JPS5810737B2 - Silver halide multilayer color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide multilayer color photographic material that can provide excellent color tone.

More specifically, during color development, a compound capable of forming a black dye image in response to exposed silver halide may be contained in a specific silver halide emulsion layer to provide a natural color image with improved tone. This invention relates to a silver halide multilayer color photographic material that can be produced.

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

In this method, the color of the subject is separated into blue, green, and red components, and these color components are combined with a yellow dye-forming coupler (hereinafter referred to as yellow coupler).

) (hereinafter referred to as blue-sensitive silver halide emulsion layer).

), magenta dye-forming coupler (hereinafter referred to as magenta coupler).

) (hereinafter referred to as green-sensitive silver halide emulsion layer).

) and cyan dye image-forming couplers (hereinafter referred to as cyan couplers).

) (hereinafter referred to as red-sensitive silver halide emulsion layer).

) (hereinafter referred to as color photosensitive material).

), and by color development, the colors of the subject can be reproduced by forming each color component as a yellow dye image, a magenta dye image, and a cyan forming dye image, each of which has a complementary color relationship with the respective color components. .

Although color dye 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 dye image is created by superimposing dye images, a sufficient braille image cannot be obtained particularly in high-density areas, which tends to result in a lack of profound feeling.

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.

In addition, in recent years, the field of photography has expanded significantly, and as a result, many monks now take photographs under various artificial light sources.

Photographing under these artificial light sources has the disadvantage that neutral gray and color reproduction often deteriorate due to differences in color temperature.

In negative-positive systems, these deteriorations can usually be corrected to some extent during enlarged printing on color paper photosensitive materials (color photographic paper), but the correction of neutral gray is incomplete. be.

On the other hand, recent trends are toward color photosensitive materials that narrow the spectral sensitivity of color photosensitive materials to make them more suitable for various light sources, but these also have imperfect reproducibility of neutral gray under various light sources. It is.

In particular, in order to reproduce the neutral gray of a part of the shadow that is susceptible to changes in sensitivity, gamma (γ), and color balance due to various light sources, it is completely insufficient to make adjustments only by adjusting the spectral sensitivity.

Furthermore, as a recent trend, pollution-free development processes are being promoted, and for this reason, bleaching solutions or bleach-fixing solutions for color photosensitive materials are replaced with conventional red blood salts or aminopolycarboxylic acid ferric salts or chlorides. The use of bleaching agents such as ferric salts has become common, but these bleaching agents have a weaker oxidizing power than red blood salts, etc., and, for example, bleach-fixing baths with EDTA ferric salts There are disadvantages such as poor recoloring of the leuco dye, which often causes a decrease in specific image density, and the reproduction of so-called "smearing" in neutral gray and shadow areas is significantly impaired.

In order to solve these various drawbacks or problems, it is desired to develop a color photosensitive material that has good neutral gray reproduction, stability, and excellent color reproduction.

On the other hand, in the field of color printing, it has traditionally been possible to improve image quality by overlaying a black image, called a black plate, on top of magenta, cyan, and yellow dye images to reduce so-called "sharpness" in the image. It is done.

However, the application of this technology to silver halide photographic light-sensitive materials has not been practiced very often, and its effectiveness has also been questioned.

For example, a method is known that uses a regular silver image made of silver halide as a black image, but when a silver image is used as a black image component, the overall opacity is strong, and in addition, paraphenylenediamine-based color development Because it is developed using a developing agent, it is difficult to obtain a black image (generally, the result is a cloudy brown color).

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

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

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a color photosensitive material which does not have the above-mentioned drawbacks, has excellent reproducibility of neutral gray to black, and has excellent color reproducibility.

A second object of the present invention is to provide a color photosensitive material that is stable against fluctuations in photographing conditions and development processing and has excellent neutral gray to black reproducibility and color reproducibility.

A third object of the present invention is to provide a color photosensitive material that prevents deterioration of saturation and opacity caused by black dye images.

The above objects of the present invention and other objects mentioned below are:
In a color light-sensitive material having 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. , separate from the silver halide emulsion layer containing each of the color couplers mentioned above, and closer to the support than any of the above emulsion layers, spectrally sensitized to at least one or more spectral regions of blue, green, or red. and its sensitivity is 1/3 or less of the silver halide emulsion layer containing a color coupler spectrally sensitized in the same spectral region, and furthermore, the sensitivity is less than 1/3 of that of the silver halide emulsion layer containing a color coupler that is spectrally sensitized in the same spectral region, and it is further reacted with the oxidation product of the raw chestnut for color development. Maximum concentration is 0
．． At least one silver halide emulsion layer (hereinafter referred to as interlayer) containing a compound that forms a black dye image of 1 to 0.7.

).

According to a preferred embodiment of the invention, at least one interlayer containing a black pigment-forming compound is coated on the support, either directly or via a non-photosensitive hydrophilic colloid layer such as a subbing layer. , a blue-sensitive silver halide emulsion layer containing a yellow coupler directly on this interface layer or via a non-light-sensitive hydrophilic colloid layer such as an intermediate layer, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a cyan-sensitive silver halide emulsion layer containing a magenta coupler. Red-sensitive silver halide emulsion layers containing couplers are sequentially coated, and the interlayer silver halide emulsion layer is blue;
Spectral sensitization may be performed in at least one spectral region of green or red. Specifically, the silver halide emulsion layer of the interlayer is blue-sensitive (blue region) of the same type of emulsion containing a yellow coupler. It may have the same kind of green sensitivity (green region) as the emulsion containing the magenta coupler, or it may have the same kind of red sensitivity (red region) as the emulsion containing the cyan coupler.

It may also be spectrally sensitized in two spectral regions, such as green sensitivity and red sensitivity, and further spectrally sensitized in the entire spectral region of blue sensitivity, green sensitivity, and red sensitivity. Good too.

In addition, it is sufficient that at least one boundary layer is provided,
Two or more may be provided.

When two or more interlayers are provided, these interlayers may be spectrally sensitized to the same or different spectral regions, and a non-photosensitive hydrophilic colloid layer such as an interlayer may be interposed between each monolayer. You may.

To be more specific, the color photosensitive material according to the preferred embodiment is provided with, for example, three interlayers, the first interlayer being blue-sensitive (blue region), the second interlayer being blue-sensitive (blue region),
The third interlayer may be spectrally sensitized to different spectral regions, such as a third interlayer sensitive to green light (green region) and a third interlayer sensitive to red light (red region).

