitized silver chlorobromide emulsion and coated (coating amount: 1.5 m9 of coupler per 100 cI?L, 0 silver). Sample D was prepared in the same manner as Sample C except for (17129).

When this was processed in the same manner as above and compared with the above sample C, it was found that sample D had a higher gradation in the high concentration area and its characteristics were improved even when the reinforcing treatment was performed according to the present invention. .

Example 3 An antihalation layer and a gelatin layer were provided on a triacetate film base, and a red light-sensitive emulsion layer was coated thereon in an amount of 17 to 100 d of silver coated.

This layer was prepared by dissolving 2-[α-(2,4-di-t-amylphenoxy)butylamide)-4,6-dichloro-5-methyl-phenol as a cyan coupler in a mixed solvent of tricresyl phosphate and ethyl acetate. , after adding a dispersant and dispersing the oil protect, 1 per 100 d.
9■ Added.

Next, a gelatin intermediate layer was provided, followed by a green-sensitive silver halide emulsion layer.

This silver halide emulsion layer contains magenta coupler -1-(2
,4.6-trichlorophenyl) -3-(3-
(2. 4-Di-t-amylphenoxy)acetamide}penzamide]-5-pyrazolone was dispersed in the same manner as the cyan coupler and then mixed.

The coating amount was 17 silver and 20 to coupler per 100 d.

Next, gelatin added with a yellow filter dye was applied as an intermediate layer, and a blue-sensitive silver halide emulsion layer was applied thereon.

This layer contains α-pivaloyl α-(1-benzy-2phenyl-3,5-dioxoimidazolidin-4yl)1/-chloro-5′-[α-(
2,4-di-tert-amylphenoxy)butylamide]acetanilide was dispersed in the same manner as the cyan coupler and then added.

The amount of silver cloth is 43■ per 100d, coupler 40rru? Met.

Finally, a protective gelatin layer was provided to prepare a 81-color reversal film sample.

(Sample E) Prepared in the same manner, but red and green light-sensitive silver halide emulsion layers were provided below the red-light-sensitive silver halide emulsion layer, and a black coupler of exemplified compound -(l3) was added to this layer. .

The amount of application is l 0 0crj. Hit 6■, coupler 8mg
It is.

This emulsion is a silver bromide emulsion having a sensitivity of about 2 of the other photosensitive layers.

(Sample F) These samples were photographed under clear skies using a cine camera, including a color chart, and processed according to the following processing steps and processing liquid prescription.

In the above processing steps, pre-hardening and neutralization may be performed before the first development, if necessary.

Add an appropriate amount of sodium hydroxide}IJum as a pH adjuster 4-amine-N-ethyl-N(β-methanesulfonamidoethyl)-n-toluidine sesquisulfate monohydride Add water to finalize Samples E and F projected onto the screen using a projector,
When compared, Sample F was clearly superior in terms of image quality, especially gradation sharpness in high-density areas, and color tone in shadow areas.

Example 4 Sample B was prepared in the same manner as Sample B in Example 1l, but the black coupler was changed to exemplified compound -(5)c, and a total amount of 1. 0ml
/100ffl was added evenly.

Therefore, although no special layer for creating a black image was provided, almost the same characteristics as Sample B were obtained.

Claims (1)

[Scope of Claims] 1. A red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler on a support. A light-sensitive silver halide multilayer color photographic material having emulsion layers, and (I) at least one of the light-sensitive silver halide emulsion layers containing said coupler, and/or (II) containing said coupler. forming a black dye corresponding to the exposed silver halide in the layer by color development in at least one photosensitive silver halide emulsion layer provided separately from the photosensitive silver halide emulsion layer; Phenols having a substituent represented by the general formula -NR1R2 (where R1 and R2 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group) ) A photosensitive silver halide multilayer color photographic material containing. 2. The light-sensitive silver halide multilayer color photographic material according to claim 1, wherein the phenol is represented by the following general formula. [In the formula, R3 and R4 each represent a hydrogen atom, a halogen atom, or a monovalent group selected from a monovalent organic group, and X, Y
each represents a monovalent group selected from a hydrogen atom, a halogen atom, a sulfo group, a mercapto group, or a monovalent organic group. However, at least one of R,, R2, R3, R4, X and Y is a group containing an alkyl group having 8 or more carbon atoms or an aryl group having an alkyl group having 4 or more carbon atoms, and at least one of X and Y is a group that can be separated during a coupling reaction with an aromatic primary amine color developing agent. [3] Claim 2, wherein at least one of X and Y is a group other than a hydrogen atom that can be separated during a coupling reaction with an aromatic primary amine color developing agent. The photosensitive silver halide multilayer color photographic material described in Section 1. 4 x and/or Y are a hydroxy group, a substituted or unsubstituted alkoxy group, an allyloxy group, an acyloxy group, an arylthio group, an arylseleno group, an amine group, a carbamoyloxy group, a cyclic imido group, allyl or alkylsulfonyloxy 4. The photosensitive silver halide multilayer color photographic material according to claim 3, wherein the photosensitive silver halide multilayer color photographic material is a monovalent group selected from a group consisting of allyl, alkyl sulfonamide, and an arylazo group. 5. In a photosensitive silver halide emulsion layer containing the coupler and/or a photosensitive silver halide emulsion layer provided separately from the photosensitive silver halide emulsion layer containing the coupler, the total amount of phenols is added to the photosensitive silver halide emulsion layer for color development. 0.0 during development.
Claim 1, characterized in that it is contained in an amount necessary to provide a maximum concentration of 1 to 1.5;
The light-sensitive silver halide multilayer color photographic material according to item 2, 3 or 4. 6. A light-sensitive silver halide emulsion in which the phenol is provided on the side closer to the support than any of the light-sensitive silver halide emulsion layers containing the coupler, and is provided separately from the light-sensitive silver halide emulsion layer containing the coupler. Claims 1 and 2 are characterized in that they are contained in the layer.
5. The photosensitive silver halide multilayer color photographic material according to item 1, 3, 4 or 5. 7. Claim No. 7, characterized in that the sensitivity of the light-sensitive silver halide emulsion layer containing phenols is lower than that of any light-sensitive silver halide emulsion layer containing the coupler. The photosensitive silver halide multilayer color photographic material according to item 6. 8. Claims 1, 2, 3, 4, 5, 6, or 7, characterized in that the support is a support for photographic paper. A photosensitive silver halide multilayer color photographic material.