Also, for example, two interfaces are provided, one for the two spectral regions and the other for the spectral region, such as a first interface for the green and red regions and a second interface for the blue region. The first interface layer may be spectrally sensitized in the green region, red region,
One may be spectrally sensitized to three spectral regions and the other to one spectral region, such as in the blue region and the second interface in the green region.

It is possible to provide two or more spectrally sensitized interface layers in various other combinations.

Furthermore, the sensitivity of these spectrally sensitized interlayers is 1/3 or less of the sensitivity of the silver halide emulsion layer containing the color couplers spectrally sensitized in the same spectral region, and more preferably The sensitivity is 1/4 to 1/10.

After the spectral sensitivity of the interlayer is spectrally sensitized into a plurality of spectral regions, the spectral sensitivity of each spectral region corresponds to I/3 of the silver halide emulsion layer containing the color coupler.
Hereinafter, it will be shown that the sensitivity is more preferably 1/4 to 1/10.

Specifically, for example, the spectral sensitivity of the interfacial layer is blue-sensitive (
When sensitized in the blue region), the sensitivity of this interlayer is 1/3 or less of the sensitivity of the blue-sensitive silver halide emulsion layer containing the yellow coupler; (Green region) When sensitized, the sensitivity of this interlayer is 1/3 or less of the sensitivity of the green-sensitive silver halide emulsion layer containing the magenta coupler.

Furthermore, when the sensitivity of the interlayer is sensitized in all blue, green, and red regions, one of the silver halide emulsion layers containing the color coupler corresponding to the sensitivity in each spectral region is
/3 or less, that is, the sensitivity in the blue region of the interlayer is 1/3 or less of the blue-sensitive silver halide emulsion layer containing the yellow coupler, and the sensitivity in the green region is less than 1/3 of the blue-sensitive silver halide emulsion layer containing the yellow coupler. This indicates that the sensitivity of the emulsion layer is 1/3 or less, and the sensitivity of 2 degrees in the red region is 1/3 or less of the red-sensitive silver halide emulsion layer containing a cyan coupler.

On the ship's side, the blue area is 400mμ~500mμ, the green area is 500~600mμ, and the red area is 600~700mμ.
The visible spectral range of μ is shown.

The interlayer of the present invention reacts with the oxidation product of the color developing agent to form a black dye image, and the maximum density of this black dye image is preferably 0.1 to 0.7, more preferably 0.
It is 2 to 0.5.

In this way, when the maximum density is below 0.1, there is little effect on the reproducibility or stability of neutral gray or black, and when it is above 0.7, the color separation of a part of the shadow deteriorates, etc. There are drawbacks.

Sensitivity here is expressed as the reciprocal of the exposure amount E, which provides a density of fog + 0.1 for a sample exposed and developed with an ordinary photosensitive needle, as practiced in the general photographic industry.

Furthermore, the density is measured using a commonly available color densitometer, and the black density is measured through a visual filter that matches visibility characteristics.

The black dye image forming compound used in the present invention is a compound that reacts with the oxidation product of a developing agent to form a black dye image.

A black dye image as used herein means that it is visually black or substantially black under various light sources;
Specifically, it is defined as follows.

In other words, the black dye image referred to here means that the visible spectral spectral density (400 to 700 mμ) exhibits substantially uniform absorption or reflection density in the entire density range. Spectral concentration distribution (400-700m
Among the characteristics of μ), the minimum spectral density is 50% or more, preferably 70% or more of the maximum spectral density.

The interface layer of the present invention is provided on the side closer to the support than any of the halogenated complex emulsion layers containing the yellow, magenta, and cyan color couplers, thereby reducing saturation caused by black dye images. and can help prevent opacity.

Various compounds can be used as the compound for generating the black dye image used in the present invention, but among these, the one particularly preferably used is disclosed in Japanese Patent Application Laid-Open No. 52-42725.
No., JP 53-46029, JP 52-4879.
Examples include the black coupler described in Specification No. 0 and the like.

These black couplers can form good black dye images by reaction with commonly used paraphenylenediamine color developing agents.

Among these, compounds represented by the following general formula CI) are examples of black couplers that form a transparent black dye image.

General formula [1] Here, R1 and H are each a hydrogen atom, an alkyl group,
X and Y are each a hydrogen atom, a halogen atom (eg, chloro, bromine, etc.), or a group that can be separated by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent (hereinafter simply referred to as a split-off group).

), or one of X and Y is a hydroxyl, mercapto, amine, alkylamino group, or arylamino group, and the other is a hydrogen atom, a halogen atom, or the above split-off group.

The alkyl group represented by R1 and horse is preferably an alkyl group having 1 to 32 carbon atoms, more preferably an alkyl group having 1 to 22 carbon atoms, and these are linear or branched. Alternatively, it may be an alkyl group having a substituent.

Examples of alkyl include methyl, ethyl, isopropyl, lobutyl, n-dodecyl, low-octadecyl, 5e
Examples include c-octadecyl and n-tocosyl.

Further, any group can be selected as the substituent of the substituted alkyl, but preferably hydroxyl, carboxyl,
Sulfo, alkylcarbamoyl group, alkylsulfamoyl group, arylcarbamoyl group, arylsulfamoyl group, alkoxycarbonyl group, alkoxysulfobutyl group, aryloxycarbonyl group, aryloxysulfonyl group, alkoxy group, aryloxy group, alkyl Examples include amide group, arylamide group, alkylsulfonamide group, and arylsulfonamide group.

Further, the aralkyl group represented by R1 and R2 preferably has 1 to 32 carbon atoms in the alkylene chain connecting the nitrogen atom of the compound represented by the general formula [1] and the aryl moiety of the aralkyl group. Preferably, the number of carbon atoms is 1 to 12, and the aryl moiety is phenyl, and may be aralkyl having a substituent.

Examples of aralkyl include benzyl, phenethyl-β-
Examples include naphthylmethyl and phenylheftyl.

Further, any group can be selected as the substituent of the substituted aralkyl, but preferably, for example, hydroxyl, carboxyl, halogen atom (e.g. chloro, bromine, etc.), alkyl group, alkylamido group, arylamido group, alkylsulfonamide group , an arylsulfonamide group, and the like.

Furthermore, the aryl group represented by R1 and R2 is
Preferably it is a phenyl group, and may be an aryl group having a substituent.

Examples of aryl include phenyl.

Further, any group can be selected as the substituent of the substituted aryl, but preferred examples include a halogen atom (e.g. chloro, bromine, etc.), an alkylamide group, an arylamido group, an alkylsulfonamide group, an arylsulfonamide group, etc. It will be done.

The alkenyl group represented by R1 and R2 is preferably a linear or branched alkenyl group having 3 to 22 carbon atoms, and may have a cyclic structure or a substituent.

Examples of alkenyl include allyl, octenyl, cyclohexenylethyl, 5,9-dimethyl-9-dodecenyl, and 9-octadecenyl.

Preferably, the substituent of the substituted alkenyl is a halogen atom (eg, chloro, brome, etc.).

The alkyl moiety of the alkylcarbamoyl group, alkylsulfamoyl group, alkoxycarbonyl group and alkoxysulfonyl group mentioned as substituents for the alkyl group represented by R1 and R2 is preferably a straight chain or branched alkyl group having 1 to 22 carbon atoms. It is an alkyl moiety and may further have a substituent.

Examples of unsubstituted alkyl moieties include methyl, ethyl,
tert-butyl, octyl, n-octadecyl, 5e
c-octadecyl, n-tocosyl, etc., and examples of the substituted alkyl moiety include 1-(low octadecylcarbamoyl)ethyl, 2-(2-sulfooctadecaamido)ethyl, occudecylsuccinimidopropyl, 2-(
N-octadecyl-N-carboxymethylaminoacetamido)ethyl, n-dodecyloxymethoxypropyl, 2,4-di-tert-amylphenoxybutyl, 3
-Pentadecylphenoxypropyl and the like.

The aryl moiety of the arylcarbamoyl group, arylsulfamoyl group, aryloxycarbonyl group, and aryloxysulfonyl group mentioned as a substituent for the alkyl group represented by R1 and R2 is preferably phenyl or naphthyl, and more preferably is phenyl.

Examples of unsubstituted aryl moieties include phenyl, naphthyl, etc., and substituted aryl moieties include, for example, p
-dodecylphenyl, m-pentadecylphenyl, 0-
Tetradecyloxyphenyl, p-octadecyloxyphenyl, 2-methoxy-5-tetradecyloxycarbonylphenyl, 3,4-di-butyloxycarbonylphenyl, p-tert-butylphenothodiphenyl, m-lauroylamidophenyl, m -dodecylbenzenesulfonamidophenyl, 4-lauroylamide naphthyl, 5-octadecyloxynaphthyl, 2-chloro-5-(2,4-di-tert-amylphenoxybutyramido)phenyl, and the like.

The alkyl moiety of the alkoxy group mentioned as a substituent for the alkyl group represented by R1 and R2 is preferably a straight chain or branched alkyl moiety having 1 to 22 carbon atoms, which further has a substituent. It's okay.

Examples of unsubstituted alkyl moieties include methyl, propyl, peptyl, n-dodecyl, n-octadecyl, etc., and examples of unsubstituted alkyl moieties include, for example, p-
Examples include tert-butylphenoxyethyl, p-octadecylphenoxyethyl, and dodecyloxyethyl.

The aryl moiety of the aryloxy group mentioned as a substituent for the alkyl group represented by R1 and R2 is preferably substituted or unsubstituted phenyl.

Examples of substituted phenyl include p-dodecylphenyl, p
-lauroylamidophenyl, p-tert-butylphenothodiphenyl, m-octadecylsulfonamidophenyl, and the like.

The alkylamide group mentioned as a substituent for the alkyl group, aralkyl group, or aryl group represented by R1 and R2 is preferably an alkanoic acid amide having 1 to 22 carbon atoms, which further has a substituent. Good too.

Examples of the alkylamides include butanamide, octaamide, dodecamide, hexadecamide, etc.
Examples of the substituted alkylamide include m-pentadecylphenoxyacetamide, 2,4-di-tert-amylphenoxybutanamide, p-tert-amylphenoxycarbonylpropanamide, m-decyloxyphenoxyacetamide, 2-lobtoxide dodecanamide, and the like. Can be mentioned.

The arylamide group mentioned as a substituent for the alkyl group, aralkyl group, or aryl group represented by R1 and R2 is preferably a benzamide group or a naphthamide group, and even more preferably a benzamide group.

Examples of the arylamide include benzamide and α-naphthamide.

Examples of substituted arylamides include preferably p-methylbenzamide, p-tert-butylbenzamide, m-lauroylamide benzamide, 0-dodecyloxybenzamide, m-(p-tert-amylphenoxy)benzamide, and the like. can be mentioned.

The alkylsulfonamide group mentioned as a substituent for the alkyl group, aralkyl group, or aryl group represented by R1 and R2 is preferably a linear or branched alkylsulfonamide group having 1 to 22 carbon atoms; may further have a substituent.

Examples of the alkylsulfonamide include methylsulfonamide, butylsulfonamide, tert-butylsulfonamide, n-dodecylsulfonamide, and n-tocosylsulfonamide.

Examples of substituted alkylsulfonamides include N-methyllauroylamide ethylsulfonamide, N-phenyl octadecaneamide ethylsulfonamide, lauroylamide ethylsulfonamide, and the like.

The arylsulfonamide group mentioned as a replacement group of the alkyl group, aralkyl group, and aryl group represented by R1 and R2 is preferably a phenylsulfonamide group,
It is a saphthylsulfonamide group, and these may further have a substituent.

Preferred examples of the arylsulfonamide include benzenesulfonamide and naphthalenesulfonamide.

Examples of substituted arylsulfonamides include tolylsulfonamide, p-octadecaneamide phenylsulfonamide, p-dodecylphenylsulfonamide, 4,8
-di-isopropylnaphth-2-yl-sulfonamide, 3-methoxy-6-octadecanamide phenylsulfonamide, and the like.

Further, the alkyl group mentioned as a substituent for the aralkyl group represented by R1 and R2 is preferably a straight chain or branched alkyl group having 1 to 22 carbon atoms.

Preferred examples include methyl, ethyl, dodecyl and the like.

The alkyl group represented by R3 and melon is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and these are linear or branched. Good too.

For example, alkyl groups include methyl, ethyl, tert-
Examples include butyl.

The alkoxy group represented by R3 and R4 is preferably an alkoxy group having 1 to 22 carbon atoms,
Preferred examples include methoxy, ethoxy, butoxy, dodecyloxy, octadecyloxy, and 5ec-octadecyloxy.

The alkylamide group represented by R3 and Y is,
Alkylamides having 1 to 22 carbon atoms are preferred, and these may be linear or branched.

Preferred examples of the alkylamides include acetamide, propionamide, hexadecamide, and the like.

The alkylsulfonamide group represented by R3 and melon is preferably an alkylsulfonamide group having 1 to 22 carbon atoms, and these may be linear or branched.

As the alkylsulfonamide, for example, preferably methanesulfonamide, propanesulfonamide, 5ec
-butanesulfonamide, n-dodecylsulfonamide, n-octadecylsulfonamide and the like.

The arylamide group and arylsulfonamide group represented by R3 and R4 above have the same meaning as the arylamide group and arylsulfonamide group listed as substituents for the alkyl group, aralkyl group, and aryl group represented by R1 and R2 above. It is.

The split-off group represented by X and Y is preferably, for example, sulfo (-803H) or a salt thereof, carboxyl (-COOH) or a salt thereof, an alkoxy group, an allyloxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, Arylcarbonyloxy group, arylsulfonyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, alkylamide group, arylamide group, alkylsulfonamide group, arylsulfonamide group, 5- or 6-membered imide group, arylthio group, Examples include an arylseleno group, an arylsulfonyl group, an arylazo group, and a 5- or 6-membered heterocyclic thio group containing 1 to 4 nitrogen atoms in the molecular structure.

The alkyl moiety of the alkoxy group as the split-off group is preferably a linear or branched alkyl moiety having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and these may further have a substituent. good.

Unsubstituted alkyl moieties include methyl, ethyl, 1so
- As the substituent for the alkyl moiety having a substituent such as propyl, any group can be selected, but preferably, for example, a halogen atom, an alkyloxycarbonyl group, an alkylcarbamoyl group, an aryloxycarbonyl group, an arylcarbamoyl group, etc. Examples include groups.

Specific examples of substituted alkyl moieties include chloroethyl, butoxycarbonylmethyl, β-hydroxyethoxycarbonylmethyl, m-hexadecaamidophenoxycarbonylmethyl, p-methoxyethoxycarbonylpropyl, 1so-propylcarbamoylmethyl, rhodecylcarbamoylmethyl, Examples include m-dodecanamidophenylcarbamoylpropyl, m-hexadecaamidophenoxycarbonylmethyl, 0-dodecyloxyphenylcarbamoylmethyl, and the like.

The aryloxy group as the split-off group is
Preferably it is a phenyloxy group, which may further have a substituent.

Examples of aryloxy include phenoxy.

Examples of the substituent of substituted aryloxy include carboxyl or a salt thereof, sulfo or a salt thereof, and a halogen atom.

The alkyl moiety of the alkylcarbonyloxy group as a split-off group is preferably a straight chain or branched alkyl moiety having 1 to 22 carbon atoms, and these are unsubstituted alkyl moieties that may further have a substituent. What is
Preferred examples include methyl, ethyl, tert-butyl, Ω-dodecyl, and rhotocodyl.

The substituent of the alkyl moiety having a substituent is preferably a halogen atom (eg, fluorine, chlorine, bromine, etc.).

The arylcarbonyloxy group as a split-off group is preferably a phenylcarbonyloxy group,
These may have substituents.

Preferred examples of arylcarbonyloxy include phenylcarbonyloxy and the like.

Examples of the substituent of the substituted arylcarbonyloxy include an alkyl group and an alkylamido group.

The alkyl group is preferably alkyl, such as methyl, tert-butyl, and the like.

Examples of the alkylamide group include dodecanamide, 2.
Examples include 4-di-tert-amylphenoxyacetamide.

The alkyl moiety of the alkylsulfonyloxy group as a split-off group is preferably a straight or branched alkyl moiety having 1 to 22 carbon atoms, which may further have a substituent.

Examples of unsubstituted alkyl moieties include methyl, tert-butyl, n-dodecyl, n-tocosyl, and the like.

Any group can be selected as the substituent for the alkyl moiety having a substituent, but an alkylamide group is preferable, and an alkylamide group is more preferable, such as lauroylamide, N-methyllauroylamide, etc. It will be done.

The aryl moiety of the arylsulfonyloxy group as a split-off group is preferably a phenyl group, which may further have a substituent.

An example of the unsubstituted aryl moiety is phenyl.

As the substituent for the aryl moiety having a substituent, for example, alkyl having 1 to 22 carbon atoms is preferable.

The alkylcarbamoyloxy group as the sfrite-off group is preferably an alkylcarbamoyloxy group having 1 to 4 carbon atoms.

The arylcarbamoyloxy group as a split-off group is preferably a phenylcarbamoyloxy group.

Examples of arylcarbamoyloxy include phenylcarbamoyloxy.

Any group can be selected as the substituent of the substituted arylcarbamoyloxy, but examples include a halogen atom, an alkoxy group (preferably unsubstituted alkoxy, such as methoxy, ethoxy, etc.), an alkylamide group (preferably an alkylamide For example, propionamide,
dodecanamide, etc.), cyan group, etc.

As for the alkylamide group as a split-off group,
Particularly preferred are halogen-substituted alkylamides, such as trichloroacetamide, trifluoroacetamide,
Examples include heptafluoropropionamide, octafluoropencunamide, and the like.

The arylamide group as the split-off group is preferably a penzamide group, more preferably a halogen-substituted penzamide, such as pentachloropenzamide, pentafluoropenzamide, and the like.

an alkylsulfonamide group as a split-off group,
The alkyl moiety and aryl moiety of the arylsulfonamide group have the same meaning as the alkyl moiety and aryl moiety of the alkylsulfonyloxy group and arylsulfonyloxy group, respectively, as a split-off group.

The 5- or 6-membered imide group as a split-off group preferably includes a succinimide group or a glucurimide group, which can be further grouped by an alkyl group (preferably a straight chain or branched alkyl group having 1 to 22 carbon atoms). It may be substituted, or it may form a condensed ring like phthalimide.

The arylazo group as the split-off group is preferably a phenylazo group, for example, a phenylazo substituted with a halogen atom or an alkyloxycarbonyl group having 1 to 22 carbon atoms, and the alkyl portion of this alkyloxycarbonyl group is further substituted. may have been done.

Examples include 2-chloro-5-(α-(dodecyloxycarbonyl)ethoxycarbonyl)-phenylazo, 0-octadecyloxycarbonylphenylazo, and the like.

A 5- or 6-membered heterocyclic thio group containing 1 to 4 nitrogen atoms in its molecular structure as a split-off group includes an imidazole group, a triazole group, a tetrazole group,
A heterocyclic thio group such as an oxazole group, a thiazole group, or a thiadiazine group is included, and this tetracyclic moiety may also form a condensed ring with another unsaturated or saturated hydrocarbon.

Examples of these include 1-phenyltetrazolyl-
5-thio, pentz triazolylthio, pentzoxazolylthio, pentzthiazolylthio, 3-benzoyl-5-
Examples include methyl-1,3,4-thiadiazin-2-yl-thio.

Preferred examples of the arylthio group, arylseleno group, and arylsulfonyl group as the split-off group include phenylthio, phenylseleno, and phenylsulfonyl, respectively.

According to a preferred embodiment of the present invention, when X and Y in general formula [1] are a hydrogen atom, a halogen atom, or a split-off group, the compound of the present invention comprises two molecules of aromatic primary amine color developing It is coupled with the base agent and is a conventional cyan coloring dye (as is well known in the art, this is a dye coupled with one molecule of aromatic primary amine developing raw chestnut).

) produces a pure black colored pigment different from that of Further, according to a more preferred embodiment of the present invention, in the general formula [I], at least one of R1 and R2 is a hydrogen atom.

These black image forming couplers used in the present invention are:
Since it does not contain a color developing agent moiety in its molecular structure, it is extremely stable against oxidation and can produce excellent images without staining.

Next, typical examples of black couplers preferably used in the present invention will be listed, but the present invention is not limited thereto.

[Typical example of black coupler]

(1) N-octadecyl-m-aminephenol (2)
N-(α-(dodecylcarbamoyl)ethyl)-m-aminephenol (3) 4-(4-lauroylamidophenethyl)-m-
Aminophenol (4) 4-chloro-N-octadecyl-m-aminophenol (5) 6-chloro-N-octadecyl-m-aminophenol (6) 2-lilo-4-(isopropylcarbamoylmethoxy)-5-N- Octadecylaminophenol (7) 4-(iso-propylcarbamoylmethoxy)-
3-N-Octadecylaminophenol (8) 4-Benzenesulfonyloxy-3-N-octadecylaminophenol The compound that produces a black dye image used in the present invention is:
The color coupler is not limited to the above black coupler, and may be a mixture of two or more color couplers.

Specifically, a black dye image according to the present invention can be obtained by mixing two or more color couplers.

For example, a black dye image can be obtained by mixing a magenta coupler and a cyan coupler with high secondary absorption, and a black dye image can be obtained by appropriately selecting and mixing ordinary color couplers such as yellow, magenta, and cyan. It is also possible to generate images.

Furthermore, it is also possible to form a black dye image by mixing four or five or more color couplers with different absorption characteristics.

That is, the compound forming a black dye image of the present invention may be any compound or a combination of a plurality of compounds as long as it reacts with the oxidation product of a commonly used color developing agent to form a black dye image.

Next, a compound that produces a black dye image (hereinafter referred to as a black dye-forming compound) is used in the present invention.

) The amount and timing of addition will be explained (the addition method will be described later).

). That is, the amount of the black dye-forming compound added is 1 to 1000 g, preferably 5 to 500 g per mole of silver, and the addition timing is after oil protection or Fischer dispersion but before coating. It is desirable to add it to a silver halide emulsion.

The color developing agent used to obtain the black dye image of the present invention is generally a compound that reacts with a color coupler to form a color dye image.

Particularly preferably used color developing agents in the present invention include para-phenylenediamine and derivatives thereof.

Among these, color developing agents that are preferably used in the present invention are listed below, but the color developing agents that can be used in the present invention are not limited to these.

[Representative examples of color developing agents]

(1) Diethyl-p-phenylenediamine hydrochloride (2)
Monomethyl-p-phenylenediamine hydrochloride (3) Dimethyl-p-phenylenediamine hydrochloride (4) 2-amino-5-diethylaminotoluene hydrochloride (5) 2-amino-5-(N-ethyl-N-dodecylamino )-Toluene (6) N-ethyl-N-β-methanesulfonamidoethyl-5-methyl-4-aminoaniline sulfate (7) N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline ( 8) 4-N-ethyl-N-β-hydroxyethylaminoaniline (9) 4-amino-3-methyl-N,N-diethylaniline hydrochlorite (10) 4-amino-3-methyl-N-ethyl -N-β
-Hydroxyethylaniline sulfate (11) 4-
Amino-3-β-(methanesulfonamido)ethyl-N
, N-diethylaniline (12) 4-amino-N-(2-methoxyethyl-m-
Toluidine) These color developing agents may be used alone or in combination of two or more, and if desired, in combination with a black and white developing agent such as hydroquinone.

Furthermore, color developing solutions containing these color developing agents generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite, etc., and various additives such as alkali metal halides such as odors. Potassium.

Alternatively, other photographic additives such as development regulators such as citradinic acid may be included.

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

Further, the color light-sensitive material according to the present invention can also be subjected to a known dye image reinforcement treatment.

In the development process of the color photosensitive material according to the present invention, when silver halide or a developer is removed from the system, generally a fixer, a combination of a fixer and a bleacher, or a bleach-fixer as a single bath are used. These are used in combination with various treatments, such as water washing, stop treatment, stabilizing solution treatment, etc., and silver halide solvents such as sodium thiosulfate and ammonium thiosulfate are used as fixing components. As a bleaching ingredient, instead of the conventional red blood salt, use of ferric aminopolycarboxylic acid salt, ferric chloride salt, ferric ammonium ethylenediaminetetraacetate, or urem salt will cause a decrease in image density. The so-called "stripes" in neutral gray and some shadows are well reproduced.

The black dye-forming compound and color coupler used in the present invention are 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, triphenyl phosphate, etc., and low-boiling point solvents such as ethyl acetate, butyl acetate, chloroform, etc. are used, and a colloid is used in the coexistence of a surfactant. This may be carried out in a conventional manner using a mill, an ultrasonic disperser, or the like.

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

Silver halides used in the coupler-containing silver halide emulsion layers and layers of the color light-sensitive material according to the present invention include, for example, silver chloride, silver bromide, silver iodide, mixed silver halides (for example, silver chlorobromide, Silver iodobromide, silver iodochlorobromide, etc. can be arbitrarily selected depending on the purpose of use.

Further, emulsions containing these silver halides can be prepared by any known method.

For example, the silver halide emulsion for constituting the silver halide emulsion layers and layers containing color couplers used in the present invention may be so-called conversion emulsions, Lippmann emulsions, covered grain emulsions, or optically or chemically capped emulsions. These may be appropriately selected depending on the type and use of the photosensitive material.

Further, the type of silver halide, content and mixing ratio of silver halide, average grain size, size distribution, etc. are similarly selected appropriately depending on the type and use of the color light-sensitive material according to the present invention.

For example, the color photosensitive material of the present invention, which requires relatively low sensitivity and high image quality, uses an emulsion mainly consisting of a silver chloride emulsion with fine grains and a narrow size distribution, and also requires relatively high sensitivity. In the color light-sensitive material according to the present invention, an emulsion with relatively large grain size and low silver chloride content is used.

Further, for color reversal, particularly direct reversal type color light-sensitive materials, emulsions which have been previously fogged are used.

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

Further, this silver halide can be used alone or in combination (for example, supersensitization) with an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, a trimethine dye, or a merocyanine dye to obtain a desired spectrum. The area can be optically sensitized.

The silver halide used in the present invention is dispersed in a suitable hydrophilic colloid and coated on a suitable support to form a halogenated silver halide containing various color couplers constituting the color photosensitive material according to the present invention. In addition to the silver halide emulsion layer and the composite layer, the color photosensitive material according to the present invention also includes other constituent layers such as an intermediate layer, a protective layer, a filter layer, an antihalation layer, It may have a hydrophilic colloid layer such as a subbing layer and an anti-curl layer.

The hydrophilic colloid commonly used in the hydrophilic colloid layer and the silver halide emulsion layer and layer is gelatin, and other derivatives such as gelatin, colloidal albumin, cellulose derivatives, or polyvinyl compounds (for example, polyvinyl alcohol) are also used. These synthetic resins can be used alone or in combination, but acetyl cellulose with an acetyl content of about 19 to 26%, water-soluble ethanolamine cellulose acetate, etc. can also be used in combination.

The color photosensitive material according to the present invention contains yellow, cyan and magenta color couplers for forming a color image.

Couplers useful in the present invention include, for example, open-chain methylene yellow couplers, 5-pyrazolone magenta couplers, phenolic or naphthol cyan couplers, and even if these couplers are of the so-called 2-equivalent type, they are 4-equivalent couplers. In addition, in combination with these couplers, it is also possible to use azo-type colored couplers for auto-masking, osazone-type compounds, development-diffusive dye-releasing couplers, etc. Furthermore, photographic properties can be improved. Couplers called so-called competing couplers, DIR couplers, BAR couplers, etc. can also be included in combination with various couplers to improve the performance.

As the yellow coupler used in the present invention, an open chain ketomethylene compound has conventionally been used, and for example, a pivalyl acetanilide type yellow coupler or a benzoylacetanilide type yellow coupler is effective, and furthermore, a so-called 2-equivalent type coupler is used. , Active point -〇-allyl substitution, Active point -〇-acyl substitution, Active point substitution with hydantoin compound, Active point substitution with urazole compound, Active point substitution with succinimide compound, Active point substitution with monooxyimide compound, Active point substitution with pirixone compound. , active point fluorine substitution, active point chlorine or bromine substitution, or active point -θ-sulfonyl substitution can also be used.

Among these yellow couplers, particularly effective ones are those disclosed in U.S. Pat.
Couplers described in JP-A-48-66834 can be mentioned.

Examples of magenta couplers used in the present invention include known pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indasilone compounds.

Particularly preferred magenta couplers used in the present invention include those described in Japanese Patent Publication No. 48-27930 and the 3-aniline pyrazolone magenta couplers described in U.S. Pat. No. 3,127,269.

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

The silver halide emulsion layer, interlayer and/or other constituent layers of the color light-sensitive material according to the present invention may contain various photographic additives depending on the purpose.

Such photographic additives include, for example, stabilizers (mercury compounds, triazoles, azaindenes, quaternary benzothiazolium, cadmium salts of zinc aloys, etc.), quaternary ammonium salts, sensitizers such as polyethylene glycols, etc. agent;
Film property improvers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, acrylic acid amides, emulsified dispersion rings of polymers; dura mater agents such as formaldehyde, halogen-substituted fatty acids such as mucochloric acid, mucobonic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, disulfonic acid chlorides, vinylesters of methanesulfonic acid, aldehyde groups having 2 to 3 carbon atoms; Sodium bisulfite derivatives of dialdehydes, bisazirines, vinyl sulfone compounds, ethyleneimines, etc.; 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 organic solvents and/or low-boiling organic solvents, specifically dibutyl phthalate, tricresyl phosphate, acetone, methanol, ethanol, ethylene cellosolve, etc.) - A so-called DIR compound that releases a color development inhibitor and produces a substantially colorless compound during color development, its fine antistatic agent, antifoaming agent, ultraviolet absorber, fluorescent whitening agent, anti-slip agent, Various agents such as matting agents, halation or irradiation inhibitors can be used alone or in combination.

Supports that can be used in the color photosensitive material of the present invention include paper, laminated paper (for example, a laminate of polyethylene and paper), glass, cellulose acetate, cellulose nitrate, polyester, polycarbonate, polyamide, polystyrene, and polyolefin. Examples include film-like or sheet-like substrates such as .

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 can be performed.

According to the present invention, a maximum density of 0.1 to 0.7 is obtained by reacting with an oxidation product of raw chestnuts for color development, such as a paraphenylenediamine color developing agent commonly used in the development of color photosensitive materials.
In order to use a compound in the formation that produces a black dye image of
As mentioned above, the image quality is significantly improved to an extent that could not have been expected from the prior art using a silver image as a black dye image component.

In addition, as in the present invention, by specifying the spectral sensitivity region, sensitivity, maximum color density, and layer structure of the layer, the layer is particularly provided on the side closer to the support than any of the color coupler-containing silver halide emulsion layers. By doing this, it is possible to obtain a color photosensitive material with excellent reproducibility of neutral gray and excellent color reproduction, and furthermore, it is possible to obtain a color photosensitive material that is stable against changes in the photographing conditions and development processing conditions of the color photosensitive material. A color photosensitive material with excellent color reproducibility and color reproducibility can be obtained.

These effects of the present invention are particularly noticeable in color positive films, color reversal films, and color papers.

Hereinafter, the effects of the present invention will be illustrated by examples, but the embodiments of the present invention are not limited to these examples.

Example-1 Samples A-E were prepared as follows.

(Sample A) Valyl on 2-(1-benzyl-2,4-dioxoimidazolidin-3-yl)-2-2'-chloro-5'- as a coupler on a resin-coated paper support.
[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 having an average grain size of 0.6 μm and coated.

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

A gelatin intermediate layer was provided on top of this.

Then, as a coupler, 3-[2-di-4-5-(1-octadecenylsuccinimide)anilino)-1-(2,4,6-drichlorophenyl)-5-
After dissolving pyrazolone in cyphthylphthalate and protecting and dispersing it in an aqueous gelatin solution, anhydro-5,5'-diphenyl-9-ethyl-3,3 was obtained with an average particle size of 0.3μ.
The mixture was mixed with a green-sensitive silver chlorobromide emulsion color-sensitized with '-di(3-sulfopropyl)oxacarbocyanine hydroxide, and then coated and dried.

The amount of coupler used in this ortho layer was 4.3 .ANG./100 cm@2, and the amount of silver was 45 .ANG./100 cm@2.

A gelatin intermediate layer is coated on top of this layer, and 2-(2-(2,4-ditert) is further applied as a coupler on top of this layer.
-pentylphenoxy)bucunamide]-4,6-dichloro-5-methyl-phenol was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and anhydro-2-[4,4-dimethyl -2-(5-methoxy-3-ethyl-2-penzothiazolinylidene)-methyl-1-cyclohexene-6-ylidene]methyl-3-(3-sulfopropyl)benzo-thiazolium-hydroxide It was mixed with a sensitized red-sensitive silver chlorobromide emulsion, 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 photosensitive material for color paper.

The amount of coupler used in the panchromatic layer was 29 m9 per 100 cm2, and the amount of silver was 3.0 square meters.

This light-sensitive material was exposed using a light source at 3200 DEG through a step wedge having a step density of 0.75, and then subjected to the following development-bleach-fixing-stable processing.

The sensitometry results obtained by measuring the obtained sample A with a Macbeth densitometer through a Status AA filter show that the neutral balance of blue region density B, green region density G, and red region density R is good in the entire concentration range. , and B
, G, and H were all 2.2.

The maximum black density was 2.0 when measured through a Wratten filter 106.

[Processing process]

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 used in the above processing is shown below.

[Color developer J [Bleach-fix solution]

[Stabilizer] (Sample B) Next, on the same support as Sample A and on the side closest to the support, add a sensitizing dye with an average particle size of 0.15μ and the same sensitizing dye as the one layer of magenta coupler. A color-sensitized green-sensitive silver chlorobromide emulsion and 4-chloro-N-octadecyl-m-amine phenol as a black dye-forming compound dissolved in dibutyl phthalate and protected and dispersed in an aqueous gelatin solution were mixed and prepared per 100 cm2. A different layer was coated so that the coating amount was 0.5 mg of black dye-forming compound and 1.2 mg of silver, and a gelatin solution was further coated on top of this. Sample B was prepared by sequentially applying silver halide emulsion layers containing sensitive and red-sensitive color couplers.
I got it.

The different layer of sample B is color sensitized in the green region, and its sensitivity is higher than that of the green-sensitive emulsion layer 1 containing the magenta coupler.
/4.

Sample B was subjected to sensitometry in the same manner as sample A, and the color balance of B, G, and H was almost the same as sample A, but the maximum black density measured using the Latten filter 106 was The concentration of sample B was 0.3 higher than that of sample A.

(Sample C) Sample C was prepared in exactly the same manner as Sample B, except that a silver chlorobromide emulsion with an average grain size of 0.23 μm was used as the different layer emulsion.

Note that the different layer of sample C has been color sensitized to green sensitivity,
Its sensitivity is 1/2 that of the green-sensitive emulsion layer containing the magenta coupler, and the sensitometric development results are B,
The color balance of G and R was almost the same as that of sample A, but the increase in maximum black density due to the different layers was 0.3.

(Sample D) Consists of the same emulsion composition as Sample B, but coated amount of 4-chloro-N-octadecyl-m-aminephenol as a black dye-forming compound in a different layer, 1.0 mg per 100 cm2 of G.
A sample sample was prepared in exactly the same manner as sample B except that the amount was increased.

The different layer of this sample was color sensitized to green, and its sensitivity was 1/4 that of the green-sensitive emulsion layer containing the magenta coupler.

Furthermore, sensitometry was performed on the sample in the same manner as sample A, and the results showed that the color balance of B, G, and H was almost the same as sample A, but the increase in maximum black density due to different layers was 0.8. there were.

(Sample E) Consists of the same emulsion composition as Sample B, but with a coating amount of 4-chloro-N-octadecyl-m-aminephenol as a black dye-forming compound in a different layer at 0.1 mg per 100 cm2.
Sample E was prepared by reducing the amount to .

The different layer of Sample E was color sensitized to green light, and its sensitivity was 1/4 or less of that of the green-sensitive emulsion layer containing the magenta coupler.

Also, the results of sensitometry similar to sample A are B, G
, R color balance was almost the same for Sample A, but the increase in maximum black density due to different layers was 0.08.

These samples A, B, C, D and E have a neutral chart (neutral gray chart with 6 levels from white to black) and a color chart (red, blue, green, cyan, magenta, yellow, purple, orange, skin tone). Magnification printing was carried out through a color negative on which the sample A was copied, and then the development process shown in the description of sample A above was carried out.

After adjusting the printing conditions several times, the evaluation of each best print obtained is shown in Table 1 below.

As is clear from the results in Table 1 below, Sample B, in which the spectral sensitization regions of different layers, the sensitivity, and the maximum density of the black dye image obtained after processing were adjusted within the present invention, is different from Comparative Sample A and the present invention. Compared to Samples U, D, and E, which have different layers that are not sufficiently adjusted, the reproduction of black, white, and neutral gray is excellent, and the color reproduction is also excellent.
It can be seen that the condition is also good.

In addition, when preparing sample B, sample F (
One layer of color coupler was not coated).

This sample F was exposed and developed in the same manner as sample A, and the spectral reflection density (400 mμ to 700 mμ) of the resulting black image at densities of 0.1 and 0.3 was measured.

As a result, both samples B and F were 400 mμ to 700 m
The minimum spectral reflection density between μ was 80% or more of the maximum spectral reflection density, and the color was almost pure black.

Example 2 Samples A and B prepared in Example 1 were photographed under various light sources as shown below, and enlarged and printed through the developed negatives.
The same treatment as in Example-1 was performed.

These photographing conditions and the evaluation of the finished prints are summarized in Tables 2 and 3 below.

[Negative subject]

1. Neutral gray chart (chart with 6 levels of reflection density from white to black) 2. Color chart (red, blue, green, cyan, magenta,
Yellow, purple, orange, skin color) As is clear from Tables 2 and 3, Sample A, which does not have the interface layer of the present invention and is not according to the present invention, is affected by the photographing light source and the reproduction of neutral gray is significantly distorted. It can be seen that, although the color reproduction also deteriorates, Sample B according to the present invention having the interfacial layer of the present invention is hardly affected by the photographing light source and has significantly improved neutral gray and color reproduction.

Example 3 Of Sample B prepared in Example 1, the interface layer emulsion was anhydro-2-[4,4-dimethyl-2-(5-methoxy-
3-Ethyl-2-benzothiaprinyritene)-methyl-
1-cyclohexene-6-yritene]methyl-3-(3
-Sulfopropyl) benzothiazolium hydroxide to red-sensitize the silver chlorobromide emulsion with an average diameter of about 0.15μ, and as a black dye-forming compound, 4-(isopropylcarbamoylmethoxy)-3- Sample G was prepared in exactly the same manner as Sample B except that N-ocucudecylaminophenol was used.

The interface layer of this sample G was color sensitized to red sensitivity, and its sensitivity was 1/6 of that of the emulsion layer containing the cyan coupler.

Sensitometry was also performed in the same manner as for sample A, and the increase in maximum black density due to the interfacial layer was 0.4.

Next, sample A (prepared in Example-1) and this sample G were
After exposure through a step wedge with a step density of 0.75 using a light source at 0.00 DEG, the following processing was carried out.

However, for bleach-fixing processing, one set was treated with a fresh bleach-fixing solution (oxidation potential, +30 mV), and the other set was processed with a fully used bleach-fixing solution (oxidation potential, -100 mV). Ta.

[Processing process]

Development (3,5 minutes) → bleach-fix (1,5 minutes) → washing with water (2 minutes) → stabilization (1 minute) → drying (processing temperature 30°C) [Color developer] Bleach-fix solution) is Example-1 Same as .

After the stabilizing solution treatment, each sample was dried and the maximum concentration of B, G, and R (
reflection density) was measured.

The results are shown in Table-4.

As is clear from Table 4, Sample A, which does not have an interfacial layer and is not according to the present invention, has a strong cyan green defect and a large decrease in light density due to treatment with a tired bleach-fix solution, but the interfacial layer of the present invention It can be seen that in Sample G according to the present invention, the reduction in light density in a fatigued bleach-fix solution is greatly improved.

In addition, when creating Sample G, Sample H was created by applying only the interlayer, and this was exposed and developed in the same manner as Sample G, and the obtained black image was evaluated in the same manner as Sample F. .

As a result, Sample H was also pure black like Sample F.

Example 4 Among Sample B prepared in Example 1, the interlayer emulsion was changed to a silver bromide emulsion with an average grain size of 03 μm, and N-occudenylaminophenol and αpivaloyl were added as black dye-forming compounds. α-(1-phenyl-2-benzyl-1,2,4-triazine-3,5-dion-4-yl)-2-chloro-
5(α-(dodecyloxycarbonyl)-ethoxycarbonyl)acedoanilide and 3-(2-chloro-5-
[1-ocucudecenylsuccinimide]anilino)-1
-(2,4,6-1-lichlorophenyl)-5-pyrazolone was mixed in a weight ratio of 0.71:0.20:0.09, dissolved in dibutyl phthalate, and dispersed in an aqueous gelatin solution. , Sample (2) was prepared in exactly the same manner as Sample B except that the coating was applied in an amount of 0.4 m9 per 100 cm2.

The interface layer of this sample (1) is blue-sensitive, and its sensitivity is 115 of that of the blue-sensitive emulsion layer containing the yellow coupler,
Furthermore, the results of sensitometry after development similar to Sample A showed that the increase in maximum black density due to the interlayer was 0.7.

This sample (1) was enlarged and printed through the negative of Example-1, and developed in the same manner as in Example-3.

The resulting print had extremely good neutral gray and black tones and sufficient color saturation.

Incidentally, when preparing sample (2), sample J was prepared in which only a different layer was coated, and after exposure, this sample J was subjected to the same treatment as sample (2).

After drying, the spectral reflection density was measured at a black density of 0.1 and 0.5.

As a result, both samples had a minimum spectral reflection density of 90% or more of the maximum spectral reflection density between 400 mμ and 700 mμ, and were almost pure black.

Comparative Example-1 A comparative sample consisting of the same emulsion structure as Sample B prepared in Example-1, but having a different layer structure in the following points, was
and M were made.

(Sample K) A photosensitive material in which the different layer of Sample B and a gelatin layer are provided between a green-sensitive emulsion layer and a blue-sensitive emulsion layer.

(Sample L) A photosensitive material in which the different layer of Sample B and the gelatin layer are provided between a green-sensitive emulsion layer and a red-sensitive emulsion layer.

(Sample M) A photosensitive material in which the different layers of Sample B and the gelatin layer are provided as the top layer.

These comparative samples were subjected to enlargement printing and development processing for L and M in the same manner as in Example-1.

After adjusting the printing conditions several times, the evaluation of each best print obtained is shown in Table 5 below.

As is clear from the comparison between the results in Table 5 and the results of sample B of the present invention shown in Table 1 of Example 1, the comparative sample in which the different layer is located outside the present invention, It can be seen that both L and M are inferior to Sample B of the present invention in terms of color reproducibility.

That is, it can be seen that excellent color reproducibility can be obtained in the case of the present invention in which the different layers are located on the side closest to the support.

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. In a silver halide multilayer color photographic light-sensitive material having an emulsion layer, at least one layer is provided on the side closer to the support than any of the above-mentioned emulsion layers, apart from the silver halide emulsion layer containing each color coupler.
one silver halide emulsion layer is provided, the other silver halide emulsion layer is spectrally sensitized in at least one spectral region of blue, green, or red, and the sensitivity is spectral sensitized in the same spectral region; It is less than 1/3 of the silver halide emulsion layer containing each of the color couplers and further reacts with the oxidation product of the color developing agent to form a black dye image with a maximum density of 0.1 to 0.7. A silver halide multilayer color photographic material containing a compound that produces a silver halide. 2. The silver halide multilayer color photographic material according to claim 1, wherein the color developing agent is paraphenylenediamine or a derivative thereof. 3. The minimum spectral density of the visible spectral density distribution characteristics of the black dye image produced when the compound that forms the black dye image reacts with the oxidation product of the color developing agent is 50% or more of the maximum spectral density. A silver halide multilayer color photographic material according to claim 1 or 2, characterized in that: 4. The silver halide multilayer according to claim 1, 2, or 3, wherein the silver halide multilayer color photographic light-sensitive material is a color positive film, a color reversal film, or a color paper. Color photographic material.